# Development of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity Concentration in Flowback and Produced Waters from Hydraulic Fracturing Operations

This report was prepared for the National Analytical Radiation Environmental Laboratory of the Office of Radiation and Indoor Air and the National Exposure 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 EP-W-13-016, task order 014, both managed by Dan Askren. This document has been reviewed in accordance with U.S. 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.



## R E S E A R C H A N D D E V E L O P M E N TEPA/600/R-14/107 July 2014



# Validation of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity Concentration in Flowback and Produced Waters from Hydraulic Fracturing Operations

Brian Schumacher U.S. Environmental Protection Agency Office of Research and Development National Exposure Research Center

Environmental Sciences Division Las Vegas, NV 89119

John Griggs and Dan Askren

Office of Air and Radiation Office of Radiation and Indoor Air National Analytical Radiat ion Environment al Laboratory Montgomery, AL 36115

Bob Litman and Bob Shannon Environmental Management Systems Silver Spring, MD 20910

Marinea Mehrhoff, Andrew Nelson, and Michael K. Schultz University of Iowa Iowa City, Iowa 52242

U.S. Environmental Protection Agency Office of Research and Development Washington, DC 20460Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# CONTENTS

Acronyms, Abbreviations, Units, and Symbols ............................................................................ vii

Radiom etric and General Unit Conversions .................................................................................. ix

1.0

3.0 Introduction.................................................................................................................. ........1

2.0

4.0 Characterization of the Sample Matrix ................................................................................5 Initial Radioanalytical Methods...........................................................................................9

Method Development Process Summary .

. .........................................................................11

5.0 Participating Laboratories..................................................................................................13

6.0 Measurement Quality Objectives .......................................................................................13

7.0 Method Development Plan ................................................................................................17 7.1 Method Uncertainty ................................................................................................. 17 7.2 Detection Capability ................................................................................................ 19
7.3 9
7.4 Method Bias ............................................................................................................. 1 Analyte Concentration Range .................................................................................. 21 7.5 Method Specificity ................................................................................................... 21
21

8.0 7.6 Method Ruggedness ................................................................................................. Techniques Used to Evaluate the Measur ement Quality Objectives for Methods Development Project ..........................................................................................................2 3 8.1 Required Method Uncertainty ................................................................................. 23 8.2 Required Minimum Detectable Concentration ........................................................ 23 9.0 Evaluation of Experimental Results ...................................................................................25 9.1 Summary of the Method .......................................................................................... 25 9.2 Required Method Uncertainty ................................................................................. 25 9.3 Required Minimum Detectable Concentration ........................................................ 31
Evaluation of the Absolute and Relative Bias

11.0 9.4 ......................................................... 36 9.5 Method Ruggedness ................................................................................................. 38
10.0 Timeline to Complete a Batch of Samples ........................................................................39 Reported Modifications Du ring Development and Recommendations for Future Work .......................................................................................................................... ........41

12.0

13.0 Summary and Conclusions ................................................................................................47

References.................................................................................................................... ......49

Attachment I: Met hod Development Trials .................................................................................51 Attachment II: Time Lapse .................................................................................................... .......59

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### Attachment III: Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in Flowback and Produced Waters from Hydraulic Fract uring Operations (FPWHFO) ........................................................................................................61Ju ly - 2014 iii Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# Figures

Figure 1 – Po-209 Alpha Spectrum

.............................................................................................. 52 Figure 2 – Alpha Spectrum of Separated 230 

### Th............................................................................ 53 Figure 3 – Liquid scintillation Spectrum of 209 

### Po ........................................................................ 55 Figure 4 – Flow Chart for Met hod Development Using Tracers ................................................. 56 Figure 5 – Elution Profile for Traced solution with 0.1 M Ammonium Bioxalate in 4 M HCl .................................................................................................................. 56 Figure 6 – Total Recovery of Tracers (%) with (0.1 M Ammonium Bioxalate in 4 M HCl)......................................................................................................................57Ju ly - 2014 iv Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFODevelopment of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# Tables

Table 1 – Non-Radiological Analysis of FPWHFO and Surrogate Sample ................................ 6 Table 2 – MQOs Targeted for Gross Alpha and Gross Beta in FPWHFO ............................... 15

Table 3 – Method Development As-Spike d Concentrations, MQOs and Mean Measured Results....................................................................................................... 16 Table 4 – Proposed Sample Proces sing and Counting Combinations ....................................... 17

18 Table 5 – Actual Sample Concen trations Used for M D Process ............................................... Table 6A – Th, U. Po Gross Alpha by LS C - Analytical Results for Required Method Uncertainty Evaluation.............................................................................................. 27

Table 6B – 226 

### Ra Alpha by Gamma Spectrometry - Analytical Results for Required Method Uncertainty Evaluation ................................................................................ 28 y Gamm Table 6C – 228 

### Ra Beta b a Spectrometry - Analytical Results for Required Method Uncertainty Evaluation ................................................................................ 29 Table 7A – Th, U, Po Gross Alpha by LSC - Experimental Standard Deviation of the Seven PT Samples by Test Level ( 230 

### Th) .................................................................. 30

Table 7B – 226 

### Ra Alpha by Gamma Spectrometry - E xperimental Standard Deviation of the Seven PT Samples by Test Level .................................................................... 30

Table 7C – 228 

### Ra Beta by Gamma Spectrometry - E xperimental Standard Deviation of the Seven PT Samples by Test Level .................................................................... 31 Table 8A – Th, U, Po Gross Alpha by LSC - Blank Water Samples ........................................... 31 ter Samples ..................................... 32

226 

### Table 8B – Th, U, Po Gross Alpha by LSC - Surrogate Wa

Table 8C – Ra Alpha by Gamma Spectrometry in Demineralized and Surrogate Water Samples ........................................................................................................... 32

Table 8D – 228 

### Ra Gross Beta by Gamma Spectrometry in Demineralized and Surrogate Water Samples ........................................................................................................... 33 Table 9A – Reported Results for Samples Containing Th, U, Po Gross Alpha by LSC at the As-Tested MDC Value (12.45 pCi/L) ............................................................. 34

MDC Value (55.2 pCi/L) .......................................................................................... 35 Table 9B – Reported Results for 226 

### Ra Alpha by Gamma Spectrometry at the As-Tested

Table 9C – Reported Results for 228 

### Ra Beta by Gamma Spectrometry at the As-Tested MDC Value (30.4 pCi/L) .......................................................................................... 36

Table 10 – Absolute and Relative Bias for Gross Alpha and Gross Beta by the Three Measurements ............................................................................................................ 37 Table 11 – Estimated Elapsed Times for Gross Alpha Analysis ................................................. 59 Table 12 – Estimated Elapsed Times for Gross Beta Analysis ................................................... 59

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# Acronyms, Abbreviations, Units, and Symbols

AAL ...............analytical action level ACS ................American Chemical Society APS ................analytical protocol specification Bq ...................becquerel

CL NC 

### ...............critical net concentration CSU ................combined standard uncertainty

Ci ....................curie d......................day EPA ................U.S. Environmental Protection Agency

ESD ................Environmental Sciences Division

FPWHFO... ...Flowback and Produced Waters fr om Hydraulic Fracturing Operations

g......................gram GPC ................gas-flow proportional counter

h......................hour ID ...................[identifier] [ide ntification number]

L .....................liter LCS ................laboratory control sample LSC ................liquid scintillation [count] [cocktail]

m ....................meter M .................... [molar]

MARLAP ....... Multi-Agency Radiological Laborat ory Analytical Protocols Manual MD.................method development MDA ..............minimum detectable activity

MDC ..............minimum detectable concentration MDRM...........method development reference material

min .................minute MQO ..............measurement quality objective

MVG .............. Method Validation Guide for Qualifyi ng Methods Used by Radiological Laboratories Participating in Incident Response Activities NAREL ..........EPA’s National Analytical Radi ation Environmental Laboratory, Montgomery, AL

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### NERC .............National Exposure Research Center NHSRC ..........EPA’s National Homeland Security Research Center, Cincinnati, OH NIST ...............National Institute of Standards and Technology ORD ...............U.S. EPA Office of Research and Development

ORIA ..............U.S. EPA Office of Indoor Air and Radiation

φ MR

........................... 

### required relative method uncertainty PT ...................proficiency testing QA ..................quality assurance QAPP .............quality assurance project plan QC ..................quality control STS .................sample test source

u MR 

### ..................required method uncertainty

y......................year

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## Radiometric and General Unit Conversions

To Convert To Multiply by To Convert To Multiply by

years (y) seconds (s) minutes (min)

hours (h) days (d) 3.16×10 7
5.26×10 5
8.77×10 3
3.65×10 2 s min

h d Y 3.17×10 –8
1.90×10 –6
1.14×10 –4
2.74×10 –3

disintegrations per second (dps) becquerels (Bq) 1 Bq dps 1

Bq Bq/kg Bq/m 3 Bq/m 3 picocuries (pCi) pCi/g pCi/L Bq/L 27.0 2.70×10 –2
2.70×10 –2
10 –3 pCi pCi/g pCi/L Bq/L Bq Bq/kg Bq/m 3 Bq/m 3 3.70×10 –2
37.0 37.0 10 3

microcuries per milliliter (μCi/mL) pCi/L 10 9 pCi/L μCi/mL 10 –9

disintegrations per minute (dpm) μCi pCi 4.50×10 –7
4.50×10 –1 pCi dpm 2.22

cubic feet (ft 3 ) cubic meters (m 3 ) 2.83×10 –2 m 3 ft 3 35.3

gallons (gal) liters (L) 3.78 L gal 0.264

gray (Gy) Rad 10 2 rad Gy 10 –2

roentgen equivalent man (rem) sievert (Sv) 10 –2 Sv rem 10 2

N OTE : Traditional units are used throughout th is document instead of the International System of Units (SI). Conversion to SI units will be aided by the unit conversions in this table.Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

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# Acknowledgments

This method development report was developed by the National Analytical Radiation Environmental Laboratory (NAREL) of the Environmental Protection Agency’s (EPA) Office of Radiation and Indoor Air (ORIA) in cooperation with the En vironmental Sciences Division of the National Exposure Research Center (ESD NERL ). Dr. John Griggs was the project lead for this document. Several individuals provided valuable support and i nput to this document throughout its development. Special acknowledgment and apprecia tion are extended to Dr. Brian Schumacher of ESD NERL. We also wish to acknowledge Ms. Marinea Mehrhoff (State Hygienic Laboratory at the Univ ersity of Iowa) and Dr. Michael Schultz and Mr. Andrew Nelson (University of Iowa), who conduc ted the method development studies . Numerous other individuals, both inside and outside of EPA, provided commen ts and criticisms of this method, and their suggestions contributed greatly to the quality, consistency, and usefulness of the final method. Technical support was provided by Environmental Management Support, Inc.Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

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# 1.0 Introduction
This report summarizes the development and testing of an improved method for the Determination of Gross Alpha and Gross Beta Ac tivity in Flowback and Produced Waters from Hydraulic Fracturing Operations (FPWHFO). Flow back and produced waters are characterized by high concentrations and complex mixtures of inorganic salts, organic compounds and other materials. They may commonly contain concentrat ions of naturally-occurri ng radionuclides from the uranium and thorium decay chains as high as 10 3 

### –10 4 

### times the level of activity routinely observed in environmental water samples. The co mplex nature and high concentration of matrix constituents in these water samples present sign ificant technical challenges especially for gross alpha and gross beta determinations in such samples.

It is critical when working with gross alpha and gross be ta measurements that one understand what the screening result s represent. These measurements are not nearly as simple as many people may believe. There is a relatively a short list of natura l chain radionuclides. Uranium and thorium chain radioactivity (i.e., 238 

### U and 232 

### Th, and progeny), and 40 

### K, usually account for >95% of the naturally occurring alpha and be ta activity. A relatively small amount of actinium (Ac) chain activity may also be present (le ss than 5% of total activ ity is associated with the Ac chain, i.e., 235 

### U and its decay progeny). Thus, five ra dioelements in the sample either directly comprise or indirect ly support the naturally occurr ing activity of the sample:

uranium 234 • 

### ( 238 

### U; 235 

### U; U);

232 230 228 23 • 

### thorium ( Th; Th; Th; 4 

### Th and its short-lived decay progeny 234m 

### Pa)

• 

### radium
228 

### Ra and its 228 o 

### short-lived decay progeny Ac;

226 222 o 

### Ra and its short-lived decay progeny Rn, 218 

### Po, 214 

### Pb, 214 

### Bi, 214 

### Po;

224 o 

### Ra and its short-lived decay progeny 220 

### Rn, 216 

### Po, 212 

### Pb, 212 

### Bi, 212 

### Po, 208 

### Tl;
lead • 

### ( 210 

### Pb and its short-lived decay progeny 210 

### Bi; and

• 

### polonium ( 210 

### Po).

Method 900.0 is the benchmark method for gro ss alpha and gross beta determinations. Method 900.0 involves evaporating the sample to a th in layer of solid residue in a stainless-steel planchet and analyzing alpha and beta partic les emitted from the source using gas-flow proportional counting. The benefit of this method is its rapidity and relatively low-cost in comparison to performing radionuclide specifi c testing. This met hod focuses heavily on identifying 226 

### Ra, with a secondary concern on natural uranium and thorium chain activity. This method will identify some non-volatile man- made radionuclides that are present as environmental contaminants.

Method 900.0 has several notab le limitations that imp act the reliability and intercomparability of gross alpha and beta m easurements, especially for naturally occurring radioactivity. The method under-responds to low-energy beta emitters such as 210 

### Pb and 228 

### Ra. Lax control of the timing of the count relative to preparation a nd collection of the sample may cause the method to dramatically over-respond, or to completely fail to detect radionuclides

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### present at the point of collec tion. For example, the gross alpha activity of samples containing
226 

### Ra will increase following the preparation with the count stabilizing at 400% of the actual
226 

### Ra activity 3–4 weeks after preparation. 1 

### In contrast, delaying the analysis of the sample for more than two weeks after collection will lead to a failure to detect 224 

### Ra or its decay progeny that were present at the time of collection. Finally, the method is not applicable for the determination of analytes that are volatile under the conditions of analysis. This would potentially impact 210 

### Po.

Finally, Method 900.0 is designed for low-solids samples such as drinking water. This is because alpha and beta particles are severely attenuated by matter they encounter as they travel to the detector (including “self-absorption” by th e solids in the sample te st source). The amount of solids in a sample limits the size of sample that can be processed and th ereby the sensitivity of the measurement. Method 900.0 restricts residue thickness for gross alpha measurements to a maximum of 5 mg/cm 2 

### . In a 50-mm diameter st ainless-steel planchet, th is is equivalent to 100 milligrams of solid residue. While this method is applicable to drinking water samples which generally have solids content unde r 500 mg/L, FPWHFO samples may have solids content in the hundreds of thousands of mg/L and sample sizes would be restricted to a small fraction of a milliliter. Since the sensitivity of the measurement is inversely proportional to the size of sample processed, the capability of the method to detect activity could be decreased by a factor of a onethousand and the ability of the evaporation a pproach to detect radi oactivity in FPWHFO becomes questionable at best.

One approach to addressing this limita tion would involve using a measurement technique that is not sensitive to the solids content of the sample being analyzed. Gamma spectrometry, for example, is capable of determ ining isotope specific gamma-ray emissions from samples of 3 - 5 kg or larger. Unfortunately, this technique is not as sens itive as techniques such gas-flow proportional counting (GPC) or liquid scintillation counting (LSC). Gamma spectrometry cannot detect pure alpha and beta em itters, of which there are several of concern for FPWHFO samples. Liquid scintillation spectr ometry is a technique that is capable of sensitive measurements of alpha and beta partic le emissions and can tolerate somewhat larger amounts of solids (up to about 1⁄2 gram in the sample test source) than can GPC.

A second approach can be taken to improve th e sensitivity of gross alpha and gross beta measurements. This involves developing chemical separation methods to remove non-radioactive constituents from the sample thereby allowing th e radioactive constituents to be concentrated into a source that can be measured using a met hod sensitive to alpha and beta particle emissions (e.g., gas-flow-proportional count ing or liquid scintillation spect rometry). Method 900.0 relies on evaporation to accomplish this. Water, which is not in itself radioactive, is removed from the sample by evaporation. For this reason, Met hod 900.0 is limited to determining non-volatile constituents in samples. 2

1 This is due to ingrowth of s hort-lived alpha-emitting decay progeny 222 Rn, 218 Po, and 214 Po. Similar effects are noted with betaemitting decay progeny of 226 Ra, 224 Ra, 238 U, and 210 Pb with time frames rangi ng from days to months.

2 This raises que stions about whether Po can be re liably determined using method 900.0.

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### As a result of these considerations, met hod development efforts in Phase 1 of this project focused on exploring:

• Detection methods that are less subject to self-absorption (e.g., gamma spectrometry or liquid scintillation), and if possible, less sens itive to differences in the energy of the decay particle;

• The viability of using chemical separation me thods that selectively isolate longer-lived radionuclides of concern from non-radioactive constituents that may be present in high enough concentrations to limit sample size (i.e., U, Th, Ra, Pb, and Po need to be separated from Ca, Sr, Ba, Mg, Na, K, Fe) ; and

• Preparation methods that are less subject to losses due to analyte volatility.

• Developing and validating a method that could rapidly achieve detection limits in the
range of those recognized for gross alpha and gross beta in drinking water.

Since each FPWHF sample matrix is different , it is important to initially characterize whether or not U/Th isotopes may be present prior to validating any method. This will ensure that necessary chemistry is addressed for each radionuclide.

Another important aspect of gross alpha a nd gross beta determinations needs to be considered. As mentioned above, the time elapse d between collection of the sample and the sample preparation, and the time between th e preparation of the sample and the count, significantly impact the final result. While it is not practicable to simulate this during the development process, the theoretica l impact of decay and ingrowth is well established and should be addressed in the scope and applicability a nd interferences statements when a laboratory adopts this method and validates it in their met hod format. Failure to de lineate these concerns may result in a failure of users to recognize that results may vary by a factor of two or more, and that delay in analysis may result in complete failure of the method to detect short-lived radionuclides such as 224 

### Ra, present in significant quantities at the time of sample collection.

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# 2.0 Characterization of the Sample Matrix
Per instruction by the Environmental Protection Agency (EPA), the method development and testing targeted a single FPW HFO sample from the Marcellus shale region of Pennsylvania. A 55-gallon drum of the water was received at the National Analytical and Radiation Environmental Laboratory (NAREL) in Montgomery, Alabama in late April, 2013. At the beginning of May 2013, it was then transferred to the Stat e Hygienic Laboratory at the University of Iowa for method de velopment and testing studies.

The sample was described by the Iowa laborat ory as a clear, light amber liquid, of high specific gravity (~1.25 g/cc) with less than ~0.5 % by volume (by visual in spection) of a light, suspended reddish-brown precipitate. The sample was not preserved prior to receipt at the laboratory. After the sample arrived at the laboratory, the drum was mixed to ensure homogeneity and two carboys of the water withdrawn. No sample filtering or preservation was performed.

Preliminary analytical work was performe d to characterize the major non-radiological (i.e., chemical) composition of the water. These analyses provided perspective on the matrix so that one could assess how best to configure a method as well as to help understand difficulties encountered while developing the method. The data we re also used to create a surrogate sample for the method development process whose composition was very similar to that of the sample. The chemical analyses of the field sample and the surrogate solutions are shown in Table 1.

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Table 1 – Non-Radiological Analysis of FPWHFO and Surrogate Sample



### Analyte Concentration (mg/L) Field Sample LOD [1] 

### (mg/L) Concentration in Surrogate (mg/L) LOD [1] 

### (mg/L) Method

Chloride (Cl

– ) 147,000±6,000 1 100,000 1 Chloride, EPA 300.0 Strontium (Sr) 36,000±2,000 200 34,000 0.10 Metals, EPA 200.7 Sodium (Na) 29,000±1,000 5,000 30,000 2.5 Metals, EPA 200.7 Calcium (Ca) 13,000±1,000 10, 000 12,000 5.0 Metals, EPA 200.7 Barium (Ba) 9,000±400 500 8,500 0.25 Metals, EPA 200.7

Magnesium (Mg) 850±40 120 850 2.5 Metals, EPA 200.7

Potassium (K) 160±10 2.5 160 5.0 Metals, EPA 200.7 Manganese (Mn) 3.4±0.2 1 — — Metals, EPA 200.7 Iron (Fe) 43±2 5 23 0.10 Metals, EPA 200.7 Lead (Pb) 1.0±0.1 0.5 — — Metals, EPA 200.7 Aluminum (Al) LOD 5 — — Metals, EPA 200.7

Fluoride (F

– ) LOD 0.1 — — Fluoride, SM 4500-F C 18 th

2– ) Sulfate (SO 4 LOD 40

— — Sulfate, EPA 300.0
Nitrate nitrogen as N (NO 3 - ) LOD 10 — — Anions, EPA 300.0

Nitrite nitrogen as N (NO 2 – ) LOD 5 — — Anions, EPA 300.0

Ortho-phosphate

as P (PO 4 3

− ) 8±1 0.02

— — ortho-Phosphate as P, LAC 10-115-01-1A

Alkalinity 10 1

— — Alkalinity as CaCO3, SM 2320 B 18 th

Bicarbonate alkalinity (HCO 3 – ) 10 1

— — Alkalinity as CaCO3, SM 2320 B 18 th

Carbonate
2– ) alkalinity (CO 3 LOD 1

— — Alkalinity as CaCO3, SM 2320 B 18th
Silicon (Si) 3.7±0.3 2.5 — — Silicon, EPA 200.7

Total Solids (TS) 278,000±6,000 1 — — Total Solids (Dried at 103°C), SM 2540 B 18 th

Total Suspended

Solids (TSS) 780 1

— — Total Suspended Solids (Dried at 103 °C) USGS 1-3765-85

Total Extractable

Hydrocarbons

(TEH)[2] 2.3±0.1 0.1

— — Total Extractable Hydrocarbons, Iowa OA-2

[1] LOD – Limit of Detection at 99% confidence determined per 40 CFR Pa rt 136, Appendix B Definition and Pr ocedure for the Determination of the Method Detection Limit (MDL).
[2] Chromatographic patterns do not conform to fuel standards for this range.

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### A radiological characterization of the wate r was also conducted dur ing the preliminary phase to determine the radionuclides present in the sample. Gamma spectrometric analysis of raw FPW showed high levels of activity for the 226 

### Ra sub-chain of 238 

### U with a 226 

### Ra concentration of 17,600 ± 1,400 pCi/L ( k =1). Significantly elevated activity of 228 

### Ra (1,950 ± 110 pCi/L) was also noted with no i ndication of significant levels of 224 

### Ra which may be present in freshly collected samples containing 228 

### Ra. This indicates that ac tivity concentrations of 228 

### Th were likely low and that the samp le had probably aged enough that 224 

### Ra and 212 

### Pb had decayed prior to receipt at the laboratory (longer th an one month). The activ ity concentrations of 238 

### U ( 234 

### Th, and 234m 

### Pa), and 235 

### U were not detectable using gamma spectrometry. 3 

### Thus, it is possible to make theoretical conclusions about the state of equilibrium at the time of sampling. Since the gross radioactivity of naturally-occurring deca y chains changes with time, control of time elapsed between sampling and preparation of the sample, and the prepara tion and analysis will be factors that will significantly impact gross alpha and gross beta measurements and which will need to be closely controlled.

Based on the elevated levels of radioactivity in the sample received, it became apparent that a method development reference material (M D R M) would need to be created that closely matched the composition of the FPWHFO but di d not contain significant concentrations of naturally occurring radionuclides. In previous met hod development studies of matrices such as air filters and soil, low concentrations of naturall y occurring radionuclides were present that could easily be accounted for when creating test sa mples of low activity. However with the high concentrations of the naturally occurring radionuc lides in this sample, an effective measure of uncertainty at low activities, or of a minimum detectable concentrati on (MDC), would not be possible.

Reproducing the predominant non-radioactive c onstituents in the sample, Cl, Ca, Ba, Sr, Mg, Na, K, and total solids in the test samples was critical both for the method development and testing process. Based on the non-radiological analysis of the sample, a “surrogate” method development reference material (M D RM) solution composition was formulated. It was evident from some of the first attempts at gros s radioactivity analysis that minimum detectable concentrations would be much highe r than that for drinking water.

The elevated concentrations of solids in the sample meant ordering very large quantities of the soluble salts needed to make the surroga te used to prepare development process blank, MDC and spiked samples.

The extremely high levels most particularly of Ca, Sr, and Ba, all Group II chemical analogues for Ra, placed into question the initia lly proposed analytical approach and required significant modification of the t echniques used. While the procurement of salts was in process, laboratory staff attempted several gross separati on and analysis processes (noted below) on the real sample to see how they would fare as preparation for the method development process.

3 Informal alpha spectrometry results ob tained from personnel working with NAREL staff in May 2013 indicated that no 238 U or
234 U was detected in the sample at the 0.1 pCi/L level.

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### Once created, the surrogate matrix was spiked with 226 

### Ra, 230 

### Th and 228 

### Ra based on the magnitude of blank analyses to create M D RMs at three levels for testing of the required method uncertainty and one M D RM for verifica tion of the required minimum detectable concentration. The radionuclides for spiking differed from the outline in the method development plan.

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# 3.0 Initial Radioanalytical Methods
A series of different approaches were e xplored for the gross alpha and gross beta analysis to identify an approach optimized to accommodate the matrix of the FPWHFO sample received from the EPA. While the testing matrix used was quite challenging, these results may or may not be applicable to matrices that differ from this sample matrix. Approaches explored ranged from tests of EPA Method 900.0 th rough attempts to explore different detection techniques, to approaches to separate/concentrate radioactive constituents of the sample. Several examples include:

• The Method 900.0 approach faile d to produce a usable test source with an extremely small 0.1 mL aliquant.

• Direct addition of the sample to liquid scinti llation cocktail resulted in precipitation of matrix components and failure to produce a useable test source.

• Gamma spectrometry analysis provided results for a number of the natural emitters in the sample. This approach to quantitation is not based on measuremen t of alpha emissions, but the results are radionuclide specific and can be used to calculate the total gross alpha activity associat ed with a radionuclide such as 226 

### Ra in a sample when it is in secular equilibrium 4 

### with its progeny (that are gamma emitters).

Attachment I provides additional details on th ese and other attempts to processing the FPWHFO sample, as well as testing if the relativ e robustness of several techniques for chemical separation of key radionuclides (Th, U, and Po).

The goal of developing a rapid, and economical ly viable approach for isolating and analyzing alpha emitting radionuclides (Ra, T h, U and Po) in a single test source and determining gross alpha activity using a single sensitive measurement of alpha emissions, however, has yet to be realized. This is due to the complex matrix composition, and the levels of Group II elements (Mg, Ca, Sr, and Ba) in the FPWHFO matrix. Group II constituents were present in overwhelming amounts (gram/liter con centrations) in this sample. The chemical behavior of these elements closely mimics that of radium, which foiled all attempts to achieve a group separation of Ra, Th, U, and Po.

As a result, the most viable approach for gross alpha analysis involved the use of two physical determinations of alpha activity. The first of these determinations involves a group separation of Th, U, and Po using a rapid so lid-phase extraction chromatographic separation technique 5 

### followed by liquid scintilla tion analysis of alpha emi ssions. This technique is described in greater detail below. The other contributor to gross alpha, 226 

### Ra (+progeny) is

4 If secular equilibrium is to be assumed steps need to be taken in a laboratory’s method th at indicates how this will be

controlled. If secular equilibrium cannot be assured then the measured values should be qualified noting that these activity concentrations maybe larger.

5 This involves the use of a commercial solid phase extraction resin such as EichromTM. This material has a very high selectivi ty

coefficient for U, Th and Po (and other high atomic number radionuclides) over first second and third row transition series elements.

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### determined by high purity germanium (HPGe) gamma spectrometric measurement of gamma emissions from the sample.

Since the gamma spectrometric determination of 226 

### Ra has very different levels of measurement uncertainty than does the liquid scintillation approach for thorium, uranium, and polonium, it was necessary to es tablish separate measurement quality objectives (MQOs) for required method uncertainty for each of the two an alyses. The results of the analyses may be used separately as the individual results are quite informative about radioactivity in the sample, or the two results and their respective uncertainti es mathematically combined to yield a single combined activity and standard uncertainty for gross alpha activity in the sample.

Attempts to perform gross beta in a method along the lines of Method 900.0 also proved fruitless as extremely elevated solids in the sample produced unacceptably high-levels of self-attenuation or resulted in sample aliquants that were far too small to provide meaningful detection levels. Preparation of a reproducible test source proved to be unsuccessful due to nonuniform drying and spattering of sample solids . While a chemical separation of naturally occurring beta emitting members and progeny of the uranium and thorium decay chains may theoretically be possible, there would still be concern about significant differences in decay energy of the beta emitters that could negatively impact quantitation. Using gamma emissions from the radionuclides, however, permits use of a non-destructive method that avoids lengthy separations, and minimizes time performing the sepa rations. The trade-off, however, is that the counting times for samples can be significan t (6 hours or more) depending upon the gamma detector efficiency.

While each gamma ray detected can be ascr ibed to a specific radionuclide and the activities of these radionuclides and their progeny are easily summed, an assessment of the total uncertainty can only account for the uncertainty of those beta-gamma emitters identified. It will not account for beta-gamma emitters present at low, sub-detectable levels. This is a more significant issue for low-activity samples where no gamma rays are detected. Based on the high activity of radium in this type of sample matr ix, this seems to be a more remote possibility.

Ju ly - 2014 10Ju ly - 2014 11 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 4.0 Method Development Process Summary

The method development (M D ) plan for gross alpha and gross beta an alysis of FPWHFO follows the guidance provided in Method Validation Guide for Q ualifying Methods Used by Radiological Laboratories Participati ng in Incident Response Activities [MVG] (EPA 2009), Validation and Peer Review of U.S. Environm ental Protection Agency Radiochemical Methods of Analysis (EPA 2006), and Chapter 6 of MARLAP (2004). This M D process was conducted under the generic Quality Assurance Project Plan Validat ion of Rapid Radi ochemical Methods for Radionuclides Listed in EPA’s Standardize d Analytical Methods (SAM) for Use During Homeland Security Events (EPA 2012). This method is considered a “first time approach.” Therefore, the method needed to be evaluated according to MARLAP me thod validation “Level D” or “Level E.”

The proposed method, for both gross alpha and gross beta, in the M D plan was validated against acceptance criteria for the re quired method uncertainty about a specified analytical action level (AAL) concentration and at the required MDC. After several modifications to the M D plan, a nd due to significant challenges related to the matrix of the sample, the technique used for gross beta analysis was changed from the traditional screening using beta particle emission counting (gas-flo w proportional counting or liquid scintillation counting) to an inferential gamma spectrometri c analysis method. Since the gamma spectrometry allows the determination of several beta-gamma emitters, the overall relative required method uncertainty for beta-gamma emitters was e xpanded to 50% to accommodate the increased uncertainties of the multiple measurements needed.

In addition to determination of the required method uncertainty and verification of the required minimum detectable concen tration, analytical results were evaluated for statistical bias, absolute bias for blank samples and relative bi as at each of the three test level radionuclide activities. The radiochemical yiel d of the method was also eval uated as a characteristic of method ruggedness.

The method development process was divi ded into four phases as follows:

1. Phase 1

a. Laboratory familiarization with the method concept.
b. Set-up of the laboratory and acquisition of reagents, stan dards and preparation of in-house performance test (PT) samples.

c. Perform preliminary tests of the methods on an actual sample.
d. Make changes to improve the method based on the preliminary tests.

2. Phase 2

a. Conduct method testing for required method uncertainty using internal PT samples.

3. Phase 3

a. Conduct verification of the required MDC using internal PT samples.Ju ly - 2014 12 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### 4. Phase 4

a. Report results.
b. Written report and narratives by laboratory describing the process/method.

c. Feedback comments on the method.
d. Method development report written by EMS and reviewed by laboratory.

The objective of Phase 1 was to have the laboratory become familiar with the draft method. While the laboratory obta ined hands-on experience, areas of the method that required optimization were identified. Based on the info rmation and experience gained during Phase 1 runs, the analysis method was optimized and modi fied prior to initiating the formal testing process in Phases 2 and 3.

The draft method was run (see Attachment I for description of Radionuclide: 226 

### Ra and Radionuclides: U, Th, and Po) with the field sa mple obtained from the EPA using the innate
226 

### Ra as a measure of the success of each purporte d separation step. The la boratory also prepared blank and spiked surrogate solutions (as desc ribed in the introduction above) to assess the feasibility of the draft method with elements re presenting the longer-lived U and Th decay chain radionuclides (i.e., 230 

### Th, natural uranium, 209 

### Po) since these radionuclide s and their short-lived progeny comprise the alpha radioac tivity of the sample. Sample test sources were prepared after the separation of the respective alpha emitters fo r alpha spectrometric analysis. The radionuclide specific testing also allowed asse ssment of the robustness of th e method to recover the added radionuclides from the matrix. Attachment 1 presents data on the recovery of these radionuclides/radioelements. Due to the challengi ng matrix, quantitative recovery was neither expected nor was it achieved, but the final met hod was effective and obtained recoveries that approached 80–90% for the targeted analytes. As a gross screening method, this is deemed to be acceptable.

The initial objective for detection levels was aimed at drinking water MPC concentrations. However, the difficulties encounter ed in this initial evaluation of the proposed methods with the matrix evoked a reevaluation of what could be the attain able action levels and detectability concentrations. The values that are found in Tables 2 and 3 were based on this reevaluation.

During Phases 2 and 3 of the M D process, th e laboratory analyzed in-house PT samples consisting of method development reference mate rials [M D RM] prepared from the surrogate solution (described in the introduction above) spiked with known amounts of 230 

### Th, 226 

### Ra and
228 

### Ra. The laboratory was instructed to spike the PT samples with concentrations consistent with test levels for the re quired method uncertainty and th e required MDC. The targeted test levels and applicable MQOs for Ph ases 2 and 3 are listed in Table 2.

Following completion of the method developkmentstudies, comments from the laboratories were evaluated per guidance in the MVG. The final method was finalized to conform to the documented “as-tested” conditions in Phases 2 and 3. The report was also ed ited to ensure clarity based on comments received from the laboratories. Thus, the test data presented in this report reflect the final method included in the attachments to this document.Ju ly - 2014 13 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 5.0 Participating Laboratories
The State Hygienic Laboratory and at the Radiology and Radiation Oncology Free Radical and Radiation Biology Pr ogram Laboratory, both at the Un iversity of Iowa, performed all of the analyses (radiologica l as well as non-radiological).



# 6.0 Measurement Quality Objectives
The gross alpha and gross beta analysis method was developed to meet MQOs established for the project. The MQOs selected include the radionuclide concentration range, the required method uncertainty at a specified radi onuclide concentration (i.e., AAL), and the required MDC. Since the EPA did not provide regulator y action levels, MQOs were defined in the method development plan based on the presumed sensitivity of the techniques to be used. Once the sample was received and initial testing prov ed how challenging nature of the matrix would be, new technical approaches were needed and MQOs were updated to maintain consistency with the capabilities of the techni ques being used. The AAL for 226 

### Ra by gamma spectrometry is higher than initially envisioned while that for gross alpha by liquid scin tillation is somewhat lower. Gross beta MQOs are based on gamma spectrometric analysis (see Attachment 1 descriptions for not using traditional gross beta analysis) with separate MQOs for 228 

### Ra (for gross beta analysis) and 226 

### Ra (contribution to gross alpha an d gross beta activity), based on the relative sensitivity for these radionuclides using gamma spectrometry. The targeted test levels and applicable MQOs for Phases 2 and 3 are listed in Table 2.

The required method uncertainty for gross alpha (liquid scinti llation count [LSC] contribution) assumes tolerable error rates of 10% (z 1- α 

### = z 1- β 

### = 1.282) for Type I and Type II errors. It is calculated for gross alpha using the following equation:

௣஼௜ ሺ ି஽௅ ሻ ሺ ଷ଴ିହ ሻ 

### ݑ ெோ 

### ܩ, ݏݏ݋ݎ ݄݌݈ܣ ܽ ஼ௌ௅ 

### , ௅ 

### ൌ ൫௭ భష ஺஺௅

ഀ ା௭ భషഁ ൯ 

### ൌ ሺ ଵ.ଶ଼ଶ ା ଵ.ଶ଼ଶ ሻ



### ൌ ଶହ

ଶ.ହ଺ସ 

### ൌ 9.8 pCi/L

Where AAL is the analytical action level a nd DL is the discrimination level for gross alpha analysis.

And the value for the relative required method uncertainty is:

φ MR 

### , Gross Alpha LSC 

### , = 100 × u MR 

### / (AAL) = (9.8 / 30) = 33%

The required method uncertainty for gross alph

as determined by the gamma spect ߮ ெோ 

### ݏݏ݋ݎܩ , ݄ܽ݌݈ܣ a (gamma spec

௚௔௠௠௔ ௦௣௘௖௧௥௢௠௘௧௥௬ 

### , ݑ trometry contribution) is:

rometry software algorithm. ெோ 

### ൌ 33%Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Ju ly - 2014 14 

### The potential contributors to the gross beta activity are 234 

### Th, 234m 

### Pa, 214 

### Pb, 214 

### Bi, 212 

### Pb,
212 

### Bi, 208 

### Tl, 228 

### Ra, 228 

### Ac, 210 

### Pb, and 210 

### Bi.

Several of these are linked in shorter decay ch ains so contributions to the gross beta at full ingrowth can be calculated by measuring one of the radionuclides and assuming secular equilibrium with the others in the respectiv e decay chain. These would be summarized as follows:

234 

### Th = 234m 

### Pa (full secular equilibrium within 10 minutes)

214 

### Pb = 214 

### Bi (full secular equilibrium within 3 hou rs, Rn-222 is in secular equilibrium with Ra-226)

212 

### Pb = 212 

### Bi = 208 

### Tl / 0.36 (full secular equilibrium 72 hours after separation)

228 

### Ra = 228 

### Ac (full secular equilibrium 36 hours)

210 

### Pb = 210 

### Bi (full secular equilibrium 15–25 days after collection)

Since only the non-bolded radionuclides are measured, the bolded radionuclides are determined inferentially. The activity and uncertainty of the measured values will be used as the values for the inferred radionuclides 234 

### Th/ 234m 

### Pa, 214 

### Pb/ 214 

### Bi, 212 

### Pb/ 212 

### Bi/ 208 

### Tl/, 228 

### Ra/ 228 

### Ac, and 210 

### Pb/ 210 

### Bi.

The gross beta activity of samples is ca lculated based on the gamma spectrometric measurement of beta-gamma emitting radionuclides from the uranium and thorium chains that are present in detectable levels in the sample. Th e concentration of beta emitters that are detected may be calculated by inference when their gamma-emitting parents or progeny where these are present at detectable levels. Ga mma emitting radionuclides are considered to be detectable when the relative combined standard uncertainty of the radionuclide is de termined by the gamma spectrometry software to be less than or equal to 50%. The overall beta un certainty is calculated as the quadratic sum of the uncer tainties of the detected radionuc lides contributi ng to the total gross beta activity. 6



### Ra-228, based on the gamma emission of its short-lived progeny 228 

### Ac, was chosen in lieu of other naturally occurring beta-gamma emi tters to determine action levels and MDC for gross beta analysis. This choi ce is based on three factors:

• The abundance of the 228 

### Ac gamma ray at 911 keV is 25.8%. The abundance of the 214 

### Bi at 609 keV peak is 45.9% and that of 212 

### Pb at 238 keV is 43.6%.

• The efficiency of the 911 keV peak is lower than the other two gamma ray peaks.

• 

### The abundance of 228 

### Ra in many geologic formations us ed for oil and gas production is much lower than that of Ra-226 or their respective progeny.

This provides assurance that if the 228 

### Ac action levels and MDC can be confirmed that those for the other principal naturally occurring beta-gamma chains can also be achieved.

6 The exception for this will be for 226 Ra with a u MR = 9.8 pCi/L and a φ MR = 33%.Ju ly - 2014 15 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### The targeted required method uncertainty for each of the beta-gamma emitters that will be measured by gamma spectrometry is 50% at the AAL of 60

Although the evaluation ߮ ெோ



### s for the oth development of the gamma spectrom ݋ݎܩ , ݏ

etry m ݏ ܽݐ݁ܤ pCi/L.

er beta/gam ௚௔௠௠௔ ௦௘௖௧௥௢



### ma e ௠௘௧



### mitters were not perfor

௥௬ 

### med pending

easuremen t, further work needs to be perfor , ൌ 50%

med with the 224 

### Ra and 226 

### Ra progeny fully ingrown to assess the achievable MDC and AALs. Table 2 also presents targeted values that will be evalua ted once a gamma spectrometry method for a broader list of analytes has been fully developed.

Table 2 – MQOs Targeted for Gross Alpha and Gross Beta in FPWHFO



### Measurement Matrix [1] 

### AAL Required MDC/MDA [2] 

### u MR [3] 

### φ MR [4]



### Gross Alpha pCi/L pCi/L pCi/L (%)

230 Th (liquid scintillation) FPWHFO 30 5 9.8 33%

226 Ra (based on the 186 keV gamma emission) FPWHFO 150 55 50 33%



### Gross Beta [4]

228 Ra ( 228 Ac) FPWHFO 60 30 30 50%
Beta-emitting progeny of 226 Ra ( 214 Pb/ 214 Bi) and other gamma emitters in sample [5] FPWHFO

-­ -­ -­ 50%

Beta-emitting progeny of 224 Ra [5] (inferred based on gamma emissions of 212 Pb) FPWHFO

-­ -­ -­ 50%

Th-234 [5] (and inferred 234m Pa) FPWHFO

-­ -­ -­ 50%

[1] A single sample of flowback and produced water supplied by EPA was used as the prototype for a surrogate matrix for method testing

. The method development reference material (M D

RM) consisted of ali quants of the surrogate matrix spiked with radionuclide solutio ns traceable to the National Institute of Standards and Technology (NIST).
[2] The MDC represents the value for the i ndividual measurement. A combined MDC for gr oss alpha or beta will no t be determined due to significant differences in the sensitivity of the respective measurement techniques.
[3] Required method uncertainty at and below the A AL.
[4] Relative required method uncertainty above the AAL.
[5] Preliminary development of the method fo r gross beta is based on measurement of 228 Ac (gamma emitting decay progeny of 228 Ra). Final testing will be conducted pending further refinemen t of the gamma spectrometry measurement technique.


### A synopsis of the final method testing results for all three test levels and the MDC is found in Table 3. The 230 

### Th values represent the results by chemical separation and liquid scintillation counting. The results for 226 

### Ra and 228 

### Ra are from direct sample analysis by gamma ray spectrometry.Ju ly - 2014 16 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 3 – Method Development As -Spiked Concentrations, MQOs and Mean Measured Results



### Concentration

Relative to Action Level Isotope Targeted PT Activity (pCi/L) Known Value [1] 

### ±

CSU [2] 

### (pCi/L) Measured Mean ±

SD [3] 

### (pCi/L) Required Method Uncertainty [4]



### u MR 

### (pCi/L) Required Relative Method Uncertainty
φ MR 

### Measured Relative Standard Deviation ( k =1)

MDC 230 Th 15 12.45±0.79 10.2 ±1.9 5 n/a 19 %

MDC 226 Ra 60 55.2±1.5 85±28 55 n/a 33 %

MDC 228 Ra 30 30.4±0.2 39±12 30 n/a 31 %

1⁄2 × AAL 230 Th 20 22.5 ± 1.2 14.9 ± 2.2 12 pCi/L n/a 15%

1⁄2 × AAL 226 Ra 90 75.0 ± 2.0 94 ± 32 54 pCi/L n/a 34%

1⁄2 × AAL 228 Ra 30 41.4 ± 0.65 43.2 ± 9.8 22 pCi/L n/a 23%

AAL 230 Th 40 37.5 ± 2.1 31.4 ± 4.2 12 pCi/L n/a 13%

AAL 226 Ra 180 164.9 ± 4.5 138 ± 18 54 pCi/L n/a 13%

AAL 228 Ra 60 62.47 ± 0.99 74 ± 12 31 pCi/L n/a 16%

3 × AAL 230 Th 120 104.9 ± 6.3 73 ± 12 n/a 33% 16%

3 × AAL 226 Ra 540 449 ± 12 431 ± 52 n/a 33% 12%

3 × AAL 228 Ra 90 180.1 ± 2.8 199.3 ± 6.8 n/a 50% 3.4%

[1] The known values were calculated by diluti on of the tracers added to the surrogate matrix.
[2] CSU – combined standard uncertainty (k=1).
[3] SD – Standard deviation of the observed measurements
[4] u MR = φ MR × as-spiked concentration of the test sample at the AAL



### All of the measurement quality objectives in the method development plan were achieved. The details of the measurement synopses in Table 3 are found in Section 9.Ju ly - 2014 17 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 7.0 Method Development Plan
The methods for gross alpha and gross beta ac tivity were evaluated for four important performance characteristics for radi oanalytical methods specified in Quality Assurance Project Plan Validation of Rapid Radiochemical Me thods for Radionuclides Listed in EPA’s Standardized Analytical Met hods (SAM) for Use During Homeland Security Events (EPA 2012). These include method uncertainty, detection cap ability, bias, and anal yte activity range. A summary of the manner in which these performan ce characteristics were evaluated is presented below. Chemical yield of the method, an importa nt characteristic for method ruggedness, is not specifically evaluated on an ongoing basis as th is method is not radionuclide specific. Tracers were used in method development to assess recovery, however, to provide information on method ruggedness. See Attachment I for further discussion.

Three counting methods were evaluated dur ing the method development to determine the counting method to be used for method testing. Gas proportional counting was eliminated as a method of gross alpha or beta analysis b ecause the high concentrat ion of dissolved solids prevented the achievement of activity concentration detection limits that were reasonable due to self-attenuation and due to challe nges encountered in preparing th e test source. The final method utilizes liquid scintillatio n counting and high purity germ anium gamma spectrometry. The proposed testing combinati ons are shown in Table 4.

Table 4 – Proposed Sample Processing and Counting Combinations



### Method Processing Method Gamma Spectrometry Liquid Scintillation Counting Gas Proportional Counting [1]

Gross Alpha Chemical Separation X X

Gross Beta Non-destructive Count X

[1] Eliminated from final testing.



## 7.1 Method Uncertainty The method uncertainty for gross alpha and gr oss beta activity was initially estimated based on the gamma analysis of the untreated fi eld sample and spiked demineralized water and surrogate M D RM sample spikes. Based on those trials, sample target concentrations were derived and finalized as noted in Table 5.Ju ly - 2014 18 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 5 – Actual Sample Concentrations Used for M D Process



### Sample Type Minimum Number Analyzed Spike Concentration Gross Alpha by LSC (as fraction of the AAL) AAL = 37.5 pCi/L 226 

### Ra by Gamma Spectrometry (as fraction of the AAL) AAL = 164.9 pCi/L 228 

### Ra by Gamma Spectrometry (as fraction of the AAL) AAL = 62.47 pCi/L

Demineralized Water Blanks 7 Blank 0 0 0

Surrogate M D RM Blanks 7 Blank 0 0 0

Surrogate M D RM Spikes 10 M DC 0. 33 0.33 0.49

Surrogate M D RM Spike s 7 1⁄2 × AAL 0.60 0.45 0.65

Surrogate M D R M Spikes 7 AAL 1. 0 1.0 1.0

Surrogate M D RM Spikes 7 3 × AAL 2.8 2.7 2.9



### Internal M D RM proficiency te st samples were prepared:

• The performance of gross alpha as evalua ted using two difference radioelements as follows:

o Thorium, uranium, and polonium: the perfor mance of the chemical separation / LSC approach was evaluated based on recovery of 230 

### Th added to the M D RMs since characterization of the method in Phase 1 de monstrated that Th, U, and Po behave similarly using this method.

o 226 

### Ra: The alpha activity as determined by ga mma spectrometry was used to validate the method based on recovery of 226 

### Ra. This M D RM contained the alpha-emitting radionuclide 226 

### Ra.

• Gross beta as determined by gamma spectrometry reflects the activity of beta-emitting decay progeny of 226 

### Ra and 228 

### Ra and the progeny of the 228 

### Ra.

The respective concentrations for the test samples are noted in Table 5. The method was evaluated against the required method uncer tainty values identified in Table 2.Ju ly - 2014 19 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



## 7.2 Detection Capability The detection capability for gross alpha by LSC (Th/U/Po) was estimated at 10 pCi/L. For 226 

### Ra by gamma spectrometry, it was estimated at 60 pCi/L, and for gross beta based on
228 

### Ra 7 

### for all significant beta emitters was estim ated at 30 pCi/L. In accordance with the guidance provided in the MVG, the critical net concentration (CL NC 

### ) of the method was to be estimated based on the results of at least seven blank samples. Results from ten replicate samples having an “as tested” concentra tion at the required MDC being tested were compared to the critical net concentration to de termine method detection capability. It should be noted that the verification of the required MDC for gross beta failed to meet criteria when tested at the 15 pCi/L level. The test was repeated using test samp les spiked at twice the initial activity indicating that the method is capable of meeting a required minimum detectable concentration value at the 30 pCi/L level.



## 7.3 Method Bias Two types of method bias were ev aluated, absolute and relative.

Absolute Bias Absolute bias was determined as a method performance parameter. The results from the seven blank samples for the required MDC evalua tion were evaluated for absolute bias according to the protocol and equation presented in the Method Validation Guide for Qualifying Methods Used by Radiological Laboratories Partic ipating in Incident Response Activities (EPA 2009). Absolute bias was to be determined as a me thod performance parameter; however, there was no acceptance limit for bias established for the method in this method development process.

The following protocol was used to test the gross alpha wa ter method for absolute bias:

1. Calculate the mean ( 

### X ) 

### and estimated standard deviation ( s X ) 

### for “N” (at least seven) blank sample net results (in the case of gamma spect rometry measurements 13 were used as the demineralized water blank and the blank surroga te were indistinguishab le from each other)

2. Use the equation below to calculate the |T| value:
X T = 

### (1)

s X 

### / N 

### 3. An absolute bias in the meas urement process is indicated if:


## T > t 1 − α / 2 

## ( N − 1) (2)

where:


### T represents the absolute value of the statisti cal t-value determined from analysis of the samples analyzed, and

The analysis for 228 Ra was performed using the gamma ray emissions of its first progeny, 228 Ac, which emits a gamma ray at 911 keV. See discussion at the end of Section 6.1. 7Ju ly - 2014 20 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### t 1 −α /2 

### (N–1) represents the (1 – α /2)-quantile of the t-distribution with N–1 degrees of freedom.

For seven blanks (or in the case of gamma spec 13 blanks), an absolute bias is identified at a significance level of 0.05, when |T| > 

### t 1

− α / 2 

### .

Relative Bias The results from the replicate samples for each of the three test levels and at the MDC level were evaluated for relative bias according to the protocol and equation presented in the Method Validation Guide for Qualifying Met hods Used by Radioanalytical Laboratories Participating in Incide nt Response Activities (EPA 2009). No acceptable relative bias limit was specified for this M D process.

The following protocol was us ed to test the gross alpha method for relative bias:

1. Calculate the mean ( 

### X ) and estimated standard deviation ( s X 

### ) of the replicate results for each method test level.

2. Use the equation below to calculate the |T| value:



### X − K T = (3)



### s 2

X 

### / N + u 2 

### ( K )
where:

| T

| is the average measured value

s x 

### is the experimental standard de viation of the measured values N is the number of replicates
K is the reference value u(K) is the standard uncertainty of the reference value

A relative bias in the measurement process is indicated if:



### T > t

1

− α / 2 ( ν eff ) 

### (3a)

The number of effective degrees of freedom fo r the t-statistic is calculated as follows:



###  u 2 

### ( K )  2



### ν

eff 

### = ( N − 1)  1 +   2 

###  (4) 

###  s X 

### / N 

Where ν eff 

### as calculated by the equation ge nerally is not an integer so ν eff 

### should be truncated (rounded down) to an integer. The n, given the significance level, 0.05, the critical value for |T| is defined to be t 1 −α /2( ν eff) 

### , the (1 – α /2)-quantile of the t-distribution with ν eff 

### degrees of freedom (see MARLAP Appendix G, Table G.2).Ju ly - 2014 21 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



## 7.4 Analyte Concentration Range The gross alpha method was evaluated for the required method uncertain ty at three test level activities. The seven replicate PT samp les from each test level concentration were analyzed. The three “targeted” and “known” test level activities are presented in Table 3. Note that the final test concentration values for the PT samples varied from the proposed test levels but that these values were within the sample preparation specifications provided to the laboratory.

The gross beta method was evaluated for re quired method uncertainty using the gamma spectrometry software criterion of ≤ 50% and the combined standard uncertainty as calculated by the gamma spectrometry software.



## 7.5 Method Specificity The purpose of this method is to perform a gross activity measurement. The specificity relates only to gross alpha or gross beta analysis. The separa tion steps employed were intended to isolate groups of radionuclides that were either alpha or beta emitters. In the development of the final method, certain tracers we re used to follow the separati on of the surrogate radionuclides used for the analysis.



## 7.6 Method Ruggedness Method ruggedness was evaluated primarily in Phase 1 of the M D process for the effects that the extreme combination of chemical compounds and high dissolved solids content would have on the method. In this phase, the method was modified to use a general chemical separation process for isotopes of uranium, thorium and polonium , and gamma spectrometry was selected for analysis of beta emitting radionuclides and 226 

### Ra. The ruggedness of the method was testing during Phase 1 using the EPA provided sample and with different radionuclides spiked into the surrogate matrix. See Attachment 1 for details on this testing.Ju ly - 2014 22 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFODevelopment of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 8.0 Techniques Used to Evaluate the Measurement Quality Objectives for Methods Development Project
A general description of the specifications a nd techniques used to evaluate the required method uncertainty, required MDC and bias wa s presented in Section 6. The detailed method evaluation process for each MQO and bi as is presented in this section.



## 8.1 Required Method Uncertainty The gross alpha and gross beta activity method was evaluated following the guidance presented for “Level E Method Validation: Adapted, Newly Developed Methods, Including Rapid Methods” in Method Validation Guide for Qualifyi ng Methods Used by Radiological Laboratories Participating in Incident Response Activities (EPA 2009) and Chapter 6 of MultiAgency Radiological Laboratory Analytical Protocols Manual (MARLAP 2004).

MARLAP “Level E” method validation re quires the laboratory to conduct a method development study wherein seven (or more) replicate samples from each of the three concentration levels are analyzed according to the method. The concentration test levels analyzed are listed in Table 3. For validation “Level E,” internally prep ared PT samples consisting of NIST-traceable
230 

### Th, 228 

### Ra and 226 

### Ra spiked into the surrogate matrix to create a method development reference material (M D RM). In order to determine if the proposed method met the project MQO requirements for the required method uncertainty, each PT sample result was compared with the method uncertainty acceptance crit eria listed in Tables 6A, 6B , and 6C. “Level E” validation stipulates that for each test sample analy zed, the measured value must be within ±3.0 u MR 8 

### for test level activities at or less than the AAL, or ±3.0 φ MR 9 

### for test level activ ities above the AAL.



## 8.2 Required Minimum Detectable Concentration The analytical results reported for the PT samples having a gross alpha and gross beta activity at the tested MDCs (Th/ U/Po by LSC alpha at 12 pCi/L; 226 

### Ra alpha by gamma spectrometry at 55 pCi/L; 228 

### Ra beta at 30 pCi/L) were evalua ted according to Sections 5.5.1 and 5.5.2 of Testing for the Required MDC in Method Validation Guide for Qualifying Methods Used by Radiological Laboratories Partic ipating in Incident Response Activities (EPA 2009). For this method development process, the terms “M DC” and “Critical Net Concentration” are used. The State Hygienic Laboratory at the University of Iowa analyzed the prepared PT samples in accordance with the final proposed method.

Critical Net Concentration

In order to evaluate whether the comb ined method can meet the required MDC (Th/U/Po by LSC alpha at 12 pCi/L; 226 

### Ra alpha by gamma spectrometry at 55 pCi/L; 228 

### Ra beta at 30 pCi/L), the critical net con centration, as determined from the results of analytical blanks, must be calculated. The critical net concentration (CL NC 

### ) with a Type I error probability of α =

8 u MR is the required method uncertainty

9 φ MR is the required relative method uncertainty

Ju ly - 2014 23Ju ly - 2014 24 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### 0.05, was calculated using the following equati on (consistent with MARLAP, Chapter 20, Equation 20.35):

CL ( pCi ) = t ( n

− 1) × S (7) NC 1

− α Blanks



### Where: S Blanks 

### is the standard deviation of the n bl ank-sample net results (corrected for instrument background) in radionuclide concentration units of pCi/L, and

t 1 −α (n-1) 

### is the (1 – α )-quantile of the t-distribution with n–1 degrees of freedom (see MARLAP Table G.2 in Appendix G). For this method development study, a Type I error rate of 0.05 was chosen. For example, for seven (minimum) blank results (six degrees of freedom) and a Type I error probability of 0.05, the previ ous equation reduces to:



## CL ( pCi ) = 1.94 × S (8) NC Blanks



### The use of the above equations assumes th at the method being evaluated has no bias.

Required MDC Each of the analytical resu lts reported for the PT sample s having concentration at the required MDC (Th/U/Po by LSC alpha at 12 pCi/L; 226 

### Ra alpha by gamma spectrometry at 55 pCi/L; 228 

### Ra beta at 30 pCi/L) were compared to the estimated critical net concentration for the method. The following protocol was used to veri fy a method’s capability to meet the required method MDC for a radionuclide-matrix combination:

I. Analyze a minimum of seven matrix blank samples for the radionuclide.

II. From the blank sample net results, calcul ate the estimated Critic al Net Concentration, CL NC 

### .

III. Analyze ten replicate samples spiked at the required MDC.

IV. From the results of the ten replicate samples spiked at the required MDC, determine the number (Y) of sample results at or below the estimated CL NC


### .

V. If Y ≤ 2, the method evaluated at the required MDC passes the test for the required MDC specification.

VI. If Y > 2, the method evaluated at the requi red MDC fails the test for the required MDC specification.Ju ly - 2014 25 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 9.0 Evaluation of Experimental Results
Only the experimental results for Phases 2 and 3 of the M D process are reported and evaluated in this study. Information presented in this section will include results for Sections 6 and 7. The gross alpha and gross beta activity concentration results were evaluated for the required method uncertainty, required MDC, and bias.



## 9.1 Summary of the Method The full method for the analysis is located in Attachment III. A brief description of each part of the method is described here.

Th, U, Po Gross Alpha by LSC A 300 mL sample is treated with permanganate in ammonaical solu tion to coprecipitate all radionuclides in the naturally occurring series . The mixture is settled and the supernatant solution discarded. The residue is dissolved in hydrochloric acid and passed through a TRU ResinTM column. 10 

### Thorium, uranium and polonium are elut ed from the resins using ammonium oxalate. The eluent is transferred to a liquid scintillation vial as th e final sample test source and counted in the alpha emission regi on of the liquid scintillation sp ectrum. The final sample test source is counted for 30 minutes.

226 

### Ra Alpha by Gamma Spectrometry A sample test source of 3 L is counted directly by gamma ray spectrometry. The activity concentration of 226 

### Ra is determined by gamma ray analysis using the 186 keV gamma ray region (assumes no significant amount of 235 

### U compared to the amount of 226 

### Ra in the sample). The sample is counted for 12 hours or long enough to achieve the required method uncertainty.

228 

### Ra Beta by Gamma Spectrometry The sample test source of 3 L is counted directly by gamma ray spectrometry. In addition to 228 

### Ra being determined indirectly by analysis of its first progeny 228 

### Ac (911 or 338 keV) several other radionuclides are determined directly by their gamma ray emission and others may be determined indirectly through analysis of a parent or progeny radionuclide that is a gamma ray emitter. The sample is counted for 12 hours or long enough to achieve the required method uncertainty.



## 9.2 Required Method Uncertainty Tables 6A through 6C show the measured results for each of the samples analyzed and the testing requirements for each level. The “known” values and combined standard uncertainty of the known values (“CSU known”) are based on the amount of NIST-traceable standards added to the samples. The allowable range of results is calculated by taking the known

10 Eichrom Technologies, LLC, Lisle, IL.Ju ly - 2014 26 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### value and adding (to get the upper value of the ra nge) and subtracting (to get the lower value of the range)

three times the required me thod uncertainty (3.0 × u MR 

### ). For example, in Table 6A, the allowable range for gross alpha for Test Level 2 is 37.5 ± (3.0 × 12) pCi/L or 1.5 to 74 pCi/L (rounded to two signifi cant figures).Ju ly - 2014 27 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 6A – Th, U. Po Gross Alpha by LSC—Analytical Results for Required Method Uncertainty Evaluation

Nuclide : Gross Alpha (Th-230) Matrix : FWHFPO AAL Tested : 37.5 pCi/L
Proposed Method : U, Th, Po Gross Alpha by LSC Required Method Validation Level : MARLAP “E” Required Method Uncertainty, u MR : 12 pCi/L at and be low AAL; 33% above AAL Acceptance Criteria : Test Levels 1 and 2: 3.0 × u MR = known value of sample in test level ± 36 pCi/L

Test Level 3: 3.0 × φ MR = quoted known value of sample ± 99% of known value of sample (pCi/L)

Test Level 1 Test Value = 22.5 ± 1.2 pCi/L

Sample # pCi/L Known CSU *
Known pCi/L Measured CSU** Measured Allowable Range (pCi/L) Acceptable Y/N

1

22.5 1.2 13.68 0.96

-14 to 59 Y 2 18.1 1.1 Y 3 14.93 0.99 Y 4 11.74 0.92 Y
5 15.7 1.0 Y 6 13.45 0.96 Y
7 16.9 1.0 Y
Test Level 2 Test Value = 37.5 ± 2.1 pCi/L

Sample # pCi/L Known CSU *
Known pCi/L Measured CSU** Measured Allowable Range (pCi/L) Acceptable Y/N

1

37.5 2.1 31.0 1.3

1.5 to 74 Y 2 38.8 1.5 Y 3 32.8 1.3 Y 4 32.0 1.3 Y 5 24.8 1.2 Y 6 33.0 1.4 Y 7 27.2 1.2 Y 8 31.5 1.3 Y
Test Level 3 Test Value = 104.9 ± 6.3 pCi/L

Sample # pCi/L Known CSU *
Known pCi/L Measured CSU** Measured Allowable Range (pCi/L) Acceptable Y/N

1

104.9 6.3 72.6 2.0

1.0 to 210 Y
2 60.7 1.8 Y 3 67.5 1.9 Y 4 60.2 1.8 Y 5 76.5 2.1 Y 6 86.5 2.2 Y 7 89.3 2.3 Y

* Quoted uncertainty (one sigma)
** Combined standard uncertainty, k = 1Ju ly - 2014 28 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 6B – 226 Ra Alpha by Gamma Spectrometry - Analytical Resu lts for Required Method Uncertainty Evaluation

Nuclide: Gross Alpha ( 226 Ra) Matrix : FWHFPO AAL Tested : 164.9 pCi/L
Proposed Method : 226 Ra Alpha by Gamma Spectrometry
Required Method Validation Level : MARLAP “E”
Required Method Uncertainty, u MR : 54 pCi/L at and below AAL; 33% above AAL Acceptance Criteria : Test Levels 1 and 2: 3.0 × u MR = known value of sample in test level ± 162 (pCi/L)

Test Level 3: 3.0 × φ MR = quoted known value of sample ± 99% of known value (pCi/L)

Test Level 1 Test Value = 75.0 ± 2.0 pCi /L

Sample # pCi/L Known CSU *
Known pCi/L Measured CSU** Measured Allowable Range (pCi/L) Acceptable Y/N

1

75.0 2.0 58.55 18.1

-87 to 240 Y 2 93.7 41.8 Y 3 107.3 36.45 Y 4 101 41.8 Y
5 153 42.8 Y 6 62.5 19.5 Y
7 84.1 33.2 Y
Test Level 2 Test Value = 164.9 ± 4.5 pCi/L

Sample # pCi/L Known CSU *
Known pCi/L Measured CSU** Measured Allowable Range (pCi/L) Acceptable Y/N

1

164.9 4.5 125.8 22

2.9 to 330 Y 2 140 21.6 Y 3 144 22.2 Y 4 110 22.6 Y 5 167 43.6 Y 6 131 22.9 Y 7 150 22.7 Y 8 125.8 22 Y
Test Level 2 Test Value = 37.5 ± 2.1 pCi/L

Sample # pCi/L Known CSU *
Known pCi/L Measured CSU** Measured Allowable Range (pCi/L) Acceptable Y/N

1

37.5 2.1 31.0 1.3

1.5 to 74 Y 2 38.8 1.5 Y 3 32.8 1.3 Y 4 32.0 1.3 Y 5 24.8 1.2 Y 6 33.0 1.4 Y 7 27.2 1.2 Y 8 364 32.2 Y

* Quoted uncertainty (one sigma)
** Combined standard uncertainty, k=1.Ju ly - 2014 29 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 6C – 228 Ra Beta by Gamma Spectrometry—Analytical Results for Required Method Uncertainty Evaluation

Nuclide: Gross Beta ( 228 Ra) Matrix : FWHFPO AAL Tested : 62.47 pCi/L
Proposed Method : 228 Ra Beta by Gamma Spectrometry
Required Method Validation Level : MARLAP “E”
Required Method Uncertainty, u MR : 31 pCi/L at and below AAL; 50% above AAL
Acceptance Criteria : Test Levels 1 and 2: 3.0 × u MR = known value of sample in test level ± 93 pCi/L

Test Level 3: 3.0 × φ MR = quoted known value of sample ± 150% of known value (pCi/L)

Test Level 1 Test Value = 41.4 ± 0.65 pCi/L

Sample # pCi/L Known CSU *
Known pCi/L Measured CSU** Measured Allowable Range pCi/L Acceptable Y/N

1

41.40 0.65 44.9 6.03

-52 to 130 Y
2 50.2 7.13 Y
3 54 6.46 Y
4 39.2 4.61 Y
5 52.2 5.08 Y
6 30.6 5.07 Y
7 31.1 5.5 Y
Test Level 2 Test Value = 62.47± 0.99 pCi/L

Sample # pCi/L Known CSU * pCi/L Measured CSU** Allowable Range pCi/L Acceptable Y/N

1

62.47 0.99 77.2 6.67

-31 to 160 Y
2 80.2 8.44 Y
3 53.2 6.13 Y
4 82.4 10.5 Y
5 85.3 10.5 Y
6 62.3 6.52 Y
7 76.7 9.17 Y
8 77.2 6.67 Y
Test Level 2 Test Value = 37.5 ± 2.1 pCi/L

Sample # pCi/L Known CSU *
Known pCi/L Measured CSU** Measured Allowable Range (pCi/L) Acceptable Y/N

1

37.5 2.1 31.0 1.3

1.5 to 74 Y
2 38.8 1.5 Y
3 32.8 1.3 Y
4 32.0 1.3 Y
5 24.8 1.2 Y
6 33.0 1.4 Y
7 27.2 1.2 Y

* Quoted uncertainty (one sigma)
** Combined standard uncertainty, k=1.Ju ly - 2014 30 

### Based on the results in Tables 6A to 6C it may be concluded that:

• A required method uncertainty of 12 pCi/L can be achieved at an action level of 38 pCi/L for gross alpha analysis using LSC

• A required method uncertainty of 54 pCi/L can be achieved at an action level of 165 pCi/L for 226 

### Ra analysis using gamma spectrometry

• A required method uncertainty of 31 pCi/L can be achieved at an action level of 62 pCi/L for 228 

### Ra analysis using gamma spectrometry. Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### These results meet the measurement quality objectives from the method development plan.

Tables 7A to 7C provide summary informati on regarding the expected variability of the results for an individual analysis and test level. In each case, the experime ntal standard deviation was considerably less than the required method un certainty indicated that the method is capable of meeting the method uncertainty MQO.

Table 7A – Th, U, Po Gross Alpha by LSC—Experimental Standard Deviation of the Seven PT Samples by Test Level ( 230

Th)



### Test Level Mean Concentration Measured (pCi/L) Experimental Standard Deviation [1]



### (pCi/L) Required Method Uncertainty (pCi/L)

1 14.9 2.2 12 2 (AAL) 31.4 4.2 12
3 73 12 35 [2]

[1] Standard deviation of the seven measurements.

[2] Calculated by multiplying the known value of Te st Level 3 by the required relative method uncertainty

.

Table 7B – 226 Ra Alpha by Gamma Spectrometry—Experimental Standard Deviation of the Seven PT Samples by Test Level



### Test Level Mean Concentration Measured (pCi/L) Experimental Standard Deviation [1]



### (pCi/L) Required Method Uncertainty (pCi/L)

1 94 32 54 2 (AAL) 138 18 54
3 431 52 150 [2]

[1] Standard deviation of the seven measurements.
[2] Calculated by multiplying the known value of Te st Level 3 by the required relative method uncertainty.Ju ly - 2014 31 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 7C – 228 Ra Beta by Gamma Spectrometry—Experimental Standard Deviation of the Seven PT Samples by Test Level



### Test Level Mean Concentration Measured (pCi/L) Experimental Standard Deviation [1]



### (pCi/L) Required Method Uncertainty (pCi/L)

1 43.2 9.8 31 2 (AAL) 74 12 31
3 199.3 6.8 90 [2]

[1] Standard deviation of the seven measurements.
[2] Calculated by multiplying the known value of Te st Level 3 by the required relative method uncertainty.



## 9.3 Required Minimum Detectable Concentration

Critical Net Concentration The method for Th, U, Po gross alpha by LS C in an FWHFO matrix was evaluated for a required MDC using surrogate wate r blanks that were taken thr ough the analytical processes of gross alpha chemical separation and LSC. Ra-2 26 and Ra-228 were evaluated for the MDC by direct analysis of the MDC veri fication samples by gamma counting.

Demineralized water blanks for the gro ss alpha determination by LSC yielded an expected blank value of zero since the average of these blanks was used to determine the background subtraction value, while surrogate sa mples yielded values greater than zero. The elevated result for surrogates is likely due to th e contribution of low levels of naturally occurring radionuclides in the reagents used to make the surrogate. Thus, th e surrogate water blanks were used to determine a matrix appropriate critical net concentration for the verification of the MDC. The results of the demineralized water and surrog ate blanks for gross alpha are shown in Tables 8A and 8B.

Table 8A – Th, U, Po Gross Alpha by LSC—Blank Water Samples


### Sample ID Concentration (pCi/L) CSU* (pCi/L)

DI Water Blank 1 0.07 0.69

DI Water Blank 2 -0.12 0.68

DI Water Blank 3 0.54 0.71

DI Water Blank 4 -0.12 0.68

DI Water Blank 5 -0.59 0.66

DI Water Blank 6 0.07 0.69

DI Water Blank 7 0.15 0.69 Mean** (pCi/Liter) 0.00 Standard Deviation ** (pCi/Liter) 0.34 Critical Net Concentration (pCi/Liter) 0.66

* Combined standard uncertainty, k=1 or coverage factor of 1.

** Mean and standard deviation were calculated before rounding.Ju ly - 2014 32 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 8B – Th, U, Po Gross Alpha by LSC—Surrogate Water Samples


### Sample ID Concentration (pCi/L) CSU* (pCi/L) Surrogate Blank 1 8.86 0.85 Surrogate Blank 2 6.95 0.85 Surrogate Blank 3 7.92 0.83 Surrogate Blank 4 6.53 0.79 Surrogate Blank 5 7.81 0.82 Surrogate Blank 6 7.03 0.80 Surrogate Blank 7 7.03 0.80 Mean** (pCi/Liter) 7.45 Standard Deviation ** (pCi/Liter) 0.79 Critical Net Concentration (pCi/Liter) 1.5

* Combined standard uncertainty, k=1 or coverage factor of 1.

** Mean and standard deviation were calculated before rounding.



### The results for the demineralized water bl anks and surrogate blanks measured by gamma ray spectrometry were indi stinguishable from each other (i .e., statistically the same). Therefore these data were pooled and used to calc ulate the critical level ne t concentration for the
226 

### Ra and 228 

### Ra measurements. The pooled results are shown in tables 8C and 8D.

Table 8C – 226 Ra Alpha by Gamma Spectrometry in Demi neralized and Surrogate Water Samples



### Sample ID Concentration (pCi/L) CSU* (pCi/L)

Surrogate 1 -12.6 17.3 Surrogate 2 -17.9 18.3 Surrogate 4 -15.78 34 Surrogate 5 -8.99 19.5 Surrogate 6 14.3 24.5 Surrogate 7 -12.1 17.4 Surrogate 8 -6.73 22.9

DM Water Blank 1 53.5 26

DM Water Blank 2 -6.4 17.8

DM Water Blank 3 -1.94 28.6

DM Water Blank 5 -45 30.7

DM Water Blank 6 -18.3 24.8

DM Water Blank 7 -9.94 21.3 Mean** (pCi/Liter) -7 — Standard Deviation ** (pCi/Liter) 22 — Critical Net Concentration (pCi/Liter) 40 —

* Combined standard uncertainty, k=1 or coverage factor of 1.

** Mean and standard deviation were calculated before rounding.Ju ly - 2014 33 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 8D – 228 Ra Gross Beta by Gamma Spectrometry in De mineralized and Surrogate Water Samples



### Sample ID Concentration (pCi/L) CSU* (pCi/L)

Surrogate 1 11.8 5.24 Surrogate 2 13.3 6.62 Surrogate 4 14.9 5.7 Surrogate 5 -9.54 11.1 Surrogate 6 -16.2 23.8 Surrogate 7 5.65 4.24 Surrogate 8 -11.8 8.19

DM Water Blank 1 -10.7 13.4

DM Water Blank 2 -1.87 1.2

DM Water Blank 3 -17.1 34.1

DM Water Blank 5 -9.42 10.1

DM Water Blank 6 -3.08 4.34

DM Water Blank 7 -11.7 13.2 Mean** (pCi/Liter) -4 Standard Deviation ** (pCi/Liter) 11 Critical Net Concentration (pCi/Liter) 20

* Combined standard uncertainty, k=1 or coverage factor of 1.

** Mean and standard deviation were calculated before rounding.



### Required MDC

The method development plan based the estimat ed MDC values for gross alpha and gross beta on demineralized water blanks. The init ial estimates of the MDCs targeted for 226 

### Ra and
228 

### Ra proved to be too low and were adjusted to a higher concentration during the method development process. The most likely reason for this was increased background counts from low activity concentration of natural radioactivity in the surrogate matrix.

The MDC data for each of the three evaluations are shown in Tables 9A through 9C. The determination of gross alpha using 226 

### Ra as the radionuclide and gamma spectrometry as the measurement technique is not as sensitive as using liquid scintillation as the measurement technique. 11 

### For this reason, the two different techni ques for the gross alpha measurement have different MDC values. This is highlighted in the MDC results shown in Tables 9A and 9B.

11 The abundance of the 186 keV gamm a ray for 226 Ra is only 3.3 % while the abundance of the alpha particle emission is 100 %.Ju ly - 2014 34 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 9A – Reported Results for Samples Containing Th, U, Po Gross Alpha by LSC [1] at the As-Tested MDC Value (12.45 pCi/L)



### Sample ID Concentration (pCi/L) CSU [ 2 ] 

### (pCi/L) Test Result ≤ CL NC 

### (Y/N)

MDC 1 12.08 0.93 N
MDC 2 7.73 0.82 N
MDC 3 13.72 0.96 N
MDC 4 9.05 0.85 N
MDC 5 11.89 0.92 N
MDC 6 8.97 0.85 N
MDC 7 8.62 0.84 N
MDC 8 10.10 0.88 N
MDC 9 10.57 0.89 N
MDC 10 9.21 0.86 N
Mean [3] (pCi/L) 10.2
Standard Deviation of Results [3] (pCi/L) 1.9
CL NC [4] (pCi/L) 1.5 Acceptable maximum values ≤ CL NC 2
Number of results > CL NC 10
Number of results ≤ CL NC 0
Evaluation PASS

[1] Samples spiked with 230 Th.
[2] Combined standard uncertainty, coverage factor k=1.
[3] Mean and standard deviation were calculated before rounding.
[4] Critical net concentration. CL NC based on the water blanks taken through the entire method.Ju ly - 2014 35 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 9B – Reported Results for 226 Ra Alpha [1] by Gamma Spectrometry at the As-Tested MDC Value (55.2 pCi/L)



### Sample ID Concentration (pCi/L) CSU [ 2] 

### (pCi/L) Test Result ≤ CL NC 

### (Y/N)

MDC 1 148 42.1 N
MDC 2 99.6 42.4 N
MDC 3 79.2 34.13 N
MDC 4 51.7 17 N
MDC 5 102 44.9 N
MDC 6 74.7 31.8 N
MDC 7 72.8 36.6 N
MDC 8 68 33.2 N
MDC 9 58.9 25.4 N
MDC 10 98.1 34 N

Mean [3] (pCi/L) 85

Standard Deviation of Results [3] (pCi/L) 28

CL NC [4] (pCi/L) 40
Acceptable maximum values ≤ CL NC 2

Number of results > CL NC 10

Number of results ≤ CL NC 0

Evaluation PASS

[1] Samples spiked with 226 Ra.
[2] Combined standard uncertainty, coverage factor k=1.
[3] Mean and standard deviation were calculated before rounding.
[4] Critical net concentration. CLNC based on the water blanks taken through the entire method.


### The initial MDC verification PTs for gross beta using gamma spectrometry turned out to be below the detection capability of the method as was demonstr ated when an initial run failed to meet the acceptance criteria. It was determined that the samples initially counted for the 1⁄2 AAL uncertainty determination (30.4 pCi/L) provided a more representative estimate of the MDC. Additional MDC test samples were prepared and counted and the results are reported in Table 9C. A new set of samples was also prepared for testing of uncertainty at the “1⁄2 AAL” (approximately 65% of the AAL) and counted with results reported in Ta ble 6C (41.4 pCi/L). The results for 228 

### Ra ( 228 

### Ac) as a measure of the gross beta activity were very reproducible. However, further work on other gamma ray emitters in the natural decay series needs to be performed to provide better estimation for th e detection limits using this method.Ju ly - 2014 36 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 9C – Reported Results for 228 Ra Beta [1] by Gamma Spectrometry at the As-Tested MDC Value (30.4 pCi/L)



### Sample ID Concentration (pCi/L) CSU [2] 

### (pCi/L) Test Result ≤ CL NC 

### (Y/N)

MDC 1 35.8 6.03 N
MDC 2 44.2 5.45 N
MDC 3 57.9 5.55 N
MDC 4 35.5 5.59 N
MDC 5 58.3 6.6 N
MDC 6 40.5 4.53 N
MDC 7 26.2 5.06 N
MDC 8 34 3.52 N
MDC 9 30.8 4.02 N
MDC 10 26.2 5.31 N

Mean [3] (pCi/L) 39

Standard Deviation of Results [3] (pCi/L) 12

CL NC [4] (pCi/L) 20
Acceptable maximum values ≤ CL NC 2
Number of results > CL NC 10
Number of results ≤ CL NC 0

Evaluation PASS

[1] Samples spiked with 228 Ra.
[2] Coverage factor k=1.
[3] Mean and standard deviation were calculated before rounding.
[4] Critical net concentration. CL NC based on the water blanks taken through the entire method.



## 9.4 Evaluation of the Absolute and Relative Bias

Test results for verification of the MDC and test levels 1–3 were evaluated for absolute and relative bias using the test proc ess described in Section 7.3 above. 12 

### The bias test results are summarized in Table 10. It should be noted that the presence of detectable le vels of bias is not a criterion for the method development until the magnitude of the bias is significant enough to cause results to fall outside the acceptance criteria of the required method uncertainty. In most cases bias was detected across the range of concentr ations tested with highe st levels of relative bias generally being associated with the lowest activity concentration samples. For example, the largest relative bias (per cent) was observed for MDC samples for gross beta using 228 

### Ra as a tracer. Please see further discus sion of the bias in Section 9.5.

12 For more complete treatments of the statistical de tection and evaluation for absolute and relative bias see Method Validation

Guide for Qualifying Methods Used by Radiological Laboratories Participa ting in Incident Response Activities (EPA 2009) and Quality Assurance of Chemical Measurements (Taylor 1987).Ju ly - 2014 37 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO

Table 10 – Absolute and Relative Bias for Gross Alpha and Gross Beta by the Three Measurements



### Type of

Bias Gross Measurement (Radionuclide

Measured) Known Value ± CSU ( k

=1), pCi/L Mean of Measurement

± SD ( k

=1), pCi/L Difference from Known, pCi/L (%) Number of Measurements/ (Effective) Degrees of Freedom [1] 

### │ T │ [1] 

### t df

[1] 

### Bias [2] 

### (Y/N)?

Absolute Gross Alpha ( 230 Th, LSC) – 7.45 ± 0.79 7.45 7/6 2.447 24.8 Y

Gross Alpha ( 226 Ra, GS) – -7 ± 22 7 13/12 2.179 1.09 N

Gross Beta ( 228 Ra/ 228 Ac, GS) – -4 ± 11 4 13/12 1.12 2.17 9 N

MDC Gross Alpha ( 230 Th, LSC) 12.45±0.79 10.2 ±1.9 2.25 (-18) 10/70 2.28 1.99 Y

Gross Alpha ( 226 Ra, GS) 55.2±1.5 85±28 27.2 (54) 10/9 3.36 2.26 Y

Gross Beta ( 228 Ra/ 228 Ac, GS) 30.4±0.2 39±12 8.6 (28) 10/9 2.32 2.26 Y

Level 1 Gross Alpha ( 230 Th, LSC) 22.5±1.2 14.9±2.2 7.6 (-34) 7/64 5.05 2.00 Y

Gross Alpha ( 226 Ra, GS) 75.0±2.0 94±32 19 (25) 7/6 1.59 2.45 N

Gross Beta ( 228 Ra/ 228 Ac, GS) 41.40±0.65 43.2±9.8 1.8 (4.3) 7/6 0.47 2.45 N

Level 2 Gross Alpha ( 230 Th, LSC) 37.5±2.1 31.4±4.2 6.1 (-16) 8/61 2.39 2.00 Y

Gross Alpha ( 226 Ra, GS) 164.9±4.5 138±18 26.9 (-16) 8/12 3.23 2.18 Y

Gross Beta ( 228 Ra/ 228 Ac, GS) 62.47±0.99 74±12 11.5 (18) 8/6 2.52 2.45 Y

Level 3 Gross Alpha ( 230 Th, LSC) 104.9±6.3 73±12 31.9 (-30) 7/55 4.14 2.00 Y

Gross Alpha ( 226 Ra, GS) 449±12 431±52 18 (-4.0) 8/11 0.76 2.20 N

Gross Beta ( 228 Ra/ 228 Ac, GS) 180.1±2.8 199.3±6.8 19.2 (11) 8/28 5.06 2.05 Y

[1] Assessment of relative bias was perf ormed at MDC and Levels 1, 2, and 3.
[2] │ T │ is the absolute value of the t -statistic, and t df is the effective degrees of freedom of the t -statistic. They are defi ned in Section 7.3 and represent the statistical factors for the actual measur ement data and for data from a normal distribution.Ju ly - 2014 38 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



## 9.5 Method Ruggedness Ruggedness represents the abil ity of a method to be unaffected by changes in the components of the sample or the measurement syst em. The matrix selected for this project was based on that of a single sample of FPWHFO and will not necessarily represent method performance in samples of significantly differe nt composition such as FPWHFO collected at different times in the life of a we ll or from different wells or regi ons. Nonetheless, this matrix is considered to be a particularly challenging one due to its extrem ely high dissolved solids content and its complexity (very elevated levels of di valent cations). This affected the bias and detectability of each of the three measurements associated with the method.

Based on testing performed at the end of th e method development process, gross alpha activity determined by liquid scintillation counting of the separated U, Th, and Po fraction of the sample was measured with recoveries ranging from 84–96 % of the expected value ( see Section 11 and Attachment II, “Flow Chart for the Alpha Beta Methods Attempted “ and Figure 6). The low bias was confirmed during form al development testing with an average gross alpha recovery for the 14 test measurements at test levels 2 and 3 of 77±11% ( k =1) of the known value and results ranging from 57–104 %. 13 

### Although these results easily meet testing acceptance criteria, the systematic low bias and the obser vation that quantitative (or near-quantitative) recovery of 230 

### Th is not achieved raises concerns about the ruggedness of the chemical separation method. Final method te sting was performed using 230 

### Th, which had the lowest recovery of the three radioelements evaluated in final prelimin ary tests, but not uranium or polonium. Since uranium and polonium were not quantitatively recovered in preliminary testing, it is reasonable to expect similar low bias for these elements with real test samples.

Ga mma spectrometry, by its nature as a non-destructive method, is more rugged than methods that rely on chemical separations since there can be no losses prior to the analytical measurement and variability of the matrix will have less potential to impact analytical results. The average recovery calculated from values pres ented in Table 6B for th e 14 test-level-2 and 3 analytical measurements of 226 

### Ra was 90±13% ( k =1) with individual values ranging from 67– 108%. The average recovery calculated from valu es presented in Table 6C for the 14 analytical measurements of 228 

### Ra spikes at test leve ls 2 and 3 was 114±14% ( k =1) with individual values ranging from 85–137%. While it likely would be possi ble to improve the process used for the gamma spectrometry measurement, better control of the sample (i.e., no introduction of added variability from chemical separations) makes gamma spectrometry a very rugged technique. Thus, there is little concern that measured values will adequately reflect the performance of the gamma spectrometry technique on real-world samples.

13 Note that the level of uncerta inty for samples for the verification of the MDC and test level 1 due to the low concentrations in these samples.Ju ly - 2014 3 9 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 10.0 Timeline to Complete a Batch of Samples
It is important for the laborat ory to know how long an analysis will take so that they can provide timely results back to their clients. Historically a batc h of gross alpha and gross beta analyses will take on the order of 3–4 days (based on the SDWA methods). There are two separate timelines for the analysis based on the two different analyt ical methods that are used for measuring the gross alpha and gross beta activit y concentrations. Gross Th, U, and Po using gross alpha analysis by LS C, from sample preparation to final results reporting, can take place in 3 hours for a single sample, or approximately one day for a batch of 20 samples (assuming a single LSC is available). The gamma spectrometry count for 228 

### Ra beta and 226 

### Ra alpha can require about 12 hours for a single sample and can process about 2 samples per day per spectrometer. Assuming a single gamma ray spect rometer is available, a batch of 20 samples would require 10 days for analysis. Laboratories will need to judge their processing times for a batch of samples based on the number of instruments they have available.

See Attachment II for a breakdown of the tim es for the individual steps shown in the flowchart in Section 17.4.Ju ly - 2014 4 0 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFOJu ly - 2014 4 1 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 11.0 Reported Modifications During Development and Recommendations for Future Work
The development of a straight-forward, in expensive, single measurement method for gross alpha and gross beta scr eening of FPWHFO samples was ha mpered by the complexity of the matrix itself. Significant preliminary effort was spent in Phase 1 modifying the approach initially conceived to accommoda te a FPWHFO matrix which turned out to be particularly challenging. The development process will be briefly summarized here to provide perspective. Attachment I is a more complete presentation of various trials and modifi cation that had to be made during the Phase 1 method development process that preceded the final method development
process.

Several classic water methods for gross activity testing were explored in hopes that a simple non-destructive analysis (i.e., an anal ysis without chemical separation) could be performed. Unfortunately solids content in the gram per liter range is 200–1000 times above the range that Method 900.0 evapora tion or direct counting by li quid scintillation (e.g., ASTM D7282) can accommodate. Digestion and fusion techni ques were considered but in view of the high non-volatile solids content of the sample matrix, would not have made the matrix more amenable to processing. All attempts to use these classic approaches failed to yield acceptable results.

A variety of classic chemical separation t echniques were explored for chemically isolating radium, thorium, uranium, or polonium . Among the approaches explored were barium sulfate precipitation t echniques (e.g., EPA Method 900.1 or 903.0, SM 7110C), barium chromate precipitations (e.g., EPA Method 905.0) and solid phase extraction with chelat ing agents, such as Empore TM 

### Radium RadDisks. Again, the gram per liter levels of barium, strontium, and calcium interfered with every attempt to chemically isolat e radium (also a divalent cation) together with thorium, uranium, and polonium.

A radon deemanation method (Rad7TM elec tronic radon detector) proved to be reasonably successful but this approach had to be abandoned due to concerns about foaming of the sample and extended turn-around times as lo ng as 7–21 days (requir ed for ingrowth of
222 

### Rn). Other radon emanation techniques, such as mineral oil extracti on of radon with liquid scintillation counting or radon d eemanation similar to the classi c approach used in EPA Method 903.1 could be considered as possible avenues for future exploration for more sensitive radionuclide-specific determinations of 226 

### Ra.

One of the methods used to initially ch aracterize the sample, gamma spectrometry, proved to be one of the most viable, attractive, and rugged alternatives for the analysis of FPWHFO. The primary advantage of gamma spec trometry is its ability for simultaneous measurement of all gamma emitters present in the sample together with its nominal insensitivity to solids in the sample. In contrast to alpha and beta emissions, where sample solids above 100– 200 mg interfere with measurements, the highly penetrating nature of gamma rays allows measurement of solid samples in the 3–5 kg range without chemical separations. The response of gamma spectrometers is also limited relative to that of liquid scint illation counters. GammaDevelopment of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### detection efficiencies are genera lly less than 10% of the efficiency for either alpha or beta emissions by liquid scintillation. Similarly, the ga mma emission rate associated with natural chain alpha and beta emitters (3% to 45%) is lo w relative to the corresponding alpha and beta particle emission rates (nearly 100 %). By increasing the size of th e aliquant and the count time, however, it is possible to compensa te, as least in part, for low response in the gamma detector. As a result, detection capabilities may be obt ained for gamma spectrometry that are generally within a factor of 10–50 of those possible by dire ct measurement of alpha and beta emissions. Gamma spectrometry was ultimately the technique chosen to perform determinations of 226 

### Ra and gross beta.

Efforts were focused on finding a group chemi cal separation for thorium, uranium and polonium. Iron hydroxide coprecipitation was initia lly explored as a preconcentration technique but due to the possibility of hi gh iron content in samples that would interfere with chemical separations and subsequent liquid scintillation m easurements, the decision was made to use a manganese dioxide coprecipitation in reducing environment (i.e., to remove iron). A number of extraction chromatographic techniques were te sted including a stacked TEVA-TRU followed by Sr Resin approach. Sr Resin is effective only for polonium and would be overwhelmed by barium resulting in low yields . Testing of the TRU Resin alon e, however, showed excellent uptake of thorium, uranium, and polonium from a 4 M HCl load solution (containing ascorbic acid to reduce iron) and effective retention of the analytes duri ng 4 M HCl rinse steps. Elution profiles (see Attachment 1, Figure 5) indicated that the three analytes could effectively be stripped from the column with 5 mL of amm onium bioxalate. Analysis of subsequent data indicated that a more complete recovery of analytes, especi ally uranium, was obtained by modifying the single 5-mL elution to five sequential 1-mL additi ons of bioxalate.

Source preparation techniques were also investigated. A number of coprecipitation techniques were explored but obt aining quantitative coprecipitation for all three radioelements in a single step proved to be elusive. In the end, a simple technique was chos en - direct addition of the eluent to liquid scintillation cocktail.

Pulse-shape discrimination liquid scintillation an alysis is an attract ive option because it was less sensitive to solids in the sample than gas flow proportional counting, has very high detection efficiencies due to the 4 π counting geometry (~90%), and reasonably low backgrounds. The result was reasonably short count times (e.g., 30 minutes) and good detection capabilities.

The final method for gross alpha (Th, U, and Po) by liquid scintillation was thus assembled based on the most successful a pproaches identified: manganese dioxide coprecipitation followed by group separation of thorium, uranium and polonium on TRU Resin, stripping with ammonium bioxala te, and pulse-shape discriminati on liquid scintillation analysis. The draft method was tested using 230 

### Th, 232 

### U, and 209 

### Po tracers and recoveries of ~89% and above were obtained for each of the three elements with 230 

### Th, the test isot ope selected for testing, sh owing the lowest recove ries (See Attachment 1, Figure 6).

Gamma spectrometry was selected for the 226 

### Ra alpha measurement and the gross beta measurement. Beyond ensuring that solids remained suspended using an agar gelling technique, the classic technique for gamma spectrometry was used without significant modification.

Ju ly - 2014 4 2Ju ly - 2014 4 3 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### No technical changes were made to the final measurement techniques following the initiation of development testing. Si nce the technical content of th e method was finalized prior to Phase 2 and 3 testing , the data obtained in Ph ases 2 and 3 alone should be used reflect the performance of the final method as presented in Attachment III.

The method validated for gross alpha by LSC measures the activity of isotopes of thorium, uranium and polonium. Alpha-emitting radi um isotopes, which are likely to be more prevalent in these samples (in terms of activ ity concentration), could not be easily or economically incorporated into a single-step gro ss alpha method at this time. The uncertainty for alpha-emitting radium isotopes determined by gamma spectrometry is much larger than that for the liquid scintillation analysis fo r the other alpha-emitting isotopes. 14 

### This result complicates the reporting process, and the determination of unc ertainty, and prevents calculation of a single meaningful value for gross alpha detection capability.

While radionuclide-specific determinations of the naturally occurring progeny of uranium and thorium decay chain members ar e possible by gamma spectrometry, the same differences in efficiency and abundance will result in counting times that are significantly longer than that for the alpha analyses. As mentioned in Section 1, gross alpha and beta activity is temporally dependent due to the inherent comple xity of radioactive ingrowth and decay in the uranium and thorium decay chains. As a result of this, the physical activity of some of the radionuclides being measured will change over time such that the results at the beginning of an analysis sequence may not be comparable to thos e at the end of the r un. Although the activity of long-lived radionuclides such as 226 

### Ra would not be impacte d, delaying count times for measurements of shorter-lived beta-emitters such as 212 

### Pb, 214 

### Pb, and 214 

### Bi will have an impact on the activity measured.

Overall the detection limits achieved, the MDC target and the action levels that were used were based on the results of the preliminary testing. These values were not as low as had originally been hoped for and can be improved upon with further analysis and development studies.

Thus, two sets of recommendations follow for use of this method and possible further development. The first set of recommendations fa lls within the scope of the current method and possible improvements (recommendation 8) on it:

1. Sample results using th is method should be reported separately as:

a. Gross alpha (U, Th, Po) – LSC

b. Gross alpha ( 226 

### Ra) – Gamma Spectrometry 15

14 The magnitude of differences in uncertaint y and counting time is attributable to the relative de tection efficiency of liquid s cintillation and

gamma spectrometry instruments and differences in the abundance of decay particle emission rates (i.e., abundance) for the radi onuclides. The detection efficiency of gamma spectrometry instruments is gene rally less than 10% of that for liquid scintillation counters. Th e abundance for gamma rays is often significantly less than 100%, but for radionuc lides that decay by alpha emission the abundance is close to 100%.

15 Combined gross alpha results provide no information about the ra dionuclides present. For example, it is not uncommon to find h igh levels of

radium in FPWHFO samples even though there may be next to no U, Th, or Po present. By separately screening samples for Ra-226, and for alpha activity associated with U, Th, or Po, it may be possibl e to decide there is no need for radionuclide-specific testing fo r U, Th, or Po. This strategy can be used to streamline the characterization of samples.Ju ly - 2014 4 4 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### c. Gross beta – Gamma Spectrometry

2. In principal, a screening test should be designed to minimize th e risk of not detecting analyte present at the analytical action level to a ra te that is acceptable in the decisionmaking process. Low bias in a screening measurement may be tolerable as long as the criteria used to decide that the analytical action level has b een exceeded take into account uncertainty and the bias associated with the measurement. Thus, additional work is needed to estimate the bias and uncertainty associated with the Th, U, Po gross alph a measurement, and to propose decision rules that ensure that measurements w ill reliably identify samples with activity that exceeds the specified analytical action level. 16



### 3. Although testing criteria were met, an obs erved low bias raises questions about the ruggedness of the gross alpha measurement, esp ecially with regard to analysis of FPWHFO of different compositions, from different regi ons, or at different times in the hydraulic fracturing life cycle. Future work should be don e to explore the chemical separation scheme to improve the individual recoveries for Th, U, and Po, and to test the approach using FPWHFO of varying compositions such as will be encountered in samples resulting from routine hydraulic fracturing operations.

4. Additional work is needed to validate the gamma spectrometry measur ement for each of the longer-lived beta-emitting members of the natura l decay chains used to quantify gross beta activity by gamma spectro metry (in addition to 228 

### Ra).

5. Additional work is needed to optimize the data inputs (e.g., libr aries), analysis parameters (i.e., spectrum analysis parameters) and cal culations used for the gamma spectrometry analysis of 226 

### Ra and radionuclides of inte rest to the gross beta analysis with a goal of minimizing levels of bias and un certainty in the measurement.

6. Additional work is needed to explore options for optimizing the preparation of the gamma spectrometry sample so that the radioeleme nts can be concentrated, thereby improving measurement sensitivity and reduc ing the sample counting time.

7. Additional work would be needed if all four of the long-lived radioelements (Ra, U, Th, and Po) associated with natural decay chain alph a-emissions are to be included in a single separation and analysis.

8. Build on experience gained in this project in the area of chemical separations in FPWHFO samples to develop sensitive radionuclid e-specific testing methods including: 226 

### Ra, 228 

### Ra,
210 

### Pb, 228 

### Th, 230 

### Th, 232 

### Th, 238 

### U, 235 

### U, 234 

### U, and 210 

### Po.

The second set of recommendations has to do with temporally dynamic processes of radioactive decay and decay-progeny relationshi ps is common to all gross alpha and beta

16 See Appendix VI of Radiological Laboratory Sample Analysis Guide for Inci dents of National Significance – Radionuclides in Water (EPA 2008) for a discussion of the directed pl anning process (DQOs/MQOs) and guidance on c ontrolling decision errors with analytical decision levels (ADLs). In this case, there is an additional concern about low bias in the measurement that must be worked out.Ju ly - 2014 4 5 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### measurements of natural decay ch ain radioactivity. As discussed above in Section 1, the activity of samples containing natural d ecay chain activity, especially 226 

### Ra and 224 

### Ra, changes over time due to radioactive ingrowth and decay processes. Specifically, the activity physically present in the sample test source and the interpretation of gross alpha and gross beta results, depend on the timing of processes preceding th e sample collection, the elapsed time between sample collection and preparation, and the elapsed time between samp le preparation and the count. Parameters that either must be controlled, or at least taken into consideration, to ensure reliable interpretation of results include:

1. How long did FPWHFO fluids re circulate in the geologic form ation prior to discharge to a settling pond, basin or waterway?

2. Does the activity present in the FPWHFO at the time of the sample measurement reflect that at key points in the life cycle of th e FPWHFO (e.g., time of discharge, point of full ingrowth, point of transport or rel ease of fluids)?

3. How does the time elapsed between collection, preparation and counting of the samples impact results. Can the timing of event be ma naged to minimize variability of results and provide useful and intercomparable m easurements for gross alpha and beta.

4. Does the use of 230 

### Th or 210 

### Po for LSC provide the best method isotope for gross alpha activity?

5. The analysis of treated FPWH FO may prove to be a completely different matrix where some radionuclides have been removed (e.g., Ra). Thus future work should also examine these types of treated matrices.

Addressing these questions as part of the entire process, or identifying individual times for each of the separate steps until the laboratory receiv es the samples will ensure that the analytical results support defensible decisionmaking regarding the handling and disposition of the fluids.Ju ly - 2014 4 6 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFOJu ly - 2014 4 7 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 12.0 Summary and Conclusions
Three parts of The Gross Alpha and Gross Beta Method in FPWHFO were tested using a matrix based on the composition of a FPWHFO sample received from the EPA to determine whether they would satisfy method development guidelines outlined in the Method Validation Guide for Qualifying Methods Used by Radiolog ical Laboratories Participating in Incident Response Activities (EPA, 2009). Two of the three parts comprise measurements of alpha emitters in the sample while the third is designed to measure beta emitters.

The MQOs for each of the three parts differed based on the matrix complexity, the instruments used for analyses, and the nuclear constants associated with the principal radionuclides used for the development process, and va riation associated with preparation of the test samples. The as-tested MQOs and measured resu lts are presented in Table 3. The final method with flow diagram used in this method development study is presented in Attachment III.

Each of the three parts of the method valid ated met all of the acceptance criteria for method uncertainty as shown in Tables 6A, 6B, and 6C. A summary of the observed levels of uncertainty at each of three activ ity levels is summarized in Ta bles 7A, 7B, and 7C. Detectable levels of bias were observed across the activity levels for each of the three measurements as summarized in Table 10. The levels of bias, howev er, were so large that they compromised the determinatoin of method uncertainty. The detection capability for each of the three parts was successfully verified as summ arized in 9A, 9B, and 9C.

Although all testing criteria were met as de scribed in this report, the complexity of the matrix prevented development of a single-m easurement method for gross alpha and beta in FPWHFO samples that will be simple, economical , and sufficiently rugged in matrices beyond the one used for the testing . Performing this anal ysis required a level of effort that was much different from previous analytic al methods in other water matrices for alpha or beta emitters. Several unique approaches were a ttempted in order to identify an analytical approach that would accommodate this particularly challenging matrix. Section 11 provides a brief synopsis of development activities and Attachment 1 prov ides additional detail supporting the method development activities preliminary to final testing

. The final approach for gross alpha require s two measurements. The first measurement involves gross alpha by liquid sc intillation counting following ch emical separation to isolate thorium, uranium and polonium fr om the matrix. Method testing in the surrogate matrix indicates that a measureable bias is associated with the technique. Average recovery were 74±11% ( k =1) of the known concentration of 230 

### Th. Recoveries ranged from 57–104% . Although all of the testing criteria were met, the observed low bias rais es possible questions a bout the ruggedness of the technique, especially with regard to use of the method for analyzing of FPWHFO of different compositions, from different regi ons or different times in the hydraulic fracturing life cycle. Possible future work should be done to improve the ruggedness of the method and to developJu ly - 2014 4 8 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### estimates of uncertainty and decision criteria that would protect against de cision errors using this screening technique. 17 

### See Section 11 for recommendations for possible future work in this area.

The second measurement for alpha activity associated with 226 

### Ra is performed by gamma spectrometry. The gamma spectrometry measurement is used to simultaneously determine the activity of longer- lived members of the thorium and uranium decay chains for calculation of gross beta activity. Although the development pro cess detected bias in the gamma spectrometry measurements at some levels, the magn itude of the bias is lower than that observed for the alpha and there is no need for con cern about the ruggedness of the non-destructive measurement technique since there are no variable s such chemical separa tions that will introduce variable levels of bias into the method. Section 11 suggests the possibility of future work to improve the sensitivity of the gamma spectrometry measurement.

Due to the physics of the measurement technologies, radionuclide determinations performed by gamma spectrometry are generally le ss sensitive and have higher uncertainty that those performed by the liquid scin tillation counting. This complicat es the reporting process, the determination of uncertainty, and prevents calculation of a single meaningful value for gross alpha detection capability. Section 11 recommends that measurements of gross alpha by LSC and of 226 

### Ra be reported and interpreted separately and suggests the possi bility of future work that would improve the sensitivity of the gamma spectrometry measurement thereby minimize the disparity in the sensitivit y of the two techniques.

Finally, as mentioned in the intr oduction in Section 1, all gross alpha and beta measurements are limited by the complexities of radioactive decay and ingrowth in the uranium and thorium decay chains which causes the alpha and beta activity physically present in the sample to change over time. Thus gross alpha and beta measurements are often not (inter-) comparable from measurement to measurement or laboratory to la boratory. This significantly complicated the interpretation of gross alpha and beta results. Section 11 recommends that future work explore the impact of timing on the performance of the me thod and the interpretati on of results, a project that would benefit gross alpha and beta measurements of natural products in all water matrices.

17 A screening test should generally be desi gned to minimize the risk of not detecting analyte when it is present at some action level to a rate

tolerable to the data end user. For this reason, screening tests tend to be structured to deliver results that systematically b ias high. Low bias in a screening measurement may be tolerable as long as the criteria used to decide whether the action level has been exceeded take i nto account uncertainty and bias associated with the measurement.Ju ly - 2014 4 9 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# 13. References

ASTM D7282 “Standard Practice for Set-up, Calibration, and Quality Control of Instruments Used for Radioactivity Measurements,” ASTM Book of Standards 11.02, current version, ASTM International, West Conshohocken, PA.

ASTM D7283 “Standard Test Method for Alpha and Be ta Activity in Water By Liquid Scintillation Counting,” ASTM Book of Standards 11.02, current version, ASTM International, West Conshohocken, PA.
Multi-Agency Radiological Laborat ory Analytical Protocols Manual (MARLAP). 2004. EPA 402-B-1304 04-001A, July. Volume I, Chapters 6, 7, 20, Glossary; Volume II and Volume III, Appendix G. Available at www.epa.gov/radiation/marlap/

. SM 7110C. “Coprecipitation Method for Gross Alpha Radioactivity in Drinking Water,” Standard Methods for the Examination of Wate r and Wastewater, curr ent version, American Public Health Association, American Water Works Asso ciation, Water Environment Federation, APHA, Washington, DC.
Taylor, John K. 1987. Quality Assurance of Chemical Measurements , Lewis Publishers, Chelsea, MI.
U.S. Environmental Protection Agency (EPA), 1980. Prescribed Procedures for Measurement of Radioactivity in Drinking Water. Office of Research and Development, Environmental Monitoring and Support Laboratory, Cinc innati, OH. EPA 60 0/4-80-032. August.
U.S. Environmental Protection Agency (EPA). 2006. Validation and Peer Review of U.S. Environmental Protection Agency R adiochemical Methods of Analysis . FEM Document Number 2006-01, November 8.
U.S. Environmental Protection Agency (EPA). 2008. Radiological Laboratory Sample Analysis Guide for Incidents of National Significance – Radionuclides in Water. EPA 402-R-07-007, January. Available at: www.epa.gov/narel

. U.S. Environmental Protection Agency (EPA). 2009. Method Validation Guide for Qualifying Methods Used by Radiological Laboratories Pa rticipating in Incide nt Response Activities

. Revision 0. Office of Air and Radiati on, Washington, DC. EPA 402-R-09-006, June. Available at: www.epa.gov/narel

. U.S. Environmental Protection Agency (EPA). 2012. Quality Assurance Proj ect Plan Validation of Rapid Radiochemical Methods For Radionuclides Listed in EPA’s Standardized Analytical Methods (SAM) For Use During Homeland Security Events. Revision 4. Office of Air and Radiation, National Analytical Radi ation Environmental Laboratory.Ju ly - 2014 5 0 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFOJu ly - 2014 5 1 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# Attachment I:

Method Development Trials

Classic Approach to Gross Alpha Beta: E vaporation and Gas Proportional Counting One ml of the field sample (no dilution or treatment) was evaporated directly onto a planchet. The dry weight was 260.3 mg and 276.4 mg for replicate samples. These values were well outside the efficiency calibration curves for either gross beta or gr oss alpha. Spattering of the material was significant wh ich would lead to an underestim ate of the count rate. Based on these two significant issues no further analysis by this method was deemed to be fruitful.

Radionuclide: 226 

### Ra Precipitation of BaSO 4 

### to coprecipitate radium was trie d once. It was evident that too much precipitate formed (other solids besides the barium/radium precipitate salt out and provide too heavy a matrix for gross analysis by GPC). Th e resulting precipitate could not be processed any further, even when small sample volumes (< 100 mL) were used.

A more selective precipitation using bari um chromate was attempted. This process yielded similar problems to using BaSO 4 

### with a large mass of other salts precipitating, forming a black/green ‘dusty’ precipitate th at could not be loaded onto a pl anchet for gas flow proportional counting. Using this material for liquid scinti llation analysis yielde d severe color quench 18



### . Radium recovery was only about 1%. 19



### Replicate aliquants of the sample (6× 250 mL and 6×40 mL) were analyzed for 222 

### Rn following a period for ingrowth to assess 226 

### Ra concentration using a Durridge Rad7 TM 

### electric radon detector. This method provides high quality a nd consistent results, when the foaming of samples, relative humidity is controlled. Some issues where encountered with foaming of the FPWHFO samples. Methods coul d be developed for unsupported 222 

### Rn/ 220 

### Rn as well. The success of this approach indicates that a radon de-emanation a pproach to the analysis of 226 

### Ra (direct analysis of 50 mL of sample without prior chemical concentration) would be capable of a reasonably sensitive determination of 226 

### Ra with MDCs of ~10 pCi/L or less. The method would require waiting several days allowing the 222 

### Rn to ingrow into the sample. This approach was not pursued further, however, because it would require significant additional development and would not provide the longer list of beta-emitting analyt es possible for gamma spectrometry analysis.

Radionuclides: U, Th, and Po A classical approach was attempted to obtai n a gross separation of uranium and thorium by Fe(OH) 3 

### precipitation. The iron hydroxide precipitat e was dissolved in hydrochloric acid and loaded onto an Eichrom TRU/TEVA column for se paration of the U/Th, and then eluted through a SR ResinTM for polonium.

18 Quench refers to any process that redu ces the production of, or transmission of light from the sample to the photomultiplier d etector. If a

correction cannot be applied, quench may result in questionable results.

19 The recovery of 226 Ra in this attempt was based on the an alysis of the original sample for 226 Ra by gamma spectrometry.Ju ly - 2014 5 2 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### In order to assess the success of the gross al pha attempts, the sample test sources were analyzed by alpha spectrometry. This not only helped to quantify yields but also to determine the effectiveness of separation of the alpha emitters.

The recovery for the radionuclides was assessed using alpha spectrometr y and was as follows:

• Th recovery indeterminate due to 228 

### Th ingrowth

• Po recovery ~29.6 ± 1.7%

• U recovery ~26-49 ± 11%

Po can be selectively electroplated onto a silv er disk. However, it must be isolated first with SR ResinTM. Attempts to electrodeposit without a SR Resin clean-up re sulted in no recovery with significant Th/Th-daughter contaminati on (as determined by alpha spectrometry). Figure 1 shows the alpha spectrum for the separated polonium (most abundant alpha in the spectrum at channel number ~ 950 is 4.88 MeV.

Figure 1 – Po-209 Alpha SpectrumJu ly - 2014 5 3 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### Group Separation Using MnO 2 

### /Fe(OH) 3 

### Precipitation This is a non-specific precipitation technique for radionuclide separation. The MnO 2 

### /Fe(OH) 3 

### precipitate is dissolved in hydroc hloric acid followed by TRU/TEVA group separation of actinides and SR-Resin for Po (U/Th). Run in quadruplicate.

Adding MnO 2 

### substantially increases recovery of U. Note that 228 

### Th cannot be used as a tracer since it may be present in th e sample as an ingrowth product from 228 

### Ra; this provides an interesting possibility for dating of flowback waters. Natural 230 

### Th and its parents are generally not detectable in samples. As such, 230 

### Th may be a suitable candidate as a Th tracer for yield calculations. The U recovery for th is mixed precipitate was 71.7±4.8%.

Thorium recovery from the field sample was indeterminate due to 228 

### Th ingrowth 20 

### from 228 

### Ra Analysis for either radium isotope wa s not attempted. When the surrogate solution was used with added 230 

### Th tracer, the alpha spectrum in Figure 2 was obtained (the most abundant alpha at channel number ~ 970 is 4.688 MeV).

Figure 2 – Alpha Spectrum of Separated 230 Th

20 Initially the concentration of 228 Th may have been very low. Howeve r the age of the sample (at least 3 months) and the high concentration of

226 Ra (determined by gamma spectrometry) ha ve allowed significant ingrowth of the 228 Th.Ju ly - 2014 5 4 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### EmporeTM RAD Disks

This method of radionuclide concentration fr om water is used for several different radionuclides. The disadvantage is that disk material shows significant uptake of barium. Additionally, high concentrations of non-radionuclides, such as Ca and Sr, can outcompete Ra and significantly decrease retention on the dis k. The recovery for radium was low, ~13.0 ± 1.1%, even with volumes as low as 50 mL of field samp le diluted ten-fold to reduce the concentration of the non-radionuclide ions. Th ere was too much competition for the exchange sites from nonradiological elements, and in particular for this sample, from barium. Th erefore the use of the Empore disks was abandoned because of the si gnificant non-radiological interfering ions.

Direct Addition to LS Cocktail Addition of 0.10 to 10 mL aliquants of the fi eld sample to liquid scintillation cocktail were used to determine the feas ibility of performing direct gro ss alpha analysis. Even less than 0.1 mL led to salting out in the cocktail yi elding a two-phase mixt ure with a high quench. Although liquid scintillation measur ement remained attractive, this experience indicated that analysis of the sample would only be possible after clean-up from the FPWHFO matrix (i.e., chemical separations).

Gamma Spectrometry Gamma spectrometry was one of the first analyses to be performed to assess the level of beta-gamma-emitting radionuclides native to th e sample. A 3-L Marinelli beaker was counted in three different manners: for 17 hours as a straight sample, for 6 hours as a straight sample, and for 17 hours with agar added to ensure that settling of suspended solids did not occur.

226 

### Ra and 228 

### Ra (or their progeny) were detectab le; however, no peaks were observed for 238 

### U ( 234 

### Th, 234m 

### Pa) or 235 

### U or 228 

### Th ( 224 

### Ra). The low concentration of 235 

### U in the sample, allowed for straightforward analysis of 226 

### Ra using the 186 keV peak.

Acid Digests Prior to Separations Gross alpha analysis was attempted using 10–100 mL of sample following digestion in nitric acid. However, the amount of residue fo rmed from this digest clogged the TRU Resin preventing completion of preparation for analysis by alpha spectrometry. In the case of LSC, the final digestate resulted in unaccep tably high amounts of color quench.

Platinum Crucible Initially acid digestion or fu sion techniques were considered as an initial step in the process. The quantities of dissolved solids in th e field sample limit the size of the aliquant making the fusion method using platinum crucibles unfeasible.

Polonium by Sulfide Precipitation A method of isolating polonium from th e bulk solution used CuS precipitation under acidic conditions was attempted as PoS will copr ecipitate with CuS. Figure 3 shows the liquid scintillation spectrum from that gross separation. However, this separation technique was notJu ly - 2014 5 5 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



### used in the final method as it caused an unaccepta ble level of quench in the liquid scintillation spectrum which would degrade the measurement sens itivity and reliability of the method.

Figure 3 – Liquid scintillation Spectrum of 209 Po



### While this separation technique was fairly specific for polonium, the low yield and the quantity of salts (high quench) made this separation technique undesirable.

Thiacalix Resins Thiacalix resins initially appeared to be a possibility for 226 

### Ra separation since they are the most selective of Ra resins. However at a Ba: Ra mass ratio of 10 4 

### , recovery drops to 20%. The field sample obtained had a mass ratio for Ba: Ra of 10 9 

### . Furthermore, these resins experience interference from othe r divalent cations such as M g, Ca, Sr, which are present in similar concentrations to Ba in our sample. Therefore this method of radium separation was not used.

Flow Chart for the Alpha Beta Methods Attempted Figure 4 shows the flow chart for the methods attempted for the analysis of gross alpha and gross beta. In this instance, tracers were used with the surrogate solution to assess the viability of these separations. The combined iron hydroxide manganese dioxide precipitate, combined with the elution of the dissolved precipitate thr ough a TRU column provided a good separation of the alpha emitters uranium, polonium and thorium. Figure 5 shows that with a few milliliters of bioxalate solution (0.1 molar), the major alpha contributors are eluted together.Ju ly - 2014 5 6 Development of Rapid Radiochemical Method for Gros s Alpha and Gross Beta Activity in FPWHFO



### Figure 6 shows the recovery of three radioelements (U, Th, Po) using the optimized method prior
to method testing

.
Figure 4 – Flow Chart for Method Development Using Tracers

Gross Alpha Analysis 300 mL original sample, filtered and acidified, 209 Po, 232 U, 230 Th Add tracers

nat U, 230 Th, 209 Po Dilute to 500 mL, boil – 60 min MnO 2 :Th + U +Po precipitates Dissolve precipitate in 10 mL 6 N HCl + 2 mL 1.0 N ascorbic acid. Add 29 mg KMnO 4 , boil,+ 6 N NH 4 OH, to pH 7.0

1. Load solution. Discard waste. Discard supernatant and wash solutions

2. Rinse with 3 5-mL portions 4 N HCl. Discard waste. Load HCl solution 1 mL/min, onto TRU resin

Discard residue. Filtrate

Gross Beta Analysis 3 – 4 L of original sample,

filtered and acidified

Direct Gamma Spectrometry Measurement 3. Elute with 10-mL 0.1 M (NH4) 2 Ox

Th, U, Po +2 , Po +4

Ce(OH) 4 (or CeF 4 ) microprecipitation Alpha Spectrometry 214 Pb, 212 Pb, 214 Bi, 212 Bi,

210 Po 226 Ra 234m Pa, 228 Ra, 210 Bi, 212 Bi

Gross Beta Add tracers

226 Ra and 228 Ra Inferential Determination

Figure 5 – Elution Profile for Traced solution with 0.1 M Ammonium Bioxalate in 4 M HClJu ly - 2014 5 7 Development of Rapid Radiochemical Method for Gros s Alpha and Gross Beta Activity in FPWHFO

Figure 6 – Total Recovery of Tracers (%) with (0.1 M Ammonium Bioxalate in 4 M HCl)

Note: These elutions were performed with 5 -1 mL (blue) volumes or 1- 5 mL volume (red).

0 10 20 30 40 50 60 70 80 90 100

Polonium Uranium Thorium 5x1 mL

1x5 mL



### These final results of the tr acer trials provided evidence that the proposed methods of chemical separation for the gross alpha (f or Th, U, and Po) would be successful.Ju ly - 2014 5 8 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFOJu ly - 2014 5 9 Development of Rapid Radiochemical Method for Gr oss Alpha and Gross Beta Activity in FPWHFO



# Attachment II:

Time Lapse

Table 11 – Estimated Elapsed Times for Gross Alpha Analysis


### Gross Alpha Analysis Step Time for 1 Sample (min.) Time for Batch of 20 (min.)
Measure aliquant, take “initial” volume of sample 2 20

Precipitation and removal of supernatant 90 200

Redissolution 5 50

Loading and elution of sample through TRU Resin 30 300

Perform eluate transfer to LSC vial 2 20
Count samples (maximum count time) 30 600 *
Data analysis and review 20 300

Total Time 179 1490

*Assumes only one LSC unit is used

Table 12 – Estimated Elapsed Times for Gross Beta Analysis


### Gross Beta Analysis Step Time for 1 sample (min.) Time for Batch of 20 (min.)
Measure aliquant, take “initial” volume of sample 4 40

Count samples (maximum count time) 720 14400 * Data analysis and review 20 300
Totals 744 14740

*Assumes only one gamma-ray spectrometer is used.Ju ly - 2014 6 0 Development of Rapid Radiochemi cal Method for Gross Alpha and Gross Beta Activity in FPWHFOJu ly - 2014 61 

# Attachment III:

Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in Flowback and Produced Waters from Hydraulic Fracturing Operations (FPWHFO) D evelopment of Rap id Radiochemical Method for Gross Alpha and Gross Beta Activity in FPWHFO



### 1. Scope and Applicability

1.1. This method was developed for flowback and produced water from hydraulic fracturing (FPWHF) operations. This type of sample will contain several radionuclides from any of the three natu ral decay chains. However, based on the variability in of chemical compounds in th e fracturing fluid, the geologic formation that is being developed and other envi ronmental factors, no assumptions about radioactive equilibrium should be ma de when performing the analyses.

1.2. The following alpha and beta activity is determined in this method:

1.2.1. All alpha radioactivity in a hydraulic fr acturing sample is associated with naturally occurring uranium, thorium and radium, short-lived progeny of these radioelements, and 210 

### Po. The gross alpha screen is accomplished with
two measurements.

1.2.1.1. The first involves a group separation of U, Th, and Po followed by liquid scintillation counting for gross alpha. This approach quantifies gross alpha activity a ssociated with uranium isotopes ( 238 

### U, 235 

### U , 234 

### U), thorium isotopes, ( 232 

### Th 230 

### Th , 228 

### Th), shortlived progeny from 228 

### Th as may have ingrown following the separations, and 210 

### Po.

1.2.1.2. A non-destructive gamma spectrometry screen is used to determine alpha-emitting radium activity, primarily associated with 226 

### Ra.

1.2.1.3. The results of the two measur ements may be used, either individually, or the measurements may be mathematically summed and their uncertainties combined to yield an estimate the combined gross alpha activity of the sample.

1.2.2. Gross beta screening is accomplishe d by gamma spectrometry measurement of radium isotopes ( 226 

### Ra, 228 

### Ra, 224 

### Ra) and other gamma-emitting natural chain radionuclides. The beta activity of Ra and its short-lived progeny (assuming equilibrium ingrowth) are summed and uncertainties combined to yield a result for the gross beta screen.

1.2.3. The gamma spectrometry measurem ent also achieves a definitive determination of the isotopic activity of gamma-emitting tracers used to assess the efficacy of the hydraulic fract uring process that have not decayed between collection and the gamm a spectrometric measurement.

1.3. The gross alpha and beta screening re sults are not corre cted for decay.Ju ly - 2014 62 

### 1.4. The method is not intended to demonstrat e compliance with the requirements of the Safe Drinking Water Act (SDWA).

1.5. FPWHFO matrices may contai n different chemical mixt ures. Method validation may need to be performed for mixtures that si gnificantly differ in composition from a fluid matrix that has been previously validated.

1.6. The method is capable of achieving the following MQOs:

1.6.1. Gross alpha screen consisting of the following two components:

1.6.1.1. Gross Alpha by liquid scintillation counting for Th, U, and Po and decay progeny. A 300 mL sample can achieve a required method uncertainty of 9.0 pCi/L at less th an or equal to an Analytical Action Level (AAL) of 40 pCi/L. This result is referenced to the radionuclide used for calibrati on of the detection system, 230 

### Th, or
210 

### Po.

1.6.1.2. 226 

### Ra alpha by gamma spectrometry: A 3.0 L sample can achieve a required method uncertainty of 33% (r elative), at less than or equal to an AAL of 165 pCi/L.

1.6.2. 228 

### Ra beta by gamma spectrometry: A 3-L sample can achieve a relative required method uncertainty of 50%, at le ss than or equal to an AAL of 60 pCi/L.

1.6.3. Application of the method must be validated by the laboratory using the protocols provided in Reference 16.1. The sample turnaround time and throughput may vary based on additi onal project MQOs, the time for analysis of the final counting fo rm and initial sample volume. D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW HFO



### 2. Summ ary of Method

2.1. See Section 17.4 for a flow char t overview of the process.

2.2. Gross Alpha

2.2.1. The sample is treated with potassium permanganate and ammonia to coprecipitate radionuclides. The alph a emitting radionuclides are separated using a TRU TM 

### resin. The activity of the eluate from the resin is determined using a liquid scintillation counter.

2.2.2. Ra-226 is determined by direct counting of the 186 keV photopeak using gamma-ray spectrometry. It may also be us ed to determine the activity of its beta-gamma emitting progeny.

2.3. Gross Beta

2.3.1. A 3L aliquant of the sample is counted directly using gamma ray spectrometry. Gross beta activity is determined by summing the gamma emitters activity plus those beta only-emitters that are progeny or parents of gamma emitters detected with less than 50% relative CSU (see Step 2.2.2 and 2.3.2).Ju ly - 2014 63 

### 2.3.2. Ra-228 is determined by direct counting of the 911 or 338 keV photopeak using gamma ray spectrometry.

3. Definitions, Abbreviations and acronyms

3.1. Analytical Protocol Specifications (APS). The output of a directed planning process that contains the project’s analytical da ta needs and requirements in an organized, concise form.
3.2. Analytical Action Level (AAL). The term “an alytical action level” is used to denote the value of a quantity that will cause the decision maker to choose one of the alternative actions.
3.3. Flowback and Produced Water from Hydr aulic Fracturing (FPWHF) Operations. A fluid used when gas or oil is extracted from shale rock formations. The produced water from fracking operations contains up to 200 different chemicals that comprise the solution, plus any minerals that are ex tracted from the shale formation during the process. Each type of FPWHF may be unique in its chemical and physical properties.
3.4. Multi-Agency Radiological Analyt ical Laboratory Protocols Manual (MARLAP) (see Reference 16.2).
3.5. Measurement Quality Objective (MQO). The an alytical data requirements of the data quality objectives that are project- or program-specific and can be quantitative or qualitative. These analytical data requir ements serve as measurement performance criteria or objectives of the analytical process.
3.6. Required Method Uncertainty ( u MR 

### ). The required method uncerta inty is a target value for the individual measurement uncertainties and is an estimate of uncertainty (of measurement) before the sample is actually measured. The required method uncertainty as an absolute value is applicable at or below an AAL.
3.7. Relative Required Method Uncertainty ( φ MR 

### ). The relative required method uncertainty is the u MR 

### divided by the AAL and is typica lly expressed as a percentage. It is applicable a bove the action level.
3.8. Sample Test Source (STS). This is the fina l form of the sample that is used for nuclear counting. This form is usually spec ific for the nuclear counting technique in the method, such as a solid deposited on a filter for alpha spectrometry analysis.

4. Interferences

4.1. Radiological:
4.1.1. The elapsed time between sampling and arrival at the laboratory and the start of the analytical process to th e counting time should be recorded for each sample. These time frames can have significant effects on the final activity concentrations determined. This is due to the various radiochemical equilibria that exist for the naturally occurring radionucli des. It will be important for the laboratory to know at which point in time (e.g., sample time, arrival at laborator y, time of discharge) the c lient desires to have the activity concentrations corrected to so that they can meet the needs of the project. D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FO

### 4.2. Non-radiological:
4.2.1. FPWHFO samples will be high in dissolved solids content as well as having a high concentration of other ionic su bstances not usually encountered in surface or drinking water samples (e.g., barium, strontium, and silica).
4.2.2. Although the method has been designed to accommodate high levels of solids, including Group II elements, concentrations of non-radioactive barium in the grams/L range may require a decreased sample size (i.e., smaller) to be selected.
4.2.3. Similarly, high concentrations of no n-radioactive calcium, magnesium or strontium in the sample may require th e use of a decreased sample size.

5. Safety

5.1. General

5.1.1. Refer to your safety manual for concerns of contamination control, personal exposure monitoring and radiation dose monitoring. 5.1.2. Refer to the laboratory chemical hygien e plan for general chemical safety rules. 5.2. Procedure-Specific Non- Radiological Hazards:

5.2.1. Solutions of potassium permanganate can rapidly oxidize organic materials and generate significant h eat. Do not mix large quantities of permanganate solution with solutions of organic solven ts as the potential for conflagration exists.

6. Equipment and Supplies

6.1. Toploader balance with a 0.1-g readability.
6.2. Beakers, Pyrex ® 

### : 250, 400 mL.
6.3. Centrifuge capable of holdi ng 300 mL vessels (optional).
6.4. Hot plate, or other suitable device for heating ammoniated sample volume.
6.5. Glass stirring rods.
6.6. Graduated cylinders: 50 0, 1000, 4000 mL capacities.
6.7. Scintillation vials: 22 mL glass.
6.8. pH paper; range 5.0–9.0 pH units.

7. Reagents and Standards

N OTES : All reagents are American Chemical Society ( ACS) reagent grade or e quivalent unless otherwise specified. Unless otherwise indicated, all references to water shou ld be understood to mean Type I Reagent water (ASTM D1193, Reference 16.3). 

### 7.1. Potassium Permanganate, (KMnO 4 

### )
7.2. Ammonium Hydroxide (NH 4 

### OH): Concentrated (15 M)
7.2.1. Ammonium Hydroxide (NH 4 

### OH): (6 M); dilute 40 mL of concentrated ammonium hydroxide to 100 mL with water.

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D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FO

### 7.3. Hydrochloric Acid (HCl): Concentrated (12 M)
7.3.1. Hydrochloric Acid (HCl): (6 M); dilu te 50 mL of concentrated hydrochloric to 100 mL with water.
7.3.2. Hydrochloric Acid (HCl): (4 M); dilu te 33 mL of concentrated hydrochloric to 100 mL with water.
7.4. Ascorbic Acid, crystals
7.4.1. Ascorbic Acid (1 M); dissolve 176 g of dried crystals in 100 mL of water
7.5. Ammonium Bioxalate, crystals
7.5.1. Ammonium Bioxalate (0.1 M); dissolve 12.4 g of dried crystals in 100 mL of demineralized water
7.6. UltimaGold AB TM 

### scintillation cocktail, (available from PerkinElmer Inc.) or equivalent.
7.7. TRU Resin TM 

### (Eichrom Technologies, LLC.); 100-150 micron
7.8. Calibration sources, Traceable to a national standards body such as the National Institute of Standards and Tec hnology (NIST) in the U.S.
7.8.1. For liquid scintillation: 230 

### Th or 210 

### Po in a counting configuration that matches that of the sample test source as closely as possible. If sample quench varies enough that the efficiency varies by more than 10%, prepare standards with varying leve ls of quench that span th e range of efficiencies encountered during the analysis of samples.
7.8.2. For gamma spectrometry: Either 228 

### Ra and 226 

### Ra or a mixed gamma source with energies spanning the entire range of energies to be used during analysis of samples. The geometry of the calibration standard shall match that of the sample test source as closely as possible (e.g., Marinelli beaker 3000-mL volume, density, average “z”, etc.). See Section 11.1.3 for a description of preparation of the sample test source.

8. Sample Collection, Preservation and Storage

8.1. None recommended

9. Quality Control

9.1. Batch quality control results shall be evalua ted and meet applicable Analytical Project Specifications (APS) prior to release of unqualified data. In the absence of projectdefined APS or a project-specific quality a ssurance project plan (QAPP), the quality control sample acceptance criteria define d in the laboratory quality manual and procedures shall be used to determine acceptable performance for this method.
9.2. A laboratory control sample (LCS) shall be run with each batch of samples. The concentration of the LCS should be at or near the action leve l or a level of interest for the project.
9.3. One method blank shall be run with each batch of samples. The laboratory blank should consist of demineralized water.

Ju ly - 2014 65

D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FO

### 9.3.1. If possible a matrix blank that incl udes a surrogate solution made from reagent grade chemical s should be analyzed.
9.4. One laboratory duplicate shall be run with each batch of samples. The laboratory duplicate is prepared by removing an aliquant from the original sample container after mixing/stirring.
9.5. A matrix spike sample may be included as a batch quality control sample if there is concern that matrix interferences, such as the presence of elemental barium in the sample, may compromise chemical yield m easurements, or overall data quality.
9.5.1. Matrix spike added activity may be diffi cult to estimate unless there is prior historical data to identify an ex isting concentration of some of the radionuclides.

10. Calibration and Standardization

10.1. The liquid scintillation count er is set-up, calibrated, ve rified, quality controls performed according to manufacturer’s spec ifications for alpha/beta discrimination, and as specified in ASTM D7282 Sections 9, 12, 13, 19, and 25.
10.1.1. Set up the scintillation counter to di scriminate between alpha and beta pulses according to manufacturer’s sp ecifications. Samples are counted in an energy window that encompasses th e alpha peak observed in the middle section of the alpha spectrum.
10.1.2. Calibrate the LSC for alpha efficiency in the same energy window of the alpha spectrum used to count samples.
10.1.3. Use standard 230 

### Th or 210 

### Po incorporated in the same counting configuration used for samples (i.e., vial type, cock tail, chemical make-up of the aqueous matrix, sample to cocktail ratio, and que nch levels should match that of the samples as closely as possible). See Sections 11.1.2.9 and 11.1.2.10 for a description of preparation of the sample test source.
10.1.4. The subtraction background is determined in the same energy window of the alpha spectrum used to count samples using a background sample that matches that of samples being analyzed.
10.2. The gamma spectrometer is set-up, calibrate d, verified, quality controls performed according to manufacturer’s specifications for alpha/beta discrimination, and as specified in ASTM D7282 Sections 9, 12, 13, 17, and 23.
10.2.1. Calibrate the gamma spectrometer across the entire energy range to be used during analysis of samples.
10.2.2. Count the calibration standa rd (Section 7.1.2) in the same juxtaposition to the detector as the samples.

11. Procedure

11.1. Water Sample Preparation
11.1.1. A well-mixed portion of the sample is take n for each of the separate analysis flow paths:

N OTE : The sample is not filtered.

Ju ly - 2014 66

D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FO

### 11.1.1.1. 300 mL for gross alpha analysis
11.1.1.2. 3.0 L for gamma spectrometry analysis
11.1.2. Gross Alpha Analysis
11.1.2.1. Add 29 mg of KMnO 4 

### and bring the solution to a boil.
11.1.2.2. Add enough concentrated ammoni um hydroxide to bring the solution into a pH range of 5.0 to 9.0.
11.1.2.3. Dilute the solution to 500 mL w ith demineralized water and bring to a boil for approximately 60 minutes.
11.1.2.4. When the solution has cooled, a nd settled, decant off and discard the supernatant solution
11.1.2.5. To the residue after decantation add approximately 10 mL of 6 M HCl and 2 mL of 1.0 M ascorbic acid.

N OTE : this is the load solution for the solid phase extraction column and should be kept to a minimum. Fresh as corbic acid should be used to ensure all the Fe +3 have been reduced to Fe +2

. 

### 11.1.2.6. Load the solution in 11.1.2.5 onto a TRU Resin column at the rate of 1 mL/min
11.1.2.7. Discard the eluate from the load solution
11.1.2.8. Rinse the TRU Resin column with three 5-mL portions of 4M HCl at a flow rate of 1 mL/min. Discard the wash solutions.
11.1.2.9. Elute the radionuclides using 10 mL of 0.1 M ammonium bioxalate solution
11.1.2.10

. Add the entire eluate to 15 mL of UltimaGold AB cocktail in a 22-mL scintillation vial. This is the sample test source (STS) for the gross alpha measurement.
11.1.2.10.1. Liquid Scintillation Counting After dark adaptation, the sample is counted for approximately 30 minutes or long enough to meet the MQOs noted in Step 1.6.
11.1.3. Determination of Gross Beta and Radium 226 activity by gamma spectrometry 11.1.3.1. If necessary to prev ent settlement of solid s during the counting time either:
11.1.3.1.1. Acidify the solution with 16 M nitric acid until solids dissolve, or
11.1.3.1.2. Add sufficient agar to suspend any solid materials.
11.1.3.2. Count the sample on a gamma ray spectrometer for approximately 6–12 hours or until the MQO’s noted in Step 1.6 can be achieved.

N OTE : The exact time to count the sample will de pend upon the exact sample size taken and the efficiency of the detectors used for the analysis. In either case the counting time should be adjusted so that the MQOs noted in Step 1.6 can be achieved. 

### 11.1.3.3. Using the information in Figure 17.1:

Ju ly - 2014 67

D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FO

### 12. Data Analysis and Calculations

12.1. Results are reported as gross alpha
12.1.1.

ݏݏ݋ݎܩ ݕݐ݅ݒ݅ݐܿܣ ݄ܽ݌݈ܣ a

, nd gross beta activity as f

ൌ ollows: Gross Alpha Activity

Where: ௅ௌ஼ ௣஼௜ ሺ ௖௣௠
௅ ሺ ௏ൈଶ.ଶଶൈ ೞ ି௖௣௠

ఢ ሻ

್ ሻ 

### (1)

cpm s 

### is the sample gross count rate, in counts per m inute

cpm b 

### is the instrument background count rate in counts per minute

ε is the detector efficiency based on the instrument quench curve and a

230



### Where: ݏݏ݋ݎܩ Th or 210



### V is the sam ݕݐ݅ݒ݅ݐܿܣ ݄ܽ݌݈ܣ Po calibration source ple volum

௚௔௠௠



### e used in liters

௔ ௦௣௘௖ 

### , ௣஼௜

௅



### I are the individual radium alpha em ൌ

itter ac ∑ ଵ

௡ 

### ሺܫ ఈିఊ 

### ሻ ௡ 

### (2)

α

- γ 

### tivities inferred from

12.1.2. Gross Beta Activity

Where: ݏݏ݋ݎܩ

gamma-em

ݕݐ݅ݒ݅ݐܽܿ ௖௘௣௦௚௔௠௠௔



### M is the activity of each measured ܽݐܾ݁ itting counterparts (usually only 226



### , ൌ Ra)

௣஼௜ ௝

௅ 

### ∑ ଵ 

### ሺܯ ఊ 

### ሻ ௝ 

### ൅ ∑ ଵ ௞ 

### ሺܫ ఊ

γ 

### a-ray em ሻ ௞ 

### (3)

gamm itting radionuclides I γ 

### are the activities of the non-gamma, beta- emitting radionuclides that are inferred.
12.1.3. Measurement uncertainty

N OTE : The uncertainty for the indirectly measured radionuclides should be made equal to the uncertainty from their gamma-emitting parent or progeny (for either the alpha-only or beta only emitters). Since this is a gross analysis this approxima tion should be satisfactory. 

### 12.1.3.1. Gross alpha 11.1.3.3.1. Determine which radionuclides that are to be inferentially determined will be in secular equilibrium based on the time between sampling and analysis.
11.1.3.3.2. Sum the activities of the radionuclides that have a CSU of less than 50% and those inferred assuming secular equilibrium.
11.1.3.3.3. Review the gamma-ray spectrum report for any gamma rays that are unidentified and ascribe identities to them.
Determine if these activities need to be added to the sum in Step 11.1.3.3.2.
11.1.3.3.4. The gross beta activity is estimated by the sum of Steps 11.1.3.3.2 and 11.1.3.3.3 (See Section 12)

Ju ly - 2014 68

D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FOJu ly - 2014 69 

### ݄ܽ݌݈ܣ ݏݏ݋ݎܩ ݕݐܽ݅݊ݐݎܷ݊ܿ݁ ൌ ݏ1 , ൜ ೎೛೘ ೞ ା ೎೛೘ ൠ భ/మ ್

௅ௌ஼ ሺ ೟ ೞ ଶ.ଶଶൈఢ ೟ ್



### ݄ܽ݌݈ܣ ݏݏ݋ݎܩ ݕݐܽ݅݊ݐݎܷ݊ܿ݁ ݏ1 , ൌ ට ൈ௏ ሻ 

### (3)

Where: ௚௔௠௠௔ ௦௣௘௖ 

### ∑ ଵ ௡ 

### ݑ ூ ଶ

ഀష ೙ ം 

### (4)

ݑ ூ ഀష ೙ ം 

### is the uncertainty of an individual gamma emitter that is used to determine the alpha activity.
12.1.3.2.

ݏݏ݋ݎܩ

Where: ܽݐ݁ܤ Gross Beta

ܷ݊ܿ݁ݐݎܽ݅݊ݕݐ ௔௠௠௔௚௦௣௘௖ 

### , 1 ݏ ൌ ට ∑ ଵ

௞,௝ 

### ݑ൤ ଶ ெ ം ௝ 

### ݑ ൅ ଶ ூ ം ௞ 

### ൨ (5)

ݑ ெ ം ௝ 

### ൌ


### and

݉݋ݎ݂ ߪ 1 ݐݎ݋݌݁ݎ ݉ݑݎݐ݁ܿ݌ݏ െ ߛ ݎ݋݂ ݁݀ݎݑݏ݉݁ܽ ݕ݈ݐ݁ܿݎ݀݅ ݏ݈ܿ݅݀݁ݑ݊݋ܽ݀݅ݎ



### ݑ ூ 

### ݎ݋݂ (6)

(7) ം ௞



### 13. Method Performance ൌ ݕ݈ݐ݁ܿݎ݅݊݀݅ ߪ 1 ݏ݈ܿ݅݀݁ݑ݊݋ܽ݀݅ݎ ݁݀ݎݑݏ݉݁ܽ

13.1. Results of method validation performance are to be archived and available for reporting purposes.
13.2. Expected turnaround times are:
13.12.1 Gross alpha ~3 hours for an individu al sample and ~25 hours per batch (see Section 17.2).
13.12.2 Gross beta ~13 hours for an individual sample and ~10 days per batch (see Section 17.3).

14. Pollution Prevention

14.1. The use of potassium permanganate to produce MnO 2 

### and a TRU ® 

### resin reduces the amount of solvents that would otherwise be needed to co-precipitate and purify the final sample test source.
14.2. Ultima Gold AB is a non-hazar dous waste after it is used.

15. Waste Management

15.1. Nitric acid and hydrochloric acid wastes s hould be neutralized before disposal and then disposed of in accordance with local ordinances.

16. References

16.1. U.S. Environmental Protection Agency (EPA). 2009. Method Validation Guide for Radiological Laboratories Participati ng in Incident Response Activities . Revision 0. D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FO

### Office of Air and Radiation, Washingt on, DC. EPA 402-R-09-006, June. Available
at: www.epa.gov/narel/in cident_guides.html

. 16.2. Multi-Agency Radiological Laborat ory Analytical Protocols Manual (MARLAP). 2004. EPA 402-B-1304 04-001A, July. Volume I, Chapters 6, 7, 20, Glossary; Volume II and Volume III, Appendix G. Available at: www.epa.gov/radiation/ marlap/index.html

. 16.3. ASTM D1193, “Standard Specification for Reagent Water,” ASTM Book of Standards 11.02, current version, ASTM International, West Conshohocken, PA.
16.4. NNDC, Brookhaven National Laboratory, sonzogni@bnl.gov

. 16.5. Data Source: National Nuclear Data Ce nter, Brookhaven National Laboratory, based on ENSDF and the Nuclear Wallet Cards (2014); http://www.nndc.bnl.gov/chart/

. 16.6. ASTM D7282 “Standard Practice for Set- up, Calibration, and Quality Control of Instruments Used for Radioactivity Meas urements,” ASTM Book of Standards 11.02, current version, ASTM Interna tional, West Conshohocken, PA.

17. Tables, Diagrams and Flow Charts

17.1. Table of Direct and Inferential Determinations for Gamma Ray Emitters

Radionuclide Gamma Ray Energy, keV Abundance,% Half-Life, Days Time from Sampling to

Counting, Days Inferred Activity

208 Tl [1] 583 85.0 2.1×10 -3 < 0.1 212 Bi

210 Pb 46.5 4.25 8.1×10 +3 365 210 Po
30 210 Bi

212 Pb 238 43.6 4.4×10 -1 2 224 Ra

212 Bi 727 6.67 4.2×10 -2 2 224 Ra

214 Pb 295 18.4 1.9×10 -2 18 226 Ra
352 35.6 1.9×10 -2 18 226 Ra

214 Bi 609 45.5 1.4×10 -2 18 226 Ra
1120 14.9 1.4×10 -2 18 226 Ra

226 Ra [2] 186 3.64 5.8×10 +5

— —

228 Ac 338 11.3 2.6×10 -1 1.5 228 Ra
911 25.8 2.6×10 -1 1.5 228 Ra

234Th 93 4.2 2.4×10 +1 < 0.1 234m Pa
63 3.7 2.4×10 +1 < 0.1 234m Pa

[1] Tl-208 also has a gamma at 2615 keV that is 99% abundant.

[2] Note that this gamma ray is inte rfered with by the gamma ray from 235 U at 185. The 226 Ra can be determined directly if no 235 U is present or if the 235 U peak issued to subtract out the inte rference at 186 keV. See Reference 16.5.

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D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FO

### 17.2. Estimated Elapsed Times for Gross Alpha Analysis

Gross Alpha Analysis Step Time for 1 Sample, Minutes Time for Batch of 20, Minutes

Measure aliquant, take “initial” volume of sample 2 20

Precipitation and removal of supernatant 90 200

Redissolution 5 50
Loading and Elution of sample through TRU resin columns 30 300

Perform eluate transfer to LSC vial 2 20
Count samples (maximum count time) 30 600 *

Data analysis and review 20 300

Total Time 179 1,490

*Assumes only one LSC unit is used.



### 17.3. Estimated Elapsed Times for Gross Beta Analysis

Gross Beta Analysis Step Time for 1 Sample, minutes Time for Batch of 20, minutes

Measure aliquant, take “initial” volume of sample 4 40

Count samples (maximum count time) 720 14,400 *

Data analysis and review 20 300

Totals 744 14,740

*Assumes only one gamma ray spectrometer is used.

Ju ly - 2014 71

D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FOJu ly - 2014 72 

### 17.4. Sample Processing for FPWHFO D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FOJu ly - 2014 73 D evelopment of Rapid Radiochemical Method for Gross Alpha and Gross Beta Activity in FPW H FOPlease make all necessary changes on the below label, detach or copy and return to the address in the upper left hand corner.

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