limestone method final · 2018-08-13 · sodium hydroxide fusion of limestone matrices 8/7/2018 4...

EPA 402-R-18-002 wwwepagov

August 2018 Revision 0

Rapid Method for Sodium Hydroxide Fusion of Limestone Matrices Prior to Americium

Plutonium Strontium Radium and Uranium Analyses for Environmental Remediation

Following Radiological Incidents

US Environmental Protection Agency

Office of Air and Radiation Office of Radiation and Indoor Air

National Analytical Radiation Environmental Laboratory Montgomery AL 36115

Office of Research and Development

National Homeland Security Research Center Cincinnati OH 45268

Sodium Hydroxide Fusion of Limestone Matrices

Revision History

Revision 0 Original release 872018

This report was prepared for the National Analytical Radiation Environmental Laboratory of the Office of Radiation and Indoor Air and the National Homeland Security Research Center of the Office of Research and Development United States Environmental Protection Agency It was prepared by Environmental Management Support Inc of Silver Spring Maryland under contract EP-W-07-037 Work Assignment 2-43 and contract EP-W-13-016 Task Order 014 both managed by Dan Askren This document has been reviewed in accordance with US Environmental Protection Agency (EPA) policy and approved for publication Note that approval does not signify that the contents necessarily reflect the views of the Agency Mention of trade names products or services does not convey EPA approval endorsement or recommendation


872018 1 Revision 0

Rapid Method for Sodium Hydroxide Fusion of Limestone Matrices Prior to Americium Plutonium Strontium Radium and Uranium Analyses

1 Scope and Application

11 This method is applicable to the sodium hydroxide fusion of limestone samples prior to chemical separation as described in the following procedures

111 Rapid Radiochemical Method for Americium-241 in Building Materials for Environmental Remediation Following Radiological Incidents (Reference 161)

112 Rapid Radiochemical Method for Plutonium-238 and Plutonium-239240 in Building Materials for Environmental Remediation Following Radiological Incidents (Reference 162)

113 Improved Rapid Radiochemical Method for Radium-226 in Building Materials for Environmental Remediation Following Radiological Incidents (Reference 163)

114 Rapid Radiochemical Method for Total Radiostrontium (Sr-90) in Building Materials for Environmental Remediation Following Radiological Incidents (Reference 164)

115 Rapid Radiochemical Method for Isotopic Uranium in Building Materials for Environmental Remediation Following Radiological Incidents (Reference 165)

12 This is a general method for limestone samples collected following a radiological or nuclear incident The limestone samples may be received as core samples crushed samples or in pieces of various sizes

13 The rapid fusion method is rapid and rigorous effectively digesting refractory radionuclide particles that may be present in the limestone samples

14 Limestone samples should be crushed and pulverized prior to taking a representative aliquant for analysis The limestone sample should be milled to achieve a particle size small enough that representative subsamples can be taken and representative aliquants analyzed

15 After a homogeneous subsample is obtained the limestone sample aliquant is taken and fused to digest the limestone sample matrix and matrix removal steps are employed to collect and preconcentrate the radionuclides from the alkaline fusion matrix This method is a sample digestion and pretreatment technique to be used prior to other separation and analysis methods The user should refer to those individual methods and any project-specific requirements for the determination of applicable measurement quality objectives (MQOs)

Note Sample count times may vary based on differences in instrument parameters such as chemical yield detection efficiency and background


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16 Application of this method by any laboratory should be validated by the laboratory using the protocols provided in Method Validation Guide for Qualifying Methods Used by Radioanalytical Laboratories Participating in Incident Response Activities (Reference 166) or the protocols published by a recognized standards organization for method validation

161 In the absence of project-specific guidance MQOs for limestone samples may be based on the analytical action levels (AALs) required method uncertainty (umr) and the required relative method uncertainty (φmr) found in the Radiological Sample Analysis Guide for Incident Response mdash Radionuclides in Soil (Reference 167)

2 Summary of Method

21 The method is based on the rapid dissolution of a representative finely milled aliquants of approximately 1 g of limestone using sodium hydroxide fusion at 600 degC

22 Plutonium (Pu) Uramium (U) and Americium (Am) are separated from the alkaline matrix using an iron hydroxidetitanium hydroxide precipitation followed by a lanthanum fluoride matrix removal step

23 Strontium (Sr) is separated from the alkaline matrix using a phosphate precipitation followed by a calcium fluoride precipitation to remove silicates

24 Radium (Ra) is separated from the alkaline matrix using a carbonate precipitation

25 The resulting solutions are subsequently processed as summarized in Steps 111ndash115

3 Definitions Abbreviations and Acronyms

31 Discrete Radioactive Particles (DRPs or ldquohot particlesrdquo) Particulate matter in a sample of any matrix where a high concentration of radioactive material is present as a tiny particle (microm [micron] range)

32 Multi-Agency Radiological Analytical Laboratory Protocol (MARLAP) Manual (Reference 168)

33 The use of the term limestone throughout this method is not intended to be limiting or prescriptive and the method described herein refers to all limestone- related materials In cases where the distinction is important the specific issues related to a particular sample type will be discussed

4 Interferences and Limitations

41 Limestone samples with larger particle size may require a longer fusion time during Step 1117

42 Information regarding the elemental composition of the sample may be helpful For example limestone may have native concentrations of uranium radium thorium (Th) strontium or barium (Ba) any of which may have an effect on the chemical


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separations used following the fusion of the sample In some cases (eg strontium analysis) elemental analysis of the digestate prior to chemical separations may be necessary to determine native concentrations of carrier elements present in the sample The amount of stable Sr added to the limestone samples is designed to minimize the impact from native stable strontium

43 Matrix blanks for these matrices may not be practical to obtain Efforts should be made to obtain independent analyte-free materials that have similar composition as the samples to be analyzed These blanks will serve as process monitors for the fusion process and as potential monitors for cross contamination during batch processing

44 Uncontaminated limestone material may be acceptable blank material for Pu Am and Sr analyses but this material will contain background levels of naturally occurring U and Ra isotopes

441 If analyte-free blank material is not available and an empty crucible is used to generate a reagent blank sample it is recommended that ~200 milligram (mg) calcium be added as calcium nitrate to the empty crucible as blank simulant for limestone This simulates the calcium present in the limestone sample which is utilized in the sample preconcentration steps

442 Tracer yields may be slightly lower for reagent blank matrices since limestone matrix components typically enhance recoveries across the precipitation steps

45 Samples with elevated activity or samples that require multiple analyses from a single aliquant may need to be split after dissolution In these cases the initial digestate and the split fractions should be carefully measured to ensure that the sample aliquant for analysis is accurately determined

451 Tracer or carrier amounts (added for yield determination) may be increased where the split allows for the normal added amount to be present in the subsequent aliquant For very high activity samples the addition of the tracer or carrier may need to be postponed until following the split in which case special care must be taken to ensure that the process is quantitative until isotopic exchange with the yield monitor is achieved This deviation from the method should be thoroughly documented and reported in the case narrative

452 When this method is employed and the entire volume of fused sample is processed in the subsequent chemical separation method the original sample size and units are used in all calculations with the final results reported in the units requested by the project manager

453 In cases where the sample digestate is split prior to analysis the fractional aliquant of the sample is used to determine the sample size The calculation of the appropriate sample size used for analysis is described in Section 12

46 Batch blank samples laboratory control samples (LCS) and duplicates should be created as early in the process as possible following the same tracercarrier additions digestion process and sample splitting used for the field samples In this method quality control (QC) samples should be initiated at the point samples are aliquanted into crucibles for the fusion


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47 Zirconium crucibles used in the fusion process may be reused

471 Before reuse the crucibles should be cleaned very well using soap and water followed by warm nitric acid (multiple rinses) and then water Blank measurements should be monitored to ensure effective cleaning and control against cross-contamination

472 Segregation of crucibles into separate groups used for low and high activity samples is recommended to minimize the risk of cross-contamination while maximizing the efficient use of crucibles

48 Centrifuge speeds of 3500 revolutions per minute (rpm) are recommended but lower rpm speeds may be used if 3500 rpm is not available Longer centrifuge times may be needed with lower speeds

49 Aluminum nitrate reagent typically contains trace levels of uranium contamination To achieve the lowest possible blanks for isotopic uranium measurements some labs have removed the trace uranium by passing ~250 milliliter (mL) of the 2 Molar (M) aluminum nitrate reagent through ~7 mL TRU Resin but this will have to be tested and validated by the laboratory

410 The high calcium (Ca) content in limestone may limit the sample size used for the determinations of some radionuclides particularly for 226Ra analyses where a calcium carbonate preconcentration step is used and high levels of calcium (Ca) could exceed resin capacity The sample aliquant is limited to 075 g and additional cation resin is prescribed to address this

411 Because of the high calcium content in limestone the native amounts of calcium in the sample aliquants are utilized during many of the preconcentration steps such as the calcium carbonate calcium phosphate or calcium fluoride precipitation steps Additional calcium is not added during these steps to avoid problems associated with having too much calcium such as undissolved solids in the final column load solutions By adding calcium to the reagent blank and laboratory control sample (LCS) crucibles to simulate the limestone samples the blank and LCS behave like the sample

412 A 1-g aliquant is used for the actinide analysis For the actinide co-precipitation step the hydroxide content is reduced by adding acid to the fusion matrix to reduce Ca in the iron hydroxide precipitate This reduces the size of the calcium fluoridelanthanum fluoride (CaF2LaF3) precipitate so that it can be dissolved effectively into the column load solution for processing

5 Safety

51 General

511 Refer to your laboratoryrsquos safety manual for concerns of contamination control personal exposure monitoring and radiation dose monitoring

512 Refer to your laboratoryrsquos chemical hygiene plan (or equivalent) for general safety rules regarding chemicals in the workplace


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52 Radiological

521 Discrete Radioactive Particles (DRPs or ldquohot particlesrdquo)

5211 Hot particles will likely be small on the order of 1 millimeter (mm) or less DRPs typically are not evenly distributed in the media and their radiation emissions are not uniform in all directions (anisotropic)

5212 Limestone media should be individually surveyed using a thickness of the solid sample that is appropriate for detection of the radionuclide decay particles

NOTE The information regarding DRPs should accompany the samples during processing as well as be described in the case narrative that accompanies the sample results

53 Procedure-Specific Non-Radiological Hazards

531 The sodium hydroxide fusion is performed in a furnace at 600 degC The operator should exercise extreme care when using the furnace and when handling the hot crucibles Long tongs are recommended Thermal protection gloves are also recommended when performing this part of the procedure The fusion furnace should be used in a well-ventilated area (hood trunk exhaust etc)

532 Particular attention should be paid to the use of hydrofluoric acid (HF) Hydrofluoric acid is an extremely dangerous chemical used in the preparation of some of the reagents and in the microprecipitation procedure Appropriate personal protective equipment (PPE) must be used in strict accordance with the laboratory safety program specification

6 Equipment and Supplies

61 Adjustable temperature laboratory hotplates

62 Balance top loading or analytical readout display of at least plusmn 001 g

63 Beakers 100 mL and 150 mL capacity

64 Centrifuge able to accommodate 225 mL (or 250 mL) tubes

65 Centrifuge tubes 50 mL and 225 mL capacity

NOTE 225-mL centrifuge tubes are specified but 250 mL centrifuge tubes may also be used instead

66 Crucibles 250 mL zirconium with lids

67 100 microliters (μL) 200 μL 500 μL and 1 mL pipets or equivalent and appropriate plastic tips

68 1ndash10 mL electronicmanual pipet(s)

69 Hot water bath or dry bath equivalent

610 Muffle furnace capable of reaching at least 600 oC

611 Tongs for handling crucibles (small and long tongs)


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612 Tweezers or forceps

613 Sample size reduction equipment (hydraulic press milling equipment mallet etc) and screens The necessary equipment will be based on a laboratoryrsquos specific method for the process of producing a uniformly ground sample from which to procure an aliquant

NOTE See Appendix A for a method for homogenization of limestone samples

614 Vortex stirrer

7 Reagents and Standards

NOTES Unless otherwise indicated all references to water should be understood to mean Type I reagent water (ASTM D1193 Reference 169)

All reagents are American Chemical Society (ACS)-grade or equivalent unless otherwise specified

71 Type I reagent water as defined in ASTM Standard D1193 (Reference 169)

72 Aluminum nitrate solution 2M (Al(NO3)3) Add 750 g of aluminum nitrate nonahydrate (Al(NO3)3

9H2O) to ~700 mL of water and dilute with water to 1 liter (L)

73 Ammonium hydrogen phosphate (32M) Dissolve 106 g of (NH4)2HPO4 in 200 mL of water heat on low to medium heat on a hot plate to dissolve and dilute with water to 250 mL

74 Boric Acid H3BO3

75 Calcium nitrate (125M) Dissolve 147 g of calcium nitrate tetrahydrate (Ca(NO3)24H2O) in 300 mL of water and dilute with water to 500 mL

76 Iron (Fe) carrier (50 mgmL) Dissolve 181 g of ferric nitrate (Fe(NO3)3 middot 9H2O) in 300 mL water and dilute with water to 500 mL This carrier does not need to be standardized

77 Hydrochloric acid (12M) Concentrated HCl

771 Hydrochloric acid (001M) Add 083 mL of concentrated HCl to 800 mL of water and dilute with water to 1 L


78 Hydrofluoric acid (28M) Concentrated HF

79 Lanthanum (La) carrier (10 mg La3+mL) Add 156 g lanthanum (III) nitrate hexahydrate [La(NO3) 3 6H2O] in 300 mL water dilute with water to 500 mL This carrier does not need to be standardized

710 Nitric acid (16M) Concentrated HNO3

7101 Nitric acid (3M) Add 191 mL of concentrated HNO3 to 700 mL of water and dilute with water to 1 L


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7102 Nitric acid (3M)ndashboric acid (025M) solution Add 154 g of boric acid and 190 mL of concentrated HNO3 to 500 mL of water heat to dissolve and dilute with water to 1 L



711 Sodium carbonate (2M) Dissolve 212 g anhydrous Na2CO3 in 800 mL of water then dilute with water to 1 L

712 Sodium hydroxide pellets

713 Titanium (III) chloride solution (TiCl3) 20 percent by mass (wt) solution in 20ndash30 wt hydrochloric acid (This reagent is typically available commercially in this concentration) Alternate concentrations (eg 10) may be used with appropriate volume adjustments

714 Radioactive tracerscarriers (used as yield monitors) and spiking solutions A radiotracer is a radioactive isotope of the analyte that is added to the sample to measure any losses of the analyte A carrier is a stable isotope form of a radionuclide (usually the analyte) added to increase the total amount of that element so that a measureable mass of the element is present A carrier can be used to determine the yield of the chemical process andor to carry the analyte or radiotracer through the chemical process Refer to the chemical separation method(s) to be employed upon completion of this dissolution technique Tracerscarriers that are used to monitor radiochemicalchemical yield should be added at the beginning of this procedure This allows for monitoring and correction of chemical losses in the combined digestion process as well as in the chemical separation method Carriers used to prepare sample test sources but not used for chemical yield determination (eg cerium (Ce) added for microprecipitation of plutonium or uranium) should be added where indicated

8 Sample Collection Preservation and Storage

Not Applicable

9 Quality Control

91 Where the subsequent chemical separation technique requires the addition of carriers and radioactive tracers for chemical yield determinations these are to be added prior to beginning the fusion procedure unless there is good technical justification for doing otherwise

92 Quality control samples are generally specified in the laboratoryrsquos quality manual or in a projectrsquos analytical protocol specifications (APS) At the very minimum the following are suggested

921 A LCS which consists solely of the reagents used in this procedure and a known quantity of radionuclide spiking solution shall be run with each batch


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of samples The concentration of the LCS should be at or near the action level or level of interest for the project

922 One reagent blank shall be run with each batch of samples The blank should consist solely of the reagents used in this procedure (including tracer or carrier noted in this analytical method added prior to the fusion process)

923 A sample duplicate that is equal in size to the original aliquant should be analyzed with each batch of samples This provides assurance that the laboratoryrsquos sample size reduction and subsampling processes are reproducible

93 Batch quality control results shall be evaluated and meet applicable APS prior to release of unqualified data In the absence of project-defined APS or a project-specific quality assurance project plan (QAPP) the quality control sample acceptance criteria defined in the laboratoryrsquos Quality Manual and procedures shall be used to determine acceptable performance for this method

10 Calibration and Standardization

101 Refer to the individual chemical separation and analysis methods for calibration and standardization protocols

11 Procedure

111 Fusion

1111 In accordance with the data quality objectives (DQOs) and sample processing requirements stated in the project plan documents remove extraneous materials from the limestone sample using a clean forceps or tweezers

1112 Weigh out a representative finely milled 1-g aliquant of sample into a 250-mL crucible (075 g aliquants for 226Ra analysis or 125 to 15 g aliquants for 90Sr analysis) See Appendix A for the limestone milling procedure

NOTE For all analyses a reagent blank of ~200-mg Ca per sample (prepared by evaporating 4 mL of 125M calcium nitrate Ca(NO3)2 should be added to the crucible as a blank simulant to ensure the blank behaves like the limestone samples during the precipitation steps

1113 Add the proper amount of tracer or carrier appropriate for the method being used and the number of aliquants needed

NOTE It is anticipated that limestone sample material will be dry enough to aliquant without a preliminary drying step In the event samples are received that contain significant amounts of moisture the samples may be dried in a drying oven at 105 degC prior to taking the aliquant

1114 Place crucibles on a hot plate and heat to dryness on medium heat

NOTE Heat on medium heat to dry quickly but not so high as to cause splattering

1115 Add the following amounts of sodium hydroxide (NaOH) based on the sample sizeanalysis required

1 g for Pu Am U 15 g NaOH


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125 g to 15 g for Sr 15 g NaOH 075 g for Ra 10 g NaOH

1116 Place the crucibles with lids in the 600 degC furnace using tongs

1117 Fuse samples in the crucibles for ~15 minutes

NOTE Longer times may be needed for larger particles

1118 Remove hot crucibles from furnace very carefully using tongs and transfer to hood

1119 Add ~25-50 mL of water to each crucible ~8 to 10 minutes (or longer) after removing crucibles from furnace and heat on hotplate to loosen and dissolve solids

11110 If necessary for dissolution add more water and warm as needed on a hotplate

NOTE If undissolved residues are visible after dissolving the fusion cake the sample should be reprocessed using sample material that has been ground or milled to a finer particle size or longer fusion times or both

11111 Proceed to Section 112 for the actinide pre-concentration 113 for strontium preconcentration or 114 for radium pre-concentration steps

112 Pre-concentration of Actinides (Pu U or Am) from Hydroxide Matrix

NOTE The iron (Fe) and La carriers may be added to the 225 mL centrifuge tubes prior to transferring the dissolved sample to the tubes

1121 After each fused sample has been transferred to a labeled 225-mL centrifuge tube ensure crucibles have been rinsed well with water and the rinses have been transferred to each tube

1122 Add 10 mL 3 M HNO3 to each crucible and heat crucibles on a hot plate until hot Transfer the 3M HNO3 rinse to the 225 mL tube followed by additional rinses of water

1123 Dilute each sample with water to ~160 mL

1124 Add 20 mL concentrated HCl to each tube and swirl to mix well Note The hydroxide content is lowered to reduce the amount of Ca in the precipitate

1125 Cool the 225-mL centrifuge tubes in an ice bath to approximately room temperature

1126 Pipet 25 mL of iron carrier (50 mgmL) into each 225-mL centrifuge tube for each sample

1127 Pipet 1 mg LamL to each tube as follows Pu U 5-mL 1 mg LamL

Am 3-mL 1 mg LamL

1128 Pipet 4 mL 32M (NH4)2HPO4 into each tube Cap and mix well NOTE If column load solution solids are encountered it may be necessary to reduce the amount of phosphate added


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1129 Pipet 4 mL of 20 wt titanium (III) chloride (TiCl3) into each tube and cap and mix well immediately

NOTE Other strengths of TiCl3 may be used with the volume aliquot adjusted to add an equivalent amount of TiCl3 for example 8 mL of 10 TiCl3 It is very important to mix well at this step to enhance uranium precipitation

11210 Cool 225 mL centrifuge tubes in an ice bath for ~ 10 minutes

11211 Centrifuge tubes for ~6 minutes at 3500 rpm or more or as needed

11212 Pour off the supernate and discard to waste

11213 Add 15M HCl to each tube to redissolve each sample in a total volume of ~80 mL

11214 Cap and shake each tube to dissolve solids as well as possible

NOTE Typically there will be undissolved solids at this point which is acceptable

11215 Dilute each tube to ~170 mL with 001M HCl Cap and mix

11216 Pipet 1 mL of 10 mg LamL into each tube

11217 Pipet 25 mL of 20 wt TiCl3 into each tube Cap and mix

11218 Add ~20 mL of concentrated HF into each tube Cap and mix well

11219 Allow centrifuge tubes to stand for ~10 minutes

11220 Centrifuge for ~5 to 10 minutes at 3500 rpm or more or as needed

11221 Pour off supernate and discard to waste

11222 Pipet 7 mL of 3M HNO3 ndash 025M boric acid into each tube

11223 Cap mix and transfer contents of the tube into a labeled 50-mL centrifuge tube

11224 Pipet 6 mL of 7M HNO3 and 7 mL of 2M aluminum nitrate into each tube cap and mix (shake or use a vortex stirrer) and transfer rinse to 50-mL centrifuge tubes

11225 Pipet 3 mL of 3M HNO3 directly into the 50-mL centrifuge tube

11226 Warm each 50-mL centrifuge tube in a hot water bath for a few minutes shaking or using a vortex mixer to dissolve

11227 If the sample does not clear up or appears cloudy add 5 mL of 3M HNO3 to the tube and mix again

11228 Remove each 50-mL centrifuge tube from the water bath and allow to cool to room temperature

11229 Centrifuge the 50-mL centrifuge tubes at 3500 rpm for 5 minutes to remove any traces of solids (may not be visible prior to centrifuging) and transfer solutions to labeled beakers or tubes for further processing Discard any solids



11230 Proceed directly to the Am Pu or U methods listed in steps 111 112 or 115

113 Pre-concentration of 90Sr from Hydroxide Matrix

NOTE The Fe carrier may be added to the 225 mL centrifuge tubes prior to transferring the dissolved sample to the tubes

1131 After each fused sample has been transferred to a 225-mL centrifuge tube ensure crucibles have been rinsed well with water and the rinses have been transferred to each tube


1133 Dilute each sample to ~ 180 mL with water


1135 Pipet 1 mL of iron carrier (50 mg mL) and 7 mL 32M (NH4)2HPO4 into each tube

1136 Cap tubes and mix well

1137 Cool 225 mL centrifuge tubes in an ice bath for 5 to 10 minutes





NOTE Typically there will be undissolved solids which is acceptable



11314 Allow tubes to sit for 5 to 10 minutes

11315 Centrifuge for ~6 minutes at 3500 rpm or more or as needed


11317 Pipet 7 mL of concentrated HNO3 and 7 mL of 3M HNO3 - 025M boric acid into each 225-mL centrifuge tube to dissolve precipitate

11318 Cap and mix well Transfer contents of the tube into a labeled 50-mL centrifuge tube

11319 Pipet 7 mL of 3M HNO3 and 7 mL of 2M aluminum nitrate into each 225 mL tube cap tube and mix

11320 Transfer rinse solutions to 50-mL centrifuge tubes and mix well (shake or use vortex stirrer)



11321 Centrifuge the 50-mL tubes at 3500 rpm for 5 minutes to remove any traces of solids

11322 Transfer solutions to labeled beakers or new 50-mL centrifuge tubes for further processing

11323 If solids remain add 5 mL 3M HNO3 to each tube cap and mix well centrifuge for 5 minutes and add the supernate to the sample solution Discard any residual solids

11324 Proceed directly to the Sr method listed in step 114

114 Pre-concentration of 226Ra from Hydroxide Matrix

1141 Transfer each sample to a 225-mL centrifuge tube rinse crucibles well with water and transfer rinses to each tube

1142 Dilute to ~ 150 mL with water

1143 Add 10 mL concentrated HCl to each tube

1144 Cap and mix each tube well

1145 Add 10 mL of 2M Na2CO3 to each tube

1146 Cap tubes and mix

1147 Allow centrifuge tubes to stand for 10 minutes

1148 Centrifuge tubes for 6 minutes at 3500 rpm


11410 Pipet 10 mL of 15M HCl into each tube to dissolve precipitate Cap and mix

11411 Transfer sample solution to a 50-mL centrifuge tube

11412 Pipet 10 mL of 15M HCl into each 225-mL centrifuge tube to rinse Cap and rinse well

11413 Transfer rinse solution to 50-mL tube and mix well using shaking or vortex stirrer Note Typically the HCl added to dissolve the carbonate precipitate is sufficient to acidify the sample If the precipitate was unusually large and suspended solids remain additional acid may be needed The pH can be checked to verify it is pH 1 or less To acidify the pH lt1 add 1 or 2 mL of concentrated hydrochloric acid to the solution and get it to clear Tubes may be warmed in a water bath or hot block to help dissolve samples

11414 If solids remain add 5-mL 15M HCl to each tube cap and mix well centrifuge for 5 minutes and add the supernate to the sample solution Discard any residual solids

11415 Proceed directly to the Ra method listed in step 113

11416 The following steps in the Ra-226 specific method listed in step 113 need to modified slightly to handle the very high Ca levels in limestone samples (Section 112)

114161 Add a water slurry (or weigh out the solid resin) of cation resin 50WX8 (200-400 mesh) into each column equivalent to 8 g of resin



114162 Add 50 mL of 3M HCl to each column at ~1-2 mLmin Discard rinse

12 Data Analysis and Calculations

121 Equations for determination of final result combined standard uncertainty and radiochemical yield (if required) are found in the corresponding chemical separation and analysis methods with the units being provided by the project manager

122 In cases where samples have elevated activity smaller initial sample aliquants may be taken from the original sample Alternately smaller aliquant volumes may be taken from the final sample volume containing the dissolved precipitate (digestate) Aliquants should be removed carefully and accurately from this final sample volume

NOTE Small aliquants taken from the final sample digestate for Sr and Ra analysis may be used in the respective analytical procedures as is Smaller aliquants for actinide analysis should be diluted to a 15-mL total volume with 3M HNO3 so that load solution acidity is maintained when valence adjustment reagents are added

For a single split the effective size of sample is calculated

s

asa D

DWW = (Equation 1)

Where

Ws = original sample size in the units designated by the project manager (eg kg g etc)

Ds = mass or volume of the entire final digestate (eg 20 mL etc) Da = mass or volume of the aliquant of digestate used for the individual

analyses (eg 50 mL etc) Note that the values for Da must be in the same units used in Ds

Wa = sample aliquant size used for analysis in the units designated by the project manager (eg kg g etc)

NOTE For higher activity samples additional dilution may be needed In such cases Equation 1 should be modified to reflect the number of splits and dilutions performed It is also important to measure the masses or volumes used for aliquanting or dilution to enough significant figures so that their uncertainties have an insignificant impact on the final uncertainty budget In cases where the sample will not be split prior to analysis the sample aliquant size is simply equal to the original sample size in the same units requested by the project manager

13 Method Performance

131 Method validation results are to be reported

132 Expected turnaround time per sample

1321 For a representative finely ground 1-g aliquant of sample the fusion steps should add approximately 1hour per batch to the time specified in the individual chemical separation methods

1322 The pre-concentration steps should add approximately 1 to 15 hours per batch



NOTE Processing times for the subsequent chemical separation methods are given in those methods for batch preparations

14 Pollution Prevention

This method inherently produces no significant pollutants The sample and fusion reagents are retained in the final product and are carried into the ensuing chemical separation techniques which marginally increases the salt content of the effluent waste It is noted that if the sampled particulates include radionuclides that may be volatile under the fusion conditions these constituents will be exhausted through the fume hood system

15 Waste Management

151 Refer to the appropriate chemical separation methods for waste disposal information 16 References

Cited References

161 EPA 2014 Rapid Radiochemical Method for Americium-241 in Building Materials for Environmental Remediation Following Radiological Incidents Revision 1 EPA 402-R-14-007 Office of Air and Radiation Washington DC Available at httpswwwepagovsitesproductionfiles2015-06documentsam-241_in_building_materials_rev_0_402r14007pdf

162 EPA 2014 Rapid Radiochemical Method for Pu-238 and Pu-239240 in Building Materials for Environmental Remediation Following Radiological Incidents Revision 1 EPA 402-R-14-006 Office of Air and Radiation Washington DC Available at httpswwwepagovsitesproductionfiles2015-06documentspu-238-239_in_building_materials_rev_0_402r14006pdf

163 EPA 2014 Improved Rapid Radiochemical Method for Radium-226 in Building Materials for Environmental Remediation Following Radiological Incidents Revision 1 EPA 402-R-14-002 Office of Air and Radiation Washington DC Available at httpswwwepagovsitesproductionfiles2017-07documentsimproved_rapid_ra-226pdf

164 EPA 2014 Rapid Radiochemical Method for Total Radiostrontium (Sr-90) in Building Materials for Environmental Remediation Following Radiological Incidents Revision 1 EPA 402-R-14-001 Office of Air and Radiation Washington DC Available at httpswwwepagovsitesproductionfiles2015-05documentssr-90_in_building_materials_rev_0_402r14001_0pdf

165 EPA 2014 Rapid Radiochemical Method for Isotopic Uranium in Building Materials for Environmental Remediation Following Radiological Incidents Revision 1 EPA 402-R-14-005 Office of Air and Radiation Washington DC Available at httpswwwepagovsitesproductionfiles2015-06documentsu_isotopes_in_building_materials_rev_0_402r14005pdf

166 EPA 2009 Method Validation Guide for Qualifying Methods Used by Radiological Laboratories Participating in Incident Response Activities Revision 0 Office of Air and Radiation Washington DC EPA 402-R-09-006 June Available at



httpwww2epagovsitesproductionfiles2015-05documentsmethod_validation_final_with_web_cover_6-24-09pdf

167 EPA 2012 Radiological Sample Analysis Guide for Incident Response mdash Radionuclides in Soil Revision 0 Office of Air and Radiation Washington DC EPA 402-R-12-006 September Available at httpswwwepagovsitesproductionfiles2015-05documents402-r-12-006_soil_guide_sept_2012pdf

168 EPA 2004 Multi-Agency Radiological Laboratory Analytical Protocols Manual (MARLAP) EPA 402-B-1304 04-001A July Volume I Chapters 6 7 20 Glossary Volume II and Volume III Appendix G Available at httpwww2epagovradiationmulti-agency-radiological-laboratory-analytical-protocols-manual-marlap

169 ASTM D1193 ldquoStandard Specification for Reagent Waterrdquo ASTM Book of Standards 1101 current version ASTM International West Conshohocken PA

Other References

1610 Maxwell S Culligan B and Noyes G 2010 Rapid method for actinides in emergency soil samples Radiochimica Acta 98(12) 793-800

1611 Maxwell S Culligan B Kelsey-Wall A and Shaw P 2011 ldquoRapid Radiochemical Method for Actinides in Emergency Concrete and Brick Samplesrdquo Analytica Chimica Acta 701(1) 112-8

1612 Maxwell S Culligan B Hutchison J and Sudowe R Rapid Fusion Method for Actinides and Sr-8990 in Limestone and Marble samples Journal of Radioanalytical and Nuclear Chemistry October 2016 Volume 310 Issue 1 pp 377ndash388

1613 US Environmental Protection Agency (EPA) 2010 Rapid Radiochemical Methods for Selected Radionuclides in Water for Environmental Restoration Following Homeland Security Events Office of Air and Radiation EPA 402-R-10-001 February Revision 01 of rapid methods issued October 2011 Available at httpscfpubepagovsisi_public_record_reportcfmsubject=Homeland2520Security2520ResearchampdirEntryId=213365



17 Tables Diagrams and Flow Chart

Note The following flowcharts and timelines address processes as they apply specifically to limestone matrices as described in this method The approach and timeline may deviate from information provided in Section 17 of the corresponding Building Materials Methods (references 161 ndash 165)

171 Fusion Flow Chart

Rapid Fusion (Step 111)1 Add limestone sample to 250-mL Zr crucible (1112)2 Add proper amount of tracerscarriers (1113)3 Dry on hot plate on medium heat (1114)4 Add 10-15 g NaOH pellets to crucible (1115)5 Heat ~15 min at 600 degC (1116-1117)6 Remove from furnace and allow to cool in hood (1118)

Rapid Fusion and Preparation ofLimestone Samples for Precipitation and Analysis

1frac12 hours

Prepare for precipitations (Step 1119)1 Add ~ 25-50 mL water to each crucibles ~8-10 minutes after removal from furnace (1119)2 Warm on hotplate to dissolveloosen solids (1119)3 If necessary add more water and warm as needed on hot plate (11110)4 Fusion solution is ready for actinide or RaSr precipitations (112-114)

Actinide Precipitation

Procedure

PhosphateFluoridePrecipitation

for Sr Procedure

CarbonatePrecipitation

for Ra Procedure

Elapsed Time

frac34 hour

Continued on appropriate procedure chart



172 Actinide Precipitation Flow Chart

3 hours

1 Add Fe and La to each tube (1121-1122)2 Add 10 mL 3M HNO3 and heat until hot Transfer to 225-mL tube (1124)3 Dilute to ~160 mL with water (1125)4 Add 20 mL concentrated HCl to each tube and swirl to mix (1126)5 Cool to room temperature in ice bath (1127)6 Add 4 mL 32M (NH4)2HPO4 to each tube Cap and mix (1128)7 Add 4 mL 20 wt TiCl3 to each tube Cap and mix (1129)8 Cool in ice bath for ~10 min (11210)9 Centrifuge for 6 min and pour off supernate (11211-11212)10 Redissolve in 15M HCl to total volume of ~80mL Cap and shake

(11213-11214)11 Dilute to ~170 mL with 001M HCl Add La (11215-11216)12 Add 25 mL 20 wt TiCl3 ~10mL HF and allow to stand for 10min

(11216-11219)13 Centrifuge for 5-10 min and pour off supernate (11220-11221)14 Redissolve in 7 mL 3M HNO3-025M H3BO3 + 6 mL 7M HNO3 + 7 mL 2M

Al(NO3)3 + 3 mL 3M HNO3 warming to dissolve in 50-mL centrifuge tubes (11222-11226)

15 If samples do not clear up add 5mL 3M HNO3 and mix again (11227)16 Remove from water bath and allow to cool to room temperature

Centrifuge to remove trace solids and transfer to beakers or tubes for processing (11228-11229)

17 Analyze sample solutions for specific actinides using rapid methods for specific actinides in building materials (11230)

Continued from 171 Fusion Flow Chart

Actinide Precipitation ProcedureElapsed Time

1frac12 hours



173 Strontium Precipitation Flow Chart

Elapsed Time

1frac12 hoursContinued from Fusion Flow Chart Step 171

2frac12 hours

1 Add 10 mL 3 M HNO3 and heat until hot Transfer to 225-mL tube (1132)

2 Dilute to ~180 mL with water (1133)3 Cool tubes to room temperature in ice bath (1134)4 Pipet 1 mL 50 mgmL iron carrier and 7 mL 32M (NH4)2HPO4 to each

tube Cap and mix well (1135-1136)5 Cool tubes to 5 to 10 min in ice bath (1137)6 Centrifuge for 6 min and pour off supernate (1138-1139)7 Redissolve in ~80 mL 15M HCl Cap and mix well (11310-11311)8 Dilute to ~170 mL with 001M HCl (11312)9 Add 20 mL concentrated HF and wait 5-10 min (11313-11314)10 Centrifuge for ~6 min and pour off supernate (11315-11316)11 Redissolve in 7 mL 3M HNO3-025M H3BO3 + 7 mL concentrated

HNO3 +7 mL 2M Al(NO3)3 + 7 mL 3M HNO3 Transfer to 50-mL tube (11317-11320)

12 Cap and mix using vortex stirrer or by shaking (11320)13 Centrifuge for 5 min and discard trace solids Transfer solutions to

new tubes or beakers (11321-11322)14 Analyze sample solutions for 90Sr using 90Sr method for building

materials (11324)

Ca3(PO4)2 CaF2 Precipitation Procedure for Sr



174 Radium Precipitation Flow Chart

Continued from Fusion Flow Chart Step 171

3 hours

1 Dilute to 150 mL with water Add 10 mL concentrated HCl Cap and mix (1142-1144)

2 Add 10 mL 2M Na2CO3 to each tube Cap and mix (1145-1146)3 Allow to stand 10 min (1147)4 Centrifuge for 6 min and pour off supernate (1148-1149)5 Redissolve in 10 mL 15 M HCl (11410)6 Transfer to 50-mL centrifuge tubes (11411)7 Rinse 225-mL tube with 10 mL 15M HCl and transfer to 50-mL

tube Cap and mix using vortex stirrer or by shaking (11412-11413)

8 If solids remain add 5 mL 15M HCL cap and mix Centrifuge for 5 min and discard trace solids (11414)

9 Analyze sample solutions for 226Ra using 226Ra method for building materials (11415)

Elapsed Time

1frac12 hours

Carbonate Precipitation for Radium Procedure

Rapid Method for Sodium Hydroxide Fusion of Limestone Matrices Prior to Am Pu Sr Ra and U Analyses


Appendix A

Rapid Technique for Milling and Homogenizing Limestone Samples

A1 Scope and Application

A11 Limestone samples may be received as core samples chunks or crushed pieces The goal is to obtain representative sample aliquants from homogeneous amounts of sample Significant effort should be applied to ensure representative sampling of the limestone materials

A12 This method describes one approach for the rapid gross preparation of limestone samples to yield representative 075ndash15 g aliquant for radiochemical analysis of non-volatile radionuclides The method addresses steps for splitting and milling of 50ndash1000-g limestone samples The limestone sample must be reduced to pieces or fragments less than ~25 mm in diameter prior to using the ball mill This can be done with a hydraulic press or mallet A mortar grinder may be needed to reduce the particle size if a mallet or hammer will not crush the particles to a fine enough size

A13 The method is designed to be used as a preparatory step for the attached methods for furnace heating and fusion of limestone for measurement of 241Am 238Pu 239240Pu U 90Sr and 226Ra It may also be applied to other matrices whose physical form is amenable to pulverization

A14 If the levels of activity in the sample are low enough to permit safe radiological operations up to 1 kg of limestone can be processed

A2 Summary of Methods

A21 This method uses disposable equipment or materials to contact the sample minimizing the risk of contamination and cross-contamination and eliminating concerns about adequate cleaning of equipment

A22 The entire sample as received (after reducing fragment size to less than ~25 mm diameter) is split by coning and quartering until ~75-150 mL of the limestone is available for subsequent processing If less than ~450 mL of limestone is received the entire sample is processed without splitting

NOTE Large chunks of limestone will require initial crushing prior to coning and quartering

A23 The limestone is transferred to a hydraulic press and crushed A ball mill approach with disposable paint cans (or equivalent) is used to mill the samples into fine particles

A24 Other milling apparatus such as lab pulverizerscrushers also may be used to mill the limestone sample to finely ground well-homogenized particles In this case effort must be made to ensure no sample carry-over effects occur between the processing of individual samples

A25 Additional replicate analyses may also be performed to provide further assurance that analytical results are representative of limestone samples received



A3 Definitions Abbreviations and Acronyms

A31 Discrete Radioactive Particles (DRPs or ldquohot particlesrdquo) Particulate matter in a sample of any matrix where a high concentration of radioactive material is contained in a tiny particle (μm range)

A32 Multi-Agency Radiological Analytical Laboratory Protocols (MARLAP) Manual (Reference A161)

A4 Interferences

A41 Radiological Interferences

A411 Coning and quartering provides a mechanism for rapidly decreasing the overall size of the sample that must be processed while optimizing the representativeness of the subsampling process By decreasing the time and effort needed to prepare the sample for subsequent processing sample throughput can be significantly improved

A412 Openly handling large amounts of highly contaminated materials however even within the containment provided by a fume hood may pose an unacceptable risk of inhalation of airborne contamination and exposure to laboratory personnel from radioactive or other hazardous materials Similarly it may unacceptably increase the risk of contamination of the laboratory In such cases coning and quartering process may be eliminated in lieu of processing the entire sample

A413 The precise particle size of the milled sample is not critical to subsequent processes However milling the sample to smaller particle sizes and thorough mixing both facilitate representative subsampling by minimizing the amount of sample that is not pulverized to fine mesh and must be discarded Additionally subsequent fusion and digestion processes are more effective when performed on more finely milled samples

A414 This method assumes that radioactivity in the sample is primarily adsorbed onto the surface of particles as opposed to being present as a hot particle (see discussion of DRPs below) Thus nearly all of the activity in a sample will be associated with sample fines By visually comparing the sample to a qualitative standard of ~50ndash100 mesh size particles it is possible to rapidly determine whether the sample is fine enough to facilitate the subsequent fusion or digestion This method assumes that when greater than 95 of the sample is as fine or finer than the 50ndash100 mesh standard bias imparted from losses of larger particles will be minimal

A415 If the sample was collected near the epicenter of a radiological dispersal device (RDD) or improvised nuclear device (IND) explosion it may contain millimeter (mm)- to micrometer (microm)-sized particles of contaminant referred to as DRPs DRPs may consist of small pieces of the original radioactive source and thus may have very high specific activity They may also consist of chemically intractable material and present



special challenges in the analytical process Even when the size is reduced to less than 50ndash100 mesh these particles may resist fusion or digestion of the solids into ionic form that can be subjected to chemical separations

A416 When DRPs are present this method isolates larger particles by passing the sample through a disposable 50-mesh screen after which they can be reliably checked for radioactivity DRPs may reliably be identified by their very high specific activity which is readily detectable since they show high count rates using hand-held survey equipment such as a thin-window Geiger-Muller (G-M) probe

A417 When present DRPs may be further milled and then recombined with the original sample Alternatively the particles or the entire sample may need to be processed using a different method capable of completely solubilizing the contaminants such that the radionuclides they contain are available for subsequent chemical separation

A5 Safety

A51 General

A511 Refer to your laboratoryrsquos safety manual for concerns of contamination control personal exposure monitoring and radiation dose monitoring

A512 Refer to your laboratoryrsquos chemical hygiene plan (or equivalent) for general safety rules regarding chemicals in the workplace

A52 Radiological

A521 Refer to your radiation safety manual for direction on working with known or suspected radioactive materials

A522 This method has the potential to generate airborne radioactive contamination The process should be carefully evaluated to ensure that airborne contamination is maintained at acceptable levels This should take into account the activity level and physical and chemical form of contaminants possibly present as well as other engineering and administrative controls available

A523 Discrete Radioactive Particles (DRPs or hot particles)

A5231 Hot particles will usually be small on the order of 1 mm or less Typically DRPs are not evenly distributed in the media and their radiation emissions are not uniform in all directions (anisotropic)

A53 Method-Specific Non-Radiological Hazards

A531 This method employs a hydraulic press andor paint can shaker should The method and equipment should be evaluated for personnel hazards associated with the crushing process

A6 Equipment and supplies

A61 Aluminum foil loaf pans disposable



A62 Balance top-loading range to accommodate sample size encountered readability to plusmn1

A63 Butcher paper or equivalent

A64 Drying oven at 110plusmn10 ordmC

A65 Disposable wire cloth ndash nominal 48 mesh size (~300 μm)

A66 Disposable sieves US Series No 50 (300 μm or 48 mesh) and US Series No 100 (150 μm or 100 mesh)

A67 Hydraulic press

A68 Disposable scoop scraper tongue depressor or equivalent

A69 Red Devil 5400 mechanical paint shaker or equivalent

A610 Steel paint cans and lids (pint quart 2 quart 1 gallon as needed)

A611 Steel or ceramic grinding balls or rods for ball milling ~15ndash25-mm diameter The size and number of grinding media used should be optimized to suit the types of limestone pieces the size of the can and the volume of limestone processed

A612 Mallet or hammer

A7 Reagents and Standards No reagents needed

A8 Sample Collection Preservation and Storage

A81 Samples should be collected in appropriately sized plastic metal or glass containers

A82 Solid sample volumes equivalent to approximately 500 mL of sample will require two splits to obtain a ~100 mL sample

A9 Quality Control

A91 Batch quality control results shall be evaluated and meet applicable analytical protocol specifications (APSs) prior to release of unqualified data In the absence of project-defined APS or a project-specific quality assurance project plan (QAPP) the quality control sample acceptance criteria defined in the laboratory quality manual and procedures shall be used to determine acceptable performance for this method

A92 Quality control samples should be initiated as early in the process as possible Since the risk of cross-contamination using this process is relatively low initiating blanks and laboratory control samples at the start of the chemical separation process is acceptable If sufficient sample is available a duplicate sample should be prepared from the two discarded quarters of the final split of the coning and quartering procedure

A10 Procedure

NOTE This method ensures that only disposable equipment or materials come in contact with sample materials to minimize the risk of sample cross-contamination and concerns about adequate cleaning of



equipment Under certain circumstances such as disposable equipment not being available careful thorough cleaning of the equipment with water and then ethanol may be an option

A101 Estimate the total volume of sample as received

NOTE Limestone samples typically do not contain large amounts of moisture Large chunks of limestone will require crushing prior to coning and quartering The next step uses absorbent paper in the reverse fashion from the normal use of this type of paper it allows for a smooth division of the sample and control of contamination

A1011 Spread a large piece of plastic in a hood (or alternate paper material which

can be discarded to waste later)

A1012 If the limestone sample is received with chunks that are too large to cone and quarter crush the larger pieces to manageable size using a hydraulic press

A10121 Wrap limestone pieces in butcher paper and place in small disposable aluminum foil pan Place another aluminum foil pan on top of wrapped limestone sample

A10122 Crush sample between the aluminum foil pans using a hydraulic press

A10123 Break crushed pieces into smaller pieces for coning and quartering A hammer or mallet can be used to crush further if needed

A10124 Unwrap crushed limestone and break apart into smaller pieces for coning and quartering then ball milling A mortar grinder may be needed to reduce the size of hard limestone rock particles further

A1013 If the sample volume is less than ~450 mL there is no benefit to coning and quartering (Reference A161)

A10131 Carefully pour the sample onto the paper

A1014 If the sample volume is greater than ~450 mL carefully pour the entire sample into a cone onto the paper

A1015 The sample is split at least twice using the coning and quartering steps that follow

NOTE Unused quarters are considered representative of the original sample and may be reserved for additional testing

A10151 Spread the material into a flat circular cake of limestone

using a tongue depressor or other suitable disposable implement Divide the cake radially and return two opposing quarters to the original sample container

A10152 Reshape the remaining two quarters into a smaller cone and repeat Step A10151 until the total volume of the remaining material is approximately 100ndash150 mL



A1016 Transfer the coned and quartered limestone sample to a tared labeled 1-

pint paint can If the initial total volume (Step A1013) was less than ~450 mL transfer the entire sample to a tared labeled 1-quart paint can

A102 Place the can (without lid) in an oven at 110plusmn10 ordmC and dry the limestone to constant mass

NOTE Limestone samples may be dry enough such that heating prior to homogenizing the sample is not required

A103 Weigh the combined mass of the can sample and lid If the percent solids are required see Section A121 calculations Remove can from oven Allow to cool

A104 Add two to five 15ndash25-centimeter (cm) stainless-steel or ceramic balls to the can Replace the lid and seal well

A105 Shake the can and contents for 5 minutes or longer as needed to produce a finely-milled well-homogenized sample

NOTE Although the precise particle size of the milled sample is not critical complete pulverization and fine particle size facilitates representative subsampling and subsequent fusion or digestion processes A qualitative standard can be prepared by passing quartz sand or other milled material through a 50-mesh and then a 100-mesh screen The portion of the sample retained in the 100 mesh screen can be used as a qualitative visual standard to determine if samples have been adequately pulverized

A106 Visually compare the resulting milled sample to a qualitative 50ndash100 mesh

pulverized sample (~150ndash300 μm or 50ndash100 mesh using the Tyler screen scale) The process is complete once 95 of the sample (or greater) is as fine or finer than the qualitative standard If by visual estimation more than ~5 of total volume of the particles in the sample appear to be larger than the particle size in the standard return the sample to the shaker and continue milling until the process is complete

A107 Following milling a small fraction of residual larger particles may remain in the sample

NOTE The following steps offer guidance that may be used if larger-particle DRPs are encountered The goal is to crush and mill and homogenize the limestone samples in a way that allows representative aliquants to be taken for analysis This guidance may be modified as needed by the incident commander

A1071 If the sample was collected close to the epicenter of an RDD or IND explosion it may also contain particles of contaminant referred to as DRPs In such a case the larger particles should be isolated by passing through a disposable 50 mesh screen and checked for radioactivity DRPs are readily identified by their very high specific activity which is detectable using hand-held survey equipment such as a thin-window G-M probe held within an inch of the particles

A10711 If radioactivity is clearly detected the sieved material is returned to the can and ball milled until the desired mesh is obtained In some cases these materials may be resistant to



further pulverization and may need to be processed according to a method specially designed to address highly intractable solids

A10712 If the presence of DRPs is of no concern (no high activities detected for specific particles) the larger particles need not be included in subsequent subsamples taken for analysis It may be possible to easily avoid including them during aliquanting with a disposable scoop If not however they should be removed by sieving through a nominal 50 mesh screen (disposable) prior to further subsampling for subsequent analyses

A108 Sample fines may be stored in and aliquanted directly from the container used for pulverization if the paint can ball mill approach was used

A11 Calibration and Standardization

A111 Balances used shall be calibrated using National Institute of Standards and Technology (NIST)-traceable weights according to the process defined by the laboratoryrsquos quality manual

A12 Data Analysis and Calculations

NOTE Limestone samples may be dry enough such that heating prior to homogenizing the sample is not required Heating to a constant mass may be difficult due to the presence of volatile organics

A121 The percent solids (dry-to-as-received mass ratio) for each sample is calculated from data obtained during the preparation of the sample as follows

100

tarerec as

taredry

MM

MMSolids

Where Mdry = mass of dry sample + labeled can + lid (g) Mtare = tare mass of labeled can + lid (g) Mas rec = mass of sample as received + labeled can + lid (g)

A122 If requested convert the equivalent mass of sample as received to dry mass Dry

mass is calculated from a measurement of the total as received mass of the sample received as follows

100

SolidsMEquivalentSampleDry recas-total

Where Mtotal-as rec = total mass of sample as received (g)

A123 Results Reporting

A1231 The result for percent solids and the approximate total mass of sample as received should be reported for each result

A13 Method Performance



A131 Results of method validation performance are to be archived and available for reporting purposes

A132 Expected turnaround time for these sample preparation steps is about 3 hours for an individual sample and about 4 hours per batch

A14 Pollution Prevention

Not applicable A15 Waste Management

A151 All radioactive and other regulated wastes shall be handled according to prevailing regulations

A16 References

A161 EPA 2004 Multi-Agency Radiological Laboratory Analytical Protocols Manual (MARLAP) EPA 402-B-1304 04-001A July Volume I Chapters 6 7 20 Glossary Volume II and Volume III Appendix G Available at httpwww2epagovradiationmulti-agency-radiological-laboratory-analytical-protocols-manual-marlap

A162 International Union of Pure and Applied Chemistry (IUPAC) 1997 Compendium of Chemical Terminology 2nd ed (the ldquoGold Bookrdquo) Compiled by A D McNaught and A Wilkinson Blackwell Scientific Publications Oxford XML on-line corrected version httpgoldbookiupacorgC01265html (2006) created by M Nic J Jirat B Kosata updates compiled by A Jenkins Last update 2010-12-22


Revision History

Revision 0 Original release 872018

This report was prepared for the National Analytical Radiation Environmental Laboratory of the Office of Radiation and Indoor Air and the National Homeland Security Research Center of the Office of Research and Development United States Environmental Protection Agency It was prepared by Environmental Management Support Inc of Silver Spring Maryland under contract EP-W-07-037 Work Assignment 2-43 and contract EP-W-13-016 Task Order 014 both managed by Dan Askren This document has been reviewed in accordance with US Environmental Protection Agency (EPA) policy and approved for publication Note that approval does not signify that the contents necessarily reflect the views of the Agency Mention of trade names products or services does not convey EPA approval endorsement or recommendation


872018 1 Revision 0















872018 2 Revision 0



2 Summary of Method














872018 3 Revision 0












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5 Safety

51 General




872018 5 Revision 0

52 Radiological






















872018 6 Revision 0




614 Vortex stirrer








74 Boric Acid H3BO3











872018 7 Revision 0









Not Applicable

9 Quality Control





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11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




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872018 2 Revision 0



2 Summary of Method














872018 3 Revision 0












872018 4 Revision 0









5 Safety

51 General




872018 5 Revision 0

52 Radiological






















872018 6 Revision 0




614 Vortex stirrer








74 Boric Acid H3BO3











872018 7 Revision 0









Not Applicable

9 Quality Control





872018 8 Revision 0







11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




872018 2 Revision 0



2 Summary of Method














872018 3 Revision 0












872018 4 Revision 0









5 Safety

51 General




872018 5 Revision 0

52 Radiological






















872018 6 Revision 0




614 Vortex stirrer








74 Boric Acid H3BO3











872018 7 Revision 0









Not Applicable

9 Quality Control





872018 8 Revision 0







11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




872018 3 Revision 0












872018 4 Revision 0









5 Safety

51 General




872018 5 Revision 0

52 Radiological






















872018 6 Revision 0




614 Vortex stirrer








74 Boric Acid H3BO3











872018 7 Revision 0









Not Applicable

9 Quality Control





872018 8 Revision 0







11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




872018 4 Revision 0









5 Safety

51 General




872018 5 Revision 0

52 Radiological






















872018 6 Revision 0




614 Vortex stirrer








74 Boric Acid H3BO3











872018 7 Revision 0









Not Applicable

9 Quality Control





872018 8 Revision 0







11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




872018 5 Revision 0

52 Radiological






















872018 6 Revision 0




614 Vortex stirrer








74 Boric Acid H3BO3











872018 7 Revision 0









Not Applicable

9 Quality Control





872018 8 Revision 0







11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




872018 6 Revision 0




614 Vortex stirrer








74 Boric Acid H3BO3











872018 7 Revision 0









Not Applicable

9 Quality Control





872018 8 Revision 0







11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




872018 7 Revision 0









Not Applicable

9 Quality Control





872018 8 Revision 0







11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




872018 8 Revision 0







11 Procedure

111 Fusion











872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References




872018 9 Revision 0



















Am 3-mL 1 mg LamL





















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References






















































































s

asa D

DWW = (Equation 1)

Where
















15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References








15 Waste Management


Cited References













Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References









Other References












1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References










1frac12 hours



Procedure


for Sr Procedure


for Ra Procedure

Elapsed Time

frac34 hour





3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References






3 hours










1frac12 hours




Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References






Elapsed Time


2frac12 hours







materials (11324)






3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References







3 hours






Elapsed Time

1frac12 hours




Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References





Appendix A



















A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References








A4 Interferences












A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References








A5 Safety

A51 General



A52 Radiological
















A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References










A67 Hydraulic press










A9 Quality Control



A10 Procedure
















































100

tarerec as

taredry

MM

MMSolids




100













A16 References

















































100

tarerec as

taredry

MM

MMSolids




100













A16 References










A16 References



limestone method final · 2018-08-13 · sodium hydroxide fusion of limestone matrices 8/7/2018 4...

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