Patent Publication Number: US-2021188654-A1

Title: Systems and Methods for Producing Elements from Mixtures, Storage/Generation Vessels, and Storage/Generation Vessel Assemblies

Description:
CROSS REFERENCE TO RELATED APPLICATION 
     This application is a continuation-in-part of U.S. patent application Ser. No. 16/894,679 filed Jun. 5, 2020, entitled “Systems and Methods for Separating Radium from Lead, Bismuth, and Thorium”, which claims priority to and the benefit of U.S. Provisional Patent Application Ser. No. 62/857,681 filed Jun. 5, 2019, entitled “Separation of Radium from Lead, Bismuth, and Thorium for Medical Isotope Production Applications”. This application also claims priority to and the benefit of U.S. Provisional Patent Application Ser. No. 62,946,592 filed Dec. 11, 2019 entitled “Fluidic System for Packing Generator Columns with Resin Containing Homogeneously Distributed Isotope”, the entirety of each of which are incorporated by reference herein. 
    
    
     STATEMENT AS TO RIGHTS TO DISCLOSURES MADE UNDER FEDERALLY-SPONSORED RESEARCH AND DEVELOPMENT 
     This disclosure was made with Government support under Contract DE-AC0576RL01830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention. 
    
    
     TECHNICAL FIELD 
     The disclosure generally relates to the isolation of metals as elements for example and assemblies for the storage/generation of metals and in more particular embodiments, to medical radionuclides and more to methods for obtaining materials and performing separations for generating such materials. 
     BACKGROUND 
     In the field of medical radionuclide separations of materials and preparation of materials for inclusion in various treatments face a number of obstacles. Availability, cost, timing, and limited shelf-life coupled with the need to perform many activities in specialized safe facilities create a number of obstacles. The existing method of  212 Pb/ 212 Bi generator preparation requires two steps: first  224 Ra must be isolated from a  228 Th stock solution; second the  224 Ra must be loaded onto a cation exchange (CatIX) resin (which becomes the  212 Pb/ 212 Bi generator column), the performance of which can expose staff to a high radiological dose. The dose is largely caused by the short-lived progeny below  212 Po. In addition, this method is cumbersome and labor intensive and can require multiple columns and boil-down steps to achieve the desired ends. 
     What are needed are more and more improved methods for simplifying these processes, increasing the yields and addressing the various barriers to use. The following description provides various examples and advances in this regard. 
     SUMMARY 
     Systems for separating Ra from a mixture comprising at least Ra, Pb, Bi, and Th are provided. The systems can include: a first vessel housing a first media and either Pb or Bi and/or Th; and a second vessel in fluid communication with the first vessel, the second vessel housing a second media and Ra, wherein the first media is different from the second media. 
     Systems for separating Ra from a mixture comprising at least Ra, Pb, Bi, and Th are also provided that can include a first vessel housing a first media and Th and/or Bi; and a second vessel in fluid communication with the first vessel, the second vessel housing a first media and Pb, wherein the first media is different from the second media. 
     Additional systems for separating Ra from a mixture comprising at least Ra, Pb, Bi, and Th can include: a first vessel housing a first media and Th or Bi; a second vessel in fluid communication with the first vessel, the second vessel housing a second media and Pb; and a third vessel in fluid communication with the second vessel, the third vessel housing a third media and Ra, wherein at least one of the first, second, or third medias are different from the other medias. 
     Methods for separating Ra from Pb, Bi, and Th are provided, the methods can include: providing a first mixture comprising Ra, Pb, Bi, and/or Th; providing a system that includes: a first vessel housing a first media; and a second vessel in fluid communication with the first vessel, the second vessel housing a second media; exposing the first mixture to the first media within the first vessel to separate the Th and Bi from the Ra and Pb; then, through the fluid communication, exposing the remaining mixture to the second media in the second vessel to associate the Pb or Ra with the second media. 
     Methods for separating Ra from Pb, Bi, and Th can also include providing a first mixture comprising Ra, Pb, Bi, and/or Th; providing a system that can include: a first vessel housing a first media; a second vessel in fluid communication with the first vessel, the second vessel housing a second media; and a third vessel in fluid communication with the second vessel, the third vessel housing a third media; and exposing the first mixture to the first media within the first vessel then, through the fluid communication, exposing the first remainder to the second media in the second vessel, then, through fluid communication, exposing the next remainder to the third media in the third vessel, the exposing separating the Th and Bi from the Ra and Pb, and the Ra from the Pb. 
     Methods for separating Ra from being associated with a media are also provided. The methods can include: exposing the Ra and media to a chelating agent to form a mixture comprising the Ra complexed with the chelating agent. 
     Methods for separating Ra from Pb, Bi, and Th are also provided that can include: providing a first mixture comprising Ra and at least Bi and/or Th; separating one or more of Bi and/or Th from the Ra, the separating associating the Bi and/or Th with a first media; and disassociating the Bi and/or Th from the first media to form a mixture comprising the Bi and Th and transferring the mixture to a vessel housing at least Ra and additional Bi and/or Th. 
     The system/methods can include providing a mixing vessel in fluid communication with both a bound element source and an acid source. The mixing vessel can be operably configured to mix contents within the mixing vessel. The systems can include a first multiport valve operably engaged with an exit of the mixing vessel, and a second multiport valve operably engaged with the first multiport valve, the acid source, and a collection vessel. 
     Methods for producing free element from a bound element are also provided. The methods can include: providing a solution comprising an element bound to a complex; exposing the solution to an acid solution to separate the complex from the element; and removing either the separated element or the complex from the solution to produce a free element. 
     Systems and/or methods for producing metal storage/generation vessel assemblies are provided. The systems can include: a first mixing vessel in fluid communication with a first and a second multiport valve; a manifold of multiport valves in fluid communication with the second multiport valve; a second mixing vessel in fluid communication with at least one of the multiport valves of the manifold; a third multiport valve in fluid communication with an exit of the second mixing vessel; and a metal storage/generation vessel in fluid communication with the third multiport valve. 
     The first and second mixing vessels define different volumes. The first mixing vessel defines a volume larger than the volume defined by the second mixing vessel. 
     Methods for producing a metal storage/generation vessel assembly are also provided. The methods can include: homogenizing a resin slurry in a first mixing vessel; supplementing the homogenized resin slurry with a free element to form a homogenized bound element resin slurry; and transferring the homogenized bound element resin slurry to a storage/generation vessel assembly. As shown and described, the resin/media alone or in combination with free element of the present disclosure, without homogenization will consolidate at the lower portion of the vessel or adhere to other portions of the vessel. Homogenizing herein keeps the resin/media alone or in combination with free element distributed throughout the solution of the vessel. This distribution can be uniform and/or without a heterogenous interface. 
     Metal storage/generation vessel assemblies are also provided that can include: sidewalls extending between entrance and exit openings to define a vessel volume; inert material proximate the exit opening: and a homogenized bound element resin bed within the vessel, the inert material being between the resin bed and the exit opening. 
    
    
     
       DRAWINGS 
       The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee. 
       Embodiments of the disclosure are described below with reference to the following accompanying drawings. 
         FIG. 1  depicts an overall scheme for isolating, freeing, and generating storage/generator vessel assemblies according to an embodiment of the disclosure. 
         FIG. 2  represents a more specific scheme also depicting an example storage/generator assembly and the generation of isotopes using the storage/generator vessel assembly according to an embodiment of the disclosure. 
         FIG. 3  depicts an example modified triple-column  224 Ra isolation scheme; green cells indicate active flow paths at each step A through E. (A) Load and wash “a” to adsorb Th, Pb, and Ra on C 1 -C 3 , respectively; (B) Secondary wash “b” for C 2 -C 3 ; (C) Water rinse through C 3  to remove H+ ions; (D) Ra elution from C 3 ; and (E) Elution of Th from C 1  for reuse. 
         FIG. 4  is a depiction of Step A: Initial 3-column load of  228 Th stock +wash “a”. 
         FIG. 5  depicts gamma spectra obtained following triple-column load/wash routine (see path A in  FIG. 4 ). The  228 Th/progeny sample is loaded (A) and washed (B) through all three columns using 6 M HNO 3 ; no activity is observed to break through the three-column stack. (C) Following load and wash steps, the AnIX poly  (defined below in Table 1) media (C 1 ) shows  228 Th,  212 Bi, and  208 Tl adsorbed on the resin beads. 
         FIG. 6  depicts gamma spectrum showing a prominent  224 Ra emission in a fraction collected immediately downstream of C 2  during the wash “a” sequence. Traces of  212 Bi / 208 Tl (unretained on C 2 ), likely generated by the  212 Pb adsorbed on C 2 , are likewise observed. 
         FIG. 7  depicts Step B: C 2 +C 3  wash “b”. 
         FIG. 8  depicts (A) Resin capacity factors (k′) for Group II divalent cations in nitric acid on Sr Resin. (B) Sr Resin effluent fraction elution profiles for unretained  212 Bi and slightly retained  224 Ra in 2 M HNO 3 . 
         FIG. 9  depicts gamma spectra obtained following double-column load/wash routine (see path B in  FIG. 7 ). (A) The  212 Pb and  224 Ra are washed through C 2 /C 3  using 2 M HNO 3 ; no activity is observed to break through the two-column stack, as  212 Pb is retained on the Sr Resin column (C 2 ) and  224 Ra is retained on the Ra-01 Resin column (C 3 ). (B) Spectrum taken of the Sr Resin column (C 2 ) at the conclusion of the wash “b” step shows pure  212 Pb. 
         FIG. 10  is Step C: C 3  water rinse. 
         FIG. 11  depicts (A) Elution of residual  212 Pb from the  224 Ra-loaded C 3  using water. (B) Decay rate of the water wash fractions indicated little to no  224 Ra loss during the water wash step. 
         FIG. 12  is Step D: C 3  elution of isolated  224 Ra. 
         FIG. 13  depicts (A) Assembled radiochromatogram of  224 Ra elute fractions. (B) Monitoring the isolated  224 Ra fraction activity over the theoretical decay rate as a function of time shows that it is radionuclidically pure. 
         FIG. 14  is Step E: C 1  elution of  228 Th stock with HCl. 
         FIG. 15  is (A) Elution of  228 Th,  212 Bi, and  208 TI from the AnIX poly  (defined below in Table 1) resin M 1  using 8 M HCl. (B) Spectrum of the AnIX poly  (defined below in Table 1) resin M 1  following the HCl elution cycle indicates incomplete  228 Th elution. 
         FIG. 16  is fluidic layout schematic of automated triple-column based  224 Ra purification system according to an embodiment of the disclosure. 
         FIG. 17  depicts (A) stepper motor driven syringe pump for  228 Th stock solution loading operations. (B) Solenoid-based fluid routing system to drive the triple-column  224 Ra isolation procedure according to embodiments of the disclosure. 
         FIG. 18  is gamma spectra of  228 Th elution chromatogram (A) using 1 M HCl on MP-1M resin (M 1 ).  228 Th elution chromatogram (B) using 8 M HCI on same. Dashed line at 10 mL indicates the beginning of an applied strip solution of EDTA to remove any residual  228 Th from the column. 
         FIG. 19  depicts (A) Load and wash “a” fractions collected from 1 cc TEVA resin effluents in 6 M HNO 3 . Arrow indicates the location of the absent  228 Th X-ray.  212 Pb,  212 Bi and  208 Tl photon peaks are observed to break through the media (the  224 Ra emission is hidden under the  212 Pb peak at ˜240 keV). (B) Analysis of the TEVA resin effluents over time indicate a decay rate consistent with that of  224 Ra; this indicates that  228 Th was well adsorbed on the media during the load/wash “a” steps. 
         FIG. 20  depicts gamma spectra of  228 Th elution chromatogram (A) using 1 M HCl on TEVA resin (M 1 ).  228 Th elution chromatogram (B) using 8 M HCl on same. Dashed line at 10 mL indicates the beginning of an applied strip solution of EDTA. 
         FIG. 21  depicts (A)  228 Th activity fractions as a function of 1 M HCl elution volume from TEVA resins of different column internal volumes. (B) Cumulative  228 Th activity yield for same. 
         FIG. 22  depicts observed activity decay rate of TEVA resin load fraction (combined loads) for a 1 cc (A) vs. 0.25 cc (B) vessel volume. Dashed line is the theoretical decay rate for  224 Ra. Positive deviation from the  224 Ra curve indicates the presence of  228 Th as TEVA resin column breakthrough. 
         FIG. 23  depicts observed activity decay rate of TEVA cartridge  228 Th load fraction for a 2 cc (A), a 1 cc (B), 0.4 cc HML (half-milliliter)(C), and 0.2 cc QML (quarter milliliter) cartridge (D). Black and grey dashed lines are the theoretical decay rate curves for  224 Ra and  228 Th, respectively. Positive deviation from the  224 Ra curve indicates the presence of  228 Th. 
         FIG. 24  (A) depicts observed activity decay rate of TEVA column  228 Th load fraction for a 1 cc hand-packed TEVA resin solid phase extraction (SPE) tube column. (B) depicts cumulative  228 Th activity fractions as a function of 1 M HCl elution volume from same. 
         FIG. 25  depicts cumulative  228 Th activity fractions as a function of 1 M HCl elution volume from machine-packed TEVA resin cartridges of decreasing internal resin volume. Cartridge are (A) 2 cc, (B) 1 cc, (C) HML, and (D) QML. 
         FIG. 26  is HML (0.41 cc) and QML (0.25 cc) cartridges that were evaluated for  212 Pb removal in the C 2  position. 
         FIG. 27  is gamma spectra of  228 Th/ 224  Ra solution effluent fractions from C 1 +C 2  during the load +wash “a” steps in 6 M HNO 3 . C 2  volume was varied between 0.41 cc (A) and 0.25 cc (B) of Sr Resin bed. Colored arrows indicate radionuclides observable in the fractions: blue= 228 Th (absent); grey= 212 Bi; yellow= 212 Pb; green= 224 Ra; orange= 208 Tl. 
         FIG. 27C  depicts metals speciation comparison i) Pb/Pb-EDTA; ii) Bi/Bi-EDTA; iii) Th/Th-EDTA; and iv) Ra/Ra-EDTA along the same pH spectrum. 
         FIG. 27  D i and ii, depicts separation of  224  Ra from  212 Bi and  212 Pb using Ra-01 resin column (3×50 mm) via protocol listed in Table 6B. Column effluent fraction categories are designated at top. Legend is elapsed days between column run and gamma analysis of fractions. (Right) Select elapsed time series indicates radionuclides present across the separation protocol. 
         FIG. 28  depicts (A) load +wash “a” effluent fractions from a 0.25 cc Ra-01 resin showing the elution of  228 Th (arrow), some  212 Pb, and  212 Bi/ 208 Tl. (B) effluent fractions from wash “b” showing no observable  228 Th X-rays (arrow).  212 Bi/ 208 Tl are observed to wash from the media. 
         FIG. 29  is Load/wash “a” column effluent fractions showing  224 Ra elution profile through C 1 +C 2 , wherein C 2  is a (A) HML cartridge or a (B) QML cartridge packed with Sr Resin. 
         FIG. 30  depicts water wash fractions from the C 3  step 3 that was inserted before the  224 Ra elution step. (A) gamma spectra of C 3  effluent fractions collected during water wash show  212 Pb removal. (B) the activity decay rate observed from water wash effluents; it matches the decay rate of  212 Pb. Data indicates that  224 Ra remains adsorbed to the media during water wash. 
         FIG. 31  depicts observed activity decay rate of the primary  224 Ra elution fraction from a Ra-01 resin column (C 3 ) loaded with a  228 Th/ 224 Ra solution. Dashed line is the theoretical  224 Ra decay rate. 
         FIG. 32  is a speciation diagram for Ra(II) and Ra(II)/EDTA complex in 0.05 M EDTA across a range of pH. 
         FIG. 33  is a schematic showing the process for loading the  224 Ra from the triple-column method onto a CatIX-based generator column. The purified  224 Ra/EDTA product solution can be acidified by adding a small volume of concentrated acid such as HNO 3  or HCl to achieve a pH of &lt;=4, which can free or dissociate the  224 Ra from the  224 Ra/EDTA complex. The acidified  224 Ra 2+  solution may then be incorporated into a storage/generator vessel assembly. 
         FIG. 34  depicts data acquired upon loading the HCl-acidified, EDTA-dissociated  224 Ra 2+  product onto a strong cation exchange media.  224 Ra load fraction (A) and wash fractions (B) plotted vs. elapsed time. Legend indicates the collected fractions (1 mL each) of wash solution delivered through the vessel containing the media. The decay rates indicate that all  224 Ra can be adsorbed onto the media during load/wash steps. (C) Direct counts of the  224 Ra-loaded cation exchange media vs. elapsed time indicates the decay rate of  224 Ra beyond the ˜1.6 day period wherein progeny equilibrium first occurs. 
         FIG. 35  is a schematic of a system for producing free isotope according to an embodiment of the disclosure. 
         FIG. 36  is a schematic of a system for producing free isotope according to another embodiment of the disclosure. a)  24 Ra bound element elution line from element isolation system; b) acid dispensing line; c) activated charcoal  220 Rn trap; d) 5 mL Rezorian™ column w/ Spin plus® PTFE stir bar &amp; hydrophobic Polyethylene (PE) frit; e) three way stopcock valve; f) servo motor (SvM); g) rinse vessel for line; h) vertical magnetic stirrer; i) inverted digital syringe pump (SP) w/8 port distribution valve; j) 0.45 pm polyethersulfone (PES) filter; and k)  224 Ra collection vessel. 
         FIG. 37  is an image of a portion of the system of  FIG. 36  configured as an EDTA precipitation/filtration device. a) activated charcoal  220 Rn trap; b) acid dispensing line from inverted digital SP; c) 5 mL Rezorian™ column; d) Spinplus® PTFE stir bar; e) hydrophobic PE frit; f) assembled servo motor with attached servo horn (SvM); g) vertical magnetic stirrer; h) three-way stopcock valve; i) 3D printed device mount; and j) line out to inverted digital SP. 
         FIG. 38  is an image of pre acidified  224 Ra-EDTA (a), acidified &amp; agitated  224 Ra-EDTA (b), and post acidified &amp; agitated  224 Ra-EDTA solution (c). 
         FIG. 39  is an image of a sequence of configurations of a system for producing free isotope according to an embodiment of the disclosure. (a) acidified &amp; agitated  224 Ra-EDTA solution mixing, precipitation, and filtration vessel; (b)  224 Ra collection vessel; (c) filtered EDTA precipitate; (d) free  224 Ra solution; (e) line rinsate reservoir; and (f) in-line membrane filter. 
         FIG. 40  is an overall schematic for preparing a storage/generation vessel assembly according to an embodiment of the disclosure. 
         FIG. 41  is a system for producing a metal storage/generation vessel assembly according to an embodiment of the disclosure. Syringe pump w/8-port distribution valve (SP); 4-port and 6-port selector valves (V 4  or V 6 ); assembled generator column (AGC); holding coil to 4-port and 6-port valves (HC/V 4  or HC/V 6 ); excess supernatant coil (ESC); transport line (TL); large mixing vessel (LMV); small mixing vessel (SMV); 3 stopcock manifold (SM); servo motor block (SVMB) with three servo motors (SVM 1 , SVM 2 , and SVM 3 ); solenoid-controlled isolation valves (SCIV 1  and SCIV 2 ); and N 2  gas regulators (R 1  and R 2 ). 
         FIG. 42  is an image of a system for producing a metal storage/generation vessel assembly according to another embodiment of the disclosure. Labels are identified in  FIG. 41 . 
         FIG. 43  is an image of a mixing vessel of the system of  FIGS. 41 and 42  according to an embodiment of the disclosure (LMV) using N 2  gas agitation for mixing. A) Resin slurry aspiration line (outlet); B) N 2  gas vent (outlet) port; and C) N 2  gas (inlet) line. Five milliliters of settled resin bed in 20 mL deionized water (D 1 ) can be seen in the vial. 
         FIGS. 44A and 44B  are images a mixing vessel and stirrers of the system of  FIGS. 41 and 42  according to another embodiment of the disclosure (LMV), using the Multi-Stirrus mixer. A) Resin slurry aspiration line (outlet); B) rotating magnet base; C) vertical magnetic spinning device; D) fabricated vane #1 with alternating 7/16″ diameter holes and edges; and E) fabricated vane #2 with alternating 3/16″ diameter holes at 5/16″ intervals. 
         FIG. 45  is an image of another mixing vessel of the system of  FIGS. 41 and 42  according to an embodiment of the disclosure (SMV). A) ESC (inlet/outlet) line; B) resin slurry dispenser (inlet) line; C) N 2  gas vent (outlet) port; and D) N 2  gas (inlet) line. 
         FIG. 46  is an image of a multiport manifold (SM) assembly for use with the systems of  FIGS. 41 and 42 . A) Resin-screening frit. 
         FIG. 47  is a schematic of a series of manifold configurations for use with the systems of  FIGS. 41 and 42  according to an embodiment of the disclosure. 
         FIG. 48  depict images of a resin slurry in a mixing vessel of the system of  FIGS. 41 and 42  (LMV) unagitated (A) and agitated (B) with a 2 PSI N 2  gas sparge. 
         FIG. 49  depicts images of a resin slurry in another mixing vessel of the system of  FIGS. 41 and 42  (SMV) unagitated (A) and agitated (B) with a 3 PSI N 2  gas sparge. 
         FIG. 50  is an image of a resin slurry in a mixing vessel of the system of  FIGS. 41 and 42  (LMV) being homogenously mixed using vane #1 at a Multi-Stirrus mixer setting of 60 RPM. A) Resin slurry aspiration line (outlet); B) rotating magnet base; and C) vertical magnetic spinning device. 
         FIG. 51  is an image of a resin slurry in a mixing vessel of the system of  FIGS. 41 and 42  (LMV) being undermixed (A), mixed homogenously (B), and overmixed (C). D) Gravity settled resin bed; E) N 2  gas (inlet) line; and F) droplets of ejected resin slurry. 
         FIG. 52  depicts color contour maps of calculated (left) and empirically determined (right) dry resin masses dispensed as a function of varying flow rates and aspirated volumes. Legend is dry AG MP-50 resin mass (g) delivered. 
         FIG. 53  is a schematic of stages of storage/generator vessel assembly preparation according to an embodiment of the disclosure. 
         FIG. 54  is an image of a storage/generator vessel assembly according to an embodiment of the disclosure. 
         FIG. 55  is an image of a storage/generator vessel assembly according to another embodiment of the disclosure. 
         FIG. 56A-56B  depict the Thorium-228 decay chain image ( 56 A) and Radium-224 decay and progeny ingrowth curves ( 56 B) over a 1 day interval. 
         FIG. 57  depicts a series of a replicate storage/generator vessel assemblies prepared according to embodiments of the disclosure. 
         FIG. 58  is a schematic of a system that includes both free isotope preparation and storage/generator vessel assembly preparation according to an embodiment of the disclosure. 
         FIG. 59  depicts individual (∘) and cumulative (□)  212 Pb fraction recovery relative to the sum eluted activity as a function of 2 M HCl volume loaded onto the  224 Ra generator column data. 
         FIG. 60  depicts data indicating some metal ( 224 Ra) breakthrough (BT) from a single storage/generator vessel assembly as a function of ten sequential  212 Pb milking cycles. Each milking cycle was 1.0 mL 2 M HCI followed by 1.0 mL deionized water (DI). 
         FIG. 61  depicts images of  224 Ra/ 212 Pb storage/generator vessel assemblies and supplemental catch bed cartridges according to embodiments of the disclosure. 
         FIG. 62A  depicts incremental breakthrough of  224 Ra from different storage/generator vessel assembly configurations across ˜20 mL of 2 M HCI  212 Pb eluent. 
         FIG. 62B  depicts cumulative  224 Ra breakthrough for the assemblies of  61 B. In this panel, the sacrificial first milking has been omitted from the cumulative plots. 
         FIG. 63A  depicts fractional  212 Pb elution profiles using 2 M HCl for the four storage/generator vessel assemblies. 
         FIG. 63B  depicts cumulative  212 Pb activity fraction yields for the assemblies of  FIG. 60A . 
     
    
    
     DESCRIPTION 
     This disclosure is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws “to promote the progress of science and useful arts” (Article 1, Section 8). 
     The present disclosure will be described with reference to  FIGS. 1-63B . Referring first to  FIG. 1 , an overall scheme  2  for producing storage and/or generator vessel assemblies is shown that can begin with an element isolation system/module  3  and continue to a free element producing system/module  4  then continue to a generator vessel producing system/module  5 . Implementations of these systems/modules can be used in the above order given or in different combinations to facilitate desired means. For example, single systems/modules can be used or they can be used as combinations of pairs of systems/modules. Specific implementations, as directed in  FIG. 1 , can utilize system/module  3  in combination with system/module  5  without utilizing system/module  4 , for example. In accordance with example implementations, embodiments of the disclosure provide techniques that can be used remotely or hands-free, as well as automated, to allow for the safe and efficient production and transfer of valuable elements such as radioisotopes, for example. 
     Generally, element isolation system/module  3  can generate an element from another element within a vessel and then isolates same via systems/methods of the present disclosure. As depicted in  FIG. 1 , this isolated element can be provided to system/module  4  or system/module  5 . Referring to  FIG. 2 , an example overview of element isolation is shown in the context of Th and Th-progeny. In accordance with the systems and methods of the present disclosure, Ra can be isolated from a mixture of Th and Ra. 
     Referring again to  FIG. 1 , upon element isolation as described herein, for example, an element can be produced that is complexed or bound to another material. In keeping with the scheme of  FIG. 2 , Ra can be isolated as a complex of EDTA. System/module  4  can provide a free element, for example a free Ra. In accordance with  FIG. 1 , this free element can be provided to system/module  5 . 
     System/module  5  can be configured to prepare a storage/generator vessel assembly. System/module  5  can receive isolated element from system/module  3  or free element from system/module  4 . In keeping with the example of  FIG. 2 , free Ra can be provided to system/module  5  and a storage/generator vessel assembly  6  can be prepared that generates Pb and/or Bi. The vessel can be configured for the storage of the element and the generation of element-progeny on demand. In accordance with example implementation, the  224 Ra can be isolated from  228 Th and then provided as a storage/generation vessel assembly  6  as shown. In accordance with example implementations, this storage/generation vessel assembly  6  can be “milked,” taking advantage of radioisotope decay to produce lead and/or bismuth isotopes as detailed herein as a  224 Ra/ 212 Pb/ 212 Bi generator column. The scope of this disclosure is not limited to Th and Th-progeny. Additional elements that can be processed/provided using one or more of the systems/modules of the present disclosure can include, but are not limited to:  99 Mo/ 99m Tc;  113 Sn/ 113m In;  44 Ti/ 44 Sc;  52 Fe/ 52m Mn;  68 Ge/ 68 Ga;  72 Se/ 72 As;  118 Te/ 118 Sb;  82 Sr/ 82 Rb;  134 Ce/ 134 La;  140 Nd/ 140 Pr;  90 Sr/ 90 Y;  188 W/ 188 Re;  166 Dy/ 166 Ho;  194 Os/ 194 Ir;  226 Ra/ 222 Rn;  225 Ac/ 213 Bi;  83 Rb/ 83m Kr;  113 Sn/ 113m In;  103 Pd/ 103m Rn; 167Tm/ 167m Er;  172 Hf/ 172 Lu;  140 Ba/ 140 La;  144 Ce/ 144 Pr;  109 Cd/ 109m Ag;  178 W/ 178 Ta;  191 Os/ 191m Ir;  62 ZN/ 62 Cu;  110 Sn/ 110m In;  122 Xe/ 122 I; and/or  128 Ba/ 128 Cs. Accordingly, the present disclosure can have particular use where elements are forming mixtures of the element and the element-progeny. Therefore, the generator vessel assemblies can include elements and element progeny, system/module  3  can be configured to isolate element progeny from element/element progeny mixtures, for example. 
     Further, the disclosure will define columns by the media present in the columns. This is to be considered media within vessels. Therefore, when an element is retained or bound to a column, it is recognized that the element is bound or retained to media within the column/vessel. 
     Additionally, chelating agents are described as ligands which bind a metal with more than one coordination site, for example, EDTA. Organic compounds that coordinate metal ions into circular structures (chelate circles) are considered chelating reagents. Most chelating reagents include oxygen, nitrogen, or sulfur atoms in their molecules. Chelate structures with five or six member rings form the most stable chelate circle. More generally, chelating agents possess an organic backbone with functional groups to coordinate to the metal. These functional groups include but are not limited to phosphonates, phosphinates, phosphines, sulfonates, carboxylates, imines, and amines. In chelating reactions of typical chelating reagents, including but not limited to ethylenediamine, acetylacetone, and oxine, molecules are coordinated with one metal ion. Ethylenediamine tetraacetic acid (EDTA), which has many coordinated atoms, forms a very stable chelate between one molecule of EDTA and metal ion. Phosphonic acid-based chelates may be used as well. 
     In accordance with example implementations, the entirety or portions of the above can be performed hands-free, automated, and/or remotely, in that users can be separated from potentially toxic or harmful elemental compounds including isotopes through the use of mechanical direction modules. In accordance with example implementations, the systems and methods of the present disclosure can be performed with mechanical servos and/or pumps including syringe pumps that can be operated and operatively coupled to computer processing circuitry that can be operable to control the pumps, servos, and valves in a predetermined manner or remotely via a computer interface, for example. 
     Example systems and/or methods for producing elements are provided below with reference to  FIGS. 3-32 . 
     Example implementations of systems and methods for free element production are described below with reference to  FIGS. 33-39 , for example. An additional step or procedure that can be accomplished after production of free element can be a system or method for producing a storage/generator vessel assembly as shown in  FIG. 1 . 
     Systems and methods for producing the storage/generator vessel assembly are described below with reference to  FIGS. 40-58 . The storage/generator vessel assemblies produced in accordance with example implementations of the present disclosure as well as the use of same are described with reference to  FIGS. 59-63B  of the present disclosure. 
     The present disclosure provides systems and methods for the separation of materials that can be used for the acquisition of targets for alpha radiation when performing targeted radioimmunotherapy applications. In one example the  212 Pb/ 212 Bi isotope pair shows good promise. The parent isotope,  224 Ra, must be periodically isolated from  228 Th via radiochemical separation. The purified  224 Ra can then be used to prepare  224 Ra/ 212 Pb/ 212 Bi generators. The present disclosure provides a  224 Ra purification method that can be safer and more efficient than existing prior art methods resulting in reduced personnel dose, reduced labor cost, and reduced preparation time; and may be fully, but at least partially, automated using laboratory fluidics. 
     With reference to  FIG. 3 , the present disclosure provides systems and/or methods for separating Ra from a mixture comprising at least Ra, Pb, Bi, and Th. As can be seen in  FIG. 3 , there are three vessels (C 1 , C 2 , and C 3 ), but there can be two or at least one. These vessels can house media. For example, C 1  can house media M 1 , C 2  can house media M 2 , and C 3  can house media M 3 . One or all three of these vessels can be in fluid communication via conduits for example. Each of the conduits can be controlled via a valve or valves for example. Referring to  FIG. 4 , in accordance with an example implementation, a mixture (Th/Ra+(“+” subsequent progeny can be present) in HNO 3 ) that can provide Ra, Pb, Bi, and Th, can be exposed to vessels C 1 -C 3  and thereby M 1 -M 3 . Each of the Media can be different from one another. 
     Accordingly, the media can be (in fluidic introduction order, and as shown in Table 1) AnIX-M 1  (AG MP-1M, Bio-Rad, or TEVA resin, Eichrom); 18-crown-6 ether in a 1-octanol diluent-M 2  (Sr Resin, Eichrom); M 3  (Ra-01 resin, IBC Advanced Technologies). In accordance with example implementations, a  228 Th/ 224 Ra/ 212 Pb/ 212 Bi/etc. mixture can be passed through all three vessels in strong HNO 3  (6M, however concentrations as low as 0.5 to 1M or even 2M HNO 3  can be utilized as well); a 3-column wash (strong HNO 3 ) can be delivered, and Th +Bi is partially retained in C 1 ; Pb retains in C 2 ; Ra retains in C 3  (the system configuration of which is shown in  FIG. 4  as (A). 
     Accordingly, systems of the present disclosure can include a first vessel housing a first media and either Pb or Bi and/or Th (C 1  or C 2 ); and a second vessel in fluid communication with the first vessel, the second vessel housing a second media and Ra (C 3 ), wherein the first media is different from the second media. Additionally, systems of the present disclosure can include a first vessel housing a first media and Th and/or Bi (C 1 ); and a second vessel in fluid communication with the first vessel, the second vessel housing a second media and Pb (C 2 ), wherein the first media is different from the second media. Embodiments of the present disclosure can also include systems having a first vessel housing a first media and Th or Bi (C 1 ); a second vessel in fluid communication with the first vessel, the second vessel housing a second media and Pb (C 2 ); and a third vessel in fluid communication with the second vessel, the third vessel housing a third media and Ra (C 3 ), wherein at least one of the first, second, or third medias are different from the other medias. 
     Methods are also provided that can include providing a mixture having Ra, Pb, Bi, and/or Th; providing the described system having vessel (C 1 ) housing the media (M 1 ), and vessel (C 2  or C 3 ) in fluid communication with vessel (C 1 ), with vessel (C 2  or C 3 ) housing media (M 2  or M 3 ); exposing the mixture to media (M 1 ) within vessel (C 1 ) to separate the Th and Bi from the Ra and Pb; then, through the fluid communication, exposing the remaining mixture to media (M 2  or M 3 ) in vessel (C 2  or C 3 ) to associate the Pb or Ra with the M 2  or M 3  media. In accordance with example implementations, Th (with Bi) of C 1  can be eluted from M 1  in strong HCl for dry-down and storage for re-use as desired. 
     Additionally, as shown and described, vessel (C 3 ) can be in fluid communication with vessel (C 2 ), and vessel (C 3 ) can house a media (M 3 ). The methods can include exposing the mixture to media (M 1 ) within the vessel (C 1 ) then, through the fluid communication, exposing the first remainder (that which passes through C 1  or is washed through C 1 ) to media (M 2 ) in vessel (C 2 ), then, through fluid communication, exposing the next remainder (that which passes through C 2  or is washed through C 2 ) to media (M 3 ) in vessel (C 3 ), the exposing separating the Th and Bi from the Ra and Pb, and the Ra from the Pb to sequester the Th and Bi in one vessel, the Pb in another vessel, and the Ra in still another vessel. 
     Upon distributing the materials within the system, and with reference to configuration B of  FIG. 3 , vessels C 2  and C 3  are washed with less strong or weaker HNO 3  (&lt;7 M, between 2 M and 7 M, or &lt;=6 M, and in some embodiments 0.5 to 1 M HNO 3 ). In accordance with example implementations, M 3  can then be washed with water to remove H+/excess Pb in configuration C. In configuration D, Ra can be eluted from M 3  (to which it was associated) with dilute EDTA solution (pH adjusted to &gt;7), or a chelating solution with a bonding constant that is higher than that of the M 3  resin in C 3 . For example, per  FIG. 32 , the Ra is EDTA bound ˜100% at a pH of ˜6, and is ˜50% EDTA bound at pH ˜5.3. Accordingly, methods of the present disclosure provide for separating Ra from being associated with a media by exposing the Ra and media to a chelating agent to form a mixture comprising the Ra complexed with the chelating agent. 
     The Ra/EDTA product solution is not compatible with loading onto a CatIX-based generator column. Adding enough HCl to the Ra/EDTA solution to drop the pH below ˜2 (Per  FIG. 32 , Ra is freed from EDTA at pH ˜4. By pH ˜2, the EDTA is rendered insoluble and precipitates out, leaving Ra in supernate) can decouple or disassociate the Ra from the EDTA (thereby producing free Ra 2+  ions in solution). The weakly acidified Ra 2+  solution can then be adsorbed onto the CatIX-based generator column. 
     The systems and methods of the present disclosure can provide isolated and free a  224 Ra product that can be loaded onto the CatIX generator column. Embodiments of the disclosure can be performed without boil-down or acid transposition steps. The purified Ra (without  212 Pb and  212 Bi progeny) can be handled in a low-dose state for several hours. This can allow for packing the generator column, removing the column from containment, and packing it for shipping before the dosage becomes an issue. Additionally, the present disclosure also provides fluidic systems to perform the methods. This can provide a fluidic platform. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Commercial resins evaluated for the triple-column process 
               
               
                 to isolate  224 Ra from  228 Th. 
               
            
           
           
               
               
               
               
               
               
            
               
                 Column 
                 Resin  
                   
                 Particle  
                   
                   
               
               
                 ID 
                 type 
                 Resin ID 
                 size, μm 
                 Manufacturer 
                 Purpose 
               
               
                   
               
               
                 C1 
                 AnIX poly    a   
                 AG MP-1M 
                 37-74 
                 Bio-Rad 
                 Th extraction 
               
               
                   
                 AnIX org    b   
                 TEVA 
                  50-100 
                 Eichrom 
                 &amp; recovery 
               
               
                 C2 
                 18-C-6  c   
                 Sr Resin 
                  50-100 
                 Eichrom 
                 Pb 
               
               
                   
                   
                   
                   
                   
                 extraction 
               
               
                 C3 
                 21-C-7  d   
                 Ra-01 
                 150-250 
                 IBC 
                 Ra extraction 
               
               
                   
                   
                   
                   
                   
                 &amp; recovery 
               
               
                   
               
               
                   a  Functional group: Quaternary amine on macroporous polystyrene divinylbenzene copolymer. 
               
               
                   b  Functional group: Aliquat 336, an organic quaternary amine salt on Amberchrom CG-71 (“Pre-Filter”) polymer support. 
               
               
                   c  Functional group: 18-crown-6 and 1-octanol on Amberchrom CG-71 polymer support. 
               
               
                   d  Functional group: Proprietary; presumed to be a 21-crown-7 (in part) on silica support. 
               
            
           
         
       
     
     An example overall fluidic protocol for the modified triple-column method is shown in Tables 2 and 3. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Protocol for modified triple-column purification of  224 Ra 
               
               
                 from  228 Th. Example resins and column volumes are included.  a   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                 Column 
                   
                 Reagent 
                 Vol., 
               
               
                 Step 
                 Purpose 
                 connections 
                 Reagent 
                 conc., M 
                 mL 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 1 
                 Col. condition 
                 C1-C3 
                 HNO 3   
                 6 
                 5 
               
               
                 2 
                 Load  b   
                 C1-C3 
                 HNO 3   
                 6 
                 3 
               
               
                 3 
                 Wash a 
                 C1-C3 
                 HNO 3   
                 6 
                 3 
               
               
                 4 
                 Wash b 
                 C2-C3 
                 HNO 3   
                 2 
                 5 
               
               
                 5 
                 Water wash 
                 C3 
                 H 2 O 
                 — 
                 5 
               
               
                 6 
                 Ra elute 
                 C3 
                 EDTA  c   
                 0.05 
                 5 
               
               
                 7 
                 Th elute 
                 C1 
                 HCl 
                 1 
                 5 
               
               
                   
               
               
                   a  C1 = 1 cm 3  TEVA resin; C2 = 0.25 cm 3  Sr Resin; C3 = 0.25 cm 3  Ra-01 resin. 
               
               
                   b 228 Th in equilibrium with  224 Ra and progeny. 
               
               
                   c  pH was adjusted to ~11. 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Description of Steps for the Schematic of FIG. 3. 
               
            
           
           
               
               
            
               
                 Step 
                 Description 
               
               
                   
               
               
                 A 
                 Load and wash “a” to adsorb Th, Pb, and Ra on Col. 1-3, respectively. 
               
               
                 B 
                 Secondary wash “b” for Col. 2-3 to assure complete transport of Ra  
               
               
                   
                 between Col. 2 and 3. 
               
               
                 C 
                 Water rinse through Col. 3 to remove nitric acid. 
               
               
                 D 
                 Ra elution from Col. 3 via transchelation with EDTA solution. 
               
               
                 E 
                 Elution of Th from Col. 1 for recovery and eventual reuse. 
               
               
                   
               
            
           
         
       
     
     During Step A, the prepared  228 Th/progeny stock solution (in 6 M HNO 3 ) can be passed through three columns, each fluidically interlinked. The 6 M HNO 3  concentration can provide high affinity of Th on the AnIX media ( 1 ) and high affinity of Pb on the Sr media (M 2 ). During the load step, Th (and Bi/TI daughters) are adsorbed on M 1 , Pb is adsorbed on M 2 , and Ra is adsorbed on M 3 . 
     Following up the load solution is wash “a”, comprising 6 M HNO 3 . This can provide for complete fluid transport of the load solution through the three tandem columns. 
     The Step A process efficacy is demonstrated by gamma spectra in  FIG. 5 . In this instance, M 1  was an AnIX poly . Solutions can be delivered to the three columns at 1 mL/min. The  228 Th/progeny load (A) and initial “wash a” solution (B) triple-column effluent fractions can be collected in test tubes and counted by gamma spectrometer. It was observed that no activity was present from the fractions that has passed through all three columns during the load and wash “a” steps; all activity was adsorbed onto the columns. 
     Additionally, a direct gamma count of the C 1  immediately after the completion of the load/wash “a” steps shows the presence of  228 Th,  212 Bi, and  288 Tl ( FIG. 5  (C)). No  212 Pb or  224 Ra gamma peaks are observed on M 1 , as these radionuclides have been adsorbed onto M 2  and M 3 , respectively. 
     The passage of  224 Ra out of C 1  and C 2  can be confirmed by evaluating a wash “a” effluent fraction that was diverted away from C 3 . In  FIG. 6 , rather pure  224 Ra in the C 2  effluent can be observed, along with a trace of  212 Bi and  208 Tl. A trace  212 Pb peak is visible at channel ˜80. The general absence of  212 Pb spectral lines indicates the good collection efficiency of Pb on the Sr Resin (C 2 ). Any freshly ingrown  212 Bi and  208 Tl daughters of the C 2 und  212 Pb would likely not be retained on M 2  during this step, but would rather be swept from C 2  and pass through C 3  to waste. 
     The role of M 2  is to adsorb  212 Pb from the  212 Pb/ 224 Ra mixture that passes through C 1 . The 18-crown-6 ether extracting agent on the Sr Resin has strong affinity for Pb(II) ions, and low affinity for Ra(II) ions and Bi(III) ions in multi-Molar concentrations of HNO 3  (see  FIG. 7  and  FIG. 8 ). Consequently,  224 Ra can pass through the Sr Resin and thereby collect onto M 3 . Any  212 Bi/ 208 Tl generated by  212 Pb on the M 2  is unretained and will pass out of C 2  along with  224 Ra to C 3 . As the  212 Bi/ 208 Tl is likewise unretained on M 3 , it will pass to waste while  224 Ra is being loaded. 
     In Step B, C 1  can be disconnected from the chain of vessels and remain static until the end of the method, when the adsorbed  228 Th is recovered via a separate elution step as Step E. By disconnecting, the fluid communication is simply blocked off, but the conduit associating C 1  and C 2  can remain. 
     Wash “b”, comprising 2 M HNO 3 , can be passed through C 2  and C 3  to assure quantitative transfer of Ra from C 2  to C 3 . The Pb is strongly bound onto M 2  and remains there. 2 M HNO 3  can be used in this step because it provides the high level of affinity of Pb on the Sr Resin. 
     The Ra has a low level of affinity for the Sr Resin (M 2 ) at 2 M HNO 3  (k′≈2,  FIG. 8 ). This is evident by the slight retardation of Ra during the load/wash “b” step shown in  FIG. 8  (B). Here, the  212 Bi trace represents an unretained ion (k′ of &lt;0.4) passing through the vessel ahead of the  224 Ra passage. Because of this slight Ra/resin affinity, wash “b” can require a volume of ˜10 mL to assure complete Ra passage through the Sr Resin column. 
     The wash “b” process data is demonstrated in  FIG. 9  (A). The C 2 /C 3  effluent fractions show no indication of  212 Pb or  224 Ra breakthrough from the columns. Once wash “b” is complete,  FIG. 9  (B) demonstrates that a pure  212 Pb spectrum is observed on the Sr Resin column (C 2 ). 
     Referring next to  FIG. 10 , in step C, C 2  can be disconnected from C 3 , as M 3  now contains the isolated  224 Ra fraction. Again, the disconnection does not remove the conduit connecting vessels C 2  and C 3 , it simply prohibits fluid flow through the conduit. 
     Water can be flushed through the C 3  in order to remove the HNO 3  from the system. Ra remains strongly bound to M 3  during the water flush as Ra affinity for Ra-01 resin generally increases as HNO 3  concentration drops. Additionally, the water wash through C 3  can result in removal of  212 Pb that may reside on the column. This  212 Pb could be from C 2  breakthrough or freshly ingrown  212 Pb produced by the M 3 -bound  224 Ra. A series of five 1 mL water effluent fractions were collected and analyzed by gamma spectroscopy. The removal of  212 Pb from C 3  during the water wash is shown in  FIG. 11(A) . By evaluating the water fraction decay rate over time, it was confirmed that the water fractions did not contain  224 Ra. The rate of activity loss was in agreement with the  212 Pb decay factor ( FIG. 11  (B)). This indicates that no  224 Ra was co-eluted with  212 Pb during the water wash. 
     As  228 Th,  212 Bi, and  208 TI are locked onto M 1  of the now-disconnected C 1  vessel and  212 Pb is locked onto M 2  of the now-disconnected C 2 , and traces of  212 Pb on M 3  were removed during the water rinse, the isolated  224 Ra that is bound onto M 3  has a low associated dose rate. This is temporary, as  224 Ra progeny ingrowth quickly escalates dose on M 3 . 
     Referring next to  FIG. 12 , in Step D, the  224 Ra on M 3  was eluted using 5 mL of 0.05 M EDTA that had been adjusted to pH 11 using NaOH. Column effluent fractions were collected, and gamma spectrometry was performed. The resulting radiochromatogram is shown in  FIG. 13  (A). In this  224 Ra elution, four milliliters contained the vast majority of the  224 Ra activity (it is hypothesized that higher concentrations of EDTA, or a stronger chelating agent, or a smaller column volume, would result in sharper  224 Ra elution peaks.). 
     The series of  224 Ra elution fractions was counted repeatedly over the course of ˜35 days in order to gauge the decay rate and assess the radionuclidic purity of the isolated  224 Ra.  FIG. 13  (B) shows that the rate of activity diminishment of the C 3  elution product tracks with the theoretical  224 Ra rate of decay across several orders of magnitude. Importantly, the decay rate data indicates that no  228 Th is present in the  224 Ra product fraction, at least down to ˜0.1% of the original activity fraction. 
     Referring next to  FIG. 14 , the recovery of  228 Th from M 1  of C 1  can be performed. In accordance with example implementations, methods for separating Ra from Pb, Bi, and Th can include separating one or more of Bi and/or Th from the Ra. The separating can associate Th and/or some of the Bi with a media (M 1 ). The method can further include disassociating the Bi and/or Th from the media (M 1 ) to form a mixture comprising the Bi and Th and transferring the mixture to a vessel housing at least Ra and additional Bi and/or Th. In accordance with some implementations, this vessel can be considered a “cow” that through decay generates additional Ra which can be used to initiate step A. In accordance with alternative implementations, to avoid a tremendous radiation dose to the C 1  resin, the Th can be eluted and keep separate from the polymer-based AnIX resin of C 1 . 
     Th was eluted from the AnIX poly  media (M 1 ) using 5 mL 8 M HCl. (Th can be eluted from 1M to 12M). About 8M will be sufficient if the concentration is sufficient to elute the Bi and/or Th.  FIG. 15  (A) shows the resulting spectra from these Th elute fractions. The first and second elutions showed most of the recovered Th. Additionally, it was observed that  212 Bi and  208 Tl were co-eluted with  228 Th, primarily in the first elute fraction. Complete  228 Th recovery from the AnIX poly  media (M 1 ) was not possible in a 5 mL delivery of 8 M HCl. A direct count of C 1  post-elution indicated that some fraction of Th remained on the column  FIG. 15  (B). Subsequent to this  228 Th retention observation, 5 mL of 0.05 M EDTA (pH ˜3.5) was passed through C 1 . This secondary elution treatment can provide Th removal from the M 1 . 
     Referring next to  FIGS. 16 and 17 , fluidic systems capable of performing the methods of the present disclosure in a fully automated fashion are provided. The fluidic system architecture is presented as a schematic in  FIG. 16 . The system was designed with an eye towards operation remotely or in a shielded facility. Two digital syringe pumps (SP 1 , SP 2 ) are responsible for reagent delivery to the vessels (C 1 , C 2 , and C 3 ); these pumps can be located outside of the shielded zone to eliminate chances of radiolytic or chemical degradation. 
     Within the shielded zone can be a third syringe pump (SP 3 ). This pump can include a stepper motor and a disposable plastic syringe, for example. A role of SP 3  is to withdraw the  228 Th “cow” solution (the first mixture, for example) into the sample injection loop indicated at the top of FIG.  16  and in  FIG. 17(B)  (upper left of image). Once the cow is loaded into the loop, the digital syringe pumps located outside of the shielded zone can access the cow solution in the loop and direct it through the columns. 
     As the stepper motor can drive the syringe pump from voltage signals originating outside the shielded zone, and the stepper motor has no integrated circuits within it, the chances of radiolytic degradation of this component is small. For example, two of these stepper motors can be irradiated using a  208  R/hr  137 Cs source within a hot cell. The motors received a total dose of 33,700 R over the course of 6.75 days. After removal of the motors from the hot cell, each was tested for functionality; both remained functional. 
     The fluids can be routed through a multitude of pathways using Teflon FEP tubing for example and solenoid-actuated valves that feature fluoropolymer wetted surfaces for example ( FIG. 18  (B)). As the solenoids are electromagnetically actuated by voltages applied from outside the shielded zone, the potential for radiation-based component failure are low. The fluidic system can be routinely utilized in a radiological fume hood (or in a glove box or shielded location using multi-mCi levels of  228 Th/224Ra) using  228 Th/ 224 Ra spiked solutions. 
       228 Th elution performance on AnIX poly  resin between 1 M and 8 M HCI were compared. The results are shown in  FIG. 18 . 
     As shown, the 8 M HCl demonstrated better  228 Th elution performance than in 1 M HCl on the AnIXpoly resin columns. TEVA resin is an extraction chromatographic resin loaded with Aliquat 336, an organic quaternary ammonium salt. The load/wash “a”/elute performance of  228 Th on 1 cc TEVA resin columns was evaluated. Load/wash “a” was again performed using 6 M HNO 3 , and elution was performed at 1 M and 8 M HCI. 
     The  228 Th load/wash “a” performance from C 1  (1 cc TEVA resin) is shown in  FIGS. 19  (A and B). No discernable break-through of  228 Th was observed. As with MP-1 M resin,  212 Bi and  208 11 had low retention; they began breaking through the column at the third load/wash “a” fraction. 
     The subsequent C 1   228 Th elutions from TEVA resin with 1 M ( FIGS. 20  (A) and  8  M HCl ( FIG. 20  (B)) are shown. Here, the reduced HCl concentration results in improved  228 Th recovery relative to that obtained from the stronger HCl concentration eluent. The use of lower concentration HCl is advantageous in a shielded environment, as less corrosion to the containment and equipment would be anticipated. 
     The 1 cc column elution recovery fractions for  228 Th from  FIG. 18  (MP-1 M) and  FIG. 20  (TEVA resin) for 1 M ((A)/(B)) and 8 M ((C)/(D)) HCI eluents are provided in Table 4. From this table, it can be concluded that the optimal  228 Th elution recovery is obtained from a TEVA resin column, using 1 M HCl as the eluting solution. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                   228 Th column yields (%) for MP-1M and TEVA resin columns 
               
               
                 (1 cm 3 ) as a function of ~1 mL elution fraction volumes in 1M and 8M  
               
               
                 HCl. Primary recovery fractions are indicated in large bolded print. 
               
            
           
           
               
               
               
               
               
            
               
                 Elution fraction 
                 TEVA resin, 
                 TEVA resin, 
                 MP-1M, 
                 MP-1M, 
               
               
                 (~1 mL) 
                 1M HCl elute 
                 8M HCl elute 
                 1M HCl elute 
                 8M HCl elute 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 0.09% 
                 0.51% 
                 1.46% 
                 0.97% 
               
               
                 2 
                      
                      
                      
                      
               
               
                 3 
                 3.29% 
                 1.75% 
                 5.59% 
                 4.99% 
               
               
                 4 
                 0.33% 
                 0.67% 
                 3.99% 
                 3.05% 
               
               
                 5 
                 0.32% 
                 0.57% 
                 3.10% 
                 3.15% 
               
               
                 6 
                 0.04% 
                 0.20% 
                 2.53% 
                 0.86% 
               
               
                 7 
                 0.03% 
                 0.19% 
                 2.21% 
                 0.72% 
               
               
                 8 
                 0.04% 
                 0.17% 
                 1.96% 
                 0.60% 
               
               
                 9 
                 0.04% 
                 0.11% 
                 1.79% 
                 0.73% 
               
               
                 10 
                 0.03% 
                 0.21% 
                 1.83% 
                 0.80% 
               
               
                 Cumulative  
                 98.13%  
                 91.35%  
                 40.77%  
                 89.53%  
               
               
                 HCl elute 
                   
                   
                   
                   
               
               
                 EDTA strip  a   
                 0.19% 
                 2.88% 
                      
                 2.70% 
               
               
                 Total recovery 
                 98.32%  
                 94.23%  
                 63.99%  
                 92.23%  
               
               
                   
               
               
                   a  Cumulative activity fraction from a 5 mL 0.05M EDTA (pH 3.5) strip, applied at the conclusion of the HCl elution. 
               
            
           
         
       
     
     As shown in Table 4, TEVA resin and MP-1M can have a roughly equivalent ability to adsorb  228 Th from a load solution in a 6 M HNO 3  matrix. 8 M HCl provides better (but incomplete)  228 Th elution from MP-1M relative to 1 M HCI. TEVA resin can provide improved  228 Th elution profiles relative to MP-1 M in both 1 M and 8 M HCI.  228 Th elution profiles from TEVA resin are better in 1 M HCl vs. 8 M HCI. 
     Other column geometries and volumes may be utilized as well. For example, the 1 cc SPE column geometry described above (0.56×4.1 cm) as well as 0.61×0.865 cm (0.25 cc volume, QML cartridge). 
     The results of the evaluation are shown in  FIG. 21  (A), where the  228 Th elution profile is plotted (fractions were aged 32 days to allow  228 Th progeny ingrowth). The smaller-volume column resulted in earlier  228 Th release;  228 Th yield reached ˜96% after a 3 mL elution ( FIG. 21  (B)). In comparison, the 1 cc column began its elution at the 2nd 1 mL fraction, and recovery reached ˜94% after a 3 mL elution. These recoveries are within experimental uncertainty of each other. 
     Parallel column evaluations were performed with identical  228 Th load solutions (6 M HNO 3 ) through a 1 cc and a 0.25 cc column of TEVA resin. The load effluents, which contain  224 Ra, were collected and aged over a ˜1 month period. The decay rate of the  224 Ra-bearing TEVA effluent fraction can be used to determine its degree of purity from  228 Th. The results are shown in  FIG. 22  (A) for a 1 cc and in  FIG. 22  (B) for a 0.25 cc TEVA media. There is a divergence of the  224 Ra-bearing fraction decay rate from the theoretical  224 Ra decay rate lay beyond ˜28 d for the 1 cc column and beyond ˜12 d for the 0.25 cc column. The 0.25 cc column exhibits significantly greater  228 Th breakthrough during the load step than the 1 cc column. 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 TEVA resin cartridges and column evaluated for  228 Th 
               
               
                 sorption, desorption, and breakthrough.  a   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Inner 
                   
                   
                   
                   
               
               
                   
                 radius, 
                   
                   
                   
                   
               
               
                   
                 cm 
                   
                 Calc. 
                 Residence 
                 Linear flow 
               
               
                   
                 (top, 
                 Height, 
                 volume, 
                 time, 
                 velocity, 
               
               
                 Col. ID 
                 bottom) 
                 cm 
                 cm 3   
                 s  b, c   
                 cm/s  b   
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 2 mL 
                 0.46 
                 2.58 
                 1.60 
                 1.45 
                 0.40 
               
               
                 Cartridge 
                 0.43 
                   
                   
                   
                   
               
               
                 1 cm 3  SPE 
                 0.28 
                 4.50 
                 1.11 
                 1.00 
                 1.00 
               
               
                 tube 
                 0.28 
                   
                   
                   
                   
               
               
                 1 mL 
                 0.46 
                 1.37 
                 0.85 
                 0.77 
                 0.40 
               
               
                 Cartridge 
                 0.43 
                   
                   
                   
                   
               
               
                 HML 
                 0.43 
                 0.70 
                 0.39 
                 0.36 
                 0.43 
               
               
                 Cartridge  d   
                 0.42 
                   
                   
                   
                   
               
               
                 QML 
                 0.30 
                 0.77 
                 0.21 
                 0.19 
                 0.90 
               
               
                 Cartridge  e   
                 0.29 
               
               
                   
               
               
                   a  Some column chambers are slightly tapered cylinders; reported volumes based on a conical frustum. 
               
               
                   b  Normalized value, relative to the 1 cm 3  SPE column 
               
               
                   c  Transit time for non-retained species in the resin bed. 
               
               
                   d  HML = “half-milliliter”  
               
               
                 QML = “quarter-milliliter 
               
            
           
         
       
     
     In both cases, the column effluent fractions were aged over 30 days to allow for nearly complete  228 Th progeny ingrowth. The resulting  228 Th +progeny gamma spectra was used to quantify the  228 Th activity in each fraction. 
     The four TEVA resin cartridges and the TEVA resin SPE column listed in Table 5 received identical  228 Th-spiked solutions in 6 M HNO 3 . Delivered flow rate was 1 mL/min. C 1  effluents were collected and aged for up to two months. During this time, the decay rate of each  224 Ra-bearing TEVA load/wash “a” effluent fractions were tracked to determine its degree of purity over  228 Th. The results are shown in  FIG. 23  for the four machine-packed cartridges and  FIG. 24  (A) for the hand-packed 1 cc SPE tube. 
     Accordingly, a 1 cc and 0.25 cc TEVA resin provided roughly equivalent  228 Th elution yields after a 3 mL elution volume in 1 M HCl ( FIG. 21 ). The 1 cc TEVA resin retained a greater fraction of  228 Th during the load/wash “a” step than the 0.25 cc column volume, as some  228 Th breakthrough was observed ( FIG. 22 ). The 1 cc TEVA resin therefore provides a higher purity  224 Ra fraction passing into the remaining fluidic system. 
     The measured column load fraction activity values can begin to deviate from the theoretical  224 Ra decay curve at progressively earlier elapsed times as the cartridge bed volume decreases. These observed decay curve deviations can be related to increasing levels of  228 Th in the  224 Ra-bearing column load fractions. Next, the  228 Th decay profile can be fitted atop the data points that lay beyond 40 elapsed days. Extrapolation of the curve to the y-intercept provided an estimate of the  228 Th activity fraction present in the  224 Ra-bearing column load effluents. It is observed that the calculated  228 Th activity fraction increases as the TEVA cartridge volume decreases ( FIG. 23 , grey dashed lines also show this). 
     These calculated  228 Th activity fractions are presented in Table 6A. From these,  228 Th decontamination factors (DF) in the  224 Ra-bearing TEVA column load fractions can be obtained. The QML cartridge (the smallest TEVA resin bed volume evaluated) had a surprisingly high calculated  228 Th load/wash “a” breakthrough of ˜1.6% (DF=61). This breakthrough fraction can be reduced to 0.018% for the largest bed volume (2 mL) cartridge (DF=548). 
     
       
         
           
               
             
               
                 TABLE 6A 
               
             
            
               
                   
               
               
                 Observed performance of TEVA resin columns/ 
               
               
                 cartridges of the resin bed geometries listed in Table 5:  228 Th 
               
               
                 decontamination factors (DF) in the  224 Ra elution fraction, and  
               
               
                   228 Th yields from the load/wash/elute process. 
               
            
           
           
               
               
               
               
            
               
                   
                   228 Th activity 
                   
                   228 Th elution 
               
               
                 Col. ID 
                 Fraction (×10 −3 )  a   
                   228 Th DF  b   
                 yields, %  c   
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 2 mL Cartridge 
                 1.82 
                 548 
                 95 
               
               
                 1 cm 3  SPE tube 
                 1.20 
                 833 
                 98 
               
               
                 1 mL Cartridge 
                 2.65 
                 377 
                 97 
               
               
                 HML Cartridge  d   
                 7.47 
                 134 
                 94 
               
               
                 QML Cartridge  e   
                 16.3 
                 61 
                 94 
               
               
                   
               
               
                   a  Values based on  228 Th “load” fraction decay profiles. 
               
               
                   b  Obtained from the inverse of  228 Th activity fraction 
               
               
                   c  Values based on sum of column load/wash/elute fractions (see cumulative yield traces in FIG. 22 and FIG. 23). 
               
               
                   d  HML = “half-milliliter”  
               
               
                   e  QML = “quarter-milliliter”  
               
            
           
         
       
     
     It is interesting to note that the  228 Th activity fractions for the four TEVA resin cartridge type load/wash “a” effluents follow a negative power function when modeled against each cartridge&#39;s resin bed volume (provided in Table 5). The modeled curve is y=0.00268x −1.1112  (R 2 =0.9797), and, the 1 cc SPE tube activity fraction does not fit this curve. 
     It is noted that the data presented may indicate that the hand-packed 1 cc SPE tube provided the highest  228 Th decontamination factor (even higher than the 2 cc TEVA cartridge). 
     The second cartridge/column performance evaluation was to assess the quality of the  228 Th elution profile. After the load/wash “a” solution had been delivered to each of the TEVA cartridges shown in Table 6A, the  228 Th was eluted with 10 mL of 1 M HCI, delivered at 1 mL/min. Approximately 1 mL fractions were collected. The cumulative  228 Th fraction yields are shown for the four TEVA resin cartridge types in  FIG. 25  and the TEVA resin in SPE tube column in  FIG. 24  (B). 
     The  228 Th elution profiles are consistent with the anticipated peak broadening associated with increasing TEVA resin bed volumes. However, even for the largest (2 mL) TEVA cartridge, the  228 Th recovery was virtually complete after the third fraction. The  228 Th cumulative yield for the 1 cc SPE tube is shown in  FIG. 24  (B); its yield is likewise virtually complete after 3 mL of eluent. The  228 Th elution yields, calculated from the sum of all load/wash / elute fractions, is shown in Table 6A.  228 Th elution yields between 94% and 98% were observed, and this spread is within experimental uncertainty. 
     The machine-packed/commercially available TEVA cartridges exhibited  228 Th breakthrough levels that increased with decreasing cartridge bed volume. The hand-packed 1 cc SPE tube provided the least degree of  228 Th breakthrough vs. the cartridges. The TEVA SPE vessel and cartridges exhibited nearly complete  228 Th elutions after 3 mL of 1 M HCl eluent had been delivered at 1 mL/min. Overall, the hand-packed 1 cc SPE TEVA column provided a higher-purity  224 Ra fraction relative to the machine-packed TEVA cartridges. 
     Regarding Media M 2 , the 18-crown-6 ether extracting agent on the Sr Resin column has strong affinity for Pb(II) ions, and low affinity for Ra(II) ions and Bi(III) ions in HNO 3 . Consequently,  224 Ra is able to pass through the Sr Resin column be collected onto C 3 , Ra-01 resin). The  212 Bi and  208 Tl, which passed with  224 Ra through the C 2 , are likewise unretained on Col. 3, so this dose-causing radionuclide pair is sent to waste while  224 Ra is being loaded. The  212 Pb removal by C 2 , and the transference to waste of  212 Bi/ 288 Tl following C 3  can reduce the radiological dose imparted by  224 Ra progeny. 
     The HML (0.41 cc) and QML (0.25 cc) cartridges both from Eichrom, as shown in  FIG. 26  may be used for M 2 . The Sr Resin-bearing cartridges were loaded into the triple-column system in the C 2  slot, and the C 1  slot was configured with 1 cc TEVA resin columns. No C 3  was installed. Flow rate was 1 mL/min. C 1 →&gt;C 2  effluent fractions of ˜1 mL each were collected during the column load +wash “a” steps, wherein the load solution was  228 Th in secular equilibrium with  224 RA and its progeny. 
     The results for the 0.41 cc HML and the 0.25 cc QML cartridge effluents are shown in  FIG. 27  (A) and  FIG. 27  (B), respectively. The gamma spectra ( FIG. 27 ) are virtually the same; in both cases,  212 Pb was successfully scrubbed from the  224 Ra-bearing stream. The cartridges are between 0.41 cc and 0.25 cc in volume, and each of these performed virtually the same at removing  212 Pb from the  224 Ra-bearing load stream. 
     In accordance with another example implementation,  228 Th/ 224 Ra can be provided as a solution directly through C 3 , and C 3  effluent fractions collected throughout the process. 
     Referring to  FIGS. 27(C)  and (D) and Table 6B below, in accordance with yet another implementation, C 2  can be removed from the triple-column method. Without the presence of C 2 , both Pb and Ra emerging from the AnIX column may bind onto a Ra-01 column, and Ra separated therefrom. Pb can be selectively removed from the column using a chelator such as EDTA that is adjusted to a pH below the point where Ra(II)/EDTA complex forms. Per  FIG. 32 , Ra is not complexed to EDTA below a pH of ˜4. However, Pb(II) is fully complexed with EDTA above a pH of around 2, with a 50% complexation at a pH around 1.3. Therefore, a solution of EDTA with a pH 3.5 can be provided through the column, which selectively complexed  212 Pb and eluted it from the column while leaving  224 Ra on the column (Pb/EDTA complex is retained at a much lower pH, so at pH 3.5, Pb/EDTA complex is 100% speciated). Next, a solution of EDTA with a pH 11 (or a pH greater than ˜6) can be provided to the C 3  to remove the Pb-free  224 Ra. 
       FIG. 27C  depicts metals speciation comparison i) Pb/Pb-EDTA; ii) Bi/Bi-EDTA; iii) Th/Th-EDTA; and iv) Ra/Ra-EDTA along the same pH spectrum. 
       FIG. 27  D i and ii, depicts separation of  224  Ra from  212 Bi and  212 Pb using Ra-01 resin column (3×50 mm) via protocol listed in Table 12. Column effluent fraction categories are designated at top. Legend is elapsed days between column run and gamma analysis of fractions. (Right) Select elapsed time series indicates radionuclides present across the separation protocol. 
     
       
         
           
               
             
               
                 TABLE 6B 
               
             
            
               
                   
               
               
                 Protocol for loading  224 Ra solution onto Ra-01 resin 
               
               
                 column, eluting  212 Pb, and eluting  224 Ra.  a   
               
            
           
           
               
               
               
               
            
               
                   
                   
                 Volume, 
                 Elapsed vol., 
               
               
                 Step 
                 Reagent 
                 mL 
                 mL  b   
               
               
                   
               
               
                 Condition 
                 2M HNO 3   
                 3 
                 — 
               
               
                 Load 
                 2M HNO 3  +  224 Ra 
                 3 
                 3 
               
               
                 Wash 
                 2M HNO 3   
                 5 
                 8 
               
               
                   212 Pb elute 
                 0.05M EDTA, pH 3.5 
                 5 
                 13 
               
               
                   224 Ra elute 
                 0.05M EDTA, pH 11.05 
                 5 
                 18 
               
               
                 Rinse 
                 DI H 2 O 
                 3 
                 21 
               
               
                   
               
               
                   a  Solution flow rate = 0.5 mL/min; column dimensions = 3 × 50 mm (0.35 cm 3 ). 
               
               
                   b  Elapsed volumes correlate to subsequent column effluent gamma activity plots. 
               
            
           
         
       
     
     The load +wash “a” fraction gamma spectra are shown in  FIG. 28  (A), and the wash “b” fractions are shown in  FIG. 28  (B).  228 Th can be eliminated from the Ra-01 column during the wash “a” steps. During the wash “b” steps, no  228 Th is apparent; the  228 Th has been largely eliminated from C 3 . This data indicates that any  228 Th that may break through C 1  and into the downstream fluidic system during the load/wash “a” step would pass, unretained, through the Ra-01 resin. 
     The spectra in  FIG. 28  also indicates that  212 Bi/ 208 Tl is largely unretained on the Ra-01. There is an obvious absence of  212 Pb in the Ra-01 effluent fractions;  212 Pb is retained on Ra-01 resin (which is why C 2  (Sr Resin) is upstream to the Ra-01 resin column to strip it out). 
     In accordance with example implementations, a water wash can be placed between wash “b” and the  224 Ra elution step. The water would be used to remove residual H±ions from the column prior to the introduction of the pH ˜11  224 Ra eluent solution. 
     It is preferable that the wash “a” volume is sufficient to assure passage of  224 Ra through C 1  and onto C 2 /C 3  (Step A), and the wash “b” volume is sufficient to assure passage of  224 Ra through C 2  and onto C 3  (Step B). The load/wash “a” volumes shown in  FIG. 29  are therefore more than adequate to accomplish the Step A objective. 
     The impact of the water wash through the Ra-01 resin is shown in  FIG. 30  (A).  212 Pb (retained on the Ra-01 column due to the lack of C 2  upstream in this experiment) is removed from the vessel in water. An evaluation of the decay rate of these column effluent fractions indicated that  224 Ra was not present ( FIG. 30  (B)). Therefore, indications were that the water wash could be employed to eliminate excess H+ions (preventing EDTA precipitation) and further remove  212 Pb from the Ra-01 resin (thus reducing  224 Ra product dose) without impacting  224 Ra elution yield. 
     Following the water wash, the Ra-01 resin contained isolated  224 Ra. The  224 Ra was eluted using the EDTA solution, and the eluent fraction&#39;s decay rate was monitored to evaluate its radionuclidic purity. 
     The results presented in  FIG. 30  indicate that the addition of a water wash between wash “a” and the  224 Ra elution serves to eliminate H±ions from the column, which in turn eliminates acidification of the basic EDTA-based  224 Ra eluent. Additionally, the water wash was observed to remove  212 Pb from the column, while  224 Ra was retained. 
     The results presented in  FIG. 31  indicate that the single-column (C 3 ) separation of  224 Ra from  228 Th with the Ra-01 resin in this experiment was capable of a 1000-fold decontamination factor (decontamination factor determination was limited by dynamic range of the analysis method). In other words, ˜0.1% of any  228 Th that manages to break through C 1  during the load / wash “a” step (the two steps wherein all three columns are inter-connected) would be expected to be found in the  224 Ra elute. It is believed that the C 1   228 Th retention factor is at least 500. If this is so, then the approximate  228 Th decontamination factor across the entire triple-column method is 5×10 5 . 
     While the radionuclidic purity of  224 Ra is essential in providing a robust isotope product, it is just as important that the output of the triple-column method be amenable to existing and future  224 Ra/ 212 Pb generators. 
     For the existing  224 Ra/ 212 Pb generator design, the  224 Ra source is loaded onto a CatIX resin column (using AG MP-50 resin beads). Therefore, the Ra output from the triple-column method should be amenable to direct loading onto CatIX resin. Unfortunately, the purified Ra product, delivered in dilute EDTA solution (pH adjusted to &gt;7), will not bind to CatIX resin as a free divalent cation; according to the speciation plots for Ra/EDTA mixtures ( FIG. 32 ), Ra is completely bound to EDTA above pH 7. The chelated complex likely progresses from [Ra(EDTA)] −  to [Ra(EDTA)] 2−  as the pH increases above 7. However, at pH values near 5, the Ra/EDTA complex is ˜50%, and at pH values ≤4, the Ra 2+  cation is completely dissociated from the EDTA complex. 
     Referring to  FIG. 1  above and with reference to module 4, free element production, systems and/or methods for producing a free element are provided. The system/methods can include providing a mixing vessel in fluid communication with both a bound element source and an acid source. The mixing vessel can be operably configured to mix contents within the mixing vessel. The systems can include a first multiport valve operably engaged with an exit of the mixing vessel, and a second multiport valve operably engaged with the first multiport valve, the acid source, and a collection vessel. 
     As detailed below the element can be Ra, however, as described above, other elements can be processed using these systems and/or methods. 
     Methods for producing free element from a bound element are also provided. The methods can include: providing a solution comprising an element bound to a complex; exposing the solution to a precipitating solution to precipitate the complex binding the element and produce a free element solution; and transferring the free element solution to a collection vessel. 
     The systems/methods can include separating the Ra from a solution comprising Ra and Th to form the solution comprising Ra bound to EDTA. The solution of the Ra bound to the EDTA has a pH greater than 11, and the free element solution can include Ra and has a pH less than 4 or even less than 2. 
     As provided herein, lowering the  224 Ra/EDTA product solution pH to 4 will result in free Ra 2+  cation in solution. The schematic shown in  FIG. 33  provides a pathway for preparing and binding free Ra 2+  onto a generator column packed with AG MP-50 CatIX resin. 
     One milliliter of the isolated  224 Ra product (5 mL) resulting from the triple-column separation can be acidified using 21.7 μL of concentrated HCI (0.26 mmoles H+ added). Next, the acidified solution can be delivered to a MP-50 resin at 0.5 mL/min. The data in  FIG. 36( a )  shows the activity observed in the column load effluent fraction as a function of elapsed days. Virtually no activity is present in the column effluent solution. Subsequent to media load, the media can be washed with four 1 mL fractions of dilute HCl solution ( FIG. 34  (B)). An elution of a short-lived daughter isotope may be observed immediately after the fractions were collected; the isotope can decay away within the first ˜0.18 days (˜4 h), and this shows no bleed-through of  224 Ra during the wash. Continuous counting of the CatIX media over -7 days shows the characteristic decay rate of  224 Ra beyond -1.6 days ( FIG. 34  (C)). 
     The results in  FIG. 34  indicate that acidification of the isolated  224 Ra product fraction from the triple-column method can provide for quantitative loading of the  224 Ra onto a CatIX media. Accordingly, the triple-column method appears to be well suited to the subsequent  224 Ra/ 212 Pb generator column preparation via a solution acidification step. 
     As can be seen in  FIG. 35 , at least one schematic depiction of the preparation of the free isotope ( 224 Ra 2+ )is shown. The chemical modification chamber or mixing vessel can receive the bound isotope ( 224 Ra/EDTA) eluent directly from the triple-column method (Step D of  FIG. 12  above) for example. Within this chamber, acid can be injected to reduce the solution pH to a point in which the Ra/EDTA complex is eliminated or uncoupled, thereby producing free isotopes ( 224 Ra 2+ )ions in solution (per  FIG. 32 ). A stir bar can be used for mixing of acid into the  224 Ra eluent. 
     If the solution is acidified to &lt;˜pH 2, not only does the  224 Ra 2+  dissociate from the Ra/EDTA complex, but the EDTA precipitates from the solution. Once the EDTA precipitate is fully formed, the supernate can be withdrawn from the base of the chemical modification chamber or mixing vessel, through a hydrophobic polyethylene frit for example, thereby removing the precipitated EDTA crystals from the  224 Ra 2+  solution. 
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Syringe pump distribution valve port and descriptions of 
               
               
                 system illustrated in FIG. 35. 
               
            
           
           
               
               
               
            
               
                   
                 Port 
                 Port Description 
               
               
                   
                   
               
               
                   
                 1 
                 Waste (out) 
               
               
                   
                 2 
                 DI water (in) 
               
               
                   
                 3 
                 Acid (in) 
               
               
                   
                 4 
                 Closed 
               
               
                   
                 5 
                 Air (in) 
               
               
                   
                 6 
                 Ra/EDTA acidification line (out) 
               
               
                   
                 7 
                 Ra filtrate line (in) 
               
               
                   
                 8 
                 Col. packing system line (out) 
               
               
                   
                   
               
            
           
         
       
     
     In accordance with another example configuration, system  100  is shown in  FIG. 36 . As shown, system  100  can include a mixing vessel  110  that is in fluid communication with both a bound isotope source  112  and an acid source  114 . In accordance with example implementations, the bound isotope source can be a source as described herein with reference to the separation of elemental Ra from thorium, for example. In accordance with other example implementations, the acid source  114  can be a syringe pump that can be mechanically controlled, for example. Mixing vessel  110  can be configured to mix contents therein utilizing, for example, a magnetic mixer such as magnetic mixer  116  that is placed lateral or underneath or about in an operable configuration of mixing vessel  110  that contains magnetic stirrer  130 . 
     System  100  can also include first and second multiport valves with first multiport valve  118  being operably connected to the exit  124  of mixing vessel  110  and a second multiport valve  120  that can be operably connected to first multiport valve  118  as well as the acid source  114  and a collection vessel  126 . In accordance with example configurations, the element being freed can be Ra such as  224 Ra. The element can be freed from a complexing agent such as a chelating agent. Example chelating agents can include but are not limited to EDTA. As described, the first and second multiport valves can be configured to be operated remotely, and this system can be coupled in tandem with a Ra production system such as that described earlier for isolating Ra from Th. 
     In accordance with at least one example implementation, mixing vessel  110  can be a 5 mL RezorianTM column (Supelco, Bellefonte, Pa.) fitted with a hydrophobic polyethylene (PE) frit  135  (Scientific Commodities Inc., Lake Havasu City, Ariz.), a PTFE Spinplus® magnetic stir bar  130  (SP Scienceware, Wayne, N.J.), a one-way stopcock valve  118  (Cole-Parmer, Vernon Hills, Ill.), a 0.45 μm PES filter  131  (Pall, Port Washington, N.Y.), a 12 mL disposable polypropylene syringe  114  (Thermo Fischer Scientific, Waltham, Mass.), and a “Multi-Stirrus” magnetic vertical mixer  116  (V&amp;P Scientific, San Diego, Calif.). 
     In accordance with example methods, the 5 mL Rezorian™ tube can receive an aliquoted volume of  224 Ra-EDTA solution from the triple-column system&#39;s column 3 (C 3 )  224 Ra elution. An inlayed hydrophobic frit (positioned at the base of the Rezorian tube) and connected one-way stopcock valve (set to “closed”) were utilized to prevent the  224 Ra-bearing solution from leaking through the bottom port. An aliquot of mineral acid can be added the  224 Ra/EDTA solution in the Rezorian tube to lower the pH, thus forming insoluble EDTA that precipitated out of solution. The vertical magnetic mixer can be used to create a magnetic field, driving the magnetic stir bar to mix the acid/Ra/EDTA solution and enhance precipitation rate. Once the EDTA precipitation was complete, the stopcock valve can be opened and the EDTA-removed  224 Ra supernate can be withdrawn from the Rezorian tube through the hydrophobic frit and into the syringe barrel. An additional syringe filter can be added to the line between the syringe barrel and the  224 Ra collection vessel to remove any fine EDTA particulates that may have passed through the larger-pored hydrophobic frit. 
     A schematic of the automated in-line EDTA precipitation and filtration system is shown in  FIG. 36 . The automated version of the precipitation and filtration system can employ an inverted digital syringe pump 114 (SP, 48,000 steps, IMI Norgren, Littleton, Colo.) with 8-port distribution valve 120, a three-way stopcock 118 (Cole-Parmer, Vernon Hills, Ill.) which can be controlled by servo motor (SvM, Dsservo, Dongguan, Guangdong, China), a “Multi-Stirrus” vertical magnetic spinning device 116, and a 0.45 μm PES filter connected to a  224 Ra collection vessel. Port assignments, flow direction, and port designation for the SP are listed in Table 8. Each component in the system is described below in more detail. Operation of the SP, the vertical magnetic mixer, and SvM can be controlled via processing circuitry through a software. 
     The present disclosure provides systems and/or methods that can be performed advantageously with the assistance of processing circuitry. The processing circuitry can include personal computing system that includes a computer processing unit that can include one or more microprocessors, one or more support circuits, circuits that include power supplies, clocks, input/output interfaces, circuitry, and the like. Generally, all computer processing units described herein can be of the same general type. The computing system can include a memory that can include random access memory, read only memory, removable disc memory, flash memory, and various combinations of these types of memory. The memory can be referred to as a main memory and be part of a cache memory or buffer memory. The memory can store various software packages and components such as an operating system. 
     The computing system may also include a web server that can be of any type of computing device adapted to distribute data and process data requests. The web server can be configured to execute system application software such as the reminder schedule software, databases, electronic mail, and the like. The memory of the web server can include system application interfaces for interacting with users and one or more third party applications. Computer systems of the present disclosure can be standalone or work in combination with other servers and other computer systems that can be utilized, for example, with larger corporate systems such as financial institutions, insurance providers, and/or software support providers. The system is not limited to a specific operating system but may be adapted to run on multiple operating systems such as, for example, Linux and/or Microsoft Windows. The computing system can be coupled to a server and this server can be located on the same site as computer system or at a remote location, for example. 
     In accordance with example implementations, these processes may be utilized in connection with the processing circuitry described. The processes may use software and/or hardware of the following combinations or types. For example, with respect to server-side languages, the circuitry may use Java, Python, PHP, .NET, Ruby, Javascript, or Dart, for example. Some other types of servers that the systems may use include Apache/PHP, .NET, Ruby, NodeJS, Java, and/or Python. Databases that may be utilized are Oracle, MySQL, SQL, NoSQL, or SQLLite (for Mobile). Client-side languages that may be used, this would be the user side languages, for example, are ASM, C, C++, C#, Java, Objective-C, Swift, Actionscript/Adobe AIR, or Javascript/HTML5. Communications between the server and client may be utilized using TCP/UDP Socket based connections, for example, as Third Party data network services that may be used include GSM, LTE, HSPA, UMTS, CDMA, WiMax, WiFi, Cable, and DSL. The hardware platforms that may be utilized within processing circuitry include embedded systems such as (Raspberry PI/Arduino), (Android, iOS, Windows Mobile)—phones and/or tablets, or any embedded system using these operating systems, i.e., cars, watches, glasses, headphones, augmented reality wear etc., or desktops/laptops/hybrids (Mac, Windows, Linux). The architectures that may be utilized for software and hardware interfaces include x86 (including x86-64), or ARM. 
     In accordance with example implementations, servos for engaging single or multiport valves as well as mechanical or electric switches for engaging valves can be configured according to software and/or hardware to engage/disengage upon achieving and endpoint such as a temperature, a time, a pressure, a volume, etc. Accordingly, much of the systems and methods of the present disclosure can be performed remotely from a processing circuitry interface and/or automatically according to a program. 
     The system can be plumbed with 0.02″ or 0.03″ or 0.04″ ID by 1/16″ OD fluorinated ethylene propylene (FEP) tubing (IDEX Health &amp; Science, Oak Harbor, WA) connected to polyether ether ketone (PEEK) ¼-28 flangeless nuts with Tefzel® ferrules (IDEX Health &amp; Science, Oak Harbor, Wash.) or PEEK 10-32 nuts with PEEK conical ferrules (Valco). 
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Description of the 8-position syringe pump distribution 
               
               
                 valve port assignments for the automated in-line precipitation  
               
               
                 and filtration system shown in FIG. 36. 
               
            
           
           
               
               
               
               
            
               
                 Port 
                 Flow 
                   
                 Tubing dimensions 
               
               
                 assignment 
                 direction 
                 Port designation 
                 (ID by OD) 
               
               
                   
               
               
                 1 
                 Out 
                 Waste 
                 0.02″ by 1/16″  
               
               
                 2 
                 In 
                 Deionized (DI) H 2 O 
                 0.03″ by 1/16″  
               
               
                 3 
                 In 
                 6M HNO 3   
                 0.03″ by 1/16″  
               
               
                 4 
                 N/A 
                 Closed 
                 N/A 
               
               
                 5 
                 In 
                 Air 
                 0.03″ by 1/16″  
               
               
                 6 
                 Out 
                 Line out to precipitation vessel 
                 0.02″ by 1/16″  
               
               
                 7 
                 In 
                 Line in from precipitation vessel 
                 0.04″ by 1/16″  
               
               
                 8 
                 Out 
                 Line out to  224 Ra collection 
                 0.02″ by 1/16″  
               
               
                   
                   
                 vessel 
               
               
                   
               
            
           
         
       
     
     The automated in-line precipitation and filtration system can utilize the same precipitation vessel described herein with the addition of a teflon cap fitted with tubing lines and an activated charcoal trap to filter  220 Rn emanation from the air space above the  224 Ra-bearing solution. The  224 Ra-EDTA solution can be dispensed from the triple column purification system through one of these tubing lines, while the other was used to dispense mineral acid into the  224 Ra-bearing eluent. EDTA precipitation rate was enhanced by the use of the vertical magnetic stirrer. 
     In the automated filtration process, the three-way stopcock valve with three ports can connect the holding vessel to the digital syringe pump, and to add a rinse vessel line that was used to clear the line of residual  224 Ra-bearing liquid. The stopcock valve can be connected to a servo motor (SvM) which is operable between each port. The inverted syringe pump with 8-port distribution valve was utilized to aspirate the supernate before dispensing it through the 0.45 μm filter and into the  224 Ra collection vessel as shown in  FIG. 36 . 
     With reference to  FIG. 37 , a custom holder can be provided to hold the precipitation vessel, servo motor, and vertical mixer in proximity. The component bracket was designed with Solidworks2017 (Dassault Systems, Waltham, Mass.) and 3D printed on a uPrint SE Plus (Stratasys, Eden Prairie, Minn.). 
     Referring to  FIG. 38 , an image of a pre acidified  224 Ra-EDTA solution (a), precipitation forming solution (b), and post precipitation solution (c) is shown. 
     With reference to  FIG. 39 , configurations of the system for the automated in-line process replicated the method described with the use of two separate tubing lines to receive first the  224 Ra-EDTA solution, and then a small volume of 6 M HNO 3  into the precipitation vessel. The precipitation vessel can be configured from a 5 mL Rezorian tube kit with an inlayed 20 μm pore size hydrophobic polyethylene frit at the base, and a Teflon-coated magnetic stir bar. Under magnetic mixing, the acid added to the  224 Ra-EDTA solution reduces the pH, thus causing EDTA to precipitate out of solution while leaving  224 Ra 2+  in the supernate. 
     Once the EDTA precipitation was complete, the automated in-line filtration process can be divided into four steps ( FIG. 39 ). In step 1, the servo motor actuated the three-way stopcock valve to 90° and the  224 Ra supernate was aspirated into the inverted syringe pump at a flow rate of 10 mL/min. During this process, the vast majority of the solid EDTA is captured by the frit. In step 2, the supernate in the syringe was dispensed through a 0.45 μm syringe filter and into the  224 Ra collection vessel (d). The in-line filter was used to remove any small EDTA crystals that may have migrated through the Rezorian tube&#39;s frit. In step 3, the servo motor actuated the three-way stopcock to 180° to form a singular flow pathway between the rinse vessel, and the SP. From the rinse vessel, a 250 pL aliquot of 0.01 M HCl (pH 2) was aspirated through the syringe delivery line and into the SP, carrying any residual  224 Ra-bearing droplets left in the tubing to the syringe. In step 4, the pH 2 rinse solution was dispensed through the 0.45 pm filter and into the  224 Ra collection vessel. 
     In accordance with the systems described above, methods for producing free isotopes are provided that can include providing a solution comprising isotope bound to a complex. In accordance with example implementations, the bound isotope can be in a solution having a pH that is sufficient to bind substantially all of the isotope and/or retain the bound isotope in solution. Additionally, the solution can be adjusted to another pH that decomplexes the isotope from the complex and/or precipitates the complex while leaving substantial amounts of the isotope in solution. 
     These example solutions include the Ra bound to EDTA, for example. This solution can be exposed to a precipitating solution such as an acidic solution to precipitate the complex binding the isotope and produce a free isotope solution as shown and depicted with reference to the mixing vessels in the previous systems. The methods can further include transferring the free isotope solution to a collection vessel. In accordance with example implementations, the solution of the isotope bound to the complex can have a pH greater than 11. Additionally, the free isotope solution can have a pH less than 2. In accordance with example implementations, these solutions can be conveyed to and/or from the mixing vessel using pressure differentiation techniques that can include suction or positive displacement, for example. Additionally, the methods can include transferring the free element or Ra through a filter to a vessel. 
     Referring next to  FIG. 40 , systems and methods are described for producing metal storage/generation vessel assemblies, including particular metals to be stored and/or generated using the vessels. Embodiments of these systems, methods, and assemblies are described with reference to  FIGS. 40-63B . 
     Systems and/or methods for producing a metal storage/generation vessel assemblies are provided. The systems can include: a first mixing vessel in fluid communication with a first and a second multiport valve; a manifold of multiport valves in fluid communication with the second multiport valve; a second mixing vessel in fluid communication with at least one of the multiport valves of the manifold; a third multiport valve in fluid communication with an exit of the second mixing vessel; and a metal storage/generation vessel in fluid communication with the third multiport valve. 
     The first and second mixing vessels define different volumes. The first mixing vessel defines a volume larger than the volume defined by the second mixing vessel. 
     Methods for producing a metal storage/generation vessel assembly are also provided. The methods can include: homogenizing a resin slurry in a first mixing vessel; supplementing the homogenized resin slurry with a free element to form a homogenized bound element resin slurry; and transferring the homogenized bound element resin slurry to a storage/generation vessel assembly. As shown and described, the resin/media of the present disclosure, without homogenization will consolidate at the lower portion of the vessel or adhere to other portions of the vessel. Homogenizing herein keeps the resin/media distributed throughout the solution of the vessel. This distribution can be uniform and/or without a heterogenous interface. 
     Metal storage/generation vessel assemblies are also provided that can include: sidewalls extending between entrance and exit openings to define a vessel volume; inert material proximate the exit opening: unbound resin (catch bed) proximate the exit opening wherein the inert material is between the unbound resin and the exit opening; and a homogenized bound element resin bed within the vessel, the inert material and unbound binding resin being between the resin bed and the exit opening. 
     Referring first to  FIG. 40 , an example sequence of events can include homogenizing a resin slurry, metering the resin bed volume to another vessel, and then mixing an element with the slurry mixture, and then transporting the element-loaded slurry to a storage and/or generation assembly  6 . 
     Referring next to  FIG. 41 , a system  200  is provided. Within this system are two mixing vessels, a first mixing vessel  210  and a second mixing vessel  212 . Mixing vessel  210  can be in fluid communication with first and second multiport valves  214  and  216 . In accordance with example implementations, system  200  can further include a manifold of multiport valves  218  which can be in fluid communication with multiport valve  216 . Mixing vessel  212  can be in fluid communication with at least one of the multiport valves within the manifold  218 . System  200  can further include a third multiport valve  220  which is in fluid communication with an exit of mixing vessel  212 . System  200  can additionally include a metal storage generation vessel  6  in fluid communication with multiport valve  220 . In accordance with example implementations,  FIG. 42  is a depiction of an implementation of system  200 . 
     The automated vessel assembly packing system is shown in  FIG. 41  and an image of the system in the fume hood is shown in  FIG. 42 . The systems can include a V 6  digital syringe pump (SP, 48,000 steps, IMI Norgren, Littleton, CO) with 8-port distribution valve at its head, a 4-port and 6-port Cheminert selector valve (V 4  &amp; V 6 , Valco, Inc., Houston, Tex.), a stopcock manifold (SM, Cole-Parmer, Vernon Hills, Ill.), three servo motors (SvM, Dsservo, Dongguan, Guangdong, China), several solution holding coils (HC), two gas regulators (R 1 /R 2 ) (McMaster-Carr, Los Angeles, Calif.), and two solenoid-controlled 3-way isolation valves (SCIV, Bio-Chem, Boonton, N.J.). Port assignments for the syringe pump (SP), including flow direction, port designation, and tubing dimensions, are listed in Table 9. Port assignments for the 4-port valve (V 4 ) and 6-port valve (V 6 ) are listed in Table 10 and Table 11, respectively. Each component in the system, and their abbreviated terms, will be described in more detail in the sections below. Operation of the SP, V 4 , V 6 , SVMB, and SCIVs using processing circuitry. 
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 Description of the 8-position syringe pump (SP) 
               
               
                 distribution valve port assignments. 
               
            
           
           
               
               
               
               
            
               
                 Port 
                 Flow 
                   
                 Tubing dimensions 
               
               
                 assignment 
                 direction 
                 Port designation 
                 (ID by OD) 
               
               
                   
               
               
                 1 
                 Out 
                 Waste 
                 0.04″ by 1/16″ 
               
               
                 2 
                 In 
                 Deionized (DI) H 2 O 
                 0.04″ by 1/16″ 
               
               
                 3 
                 In 
                 0.25M HCl 
                 0.04″ by 1/16″ 
               
               
                 4 
                 In/Out 
                 Excess supernatant coil (ESC) 
                 0.04″ by 1/16″ 
               
               
                 5 
                 In 
                 Air 
                 0.04″ by 1/16″ 
               
               
                 6 
                 Out 
                 Transport line (TL) 
                 0.04″ by 1/16″ 
               
               
                 7 
                 In/Out 
                 Holding coil to V4 (HC/V4) 
                 0.063″ by ⅛″ 
               
               
                 8 
                 In/Out 
                 Holding coil to V6 (HC/V6) 
                 0.063″ by ⅛″ 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 10 
               
             
            
               
                   
               
               
                 Description of the 4-position Cheminert selector 
               
               
                 valve (V4) port assignments. 
               
            
           
           
               
               
               
               
            
               
                 Port 
                 Flow 
                   
                 Tubing dimensions 
               
               
                 assignment 
                 direction 
                 Port designation 
                 (ID by OD) 
               
               
                   
               
               
                 1 
                 Out 
                 Waste 
                 0.063″ by ⅛″ 
               
               
                 2 
                 In 
                 Air 
                 0.04″ by 1/16″ 
               
               
                 3 
                 In/Out 
                 Large mixing vessel (LMV) 
                 0.063″ by ⅛″ 
               
               
                 4 
                 Out 
                 V4 to 3 stopcock manifold (SM) 
                 0.063″ by ⅛″ 
               
               
                 Center 
                 In/Out 
                 Holding coil to V4 (HC/V4) 
                 0.063″ by ⅛″ 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 11 
               
             
            
               
                   
               
               
                 Description of the 6-position Cheminert selector valve 
               
               
                 (V6) port assignments. 
               
            
           
           
               
               
               
               
            
               
                 Port 
                 Flow 
                   
                 Tubing dimensions 
               
               
                 assignment 
                 direction 
                 Port designation 
                 (ID by OD) 
               
               
                   
               
               
                 1 
                 Out 
                 Waste 
                 0.063″ by ⅛″ 
               
               
                 2 
                 In 
                 Air 
                 0.04″ by 1/16″ 
               
               
                 3 
                 In/Out 
                 Small mixing vessel (SMV) 
                 N/A 
               
               
                 4 
                 In 
                   224 Ra stock solution 
                 0.04″ by 1/16″ 
               
               
                 5 
                 In 
                 1M HCl 
                 0.04″ by 1/16″ 
               
               
                 6 
                 Out 
                 Column body 
                 0.063″ by ⅛″ 
               
               
                 Center 
                 In/Out 
                 Holding coil to V6 (HC/V6) 
                 0.063″ by ⅛″ 
               
               
                   
               
               
                 a. The part was connected without use of tubing. 
               
            
           
         
       
     
     In accordance with example implementations, the mixing vessels (e.g., LMV and SMV) can define different volumes wherein the first mixing vessel can be a larger volume than the second mixing vessel. In accordance with example implementations and with reference to  FIG. 43 , an image of a first mixing vessel configured for N 2  agitation for mixing is shown. The mixing vessel of  FIG. 43  can be considered the first or Large mixing vessel (LMV) and contain a known ratio of CatIX resin to water and is capable of forming a homogeneous suspension of these solid/liquid phases. 
     Two resin/liquid suspension large mixing vessels (LMVs) were evaluated for the system. The first LMV employed N 2  gas or air to create a homogeneous resin/water slurry (LMV). The vessel was a 50 mL polyethylene centrifuge tube containing a reservoir of MP-50 resin and water at a known solid/liquid volume ratio. The LMV had a cap fitted with three holes, through which a N 2  gas (inlet) line, a resin slurry aspiration line (outlet), and a N 2  gas vent (outlet) port were fixed. A stream of N 2  gas or air was used to agitate the resin/water mixture in order to obtain a homogeneous slurry while the slurry aspiration line was used to withdraw a metered volume from the LMV. An image of the LMV as shown in  FIG. 43 . 
     Referring next to  FIGS. 44A and 44B , a first mixing vessel configuration is disclosed that depicts a mixing vessel that can be mechanically stirred, for example. 
     Another LMV was evaluated that defined a 50 mL centrifuge tube and resin/water reservoir configured with a plastic vane placed down its center ( FIG. 44A ). This LMV was in turn positioned onto a base that oscillated in a back-and-forth “washing machine” pattern. The oscillations were driven by a rotating magnetic field using a “Multi-Stirrus” mixer (V&amp;P Scientific, San Diego, CA) that caused angular rotation of the vane, agitating the slurry by turbulent action. Two vanes designs of  FIG. 44B  were evaluated; they were fabricated with holes along the edges, as shown in  FIG. 44B . The slurry aspiration line was used to withdraw a metered volume from the LMV. 
     In accordance with  FIG. 45 , a second mixing vessel is depicted that is configured for N 2  gas or air mixing that includes a gas inlet and outlet, for example. This second or small mixing vessel (SMV) is configured to 1) receive the aliquoted volume of MP-50 resin (from the LMV) as a slurry, and 2) contact a  224 Ra-bearing solution with the resin slurry received to obtain a homogeneous distribution of  224 Ra adsorbed to the MP-50 resin. The SMV can be defined by a 10 mL polyethylene syringe barrel that was mounted to the V 6  valve via a female luer to ¼-28 connector. The tube barrel cap, custom-machined from Teflon FEP, was fitted with four holes through which a N 2  gas or air (inlet) line, a resin slurry dispenser (inlet) line, an excess supernatant coil (ESC) line (inlet/outlet), and a N 2  gas or air vent (outlet) port were passed. The ESC line, with 2.00 ±0.02 mL inner volume, could be used to aspirate excessive supernatant from the dispensed resin slurry. The  224 Ra solution could be introduced into the SMV via the V 6  valve; the post-contacted  224 Ra/resin slurry mixture could be aspirated from the SMV via the same valve. A stream of N 2  gas or air was used to agitate the mixture of resin slurry and  224 Ra solution to affect homogeneous adsorption of  224 Ra onto the resin particles. 
     In accordance with example configurations and with reference to  FIG. 46 , a configuration of the manifold  218  of system  200  is shown that includes the configuration of the multiport valves of the manifold, for example. The stopcock manifold (SM) system was constructed from a stack of three 3-way stopcock luer valves (Cole-Farmer). The SM was connected between the V 4  and the SMV as a pathway to transport and meter resin for eventual  224 Ra contact in the SMV followed by subsequent column packing. Based on the inner volume of a stopcock (0.120 mL) and a connecting cylinder between either pair of stopcocks (0.130 mL) in the manifold system, a set volume of slurry could be packed and partitioned into a 0.250 mL column bed. A custom trimmed high-density polyethylene 5 mL pipette filter (Eppendorf, Hauppauge, New York, USA) was used as a bottom frit to allow water, but no resin, to pass through the bottom port of the SM. A packed bed of resin therefore forms above the frit. 
     Configuration of stopcock positions in the SM allowed for a transport line (TL) to push excess resin to waste while the set metered volume was held, and subsequently transported, into the SMV. Adjustment of the stopcock valve positions can be performed using processing circuitry. An image of the SM is shown in  FIG. 46 , with port designations and flow direction provided in Table 12. 
     
       
         
           
               
             
               
                 TABLE 12 
               
             
            
               
                   
               
               
                 Description of the stopcock manifold system (SM) shown  
               
               
                 in FIG. 46 and FIG. 47. 
               
            
           
           
               
               
               
               
            
               
                 Port 
                 Flow 
                   
                 Tubing dimensions 
               
               
                 assignment 
                 direction 
                 Port designation 
                 (ID by OD) 
               
               
                   
               
               
                 1 
                 In 
                 V4 to stopcock manifold (SM) 
                 0.063″ by ⅛″ 
               
               
                 2 
                 Out 
                 Excess resin to waste 
                 0.063″ by ⅛″ 
               
               
                 3 
                 In 
                 Transport line (TL) 
                 0.04″ by 1/16″ 
               
               
                 4 
                 Out 
                 Small mixing vessel (SMV) 
                 0.063″ by ⅛″ 
               
               
                 5 
                 Out 
                 Waste 
                 0.063″ by ⅛″ 
               
               
                   
               
            
           
         
       
     
     A schematic of the SM resin bed metering and partitioning sequence is shown in  FIG. 47 . Each of the stopcocks within the manifold can be operably engaged with a servo block motor. Referring to  FIG. 47 , again for moving the slurry between the prep slurry and the generator vessel and/or mixing the slurry with elements is shown with manifold configurations as shown in  FIG. 47 . 
     The importance of agitation of the slurry is shown with reference to  FIGS. 48-52  that depicts unagitated and agitated slurry in the first mixing vessel, for example. 
     Two methods were evaluated to promote a homogenous resin suspension from which to feed into the fluidic system. A consistent resin concentration in the LMV was beneficial when aspirating volumes of slurry to deliver adequate resin mass to the SM for precise resin bed metering. In the LMV, a 20 mL resin/water mixture containing 5 cm 3  of gravity-settled resin was used. In the SMV, a 4.25 mL resin/water mixture consisting of 0.25 cm 3  gravity-settled resin metered from the SM was used. 
     As discussed, the first method of resin suspension we evaluated employed a stream of N 2  gas or air controlled via gas regulator to agitate gravity-settled resin bed causing dispersion of resin beads within the water volume until uniform. We termed the gas-agitated LMV as “LMVg”. The regulator was opened at increasing increments of 0.5 pounds per square inch (PSI) followed by 5 minutes of observation to determine if the entire gravity settled resin bed was suspended and became homogenous (i.e., demonstrated no stratification of resin beads with liquid depth). This process was repeated until mixing became overly vigorous. A minimum and maximum PSI was noted for the LMVg and SMV. Images of these vessels in an unagitated and homogeneously agitated state are shown in  FIG. 48  (LMVg) and  FIG. 49  (SMV). 
     As discussed, the second method employed a magnetically rotating base (Multi-Stirrus mixer, V&amp;P Scientific, San Diego, Calif.) to induce an oscillating angular rotation of the LMV. The spin vane-agitated assembly was termed “LMVv”. The oscillating vessel containing the fixed vane creating turbulent eddies within the vessel, thus inducing mixing. Angular rotation of the system was increased at increments of 10 revolutions per minute (RPM) followed by 5 minutes of observation to determine if the entire gravity settled resin bed was suspended and became homogenous. This process was repeated until 100 RPM (the maximum) was reached. A minimum and maximum RPM was noted for each of two vane designs evaluated. An image of the LMVv being mixed using vane #1 is shown in  FIG. 50 . 
     A method for forming homogeneous resin suspensions in water was evaluated using N 2  gas or air agitation. An optimal gas regulator pressure range, which provides proportional gas flow rates, was determined to affect good resin suspension formation. Below this range, a partial suspension (a heterogeneous resin suspension) was formed ( FIG. 51(A) ). Within this range, a homogenous suspension was formed ( FIG. 51  (B)). Beyond this range, resin slurry could be lost or ejected from the LMV (Large Mixing Vessel (gas-agitated resin/water mixture for resin delivery into system) or SMV (Small Mixing Vessel for  224 Ra adsorption onto suspended resin mixture) due to overly vigorous agitation ( FIG. 51  (C)). Use of excessive gas flow also enhanced the water evaporation rate, thus eventually altering the resin concentration in the suspension. 
     The most significant issue caused by overmixing occurs in the SMV after  224 Ra solution has been added. Resin dispersed above the mixing line (at 22.5 mL in  FIG. 51  (B)) may not re-incorporate into the suspension due to wall cohesion, leading to a loss in  224 Ra-bound resin loaded onto each generator column due to the lack of resin mixture transferred to the SMV. 
     A gas regulator pressure range of 1.5 to 2.5 PSI, and 2 to 4 PSI was determined to be optimal for the LMVg, and SMV, respectively. In subsequent studies, the gas regulator pressures were set to 2 PSI for the LMVg and 3 PSI for the SMV to optimize the degree of resin/water mixing. 
     An evaluation of resin mass delivery using the gas mixing system was performed to determine the resin mass of an aspirated slurry volume as a factor of aspiration/dispensation flow rate. To ensure reproducibility in the column packing system, the slurry aspirated from the LMVg required a consistent resin concentration to deliver a sufficient resin mass. Maximizing resin slurry flow rate is important for reducing the overall time of automated column packing procedure, which will reduce  224 Ra daughter product ingrowth during the process. However, excessive flow rates could cause cavitation of the aspirated solution and needed to be avoided. 
     Using the determined dry resin density of 0.347 ±0.009 g/cm 3  for a 1 cm 3  packed semi-wet column bed, a theoretical resin concentration of 0.087±0.002 g/cm 3  was calculated for a uniform 20 mL suspension containing 5 cm 3  of gravity-settled resin. Using this theoretical value, delivered resin mass bias could be evaluated against aspirated suspension volumes ranging between 5 and 30 mL/min. Contour plots displaying the empirically measured and calculated dry resin masses as a function of aspirated volume and flow rate are shown in  FIG. 52 . A comparison of the data sets is shown in Table 13. 
     
       
         
           
               
             
               
                 TABLE 13 
               
             
            
               
                   
               
               
                 Comparison of empirically determined and calculated resin masses 
               
               
                 at varied flow rates and aspirated volumes. Mass biases ≥10% are in 
               
               
                 bold font. 
               
            
           
           
               
               
               
               
               
            
               
                 Flow rate, 
                 Aspirated vol., 
                 Determined mass, 
                 Calculated mass, 
                 Bias, a   
               
               
                 mL/min 
                 cm 3   
                 g 
                 g 
                 % 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                  5 
                 0.5 
                 0.035 
                 0.043 
                 − 18.8   
               
               
                   
                 1 
                 0.080 
                 0.087 
                 −7.5 
               
               
                   
                 2 
                 0.164 
                 0.173 
                 −5.6 
               
               
                   
                 3 
                 0.247 
                 0.260 
                 −5.2 
               
               
                 10 
                 0.5 
                 0.035 
                 0.043 
                 − 19.5   
               
               
                   
                 1 
                 0.082 
                 0.087 
                 −5.9 
               
               
                   
                 2 
                 0.175 
                 0.173 
                 0.8 
               
               
                   
                 3 
                 0.257 
                 0.260 
                 −1.1 
               
               
                 20 
                 0.5 
                 0.037 
                 0.043 
                 − 15.3   
               
               
                   
                 1 
                 0.084 
                 0.087 
                 −3.2 
               
               
                   
                 2 
                 0.169 
                 0.173 
                 −2.7 
               
               
                   
                 3 
                 0.246 
                 0.260 
                 −5.4 
               
               
                 30 
                 0.5 
                 0.038 
                 0.043 
                 − 11.7   
               
               
                   
                 1 
                 0.084 
                 0.087 
                 −2.7 
               
               
                   
                 2 
                 0.173 
                 0.173 
                 &lt;0.01 
               
               
                   
                 3 
                 0.250 
                 0.260 
                 −4.0 
               
               
                   
               
               
                 
                   
                     
                       
                         
                           
                             
                                 
                               a 
                             
                              
                             Relative 
                           
                            
                           
                               
                           
                            
                           bias 
                         
                         , 
                         
                           % 
                           = 
                           
                             100 
                              
                             
                                 
                             
                             * 
                             
                                 
                             
                              
                             
                               ( 
                               
                                 
                                   
                                     Determined 
                                      
                                     
                                         
                                     
                                      
                                     Value 
                                   
                                   - 
                                   
                                     Calculated 
                                      
                                     
                                         
                                     
                                      
                                     Value 
                                   
                                 
                                 
                                   Calculated 
                                    
                                   
                                       
                                   
                                    
                                   Value 
                                 
                               
                               ) 
                             
                           
                         
                       
                     
                   
                 
               
            
           
         
       
     
     Contour maps of the calculated and empirical data display a similar mass distribution, with a consistent increase in delivered resin mass relative to increasing aspirated volume. In addition, empirically determined dried resin masses showed a trend of reduced bias as a function of aspirated volume increase for a given flow rate from 0.5 to 3 mL. Minimal loss of resin mass per unit volume was observed (less than 7.5%) for aspirated volumes of at least 1 mL for each flow rate. However, a mass of 0.087 grams is needed to pack a 0.250 cm 3  resin bed, based on the determined dry resin density; therefore, aspirated volumes &lt;1 mL would not provide sufficient resin mass at any flow rate. 
     In the vessel assembly packing method, excess resin mass can be removed during the SM resin metering process, so a larger aspirated volume (˜2 mL) can be utilized. Additionally, the method must be performed in a rapid manner due to the ingrowth of short-lived daughter products from  224 Ra. To minimize the elapsed processing time, higher flow rates will be used in the system. Based on the data, aspirating 2 mL at a flow rate of 30 mL/min may be beneficial, as it is rapid and has the lowest relative bias (less than 0.01%). 
     For the vessel assembly packing sequence, the aspirated volume of resin slurry was reduced to 1.85 mL (0.161 grams), based on the 0.25 cm 3  inner volume of the SM. This delivered slurry volume will allow an observable slight resin excess without unnecessary overfilling of the SM. 
     Referring to  FIG. 53  an example progression for the preparation of a storage/generator vessel assembly is shown with component label descriptions of the generator column in Table 14. 
     
       
         
           
               
             
               
                 TABLE 14 
               
             
            
               
                   
               
               
                 Example Component details of the generator column. 
               
            
           
           
               
               
               
               
            
               
                   
                   
                   
                 Length, 
               
               
                 Label 
                 Description 
                 Dimensions 
                 cm 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 300 
                 Column body (Teflon PFA tubing) 
                 0.156″ by ¼″ 
                 5.00 
               
               
                 310 
                 Male luer-lok to barbed tube  
                 0.094″ ID 
                 1.47 
               
               
                   
                 coupler 
                 0.44″ barb OD. 
                   
               
               
                 312 
                 Top/bottom-silicone rubber tubing 
                 0.031″ by 1/16″ 
                 ~15 
               
               
                 A/B 
                   
                   
                   
               
               
                 314 
                 Top/bottom-straight barbed  
                 0.063″ by ⅛″ 
                 2.14 
               
               
                 A/B 
                 reducer 
                 ⅜″ by ⅜″  
                   
               
               
                   
                   
                 barb OD. 
                   
               
               
                 316 
                 Glass wool 
                 0.05 g 
                 0.21 
               
               
                 318 
                 Teflon frit 
                    0.04 cm 3   
                 0.31 
               
               
                 320 
                 Resin catch bed (sans  224 Ra) 
                    0.05 cm 3   
                 0.40 
               
               
                 322 
                 Polypropylene felt frit 
                    0.02 cm 3   
                 0.18 
               
               
                 324 
                 Resin column bed  c   
                 ~0.259 cm 3   
                 2.06 
               
               
                   
                 (w/distributed  224 Ra) 
                   
                   
               
               
                 326 
                 Female luer-lok to barbed tube 
                 0.094″ ID, 
                 1.37 
               
               
                   
                 coupler 
                 0.44″ barb OD. 
                   
               
               
                 328 
                 One-way luer-lok check valve 
                 0.44″ barb OD. 
                 3.30 
               
               
                   
               
            
           
         
       
     
     After the chemically resistant polypropylene felt frit ( 322 ) was packed above the catch bed ( 320 ), the open column body was enclosed with a barbed polycarbonate reducer ( 314 B) connected by silicone tubing ( 312 B) to a female luer-lok/barbed tube coupler ( 326 ). In the automated  224 Ra-loaded column packing step, the bed of uniformly distributed  224 Ra-sorbed resin ( 324 ) was dispensed as a slurry through the inlet tubing ( 326 ,  312 B, and  314 B) and into the column body, packing the column bed. In the final assembly, a one-way check valve ( 328 ) was used to connect the inlet/outlet silicone tubing lines ( 312 A and  312 B) by their luer-lok fittings ( 310  &amp;  326 ). 
     In accordance with another implementation, the column body  300  was enclosed within a polyethylene vial prior to column bed packing so as to remove the risk of contamination, and reduce hand dose caused by the previous process (plugging the top with wool, and enclosing the column after the bed was delivered). In addition, the one-way check valve was installed to provide back pressure, thus preventing the uniform resin bed from deforming during transport. 
     As described above, this system is configured to be hands-free, as well as remotely and/or operable automatically. As shown in the systems, methods for producing a metal storage generation vessel can include homogenizing a resin slurry in a first mixing vessel, then supplementing the homogenized resin slurry with a metal to form a homogenized bound metal resin slurry and transferring the homogenized bound metal resin slurry to a storage generation vessel. In accordance with example implementations, these methods can provide for the stable transfer and distribution of these elements into storage and/or generation vessels. Additionally, the storage and generation vessel can include a “catch bed” 320 that includes an unbound or element free resin portion that is proximate the exit of the vessel. This resin portion can be above a frit or porous material  318  to alleviate the transfer of resin out of the storage vessel. Another frit  322  placed atop the catch bed  320  allows separation of the catch bed  320  from the  224 Ra-sorbed resin bed  324 . 
     Accordingly, the metal storage generation vessel assembly is described with reference to  FIGS. 54-61 . Vessel  6  can have a metal free catch bed  320  that is below a metal and resin distributed bed  324 . In accordance with example implementations, eluent solution can be provided to the intake conduit, and the metal generated can be provided through the eluted out conduit. In accordance with example implementations, this eluted out conduit can be a decay product of the element or isotope present or provided to the storage and generation vessel. 
     Referring next to  FIG. 55 , a more detailed view of an implementation of a storage generation vessel is shown with a more detailed description of the dimensions and materials. 
     Referring to  FIGS. 56A-56B , a decay chain image is provided demonstrated the Pb production from an Ra storage/generator vessel assembly according to an embodiment of the disclosure. 
     Referring next to  FIG. 57 , an example series of storage and generation vessels prepared by the described apparatus are shown. This series was used to evaluate the reproducibility of resin bed deliveries. 
     The generator column preparation and packing process time should be minimized to the extent possible, so as to minimize  224 Ra progeny ingrowth. Based on an elapsed time of up to 15 minutes, less than 0.1% per min of  212 Pb, and 0.01% per min of  212 Bi,  208 Tl, and  212 Po would grow in relative to the initial  224 Ra activity. Minimization of  224 Ra progeny ingrowth during the execution of the column packing process is essential to reduce radiological dose from high energy photons (up to 2.6 MeV from  208 Tl). 
     The process for minimizing the elapsed time of the automated column packing sequence can be broken into four parts: A) maximization of reagent flow rates, B) reduction in tubing path lengths, C) simplification of the sequence code, and D) reduction in software cycling time. 
     Similar to the resin slurry delivery studies, water delivery studies were performed at 10 mL/min increments up to 50 mL/min to determine an upper limit for each tubing inner diameter employed and the SP. An upper flow rate limit was designated when cavitation within the tubing or syringe pump occurred and/or the reagent was not completely transferred. Optimal flow rates determined from this study are shown in Table 15. 
     
       
         
           
               
             
               
                 TABLE 15 
               
             
            
               
                   
               
               
                 Maximum aspiration and dispensation flow rates for the  
               
               
                 column packing system. 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Tubing ID, 
                 Water, 
                 Resin slurry, 
               
               
                   
                 Flow pathway 
                 in 
                 mL/min 
                 cm 3 /min 
               
               
                   
                   
               
               
                   
                 Syringe pump (SP) 
                 — 
                 40 
                 n/a 
               
               
                   
                  1/16″ OD tubing 
                 0.04 
                 20 
                 n/a 
               
               
                   
                 ⅛″ OD tubing 
                 0.063 
                 30 
                 20 
               
               
                   
                   
               
            
           
         
       
     
     When operating the fluid delivery sequence under elevated flow rates, significant pressure could build into the lines, thus requiring additional steps to vent pressure. This was performed by adjusting the SP distribution valve to the waste port, which ensures that pressures equilibration is attained before the next step is initiated (e.g., before switching flow paths). Further time minimization was performed through a reduction of various tubing lengths to shorten the path required for a reagent to traverse the system. 
     Additional time delays originally programmed into the code during troubleshooting activities were reduced or removed. Finally, an inhouse software package was implemented enabling full automation of the system while providing additional controls over each electromechanical component in the system. 
     Using an interface, the idle time associated with cycling port position on the SP, V 4 , and V 6  was reduced. Elapsed times for the automated column packing sequence is shown in Table 16. 
     The elapsed time for the entire column packing process was reduced from ˜18 to ˜12 minutes, with the column packing stage requiring 8.9 minutes. This time can be further reduced by separating the column packing stage into two parts. Steps 2 through 7 can be performed prior to purification and delivery of  224 Ra to the column packing system while steps 8 through 13 can be performed after. Separating this stage will reduce the ingrowth time by 5.2 minutes, thus requiring only ˜3.7 minutes to dispense/contact  224 Ra and packing the column bed for shipping. Note that this elapsed time may increase slightly based on the sorption rate of  224 Ra onto the MP-50 resin, which can be &gt;=60 sec. 
     
       
         
           
               
             
               
                 TABLE 16 
               
             
            
               
                   
               
               
                 Elapsed times for the automated column packing  
               
               
                 sequence. Non-bolded steps performed before or after  224 Ra isolation and  
               
               
                 delivery; bolded steps performed upon  224 Ra delivery. 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                   
                 Time, 
                 Cumulative 
                 Sum time, 
               
               
                 Stage 
                 Step 
                 Segment description 
                 min 
                 time, min 
                 min 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 System priming 
                 1 
                 Filling the reagent lines 
                 0.7 
                 0.7 
                 0.7 
               
               
                 Column packing 
                 2 
                 Dispense water/air to fill HCs 
                 1.3 
                 1.9 
                 8.9 
               
               
                   
                 3 
                 Aspirate resin slurry from LMV g ; 
                 0.5 
                 2.4 
                   
               
               
                   
                   
                 dispense to SM 
                   
                   
                   
               
               
                   
                 4 
                 Dispense air to clear residual resin 
                 0.3 
                 2.7 
                   
               
               
                   
                   
                 slurry from lines 
                   
                   
                   
               
               
                   
                 5 
                 Dispense water/air to remove 
                 1.7 
                 4.3 
                   
               
               
                   
                   
                 excess resin metering the column bed 
                   
                   
                   
               
               
                   
                 6 
                 Condition resin with 0.01M HCl; 
                 1.1 
                 5.4 
                   
               
               
                   
                   
                 dispense to SMV 
                   
                   
                   
               
               
                   
                 7 
                 Aspirate resin supernatant to ESC 
                 0.4 
                 5.9 
                   
               
               
                   
                 
                   8 
                 
                 Dispense mock  224 Ra to SMV; 
                 0.8 
                 6.6 
                   
               
               
                   
                   
                 contact resin using gas agitation 
                   
                   
                   
               
               
                   
                 
                   9 
                 
                 Aspirate contacted resin; 
                 0.7 
                 7.3 
                   
               
               
                   
                   
                 dispense to pack column 
                   
                   
                   
               
               
                   
                 
                   10 
                 
                 Dispense ESC supernatant to SMV; 
                 0.4 
                 7.7 
                   
               
               
                   
                   
                 contact residual resin using gas 
                   
                   
                   
               
               
                   
                   
                 agitation  a   
                   
                   
                   
               
               
                   
                 
                   11 
                 
                 Aspirate residual resin; 
                 0.7 
                 8.4 
                   
               
               
                   
                   
                 dispense to pack column 
                   
                   
                   
               
               
                   
                 
                   12 
                 
                 Dispense 1M HCl to wash column 
                 0.4 
                 8.8 
                   
               
               
                   
                 
                   13 
                 
                 Dispense water/air to rinse; 
                 0.8 
                 9.5 
                   
               
               
                   
                   
                 then air-dry column and lines 
                   
                   
                   
               
               
                 Remediation 
                 14 
                 Dispense water/air to rinse; 
                 1.1 
                 10.6 
                 2.3 
               
               
                   
                   
                 then air-dry Ra and HCl lines 
                   
                   
                   
               
               
                   
                 15 
                 Dispense air to remove residual 
                 1.3 
                 11.9 
                   
               
               
                   
                   
                 water in lines 
                   
                   
                   
               
               
                   
               
            
           
         
       
     
     The generator column packing system was evaluated through extensive testing to ensure a reproducible column bed with less than 5% variability in resin bed volumes. This was essential, as each generator column was preassembled with only enough empty space for the column bed and the subsequent addition of a barbed end fitting placed atop the column bed. This required that the generator column inserted into the fluidic system receive a consistent volume of resin in a uniform configuration above the felt frit  322  and catch bed  320 . 
     Packed bed reproducibility testing was performed through the use of gravimetric and volumetric determination. Based on the optimal conditions described above, gravimetric analysis was used to evaluate mass loss when delivering the 1.85 mL of aspirated resin slurry (from the LMV g ) through the system. 
     Once a consistent resin mass was delivered, volumetric analysis was used to evaluate the column beds being packed in each generator column. This was performed to ensure uniform column beds were packed without disturbing the catch bed, and to ensure that there was no entrapment of air bubbles within the resin bed. A resin bed containing trapped air bubbles can significantly alter the flow pathway for the mobile phase through the resin, causing an inconsistent  212 Pb elution recovery 
     The automated packing method was evaluated to quantify the reproducibility of the resin mass delivered to the column delivery line. Five sets of six runs (n=30) were performed where each column bed was dispensed into a tared 20 mL LSC vial, then vacuum oven dried and weighed per the method described. The results of all thirty runs are shown in Table 17. 
     Systems demonstrated that a consistent resin mass could be delivered with less than 3% relative standard deviation (RSD) over thirty replicates. In addition, each individually prepared batch of resin/water suspension could be used for at least six sequential replicates without refill or replacement. Small deviations observed in mass deliveries could be caused by variance in size distribution of aspirated resin beads or human error in drying down samples. 
     
       
         
           
               
             
               
                 TABLE 17 
               
             
            
               
                   
               
               
                 Measured masses of dry resin in the bed from the  
               
               
                 automated column packing process. 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                   
                   
                 Resin mass, 
                 Ave. mass, 
                   
                 RSD, 
               
               
                   
                 Set 
                 Run 
                 g 
                 g 
                 ±1 s 
                 % 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 1 
                 1 
                 0.0826 
                 0.0864 
                 0.0029 
                 3.34 
               
               
                   
                   
                 2 
                 0.0887 
                   
                   
                   
               
               
                   
                   
                 3 
                 0.0830 
                   
                   
                   
               
               
                   
                   
                 4 
                 0.0889 
                   
                   
                   
               
               
                   
                   
                 5 
                 0.0882 
                   
                   
                   
               
               
                   
                   
                 6 
                 0.0868 
                   
                   
                   
               
               
                   
                 2 
                 7 
                 0.0873 
                 0.0873 
                 0.0019 
                 2.19 
               
               
                   
                   
                 8 
                 0.0862 
                   
                   
                   
               
               
                   
                   
                 9 
                 0.0885 
                   
                   
                   
               
               
                   
                   
                 10 
                 0.0850 
                   
                   
                   
               
               
                   
                   
                 11 
                 0.0867 
                   
                   
                   
               
               
                   
                   
                 12 
                 0.0904 
                   
                   
                   
               
               
                   
                 3 
                 13 
                 0.0846 
                 0.0886 
                 0.0034 
                 3.89 
               
               
                   
                   
                 14 
                 0.0927 
                   
                   
                   
               
               
                   
                   
                 15 
                 0.0885 
                   
                   
                   
               
               
                   
                   
                 16 
                 0.0897 
                   
                   
                   
               
               
                   
                   
                 17 
                 0.0915 
                   
                   
                   
               
               
                   
                   
                 18 
                 0.0846 
                   
                   
                   
               
               
                   
                 4 
                 19 
                 0.0853 
                 0.0874 
                 0.0013 
                 1.49 
               
               
                   
                   
                 20 
                 0.0883 
                   
                   
                   
               
               
                   
                   
                 21 
                 0.0877 
                   
                   
                   
               
               
                   
                   
                 22 
                 0.0887 
                   
                   
                   
               
               
                   
                   
                 23 
                 0.0863 
                   
                   
                   
               
               
                   
                   
                 24 
                 0.0882 
                   
                   
                   
               
               
                   
                 5 
                 25 
                 0.0899 
                 0.0879 
                 0.0031 
                 3.58 
               
               
                   
                   
                 26 
                 0.0880 
                   
                   
                   
               
               
                   
                   
                 27 
                 0.0932 
                   
                   
                   
               
               
                   
                   
                 28 
                 0.0856 
                   
                   
                   
               
               
                   
                   
                 29 
                 0.0850 
                   
                   
                   
               
               
                   
                   
                 30 
                 0.0860 
                   
                   
                   
               
               
                   
                 Grand 
                   
                   
                 0.0875 
                 0.0026 
                 2.95 
               
               
                   
                 Mean 
               
               
                   
                   
               
            
           
         
       
     
     Overall, the system demonstrated that a consistent mass of resin can be delivered to the column. An average AG MP-50 resin mass delivery of 0.0875 ±0.0026 grams of dried resin (n=30) was observed. 
     The automated packing methods were evaluated to quantify the reproducibility of packing consistent resin bed volumes prior to use of the  224 Ra stock solution. Two sets of six runs (n=12) were performed using the semi-automated packing method; an image of each packed column is shown side by side in  FIG. 57 . Two additional sets of six runs (n=12) were performed using the fully automated system through implementation of the SVMB and SCIVs. The packed resin bed volume of each column was calculated using the column bed height and inner diameter of the column tubes. Results for these twenty-four runs are shown in Table 18. It is noted that the presence of entrapped air pockets within the packed beds were not observed. 
     
       
         
           
               
             
               
                 TABLE 18 
               
             
            
               
                   
               
               
                 Determined column bed volumes from automatically-  
               
               
                 packed columns. 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                   
                   
                 Bed vol.  a , 
                 Ave. mass, 
                   
                 RSD, 
               
               
                   
                 Set 
                 Run 
                 cm 3   
                 cm 3   
                 ±1 s 
                 % 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 1 
                 1 
                 0.263 
                 0.261 
                 0.004 
                 1.4 
               
               
                   
                   
                 2 
                 0.263 
                   
                   
                   
               
               
                   
                   
                 3 
                 0.265 
                   
                   
                   
               
               
                   
                   
                 4 
                 0.257 
                   
                   
                   
               
               
                   
                   
                 5 
                 0.256 
                   
                   
                   
               
               
                   
                   
                 6 
                 0.261 
                   
                   
                   
               
               
                   
                 2 
                 7 
                 0.252 
                 0.257 
                 0.005 
                 1.9 
               
               
                   
                   
                 8 
                 0.254 
                   
                   
                   
               
               
                   
                   
                 9 
                 0.263 
                   
                   
                   
               
               
                   
                   
                 10 
                 0.253 
                   
                   
                   
               
               
                   
                   
                 11 
                 0.263 
                   
                   
                   
               
               
                   
                   
                 12 
                 0.258 
                   
                   
                   
               
               
                   
                 3 
                 13 
                 0.259 
                 0.261 
                 0.006 
                 2.3 
               
               
                   
                   
                 14 
                 0.259 
                   
                   
                   
               
               
                   
                   
                 15 
                 0.267 
                   
                   
                   
               
               
                   
                   
                 16 
                 0.269 
                   
                   
                   
               
               
                   
                   
                 17 
                 0.263 
                   
                   
                   
               
               
                   
                   
                 18 
                 0.252 
                   
                   
                   
               
               
                   
                 4 
                 19 
                 0.254 
                 0.256 
                 0.004 
                 1.7 
               
               
                   
                   
                 20 
                 0.261 
                   
                   
                   
               
               
                   
                   
                 21 
                 0.257 
                   
                   
                   
               
               
                   
                   
                 22 
                 0.257 
                   
                   
                   
               
               
                   
                   
                 23 
                 0.248 
                   
                   
                   
               
               
                   
                   
                 24 
                 0.259 
                   
                   
                   
               
               
                   
                 Grand 
                   
                   
                 0.259 
                 0.005 
                 2.0 
               
               
                   
                 mean 
               
               
                   
                   
               
               
                   
                   a  Bed volumes were determined using the column inner diameter (0.4 cm). 
               
            
           
         
       
     
     Based on volumetric measurements of the  224 Ra distributed generator column bed, the grand mean of all twenty-four runs was 0.259 ±0.005 cm 3  (±2.0% RSD). 
     Referring next to  FIG. 58 , a tandem EDTA precipitation/filtration module and vessel assembly module is depicted and evaluated. The automated precipitation/filtration module can be coupled in tandem for the purpose of reducing the number of electronic components and extraneous process time between steps in the process. By coupling the two systems, only one microcontroller and computer was required to operate both systems. Additionally, this enabled both sets of process steps to be incorporated into a single process sequence which minimized the number of lines of code and system idle time. A schematic of the tandem two module system excluding components of the column packing system prior to  224 Ra delivery is shown in  FIG. 58 . Descriptions of each component are shown in Table 19. 
     
       
         
           
               
             
               
                 TABLE 19 
               
             
            
               
                   
               
               
                 EDTA precipitation/filtration module and column packing  
               
               
                 system module schematic labels (FIG. 58). 
               
            
           
           
               
               
            
               
                 Label 
                 Component description 
               
               
                   
               
               
                 a 
                   224 Ra-EDTA inlet line (C3 eluent from triple- 
               
               
                   
                 column system) 
               
               
                 b 
                 Acid dispensing line 
               
               
                 c 
                 Activated charcoal  220 Rn trap 
               
               
                 d 
                 5 mL Rezorian ™ column w/Spinplus ® PTFE stir  
               
               
                   
                 bar &amp; hydrophobic PE frit 
               
               
                 e 
                 Three-way stopcock valve 
               
               
                 f 
                 Servo motor (SvM) 
               
               
                 g 
                 Rinse vessel for filtrate line 
               
               
                 h 
                 “Multi-Stirrus” vertical magnetic stirrer 
               
               
                 i 
                 Inverted digital syringe pump w/8-port distribution valve 
               
               
                 j 
                 0.45 μm PES membrane syringe filter 
               
               
                 k 
                   224 Ra collection vessel 
               
               
                 l 
                 Nitrogen gas regulator 
               
               
                 m 
                 Solenoid-controlled isolation valve (SCIV) 
               
               
                 n 
                 Small mixing vessel (SMV) 
               
               
                 o 
                 Cheminert 6-port selector valve (V6) 
               
               
                 p 
                 Holding coil to 6-port selector valve (HC/V6) 
               
               
                 q 
                 Syringe pump w/8-port distribution valve 
               
               
                 r 
                 Assembled generator column (AGC) 
               
               
                   
               
            
           
         
       
     
     In performing the automated process, time minimization was performed to ensure minimal ingrowth of  212 Pb/ 212 Bi/ 208 Tl after the initial  224 Ra purification. Through integration of the two modules, the required process time to precipitate and filter EDTA, deliver  224 Ra to the column packing module, and pack the generator column was minimized. A summary of the steps for these processes are shown in Table 20. 
     The overall process can be reduced from the total elapsed time of 16.6 minutes to 8.8 minutes by preforming the system preparation (steps 1 to 5) and remediation (steps 14 to 15) before and after the  224 Ra was delivered. Compared to the individual column packing modular process described herein, the elapsed time of the two module sequence steps performed upon  224 Ra delivery increased only 5.0 minutes (from 3.8 to 8.8 minutes). 
     
       
         
           
               
             
               
                 TABLE 20 
               
             
            
               
                   
               
               
                 Elapsed times for the automated in line EDTA  
               
               
                 precipitation/filtration and column packing sequence. Non-bolded steps were  
               
               
                 performed before or after  224 Ra delivery. Bolded steps were performed upon  
               
               
                   224 Ra delivery from the triple-column module. 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                   
                 Time, 
                 Stage time, 
                 Elapsed time, 
               
               
                 Stage 
                 Step 
                 Segment description 
                 min 
                 min 
                 min 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 System priming 
                 1 
                 Filling the reagent lines 
                 0.7 
                 0.7 
                 0.7 
               
               
                 Pre Ra- 
                 2 
                 Dispense water/air to fill HCs 
                 1.3 
                 3.8 
                 2.0 
               
               
                 Column packing 
                 3 
                 Aspirate resin slurry from LMV g ; 
                 0.5 
                   
                 2.5 
               
               
                   
                   
                 dispense to SM 
                   
                   
                   
               
               
                   
                 4 
                 Dispense air to clear residual resin 
                 0.3 
                   
                 2.8 
               
               
                   
                   
                 slurry from lines 
                   
                   
                   
               
               
                   
                 5 
                 Dispense water/air to remove excess 
                 1.7 
                   
                 4.5 
               
               
                   
                   
                 resin, metering the column bed 
                   
                   
                   
               
               
                 Precipitation/ 
                 
                   6A 
                 
                 Acidification of  224 Ra-EDTA solution/ 
                 0.8 
                 5.0 
                 5.3 
               
               
                 column packing 
                   
                 stir bar agitation to form precipitate 
                   
                   
                   
               
               
                   
                 
                   6B 
                 
                 Condition resin with 0.01M HCl; 
                 1.2 
                   
                 6.5 
               
               
                   
                   
                 dispense to SMV; aspirate resin 
                   
                   
                   
               
               
                   
                   
                 supernatant to ESC 
                   
                   
                   
               
               
                   
                 
                   7 
                 
                 Withdraw Ra filtrate; 
                 3.0 
                   
                 9.5 
               
               
                   
                   
                 dispense to CP system 
                   
                   
                   
               
               
                 Column packing 
                 
                   8 
                 
                 Dispense mock  224 Ra to SMV; 
                 0.8 
                 3.8 
                 10.3 
               
               
                   
                   
                 contact resin using gas agitation 
                   
                   
                   
               
               
                   
                 
                   9 
                 
                 Aspirate contacted resin; 
                 0.7 
                   
                 11.0 
               
               
                   
                   
                 dispense to pack column 
                   
                   
                   
               
               
                   
                 
                   10 
                 
                 Dispense ESC supernatant to SMV; 
                 0.4 
                   
                 11.4 
               
               
                   
                   
                 contact residual resin using gas 
                   
                   
                   
               
               
                   
                   
                 agitation 
                   
                   
                   
               
               
                   
                 
                   11 
                 
                 Aspirate residual resin; 
                 0.7 
                   
                 12.1 
               
               
                   
                   
                 dispense to pack column 
                   
                   
                   
               
               
                   
                 
                   12 
                 
                 Dispense 1M HCl to wash column 
                 0.4 
                   
                 12.5 
               
               
                   
                 
                   13 
                 
                 Dispense water/air to rinse; 
                 0.8 
                   
                 13.3 
               
               
                   
                   
                 then air-dry column and lines 
                   
                   
                   
               
               
                 System 
                 14 
                 Dispense water/air to rinse; 
                 1.1 
                 3.3 
                 14.4 
               
               
                 remediation 
                   
                 then air-dry Ra and HCl lines 
                   
                   
                   
               
               
                   
                 15 
                 Dispense residual water in lines to 
                 2.2 
                   
                 16.6 
               
               
                   
                   
                 waste 
                   
                   
                   
               
               
                   
               
            
           
         
       
     
     An assessment of the tandem two module system was performed to evaluate the  224 Ra yield from each process in-line using a fully automated system. The automated precipitation and filtration method was connected in-line with the automated column packing process described herein. A partial schematic of the two-module system is shown in  FIG. 58 . A  224 Ra/resin contact time of 1 minute was utilized for this assessment. A series of six replicates were performed, with results shown in Table 21. 
     
       
         
           
               
             
               
                 TABLE 21 
               
             
            
               
                   
               
               
                 Assessment of  224 Ra fraction recovery using the automated  
               
               
                 in-line EDTA precipitation/filtration, and column packing systems.  
               
               
                 The grand mean results are in bold. 
               
            
           
           
               
               
               
               
            
               
                   
                 EDTA precipitation 
                   224 Ra generator 
                 Cum.  224 Ra 
               
               
                 Replicate 
                 and filtration 
                 column packing 
                 yield 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 1 
                 0.871 
                 0.982 
                 0.855 
               
               
                 2 
                 0.859 
                 0.981 
                 0.843 
               
               
                 3 
                 0.880 
                 0.972 
                 0.855 
               
               
                 4 
                 0.890 
                 0.985 
                 0.877 
               
               
                 5 
                 0.865 
                 0.992 
                 0.858 
               
               
                 6 
                 0.864 
                 0.979 
                 0.846 
               
               
                 Mean 
                 0.872 
                 0.982 
                 
                   0.856 
                 
               
               
                 ±1 s 
                 0.012 
                 0.007 
                 
                   0.012 
                 
               
               
                 RSD, % 
                 1.3 
                 0.7 
                 
                   1.4 
                 
               
               
                   
               
            
           
         
       
     
     Each module displayed mean recoveries within 1% of their previous individual assessments. 
     The EDTA precipitation/filtration system and column packing system were successfully incorporated into a tandem in-line system. The  224 Ra yield for the precipitation/filtration step (0.872 ±0.012) was in agreement with previous evaluation (0.867 ±0.010), and the generator packing yield of 0.982 ±0.007 was in agreement with the prior evaluation (0.980 ±0.010). Overall, a cumulative  224 Ra yield of 0.856 ±0.012 was demonstrated. In addition, the elapsed time of the process was reduced to 8.8 minutes by reorganizing sequence steps, thereby minimizing ingrowth of  224 Ra progeny (dose to user). 
     An assessment of the  224 Ra yield through the entire three module automated process was performed through incorporation of the  224 Ra isolation module, using the triple-column system and method, followed by the EDTA precipitation/filtration module, and the column packing system module. In the three-module process, the  224 Ra elution outlet line of the triple-column fluidic module was connected directly to the precipitation vessel (label a in  FIG. 58 ) so that an assessment of the entire in-line process could be performed. A summary of the elapsed process times for the entire three-module process is shown in Table 22. 
     
       
         
           
               
             
               
                 TABLE 22 
               
             
            
               
                   
               
               
                 Summary of the elapsed process times for the automated  
               
               
                 three module process to obtain a  224 Ra-packed generator column when  
               
               
                 starting from a  228 Th stock solution. 
               
            
           
           
               
               
               
               
            
               
                   
                 Time, 
                 Stage time, 
                 Elapsed time, 
               
               
                 Segment description 
                 min 
                 min 
                 min 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 Preparatory steps before three  
                 9.0 
                 9.0 
                 9.0 
               
               
                 module process 
                   
                   
                   
               
               
                   224 Ra isolation module 
                 50.2 
                 59.0 
                 59.2 
               
               
                 EDTA precipitation and  
                 5.0 
                   
                 64.2 
               
               
                 precipitation module 
                   
                   
                   
               
               
                   224 Ra/CatIX loading &amp; column  
                 3.8 
                   
                 68.0 
               
               
                 packing module 
                   
                   
                   
               
               
                 Remediation of three module  
                 21.9 
                 21.9 
                 89.8 
               
               
                 system 
               
               
                   
               
            
           
         
       
     
     In the assessment of the integrated three module process, the segments were reorganized so that all system preparatory steps were performed prior to the  224 Ra isolation module, while all system remediation steps were performed after the generator column was assembled. Based on the process times described, total elapsed time for isolation of  224 Ra, precipitating/filtering EDTA,  224 Ra/CatIX loading, and column assembly was 59.0 minutes, with the entire process (inclusive of preparatory and system remediation steps) taking ˜1.5 hours. 
     A series of twenty-one replicates were performed to evaluate the  224 Ra yield at the completion of each modular step and to determine the cumulative  224 Ra yield. Results of the assessment are shown in Table 23. 
     
       
         
           
               
             
               
                 TABLE 23 
               
             
            
               
                   
               
               
                 Assessment of  224 Ra yields through the automated in-line  
               
               
                 three module system, starting from a  228 Th stock solution. The  
               
               
                 grand mean results are in bold. 
               
            
           
           
               
               
               
               
               
            
               
                   
                   224 Ra 
                 EDTA precipitation  
                   224 Ra generator  
                 Cum.  224 Ra 
               
               
                 Replicate 
                 isolation 
                 and filtration 
                 column packing 
                 yield 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 0.985 
                 0.861 
                 0.993 
                 0.843 
               
               
                 2 
                 0.991 
                 0.870 
                 0.993 
                 0.857 
               
               
                 3 
                 0.975 
                 0.865 
                 0.987 
                 0.832 
               
               
                 4 
                 0.983 
                 0.872 
                 0.987 
                 0.846 
               
               
                 5 
                 0.969 
                 0.858 
                 0.987 
                 0.821 
               
               
                 6 
                 0.980 
                 0.852 
                 0.987 
                 0.824 
               
               
                 7 
                 0.973 
                 0.850 
                 0.988 
                 0.817 
               
               
                 8 
                 0.999 
                 0.861 
                 0.977 
                 0.841 
               
               
                 9 
                 0.976 
                 0.863 
                 0.978 
                 0.823 
               
               
                 10 
                 0.962 
                 0.894 
                 0.980 
                 0.842 
               
               
                 11 
                 0.964 
                 0.900 
                 0.971 
                 0.843 
               
               
                 12 
                 0.964 
                 0.896 
                 0.991 
                 0.856 
               
               
                 13 
                 0.984 
                 0.902 
                 0.983 
                 0.873 
               
               
                 14 
                 0.950 
                 0.856 
                 0.980 
                 0.797 
               
               
                 15 
                 0.958 
                 0.861 
                 0.972 
                 0.801 
               
               
                 16 
                 0.950 
                 0.889 
                 0.981 
                 0.829 
               
               
                 17 
                 0.952 
                 0.910 
                 0.970 
                 0.840 
               
               
                 18 
                 0.970 
                 0.863 
                 0.997 
                 0.835 
               
               
                 19 
                 0.941 
                 0.872 
                 0.976 
                 0.801 
               
               
                 20 
                 0.979 
                 0.886 
                 0.971 
                 0.843 
               
               
                 21 
                 0.967 
                 0.855 
                 0.980 
                 0.811 
               
               
                 Mean 
                 0.970 
                 0.873 
                 0.982 
                 
                   0.832 
                 
               
               
                 ±1 s 
                 0.015 
                 0.019 
                 0.008 
                 
                   0.029 
                 
               
               
                 RSD, % 
                 1.5 
                 2.1 
                 0.8 
                 
                   3.5 
                 
               
               
                   
               
            
           
         
       
     
     The automated in-line three module system demonstrated a reproducible mean yield of 0.832 ±0.029. In addition, the EDTA precipitation / filtration and column packing modules demonstrated excellent performance consistency with  224 Ra yields within the 1 sigma uncertainty between this and the previous system, wherein only modules 2 and 3 were employed (Table 21). 
     In summary, the integrated three module process has demonstrated that  224 Ra can be isolated, EDTA-purified, resin-loaded, and packed into a generator column assembly reproducibly, with a mean yield of 0.832 ±0.029 in a process that takes less than 1 hour with only an additional ˜0.5 hours to set up and remediate the system. 
     Using  224 Ra/ 212 Pb generator columns that were prepared via the three-module fluidic system, performance parameters were assessed, which included: 1) the  212 Pb elution profile during milking, and 2)  224 Ra breakthrough from the column. 
     An assessment of the  212 Pb elution behavior was performed using a  224 Ra generator column produced by the three-module process. A 3 mL aliquot of 2 M HCl was loaded onto the generator column to measure  212 Pb recovery as a function of eluent. Once complete, the generator column was flushed with 1 mL of water delivered through the generator column for storage. A plot of the  212 Pb elution profile in 2 M HCl is shown in  FIG. 59 . 
     The storage/generator vessel assembly demonstrated that ˜55% of the ingrown elutable  212 Pb was recovered within the first 0.5 mL fraction collected, while ˜95% was recovered within the first 1 mL. For the  224 Ra generator milking process, 1 mL is sufficient to recover the majority of the elutable  212 Pb, while each additional 0.25 mL fraction will only slightly increase the recovery (&lt;1% gain). 
       224 Ra breakthrough levels from generators prepared via the automated three-module process were also determined. 
     In order to confirm the  224 Ra breakthrough value on a freshly-packed  212 Pb generator column, 10 milking cycles were performed using a 1 mL 2 M 
     HCl load followed by a 1 mL DIW rinse. A plot comparing the fractional loss of  224 Ra in each of these milking cycles is shown in  FIG. 60 . Before  224 Ra level was determined by gamma counting, each fraction was allowed to decay for several days to ensure that  224 Ra and  2 Pb were in secular equilibrium. 
     A decrease in  224 Ra breakthrough was observed between the 1 st  milking cycle and 2 nd  milking cycle, while a steady  224 Ra breakthrough was noted from the 2 nd  to 10 th  cycle. The 1 st  milking cycle is typically discarded (as it represents the 1 st  milking after the generator column arrives to the end-user facility), since it grows in stable Pb during transport. Excluding this first milking cycle, the system&#39;s breakthrough is ˜0.14% per elution cycle. Based on these observed results, a careful assessment of the milking process was performed in an attempt to understand and minimize the  224 Ra breakthrough observed from auto-packed generator columns. 
     The distribution coefficient (K d ) for Ba (a close Ra chemical analogue) on macroporous CatIX resin is estimated to be only ˜300 mL/g in a  212 Pb elution matrix of 2 M HCI. In comparison, the K d  for Pb on the same is ˜5 mL/g. So,  212 Pb elutes from the column with ˜60-fold less resin affinity relative to that of Ba (Ra). As depicted in  FIG. 59 , the low CatIX resin affinity of Pb is apparent from the sharp elution from the generator column. 
     For the moderately-adsorbed  224 Ra, the Ra 2+  ions at the base of the distributed CatIX bed have a ˜50 μL resin catch bed (˜0.4 mm bed height) to prevent them from co-eluting with  212 Pb. The volume of this catch bed may be insufficient to assure a high-purity milked  212 Pb product. 
     In an effort to better understand the loss of  224 Ra from the distributed bed generator column, the end-to-end fluidic system was employed to prepare a generator column without the ˜50 μL catch bed, and also three columns that each contained the standard catch bed at the column base. The column without the catch bed would allow evaluation of the distributed  224 Ra elution rate without the protective catch bed being present. With the three catch bed-bearing columns,  224 Ra breakthrough was compared with and without the presence of a supplemental catch bed cartridge. The supplemental catch beds were prepared from trimmed-down SPE tube columns (5.6 mm ID) and employed 20 μm pore size polyethylene frits above and below the supplemental resin beds. The prepared columns used in this evaluation are shown in  FIG. 61 , and described in Table 24. 
     
       
         
           
               
             
               
                 TABLE 24 
               
             
            
               
                   
               
               
                 Description of  224 Ra/ 212 Pb generator column  
               
               
                 configurations shown in FIG. 61. 
               
            
           
           
               
               
               
               
            
               
                 Column  
                   224 Ra distributed bed 
                 50 μL 
                 Supplemental catch 
               
               
                 ID 
                 vol., μL 
                 catch bed? 
                 bed cartridge vol., μL  a   
               
               
                   
               
               
                 a 
                 0.260 ± 0.004 
                 N 
                 — 
               
               
                 b 
                   
                 Y 
                 — 
               
               
                 c 
                   
                 Y 
                 100 
               
               
                 d 
                   
                 Y 
                 200 
               
               
                   
               
               
                   a  Prepared in a trimmed down SPE tube column (5.6 mm dia.) 
               
            
           
         
       
     
     Given that  212 Pb is milked from the generator columns using 2 M HCI (˜1 mL), this reagent was used to deliver the equivalent of ˜20  212 Pb milking cycles. This study excluded the injection of water between each ˜1 mL  212 Pb eluent injection. The column effluents were collected generally in 1.0 ±0.1 mL fractions, and were allowed to decay until any  224 Ra bleed-out in the effluent fractions were in secular equilibrium with  212 Pb. Analysis of the fractions by auto-gamma detector counts provided the fraction of  224 Ra breakthrough, relative to the  224 Ra activity loaded onto each generator column. 
     The incremental  224 Ra breakthrough fraction as a function of  212 Pb eluent volume is shown in  FIG. 62A . As was apparent in  FIG. 60 , a slightly higher release of  224 Ra eluting from the column in the first ˜1 mL of 2 M HCl for the column without the catch bed (Column a). After the first ˜1 mL of  212 Pb eluent, the degree of  224 Ra breakthrough is generally reduced to a plateau level around 0.8% per mL. This plateau makes sense, as the  224 Ra is distributed evenly in the CatIX resin bed; there is as much  224 Ra at the top of the column as there is at the very bottom of the column. As the  224 Ra migrates down the column, a continuous level of bleed-out would be anticipated. In  FIG. 61  B, the same data is shown, but as a cumulative plot. If the first “sacrificial” elution volume (˜1 mL) is discarded, ˜8% of the  224 Ra is lost from Column a after 10 mL, and ˜15% is lost after 20 mL. 
     The standard column (column b), with the distributed  224 Ra bed and embedded ˜50 μL catch bed behaves differently. Initially, a lower degree of  224 Ra breakthrough (˜25-fold decrease), as the catch bed successfully captures a portion of the  224 Ra as it migrates from the distributed CatIX bed. However, as the volume of 2 M HCl delivered through standard column b increases, the degree of  224 Ra breakthrough likewise increases. This is evidence that  224 Ra does eventually migrate through the catch bed. If provided sufficient 2 M HCl volume, it is anticipated that the  224 Ra breakthrough would increase until it reaches the plateau level obtained by Column a. For long-term milking, Column b achieved a cumulative  224 Ra loss of ˜1.4% and ˜4.0% after 10 mL and 20 mL of eluent delivery, respectively. 
     Columns c and d, with the supplemental 100 μL and 200 μL resin cartridges attached to the generator column outlets, respectively, show additional reductions in  224 Ra breakthrough. Column c starts at 0.005% breakthrough, and rises to 0.016% breakthrough per mL at ˜20 mL. The rise in breakthrough level, although slight, indicates some progressive  224 Ra levels emerging from the cartridge. At 10 mL and 20 mL elution volumes, the cumulative  224 Ra breakthrough levels are ˜0.08% and ˜0.2%, respectively. 
     In comparison, Column d shows extremely low  224 Ra loss; the data trace plots the minimum detectable activity (MDA) level beyond 3 mL. Even with accumulation of the MDA levels vs. volume, Column d shows ˜0.001% and ˜0.003%  224 Ra loss at 10 mL and 20 mL of  212 Pb eluent solution delivery, respectively. 
     The four generator column configurations discussed herein can be preserved for over two weeks following the  224 Ra breakthrough study. At the conclusion of the ˜20 mL delivery of 2 M HCI, the columns were blown out with air, capped, and stored. 
     Respective  212 Pb milking profiles for each of the column configurations were evaluated. Each column (with or without the supplemental cartridges described in Table 24) received 2 M HCl at a flow rate of 1.0 mL/min to milk the in-grown  212 Pb. Fractions of ˜0.5 mL were collected for each column elution cycle. The results are shown in  FIGS. 63A  and 63Bb. Here, it is observed that  212 Pb elution volume between Columns a and b are virtually identical; the presence of the ˜50 μL catch bed has no observable impact on  212 Pb elution profiles (which is consistent with the low Kd of  212 Pb on MP-50 resin). The  212 Pb yields for Columns a and b after a 1 mL elution volume was ˜88%. 
     The two columns with the supplemental resin cartridges (Columns c and d) did exhibit some degree of  212 Pb elution broadening. The  212 Pb activity was distributed relatively evenly between the first two ˜0.5 mL fractions; Columns c and d had 1 mL  212 Pb yields of ˜85% and ˜81%, respectively. At fractions 3 and beyond, the  212 Pb tailing was consistent with those observed for Columns a and b, those without the supplemental resin cartridges. At the 1.5 mL elution volume, all column  212 Pb elution yields were &gt;90%. 
     The presence of the 100 μL and 200 μL supplemental resin cartridges placed immediately downstream of the  212 Pb generator columns had similar  212 Pb yields at 1.0 mL elution volume, relative to the standard generator column configuration (Column b). Therefore, the supplemental resin cartridges did not adversely affect the  212 Pb recovery, while providing  212 Pb products that contained significantly higher radionuclidic purity from  224 Ra. 
     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.