PENNSYLVANIA INDEPEN DENT OIL AND GAS ASS OCIATION MARCELLUS SHALE COAL ITION



# FIELD SAMPLING PLAN

Characterization of Naturally Occurring Radioactive Materials in the Oil and Gas Field

November 4, 2013PIOGA / MSC Field Sampling Plan November 4 , 2013



## TABLE OF **C ONTENTS** 

1.0 INTRODUCTION

................................ ................................ ................................ ................................ ....... 1

2.0 SITE DESCRIPTION

................................ ................................ ................................ ................................ ... 4
2.1 Facilities to be Sampled

................................ ................................ ................................ ...................... 4

2.2 Constituents of Concern

................................ ................................ ................................ ..................... 5

3.0 SCOPE AND OBJECTIVES

................................ ................................ ................................ .......................... 6
3.1 Scope of Field Screenin g Activities

................................ ................................ ................................ ...... 6
3.2 Scope of Field Sampling Activities

................................ ................................ ................................ ....... 6

4.0 FIELD SCREENING AND TESTING ACTIVITIES

................................ ................................ ........................... 8
4.1 Radiological Surveys of Solid Sample Areas

................................ ................................ ........................ 8
4.2 Radiological Surveys of Aqueous Sample Areas

................................ ................................ ................. 8
4.3 Radiological Surveys of Equipment and Structures

................................ ................................ ............ 8
4.4 Radiological Surveys of Samples

................................ ................................ ................................ ......... 9

5.0 FIELD SAMPLING ACTIVIT IES

................................ ................................ ................................ ................. 10
5.1 Objectives

................................ ................................ ................................ ................................ .......... 10
5.2 Solid Samples

................................ ................................ ................................ ................................ .... 10
5.2.1 Sample Types and Locations

................................ ................................ ................................ ...... 10
5.2.2 Sampling Methods

................................ ................................ ................................ ..................... 11
5.2.3 Quality Control

................................ ................................ ................................ .......................... 12
5.2.4 Laboratory Analysis

................................ ................................ ................................ .................... 13
5.3 Aqueous Samples

................................ ................................ ................................ .............................. 13
5.3.1 Sample Type and Location

................................ ................................ ................................ ......... 13
5.3.2 Sampling Methods

................................ ................................ ................................ ..................... 14
5.3.3 Quality Control

................................ ................................ ................................ .......................... 14
5.3.4 Laboratory Analysis

................................ ................................ ................................ .................... 15
5.4 Gas Samples

................................ ................................ ................................ ................................ ...... 15
5.5 Equipment Decontamination Procedures

................................ ................................ ........................ 16

6.0 DOCUMENTATION

................................ ................................ ................................ ................................ 17PIOGA / MSC Field Sampling Plan November 4 , 2013

6.1 Field Documentation

................................ ................................ ................................ ......................... 17
6.1.1 Log Books and Field Data Sheets

................................ ................................ ............................... 17
6.2 Sample Documentation

................................ ................................ ................................ .................... 18
6.2.1 Sample Numbering System

................................ ................................ ................................ ........ 18
6.2.2 Sample Labels

................................ ................................ ................................ ............................. 18
6.2.3 Container Receipt Checklist

................................ ................................ ................................ ....... 18

6.2.4 Chain

- of

- Custody Records

................................ ................................ ................................ .......... 18
6.2.5 Receipt of Sample Forms

................................ ................................ ................................ ........... 19

6.2.6 Documentation Procedures

................................ ................................ ................................ ....... 19

6.2.7 Corrections to Documentation

................................ ................................ ................................ .. 20
6.3 Sample Packaging and Shipping

................................ ................................ ................................ ........ 20
6.4 Management and Retention of Records

................................ ................................ ........................... 20

7.0 LABORATORY ANALYSIS

................................ ................................ ................................ ........................ 21
7.1 Gamma Spectroscopy

................................ ................................ ................................ ....................... 21
7.2 Quality Control

................................ ................................ ................................ ................................ .. 21

8.0 Tables

................................ ................................ ................................ ................................ .................... 22
Table 8.1 Field Screening Equipment

................................ ................................ ................................ ...... 23
Table 8.2 Summary of Materials to be Sampled

................................ ................................ ..................... 24
Table 8.3 Analytical Requirements for Solid Samples

................................ ................................ ............ 26
Table 8.4 Analytical Requirements for Aqueous Samples

................................ ................................ ..... 27

9.0 Appendices

................................ ................................ ................................ ................................ ............ 28
Appendix A Exposure Rate Measurements

................................ ................................ ................................ 29
Appendix B Surface Contamination Measurements

................................ ................................ .................. 31
Appendix C Sampling Protocol for Conventional & Unconventional Oil or Gas Drill Cuttings

.................. 33
Appendix D Sampling Protocol for Conventional & Unconventi onal Cuttings from a Pit

.......................... 35
Appendix E Characterize LPG Processing Equipment

................................ ................................ ................ 37
Appendix F Example of Chain of Custody

................................ ................................ ................................ ... 38PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 1 of 3 8



## 1.0 INTRODUCTION

The Pennsylvania Independent Oil and Gas Association (PIOGA) and the Marcellus Shale Coalition (MSC)
ha ve developed this Field Sampling Plan (Plan) to describe the manner to collect data and analyze samples of naturally occurring radioactive material (NORM) and technologically enhanced NORM (TENORM) related to the oil and gas (O&G) exploration activities

. The p urpose of this study is to obtain representative samples from potential sources of NORM associated wi th all aspects of O & G drilling and operations and reach definitive conclusions about the potential for exposure. Sites and facilities that are candidates to be sampled includ e conventional and unconventional drilling through geological
formations and as sociated waste water operations throughout the Commonwealth of Pennsylvania (PA). The following types of materials and processes are recommended to be sampled, including:

• Ambient air;

• Drill cuttings (vertical and horizontal);

• Natural gas;

• Natural gas processing pipes and equipment;

• Reuse and w aste water generated on drilling sites;

• Sludge resulting from the processing of reuse and waste water from the well pad development process; and

• Landfill leachate.

The Commonwealth of Pennsylvania, Department o f Environmental Protection (DEP) published a Field Sampling Plan and Quality Assurance Project Plan in April, 2013. 1
, 2 The study by PIOGA and MSC is
intended to augment the DEP study and provide samples that are representative of the media be ing
tested an d use the proper sampling and testing procedures in order to compare results

. Members of
PIOGA and MSC perform exploration activities by conventional and unconventional drilling through various subsurface layers of rock to produce oil and natural gas. Th e production of oil and gas creates produced water and flowback water, as well as drill cuttings and sources of off gassing, which are potentially impacted by NORM and/or TENORM. Unconventional O&G process water (e.g., flowback and produced water) sample r esults indicate elevated concentrations of radium

- 226 (Ra

- 226), a common
NORM radionuclide and the element associated with the natural uranium decay series with the highest mobility. T he scope of work for this Plan is focus ed on the O&G operations, equipm ent, and features related to the exploration and production of natural gas from various geologic formations and also the potential for TENORM in water transferred to treatment facilities for processing. Sampling activities will
include but are not limited to:

1 Pennsylvania Department of Environmental Protection, “Part I

- Field Sampling Plan”, April, 2013.

2 Pennsylvania Department o f Environmental Protection, “Part II

- Quality Assurance Project Plan ” , April, 2013.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 2 of 3 8

• Vertical and horizontal drill cuttings;

• Onsite pits containing cuttings;

• Production water;

• Flowback water;

• Filter socks;

• Filter presses;

• Compressed gas lines;

• Off gassing;

• Well pads;

• Centralized impoundments;

• Waste water facility sludge;

• Waste water facility influent and effluent water;

• Piping and casing scale;

• Vapor capture systems;

• Fresh proppant sands; and

• Drilling muds.

The DEP has not established occupational exposure regulations/standards for NORM or TENORM. The
American Nation al Standards Institute (ANSI) published a standard addressing the control and release of
NORM and TENORM

. 3 The standard applies to industries or activities that are not covered by existing
federal or state regulations. The standard provides radiation expos ures be limited to less than 100 millirem (mrem) , above background, from all pathways and sources of radioactivity (except radon and
its short

- lived decay products) and practices associated with site and facility operations

.
Pennsylvania established dispo sal criteria for solid waste impacted with TENORM. 4 Specifically

, the Commonwealth limits the exposure of future residents, the hypothetical resident farmer, from a permitted landfill t o 25 mrem/yr from all pathways

, including radon. This Plan d escribes an d presents procedures and protocols for field radiological surveys and sampling that is suitable to characterize
NORM and TENORM , including types, quantities, sample technique, chain of custody, onsite radiological analysis

, off

- site physical, chemical, an d radiological laborato ry analysi s.

It is important to understand the movement and exposure pathways of TENORM through the entire O&G process. In this regard, the purpose of this comprehensive study is to have a more complete understanding of TENORM in O& G activities and waste disposal operations, and to document and evaluate potential radiation exposure to workers and the public, as well as to ensure protection of the

3 American National Standards Institute

, "Control and Release of Technologically Enhanced Naturally Occurrin g Radioactive Material (TENORM) "

, ANS I/ HPS N13.53

- 2009 , March, 2009

. 4 Pennsylvania Department of Environmental Protection, “Final Guidance Document on Radioactivity Monitoring at Solid Waste Processing and Disposal Facilities”, Document Number 250

- 3100

- 001
, January 2, 2004

.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 3 of 3 8

environment. The sampling and analysis will assist in determining radiological isotopes of concern and in evaluating their potential mobility in the environment. The members of PIOGA and MSc are encouraged

to participate in this study and collect representative samples at the same time as the DEP. At such time as data are available, each m ember should provide the results and the entire laboratory report so that the results can be summarized by PIOGA and MSC. The names of the operators and location of the well sites will be kept confidential.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 4 of 3 8



## 2.0 SITE DESCRIPTION

**2.1 Facilities to be S**  **ampled** The sampling locations associated with O&G activities will vary from site to site throughout the state. The study will include survey and sample events on active and inactive O&G sites, and waste water facilities. Each site may have its own discret e water storage and residual waste storage location s

.

Various O&G facilities will be evaluated for TENORM generation and handling. PIOGA and MSC intend

to identify O&G facilities across the state, including conventional and unconventional wells, which
sh ould be characterized

. The overall approach is to select sites that will be representative of radiological
conditions of O&G facilities throughout Pennsylvania. Previous studies indicate that the presence of TENORM varies according to the location, depth and the operational phase of the well. Consequently,
discrete grab samples from multiple sampling events at each site will be composited . This approach will ensure representative samples of both fluids and solid waste generated by O&G drilling and produc tion practices and will more accurately reflect statewide geologic conditions, drilling methods and well types.

Preferred locations are well sites, waste water treatment facilities, gas distribution facilities and reconditioning well equipment facilities. The type s of samples are described as follows , including :

Well Sites Selection Criteria:

• Select well sites in unconventional shale formations from the “ dry ” gas areas predominantly in the northern and central parts of the state and “wet” gas area found

p redominantly in the southwestern part of the state;

• Select one or more Utica formation well site s and other conventional shale formations (e.g., Geneseo, Burket and Rhinestreet) as they become available. Include conventional
shallow O&G well sites in t he Oriskany sandstone formation;

• Sample from conventional horizontal wells (e.g., Penneco wells);

• Sample, as applicable, during the five p hases of development including, vertical drilling, horizontal drilling, frac turing, flowback and production; and

• Docume nt the activities associated with well development and production equipment and operational facilities at each above

- referenced site.

Waste Water Treatment Facility Selecti on Criteria:

• Select one or more representative sample s of each type of waste water t reatment plants

, including CWT facilities, zero limit discharge ( ZLD ) facilities and well site
treatment units ; andPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 5 of 3 8

• Select w aste water treatment facilities that accept waste material from unconventional
well sites in both wet gas as well as dry gas produc tion areas.

Gas Distribution and End Use Operations Facility Selection Criteria:

• Assess f acilities that compress, carry and distribute gas from the 'wet gas ' producing area of the state; and

• Assess f acilities that compress, carry and distribute gas from the 'dry gas' producing area of the state. Include facilities that handle gas produced in Pennsylvania as opposed to
those which handle gas imported from out of state. Include any major gas user (e.g., electrical generator), pr ocessing and storage facil ities.

Well component reconditioning facilities

, in clud ing major well casing or pipe reconditioning or de

scaling facilities in the Commonwealth

, will also be selected for assessment

.



### 2.2 **C onstit**  **uents of C oncern**  Primary constituents of concern (COCs) for O &G production radiological characterization include uranium (U

- 238), thorium

- 232, radium (Ra

- 226 and Ra

- 228), radon (Rn

- 220 and Rn

- 222) and any

unsuppo rted decay chain radionuclides. Radiological characterization will consist of field radiation surveys (g amma exposure rate ) using portable survey meters, collection and screening of representative samples of solids and liquids, collection of swipe (smear) samples to determine removable alpha and
beta surface contamination, and sampling of gas for radon anal ysis as appropriate.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 6 of 3 8



## 3.0 SCOPE AND OBJECTIVES

This scope of this Plan is to examine the nature and extent of TENORM in the Pennsylvania O&G
activities

. Radiological support surveys and sampling performed for this TENORM study may consist of: (a) field alpha

, beta and gamma screening measurements , and (b) sampling of various media for off

- site radiological and laboratory analyses. This section summarizes the scope and objectives of these survey
activities . A detailed description of field screening and s ampling procedures are pr ovided in subsequent
sections

. 

### 3.1 Scope of Field Screening Activities Field screening activities will consist of using field measurement instruments to identify the presence and approximate amounts of NORM and TENORM in cutting pi ts (open and closed), flowback and produced water, temporary water storage vessels and recycle systems, drilling rigs and associated equipment, of fices, trailers and trucks , production equipment, waste water facilities, landfill leachate,
and beneficial re use areas. Screening of solid and aqueous samples and swipes (smears) samples will
also be performed.

Direct

- read radiological survey instruments will be used throughout the field operations of the project for scanning and surveying of personnel, equipmen t, materials and general areas. The survey instruments will be operated and maintained by P IOGA, MSC personnel or qualified contractors. Additional equipment that may be used on

- site will be maintained and operated by the operator's technician(s) or subc ontractors. Proposed instruments, detectors, and equipment (or their equivalents)
to be used on

- site during field screening are listed in Table 8.1 , using the procedure described in Appendix A and B

. 

### 3.2 Scope of Field Sampling Activities Field sampling wi ll consist of collecting representative samples of environmental media from sources for
either on

- site measurements or off

- site laboratory analysis. The following types of field samples will be
collected are su mmarized in Table 8.2 and inclu de :

• Drill cutt ings, accumulated solids, scale, treatment water sludge, discharge sediment,
soil samples and crystalline salts from brine water evaporation as appropriate for off

site radiological laboratory analyses for characterization and evaluation of potential
mobil ity in the environment;

• Flowback and produced water, and waste water treatment influent and effluent, for off

site radiological laboratory analysi s for characterization purposes;

• Solid and aqueous ph ases to be evaluated separately;PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 7 of 3 8

• Radon sampling of gas as appropriate to assess potential occupant/worker/public

exposure s ; and

• Swipe (smear) samples to determine removable alpha and beta surface contamination

as an indicator of potential inhalation or incidental ingestion exposure s

.

Off

- site analysi s of solid a nd aqueous samples may include the following parameters as specified in
Section 5 .0, g ross alpha and beta

, g amma spectroscopy to identify radionuclides , a lpha spectroscopy for uranium (U

- 238, U

- 235, and U

- 234), radium (Ra

- 226), thorium (Th

- 232, Th

- 230
, and Th

- 228), and for any unsupported decay chain radionuclides, and for radon (Rn

- 220 + Rn

- 222)

. The sample types and laboratory analysis requirements are summarized in Table 8.2 . M inimum sample quantities, containers,
and desired detection limits are summa rized in Tables 8.3 and 8.4 , using the procedure in Appendix C or

D

.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 8 of 3 8



## 4.0 FIELD SCREENING AND TESTING ACTIVITIES Procedures and activities for radiological field surveys and screening of solid and aqueous samples and sampling areas are described below. A summary of the materials to be sampled is provided in Table 8.2.



### 4.1 Radiological Surveys of Solid Sample Areas Radiological surveys will be performed in areas where solid samples are collected , including:

• Gamma exposure rate surveys in units of micro

- r oentgen per hour (u R/hr) within and

near samp ling areas when possible; or

• Gross gamma surveys in units of counts per minute ( cpm) in and around sampling areas ; and

• Background exposure rate and/or gross gamma count rates measured outside the
influence of s ampling areas.

Background radiation levels will be documented in areas that are not impacted by the field operations or facilities. Results from any radiation survey equipment capable of measuring beta or gamma radiation will be recorded in the designated background location. Background radiation is established in order to verify that the results are not influenced by imported materials or equipment that may contain
elevated concentrations of NORM or TENORM

. The procedure to conduct a radiation survey fo r gamma exposure rates and the associated radiation background is provided in Appendix A.



### 4.2 Radiological Surveys of Aqueous Sample Areas Radiological surveys will be performed on containerized water and/or sludge, and effluent discharge points includi ng:

• Gamma exposure rate surveys in units of uR/hr a round
, on contact with , and one meter
from water tanks/trucks full or partially full of water/sludge prior to sampling when possible, and/or at effluent discharge points; and

• Background exposure rate s and/ or gross gamma count rates measured outside the
influence of sampling areas.



### 4.3 Radiological Surveys of Equipment and Structures Radiological surveys will be performed on drilling rigs and well development equipment (e.g., platforms, pipes, tanks, etc.), including:

• Gamma exposure rate surveys in units of uR/hr o n contact and at 1 meter from the
surface of equipment and/or structures prior t o sampling when possible; orPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 9 of 3 8

• Gross gamma surveys in units of cpm on contact with equipment and/or structures to
be sa mpled ;

• Total alpha and beta surface contamination in units of disintegrations per minute per
100 square centimeters (dpm/100 cm 2 );

• Removable alpha and beta surface contamination ( smear) in units of dpm/1 00 cm 2 ; and

• Background exposure rate s and/or gross g amma count rates measured outside the influence of sampling areas.

The procedure to conduct a radiation survey for gamma exposure rates and the associated radiation background is provided in Appendix A. The procedure to conduct a radiation survey for tot al and removable surface contamination, gross alpha and beta, is provided in Appendix B

. 

### 4.4 Radiological Surveys of Samples Radiological surveys will be performed on all samples, including:

• Gamma exposure rate surveys in units of uR/hr on contact with sample container; and/or Gross gamma surveys in units of cpm on contact with sample container;

• Total alpha and beta surface c ontamination in units of dpm /1 00 cm 2 ; and

• Removable alpha and beta contamination (smear) in units of dp m/1 00 cm 2

.

Background expos ure rate s and/or gross gamma count rates will also be measured outside the influence of samples and sampling areas.

The procedure to conduct a radiation survey for gamma exposure rates and the associated radiation background is provided in Appendix A. Th e procedure to conduct a radiation survey for total and removable surface contamination, gross alpha and beta radiation, is provided in Appendix B.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 10 of 3 8



## 5.0 FIELD SAMPLING ACTIVIT **I ES** 

This section of the P lan describes sampling and analyses to be performed by off

- site laboratories. Field sampling will be performed for solid, aqueous, and gas samples as described below. Specific sampling parameters, laboratory analytical methods and numbers of samples are discussed further in Section 7.0
and summarized in Ta ble 8.2 , while analy tical methods and sample volume, preservation, and holding
times are summarized in Tables 8.3 and 8.4

. 

### 5.1 Objectives The concentration of NORM and TENORM in each of the media types is variable. PIOGA and MSC
recommend that m ultiple, r epresentative samples of solid and aqueous media be collected and composited . The samples should be collected randomly from each medium in order to create an average sample for analysis. PIOGA and MSC are committed to avoid potential sample bias and not create a sample or a database of sample results that are the worst case or best case ( biased with high
results or low results, respectively)

. 

### 5.2 Solid Samples Various types of solid samples may be collected:

• Rock cuttings as produced on a drill rig inclu ding cuttings stored temporarily on site in lined pits or containers;

• Solid phase from flowback and produced water;

• Solids accumulated in vessels or on equipment;

• Scale from drill rigs and associated equipment;

• Wastewater treatment facility sludge;

• Wastewa ter treatment facility discharge sediments;

• Soil/salt samples from beneficial reuse areas;

• Fresh proppant sands; and

• Drilling muds.



### 5.2.1 Sample Type **s and Location**  **s** Samples will be collected as outlined below:

5.2.1.1 Exploration and Production Site Sampl ing

- This study will include sample events on active and inactive sites, including:

• Open/Operating Cuttings Pits

- Sampling and laboratory analysis of the drill cuttings (solid material) sto red in the open/operating pits. Cuttings from both the vertical and
horizontal drilling phases will be sampled;PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 11 of 3 8

• Cuttings from closed

- loop drill cutting systems ;

• Flowback and produced water on sites, evaluate solid and aqueous phases separately;

• Temporary Water Storage Vessels and Recycle Systems ( i.e.
, Hydraulic Fractu ring Water Storage Tanks, Produced Fluids Tanks, Filtration Equipment, Water Trucks)

- Collect and screen samples of solids accumulated in vessels for gross activity;

• Drilling Rigs and Associated Equipment

- Collect and screen samples of solids (scale)

acc umulated on rigs, pipes used well c asings and associated equipment; and

• Production Equipment (Separators, Heater/Treaters, Dehydration Units, Compressors)

- If possible, collect and screen samples of solids accumulated in/on production equipment.

5.2.2. 2. Waste Water Facilities Sampling

• Facilities that treat water from unconventional shale formations . A majority of those
facilities are located in the w estern sector of Pennsylvania. Some of these facilities are
also located in the Central or Eastern secto r of the state ;

• Facilities will include normal POTWs, specialized CWT facilities used for unconventional shale hydraulic fracturing water treatment operations and zero limit discharge ( ZLD )
facilities

.

• Samples at e ach of the waste water facilities will be sampled on at least three different
times ;

• S olid samples will be taken at each facility during each of the 3 sample events: sludge
from the treatment of the water and sediments at the effluent discharge point; and

• The operator will record any other pertin ent data during each sample event, e.g.,
influent volume from unconventional shale operations , total influent flow, and effluent flow. To the extent possible , the operator will schedule the sampling of the sludge at its facilit y such that the samples are a ll related to the processing of the influent unconventional shale operations

. 

### 5.2.2 Sampling Methods Solid samples will be collected using reusable or disposable sampling tools (e.g., stainless steel trowels or tubes). Sampling tools will be decontaminated prior to first use on

- site, between sampling locations, and following last use on

- site (i .e., before demobilizing that equipment) as ap propriate based on survey
data. The samples selected for analysis will be placed into laboratory approved containers i mmediately following collection and labels promptly af fixed to the sample containers. The samples will be transported via delivery service under chain

- of

- custody control to the off

- site subcontract laboratory for analysis. Table 8.3 identifies container t ypes that will be used for collection of these samples. Minimum sample quantities required for laboratory analysis are also identified in Table 8.3. S ampling protocols for collecting samples of drill cuttings from conventional and unconventional wells are provided in Appendix C and D

.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 12 of 3 8

In the event that the operator is collecting its samples at the same time as the representatives from the DEP, the samples should be split or otherwise composited and homogenized before the samples are packaged. A split sam ple represents an industry practice for purposes of compari ng testing results. All of the materials collected from that location are homogenized in a stainless steel bowl or disposable aluminum pan to the best that the material will allow. Multiple sampl es are collected from the homogenized material and s ubmitted f or the appropriate analysis.

Subsurface sampling, e.g.

, by hand auger will be considered when a gradient in the media sampled is suspected and the volume of material represented is not homo gene ous. For example, for drill cuttings, in order to access cuttings from the horizontal zone, subsurface sampling of a cuttings pile maybe necessary. Samples will be collected at depth intervals , each approximately 15 centimeters deep, either using a hand au ger or other appropriate sampling tool. Each segment will be field screened for gross gamma activity and/or exposure rate to determine if materials above ambient background are present in the sample. If materials are present in multiple contiguous interv als, all of the materials in those
intervals will be homogenized in a stainless steel bowl or disposable aluminum pan to the best that the
material will allow. A sample will be collected from the homogenized material and sent for the appropriate analysis. If conditions allow, an attempt may be made to down

- hole log the auger hole to
estimate the depth of activity encountered within the sample location.

For surfaces of internal components of natural gas production or processing equipment, samples will be

c ollected in order to characterize the concentration s of lead (Pb

- 21 0 ) and polonium (Po

- 210). Previous studies indicate that the concentrations of TENORM are potentially elevated especially for the equipment that separate propane

. The radiation surveys and measurement protocol s, including smears, and scrapings for this equipment are provided in Appendix E. Sample locations will be based on the operational his tory of the equipment or the presence of elevated gamma radiation levels

. After the equipment or pipe is opened, the wipe test and scraping can be collected from the inner surface s

.
Additional sample preparation as specified by the laboratory for specific analyses may be required. For gamma spectroscopy usually no field prep aration is necessary. How ever, for gross alpha and beta analyses additional sample preparation may be necessary in the laboratory. For the purposes of radioactivity analysis, a consistent temperature for transport and storage , as low as 4° Celsius (C) , is not required for any sam ples.



### 5.2.3 Quality Control Quality Control samples will be collected to verify results of off

- site laboratory and submitted at least 5% field replicate or split samples collected per total samples in a calendar quarter. Ten percent (10%) of the samples, based on the gross alpha and beta, and gamma spectroscopy results, will also be analyzed by alpha spectroscopy for isotopic uranium (U

- 238, U

- 235 and U

- 234), isotopic thorium (Th

- 232, Th

- 230
and Th

- 228)

, isotopic radium (Ra

- 226 and Ra

- 228), for any unsupp orted decay chain radionuclides (e.g.,
Pb

- 210 and Po

- 210) , and for radon (Rn

- 220 and Rn

- 222).PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 13 of 3 8



### 5.2. **4 Laboratory Analysis**  Solid samples will be analyzed by gamma spectroscopy to identify TENORM radionuclides. Approximately 1 0% of the samples, based on the g amma spe ctroscopy results, will also be analyzed by alpha spectroscopy for uranium (U

- 238, U

- 235 and U

- 234), thorium (Th

- 232, Th

- 230 and Th

- 228) radium (Ra

- 226) and isotopic analysis for Ra

- 228 (a beta emitter) and for any unsupported decay chain
radionucl ides; and for radon (Rn

- 220 and Rn

- 222)

. Samples from gas processing equipment will be analyzed by appropriate analytical methods (low

- energy gamma spectroscopy for Pb

- 210, and radiochemical analysis for Po

- 210).

Solid samples (excluding samples from gas processing equipment) will be dried and homogenized before being packaged for gamma spectroscopy. For samples being analyzed for Ra

- 226, the dried sample s will
be sealed in an air

- tight container and stored for approximately 21 days in order to achieve se cular equilibrium with the progeny of Ra226. The desired detection limits are provided in Table 8.3 and 8.4. For example, t he detection limits for the analysis of solids should be able to achieve at least 1 picocurie
of Ra

- 226 per gram.



### 5.3 Aqueous Samp **les** Various types of aqueous samples may be collected:

• Flowback, brines and other produced waters;

• Accumulated liquids from production equipment;

• Influent water from wells located in the Marcellus shale play ;

• Waste water treatment facility effluent dischar ge water; and

• Various receiving w ater body samples.



### 5.3.1 Sample Type and Location Grab samples will be collected as outlined below:

5.3.1.1 Exploration and Production Site Sampling

• Samples will be collected on active and inactive drill sites;

• F lowback and produced water on sites, evaluate solid and aqueous phases separately;

• Temporary Water Storage Vessels and Recycle Systems (Hydraulic Fracturing Water Storage Tanks, Produced Fluids Tanks, Filtration Equipment, Water Trucks)

- Water tanks screened at g reater than five (5) times background should be sampled and analyz ed;
and

• Production Equipment (Separators, Heater/Treaters, Dehydration Units, Compressors)

- If possible, collect and screen samples of liquids accumulated in side production equipment.

5.3.1

. 2. Waste Water Facilities Sampl ingPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 14 of 3 8

• Facilities that treat water from unconventional shale formations . A majority of those facilities are located in the western sector of Pennsylvania. Some of these facilities are
also located in the Central or Eastern s ector of the state;

• Facilities will include normal POTWs, specialized CWT facilities used for Marcellus shale hydraulic fracturing water treatment operations and zero limit discharge (ZLD) facilities.

• Samples at each of the waste water facilities will be sampled at least three different times;

• A t least two (2) aqueous samples will be taken at each facility during each of the three ( 3 ) sample events: influent from unconventional shale operations , total influent flow, and facility effluent discharge water. An additional solid sample will be collected from
the waste

- water sludge generated at the facility and a sediment sample will be collected
at the effluent d ischarge point where applicable; and

• The operator will record any other pertinent data during each s ample event, e.g.,
influent volume from unconventional shale operations , total influent flow, and effluent
flow. To the extent possible, the operator will coordinate the sampling of the influent
water and the effluent water with the facilities such that th e samples are all related to
the processing of the influent unconventional shale formations

. 

### 5.3.2 Sampling Methods
PIOGA and MSC recommend that representative samples be collected for flowback and production

water by perform ing multiple collection events over the entire flowback period and initial production. A representative grab sample will be collected from the appropriate tank/outlet using a disposable Teflon® bailer or a reusable stainless steel thief sampler; contents of the selected sampling implem ent will be added directly to sample containers. Samples will be placed into laboratory

- prepared containers immediately following collection and caps and labels promptly affixed to the sample containers. In cases where sample valves are available, samples may be collected directly into approved sample containers. The samples will be transported via overnight delivery service under chain

- of

- custody control to the off

site subcontract laboratory for analysis or transported to the on

- site lab. Table 8.4 identi fies container types to be used for collection of these samples. Once the sample is received by the off

- site analytical laboratory

, the laboratory personnel will immediately filter the sample using a 0.45 micron filter s . The filtered sample will placed int o a new pre

- cleaned container and properly preserved. If a stainless steel thief sampler is used, it will be decontaminated prior to first use, between sampling lo cations, and following last use . Sampling equipment decontamination procedur es are described in Section 5.5

. For the purposes of radioactivity analysis, a consistent temperature, as low as 4° Celsius (C), is not required for any aqueous samples

. Samples should be analyzed within 180 days of the sample date.



### 5.3.3 Quality Control Quality Contro l samples will be collected to verify results of off

- site laboratory and submitted at least 5% field replicate or split samples collected per total samples in a calendar quarter. Ten percent (10%) ofPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 15 of 3 8

the samples, based on the gross alpha and beta, and gam ma spectroscopy results, will also be analyzed by alpha spectroscopy for isotopic uranium (U

- 238, U

- 235 and U

- 234), isotopic thorium (Th

- 232, Th

- 230
and Th

- 228)

, isotopic radium (Ra

- 226 and Ra

- 228), for any unsupported decay chain radionuclides, and
for ra don (Rn

- 220 and Rn

- 222).



### 5.3. **4 Laboratory Analysis**  Each of the samples will be split in two so that one sample is analyzed "as is" and the other sample is preserved, filtered (by the off

- site laboratory), then analyzed (both the aqueous and the filter medi um). Each of the samples will be analyzed for gross alpha and beta and by gamma spectroscopy to identify radionuclides. Approximately 10% of the samples, based on the gross alpha and beta, and gamma spectroscopy results, will also be analyzed by alpha spec troscopy for uranium (U

- 238, U

- 235 and U

- 234), thorium (Th

- 232, Th

- 230 and Th

- 228) radium (Ra

- 226) and isotopic analysis for Ra

- 228 (a beta emitter) and for any unsupported decay chain radionuclides; and for radon (Rn

- 220 and Rn

- 222)

. Laboratory analysis methods and the required detection limits for these parameters are identified in Table 8.4. For liquids, the preferred method should be able to achieve 5 picocuries of radium 226 and radium 228 combined per liter.



### 5.4 Gas Samples Radon gas sampling occurs via several methods. The locations for samples will be those where persons are located routinely, such as control rooms or break rooms. Samples will not be collected in the head spaces of production equipment, such as evaporators, chemical tanks, or filt er presses . Samples will
also be collected for the processed natural gas, inside the distribution line. Samples for radon, in occupied areas and inside high pressure gas distribution lines, will be collected by qualified contractors.

The specific method chosen will depend on the characteristics of the sampling location, such as indoor
or outdo or locations, relative humidity c onsiderations and length of time of samples. The sampling
methods available are activated charcoal analysis, electret ion chambers ( both short

- and long

- term), alpha track detectors, continuous ra don monitors and grab sampling. The contractor will determine the optimum method, according to the potential for exposure.

I t will be necessary to determine the amount of radon that is contai ned within the p roduct side mixed with methane, such as downstream processors a nd distributers of natural gas. Natural gas samples will
be collected in an industry

- approved sample container capable of direct sampling from the high pressure 800 to 1000 psi distribution lines. These sample containers will be delivered to the laboratory by the sample collector or some other ground transport method. Regulators will be applied to the sample container so the laboratory can collect a specific volume of methane. The methane will be captured inside a device typically used for capturing radon during radon emanation analysis. Standard radon emanation counting via gamma spectroscopy, L ucas cell, or equivalent as appropriate will be
utilized to determine the concentrat ion of radon.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 16 of 3 8



### 5.5 Equipment Decontamination Procedures Disposable sampling equipment will be used wherever possible to reduce decontamination requirements. When reusable equipment is used, such equipment will be decontaminated both prior to sampling in th e field

, between uses , and following the last use on each site , as appropriate. The following decontamination steps will be performed for reusable equipment, in the following order as

necessary:

1) Potable water rinse;

2) Wash with laboratory

- grade deterg ent (Alconox®, Liquinox® or equivalent);

3) Distilled water rinse;

4) Acetone, Isopropanol or Methanol rinse;

5) Distilled water rinse; and

6) Air drying.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 17 of 3 8



## 6.0 DOCUMENTATION

**6.1 Field Documentation**

**6.1.1 Log Books and Field Data Sheets** Information pertine nt to field activities will be recorded on field logbooks. The logbooks will be bound and the pages will be consecutively numbered. Sufficient information will be recorded in the logbooks to permit reconstruction of site sampling activities. Information re corded on official project documents (e.g., survey forms, chains

- of

- custody, etc.) will not be repeated in the log books except in summary
form or cross

- reference notation where determined necessary. Field log books will be kept in the possession of the ap propriate field personnel, or in a secure place when not be ing utilized during field
work. Logbooks will become part of the final project file upon completion of the field activities. Entries recorded in log books will be made in blue or black, waterproof ink and may include, but not be limited to, the following information:

• Surveyor/sampler, date, and times of arrival at and departure from the site;

• Description of the field activity and summary of daily tasks;

• Names and responsibilities of field crew mem bers;

• Sample collection method and number/volume of sample(s) collected;

• Information regarding activity changes and scheduling modifications;

• Field observations and weather conditions;

• Types of field instruments used and purpose of use, including calibr ation methods and results;

• Field measurements made and quantities/volumes of material sampled;

• Scanning/surveying of equipment and materials;

• Global Positioning System (GPS) coordinates as appropriate; and

• Days elapsed since flowback as applicable.

Addi tionally, the sampler will record any other pertinent data during each sample event, e.g., influent volume from Marcellus shale, total influent flow, and effluent flow. To the extent possible , the operator will coordinate the sampling of the influent water , the sludge and the effluent water with the facilities such that the samples are all related to the processing of the influent Marcellus shale industry water.
Field data sheets and r adiological s urvey forms may be used to record field information in addi tion to the use of log books. Information from the log books and sketches will be used in the summary report to document the conditions when samples were collected.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 18 of 3 8



### 6.2 Sample Documentation

**6.2.1 Sample Numbering System** A unique sample numbering scheme w ill be used to identify each sample collected and designated for

on

- site an d off

- site laboratory analysis. The purpose of this numbering scheme is to provide a tracking system for the retrieval of analytical and field data on each sample. Sample identifi cation numbers will be recorded on sample labels or tags, field data sheets and/or logbooks, chain

- of

- custody records and all other applicable documentation used during the project.



### 6.2.2 Sample Labels Labels will be affixed to all sample containers during sampling activities. Information will be recorded on each sample container label at the time of sample collection. The information to be recorded on the
labels will be as follows:

• Sample identification number;

• Sample type (discrete or composite);

• Site name and area/location number;

• Analysis to be performed;

• Type of chemical preservative present in container;

• Date and time of sample collection; and

• Sample collector's name and initials.



### 6.2.3 **Container Receipt Checklist**  The condition of shipping packa ge and enclosed sample containers will be documented upon receipt at the analytical laboratory. This documentation will be accomplished using a container receipt checklist utilized by the contract laboratory.



### 6.2.4 Chain

**- of** 

**- Custody Records** 
Chain

- of

- custo dy procedures implemented for the project will provide documentation of the handling of each sample from the time of collection until completion of laboratory analysis. The chain

- of

- custody form serves as a legal reco rd of possession of the sample. An exa mple is provided in Appendix F. A sample is considered to be under custody if one or more of the following criteria are met:

• The sample is in the sampler's possession;

• The sample is in the sampler's view after being in possession;

• The sample was in the sampler's possession and then was placed into a locked area to prevent tampering; and/or

• The sample is in a designated secure area.

Custody will be documented throughout the project field sampling activities by a chain

- of custody form initiated each day d uring which samples are collected. The chain

- of

- custody will accompany the samplesPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 19 of 3 8

from the site to the laboratory and will be returned to the laboratory coordinator with the final analytic al report. Personnel with sample custody responsibilities will be required to sign, date and note
the time on a chain

- of

- custody form when relinquishing samples from their immediate custody or placing the samples i nto designated secure areas for tempor ary storage prior to shipment. Bills of lading
or air bills will be u sed as custody documentation during times when the samples are being shipped
from the site to the laboratory, and will be retained as part of the permanent sample custody
documentation. Chain

- of

- custody forms will be used to document the integrity of all samples collected.
To maintain a record of sample collection, transfer between personnel, shipment, and receipt by the laboratory, chain

- of

- custody forms will be filled out for sample sets as determined appropriate during
the course of fieldwork. The indi vidual responsible for shipping the samples from the field to the laboratory will be responsible for completing the chain

- of

- custody form and noting the date and time of shipment. This individual will also inspect the form for completeness and accuracy. Af ter the form has been inspected and determined to be satisfactorily completed, the responsible individual will sign, date,
and note th e time of transfer on the form. The chain

- of

- custody form will be placed in a sealable plastic bag and placed inside the container used for sample transport after the field copy of the form has been detached. The field copy of the form will be appropriately filed and kept at the site for the duration of
the site O&G activities.

Chain

- of

- custody seals may also be placed on ea ch container used for sample transport. These seals will consist of a tamper

- proof adhesive material placed across the lid and body of the container s. The chain

of

- custody seals will be used to ensure that no sample tampering occurs between the time the s amples are placed into the container s and the time the container s are opened for analysis at the laboratory.
Container custody seals will be signed and dated by the individual responsible for completing the chain

of

- custody form contained within the contai ner

. 

### 6.2.5 Receipt of Sample Forms The subcontract laboratory will document the receipt of samples by accepting custody of the samples from the approved shipping company

. In addition, the subcontract laboratory will document the
condition of the environme ntal samples upon receipt.



### 6.2.6 Documentation Procedures The tracking procedure to be utilized for documentation of all samples collected during the project will involve the following steps:

• Collect and place samples into laboratory sample containers; 5

• C omplete sample container label information;

• Complete sample documentation information in the field logbook;

• Complete project and sampling information sections of the chain

- of

- custody form(s);

• Complete the air bill for the co ntainer to be shipped to off

- site laboratory, if applicable;

5 For the purposes of radioactivity analys is, a consistent temperature, as low as 4° Celsius (C), is not required.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 20 of 3 8

• Perform a completeness and accuracy check of the chain

- of

- custody form(s);

• Complete sample relinquishment section of form(s) and place the form(s) into shipping
container ;

• Place chain

- of

- custody seals on the exterior of t he co ntainer ; and

• Package and ship the co ntainer to the laboratory.

The following steps will be made upon receipt of the container at the subcontract laboratory:

• Inspect each container and its contents;

• Perform the requested analyses; and

• Transmit origina l chain

- of

- custody form(s) with final analytical results from laboratory.



### 6.2.7 Corrections to Documentation Original information and data in field logbooks, on sample labels, on chain

- of

- custody forms, and on any other project

- related documentation will b e recorded in blue or black waterproof ink and in a completely legible manner. Errors made on any document will be corrected by crossing out the error and entering the correct information or data. An error discovered on a document will be corrected by
th e individual responsi b le for the entry, if possible. Erroneous information or data will be corrected in a manner that will not obliterate the original entry, and corrections will be initialed and dated by the individual responsible for the entry.



### 6.3 Samp **le Packaging and Shipping** Sample containers destined for off

- site laboratory analysis will be packaged in rigid

- body container s, and will be stored in a secure area during the time period between collection and shipment to the off

- site
subcontract lab orato ry. For the purposes of radioactivity analysis, a consistent temperature, as low as 4° Celsius (C) , is not required. Samples that exhibit elevated radiation levels may be subject to the US Department of Transportation (DOT) regulations , specifically Clas s 7, radioactive materials

. 6 The shipper is responsible to verify that the regulations are satisfied.



### 6.4 Management and Retention of Records Original copies of field data, field records, analytical data, training records, and other project specific
docum entation will be retained by the operator

. Selected representatives of PIOGA and MSC will review
and summarize the data.

6 Title 49

, Code of Federal Regulations , Part 173, Subpart I. "Class 7 (Radioactive) Materials. " April

, 2013

.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 21 of 3 8



## 7.0 LABORATORY ANALYSIS

The operator will select a radiochemistry laboratory, approved by the DEP, to complete the radiological
anal ysis of solid and aqueous samples for characterization. Table 8.2 summarizes sampling and analysi s requirements for the project. Table s 8.3 and 8.4 summarize sample collection, preservati on , and holding time requirements for each ap plicable medi um on thi s project

. S amples will be transported to

o ff

- site laboratories for analysi s in accordance with documented laboratory

- specific standard methods listed in the Analysis Methods column of Table 8.2

.



### 7.1 **Gamma Spectroscopy** Radiological COCs for these samples may be quantified for activity concentrations directly via gamma decays, or inferred via decays of gamma

- emitting progeny, after the laboratory ha s established that secular equilibrium exists between the parent and progeny radionuclides. Ra

- 226 may be me asured directly by detection of i ts 186 kilo

- electron volt (ke V) energy line for high activity waste

- sludge samples. However, the presence of U

- 235 can cause interference with direct Ra

- 226 detection since it has a

gam ma line of similar energy, 185 ke V

. The short

- lived progeny of rad ium will be used to determine Ra

226 concentrations in the soil when background levels of Ra

- 226 are en countered, in the range of 1 to 10 p C i/g. After the sample is processed by the laboratory, dried and homogenized, the samp le must be
stored in an airtight container so the short

- lived progeny can reach secular equilibrium. The sample is typically stored for at least 21 days before the sample is analyzed by gamma spectroscopy . The Ra

- 226 progeny, Bi

- 214, will then be in secu lar equilibrium with Ra

- 226 and will be analyzed to establish the
concentration of Ra

- 226. Gamma spectroscopy will also be used to identify and determine the
concentrations of other gamma emitting radionuclides that may be present in samples (e.g., Ra

- 228 by its short lived progeny Ac

- 228)

.



### 7.2 **Quality Control** Initial and daily calibrations of the off

- site laboratory gamma spectroscopy system will be performed using a mixed

- gamma National Institute of Standards and Technology (NIST) traceable source. Syste m QC will be ensured by tracking peak energy, peak resolution and net peak area for a high and low energy peak, based on daily source counts. These QC checks will be performed in accordance with applicable laboratory QC procedures.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 22 of 3 8



## 8 **.0 Tables**PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 23 of 3 8



### Table **8 .1**  **Field Screening Equipment**

Instrument Detector Parameter
Ludlum Model 2224, or equivalent Ludlum Model 43

- 89, alpha/beta scintillator, or equivalent Portable scaler/ ratemeter for detecting alpha and beta radiation Ludlum Model 2221, or equivalent Ludlum Model 44

- 10, gamma scintillator, or equivalent Portable scaler/ ratemeter for detecting gamma radiation Ludlum Model 2929, or equivalent Ludlum Model 43

- 10

- 1 , or equivalent Table top counter for detecting alpha and beta radiation

Bicron Microrem, or equ ivalent Internally

- mounted plastic gamma scintillator Portable exposure rate survey meter for gamma radiation
Ludlum Model 3, or equivalent Ludlum Model 44

- 9, thin window GM detector , or equivalent Portable survey meter for detecting beta radiation Ludlu m Model 19, MicroR meter

, or equivalent Internally

- mounted 1x1 NaI gamma scintillator Portable exposure rate survey meter for gamma radiationPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 24 of 3 8



### Table **8 .2 Summary of Materials to be Sampled** 

Sample Type Medi um Analytical
Parameters Analytical Methods Frequ ency

Vertical and Horizontal Phase Drill Cuttings

Vertical and horizontal drilling

- radionuclides phase cuttings including cuttings stored temporarily on site in lined pits or containers

Solid phase from flowback and produced water

Solids accumulated i n vessels or on equipment

Scale from drill rigs and associated equipment Soil or soil

- like Gamma spectroscopy to

Identify and

measure concentrations of TENORM radionuclides USEPA 901.1 Modified Once per site

Wastewater treatment facility sludge

Wast ewater treatment facility discharge sediments Soil or soil

- like Gamma spectroscopy to

Identify and

measure concentrations of TENORM radionuclides USEPA 901.1 Modified At least three sample events

Flowback and produced
waters

Accumulated liquids from
pr oduction equipment Aqueous Gross alpha and beta

Gamma spectroscopy

Ra

- 226

Ra

- 228 USEPA 900.0 or EPA Standard Method 7110C

USEPA 901.1

Modified

USEPA Method 903.0 Modified

USEPA Method 904.4 Modified Once per site (Composite)PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 25 of 3 8



### Table 8.2 Summary o **f Materials to be Sampled (Continued)**

Sample Type Medium Analytical
Parameters Analytical Methods Frequency

Influent Marcellus shale industry water

Wastewater treatment facility discharge water Aqueous, filtered

and unfiltered Gross alpha and beta

G amma spectroscopy

Ra

- 226

Ra

- 228 USEPA 900.0 or EPA Standard Method 7110C

USEPA 901.1

Modified

USEPA Method 903.0 Modified

USEPA Method 904.4 Modified At least three sample events

Samples collected from interior surfaces of gas processing equipment Solids Pb

- 210

Po

- 210 EML Pb

- 01 Modified

EML Po

- 2 Modified Once per site

Gas sampling Gaseous Radon To be determinedPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 26 of 3 8



### Table 8 **.3 Analytical Requirements for Solid Samples**

Parameter Analysis Method Sample Quantity Container Type Detection Limit

Gross alpha and beta USEPA 900.0 or EPA Standard Method 7110C 100 grams Plastic 10 dpm

Ra

- 226 and Ra

- 228 USEPA 901.1 Modified 500 grams Plastic 1 pCi/g
Isotopic Thorium ASTM D3972

- 90M 100 grams Plastic 0.1 pCi/g Isotopic Uranium ASTM D3972

- 90M 100 grams Plas tic 0.1 pCi/g Gamma emitting

radionuclides USEPA 901.1 Modified 1 liter Plastic 1 pCi/g

Pb

- 210 EML Pb

- 02 Modified > 10 grams Plastic 0.5 pCi/g

Po

- 210 EML Po

- 2 Modified > 10 grams Plastic 0.5 pCi/g

Note: There are no requirements for holding times or preservative. For the purposes of radioactivity analysis, a consistent temperature, as low as 4° Celsius (C), is not required.

Samples should be double bagged so as to avoid damage during shipping.

Samples should be analyzed within 180 days after sampli ng.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 27 of 3 8



### Table 8 **.4 Analytical Requirements for Aqueous**  **Samples**

Parameter Analysis Method Sample Quantity Container Type Detection Limit Gross alpha and beta USEPA 900.0 1 gallon Plastic or glass 5 pCi/liter

Ra

- 226 (Total radium by alpha) USEPA 90 3.0 1 gal lon Plastic or glass 1 pCi/liter

Ra

- 226 (Radon

emanation) USEPA 903.1 1 gallon Plastic or glass 1 pCi/liter

Ra

- 228 USEPA 904.0 1 gallon Plastic or glass 1 pCi/liter Isotopic Thorium ASTM D3972

- 90M 1 gallon Plastic or glass 1 pCi/liter Isotopic Uranium ASTM D3972

- 90M 1 gallon Plastic or glass 1 pCi/liter Gamma emitting

radionuclides USEPA 901.1 Modified 1 gallon Plastic or glass 5 pCi/liter

Note: There are no requirements for holding times or preservative. For the purposes of radioactivity analysis, a consistent temperature, as low as 4° Celsius (C), is not required.

Samples should be analyzed within 180 days after sampling.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 28 of 3 8



## 9 **.0 Appendices**PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 29 of 3 8



## Appendix **A Exposure Rate Measurements**

1. Surveys shall be performed with a portable radiation survey instrument that is sensitive to gamma radiation (e.g., sodium iodide detector, microR meter, or microrem meter).
2. The instrument shall be turned on and permitted to stabilize for a minimum of 30 seconds prior to performing measurements

.

3. Pre Operational Checks
3.1. Pre

- op erational checks shall be completed at the start and end of each day the instrument is
used

. 3.1.1. Each instrument shall be labeled with a unique identifier (e.g., serial number of detector and rate meter) to enable traceability to surveys and records.
3.1.2. Prior to each use, or at the start and end of each day the instrument is used , each instrument shall be checked for the following : b att ery function, operating voltage, r eset b utton function, a udible response function, p hysical damage,
3.1.3. Verify that the instrument wa s calibrated within 1 2 months prior to its use

. 3.2. Test the instrument r esponse to a reference radioactive source. 3.2.1. If any response is different from the mean measurement by more than 3 standard deviations (±3δ ) , that instrument shall be removed from service.
3.2.2. If any two consecutive daily responses exceed the mean measurement + the 2σ value, the instrument may be removed from service pending an evaluation of its operational status.
3.3. Document the instrument response to background radiation.
3.3.1. Response to background radiation shall be determined at the start and end of each day the instrument is used, at a reproducible locati on in the vicinity of the measurement site
but not near known radiation sources.
3.3.2. Three readings should be obtained at the start of each work shift, and three readings
obtained at the end of each work shift.
3.4. The results of the daily check s shall be recorded on a record sheet.
3.5. Instruments failing any pre

- operational check shall be taken out of service, segregated from other instruments, tagged as "out of service", and repaired prior to use.

4. Radiation Survey
4.1. Surveys shall be conducted by walking slowly over t he area of interest with the detector held at a height of approximately one meter above the ground (waist high).
4.1.1. An increase in the audible response or in the needle/indicator movement may indicate the presence of radioactivity.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 30 of 3 8

4.1.2. The instrument shall be hel d stationary in the locations where the increased response is
noted.
4.2. Readings shall be recorded on a radiation survey form

. 4.3. Carefully note the position of the range selector switch when observing the survey meter reading.
4.4. Any comments and notations that ma y be necessary for interpretation of results should be
recorded on the survey form

. 4.5. The individual performing the survey shall sign and date the completed Radiological Survey

Form.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 31 of 3 8



## Appendix B Surface Contamination **Measurements**

1. Total Contamination on Su rfaces
1.1. Total (fixed plus removable) contamination shall be measured by direct survey with portable radiation survey instruments sensitive to beta/gamma radiation (e.g., pancake Geiger

- Mueller detector, or equivalent) or alpha radiation (e.g., alpha scintil lation detector), or equivalent).
1.2. The instrument shall be turned on and permitted to stabilize for a minimum of 30 seconds) prior

to performing surveys

.

2. Pre Operational Checks
2.1. Pre

- operational checks shall be completed at the start and end of each day the instrument is
used

. 2.1.1. Each instrument shall be labeled with a unique identifier (e.g., serial number of detector and rate meter) to enable traceability to surveys and records.
2.1.2. Prior to each use, or at the start and end of each day the instrument is used, eac h instrument shall be checked for the following : b attery function, h igh voltage, r eset b utton function, a udible response function, p hysical damage,
2.1.3. Verify that the instrument was calibrated within 12 months prior to its use

. 2.2. Test the instrument response t o a reference radioactive source.
2.2.1. If any response is different from the mean measurement by more than 3 standard deviations (±3δ), that instrument shall be removed from service.
2.2.2. If any two consecutive daily responses exceed the mean measurement + the 2σ va lue, the instrument may be removed from service pending an evaluation of its operational status.
2.3. Document the instrument response to background radiation.
2.3.1. Response to background radiation sh all be determined at the start and end of each day
the instrument is used, at a reproducible location that is in the vicinity of the
measurement site but not near known radiation sources.
2.3.2. Three readings should be obtained at the start of each work shift, and three readings
obtained at the end of each work shift.
2.4. The res ults of the daily check s sh all be recorded on a record sheet.
2.5. Instruments failing any pre

- operational check shall be taken out of service, segregated from other instruments, tagged as "out of service", and repaired prior to use.

3. Radiation Survey for Total Activity on a Surface
3.1. Surveys shall be conducted by moving the detector at a pre

- determined rate and within 0.25
inch of the surface.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 32 of 3 8

3.2. The speed that the detector moves over the surface is important. The detector should move at a speed less than 2 inches per second.
3.3. An increase in the audible response or in the needle/indicator movement may indicate the presence of radioactivity.
3.4. The detector shall be held stationary over the areas where an increased response i s noted.
3.5. Any changes in the surface structure that may affect instrument response shall be documented
on the radiation s urvey f orm. 3.6. S urvey points with the highest count rates shall be identified and recorded on the radiation survey form , along with an estimate of the physical dimensions of the area w ith elevated readings.
3.7. T he position of the range selector switch shall be noted when observing the meter reading.
3.8. Any comments and notations that may be necessary for interpretation of the results should be
recorded on the radiation survey form

. 3.9. The indiv idual performing the survey shall sign and date the completed radiation survey form

.

4. Survey Methods for Determining the Extent of Removable ( Loose ) Contamination on Surfaces
4.1. Loose contamination shall be measured with numbered dry disc smears wiped over a surface
area of at least 100 cm 2 , with the unnumbered side in contact with the surface.
4.2. If the item/area to be smeared is less than 100 cm 2 , the smear results shall be recorded as “per smear”, with the size of the smeared area noted on the radiation survey form

. 4.3. A filter paper disc (unnumbered side down) shall be placed on the surface to be smeared.

4.4. The disc shall be moved over an "S"

- shaped area using moderate pressure, covering approximately 100 cm 2 (16 square inches), or about 16 inches in length, or the entire surface, if
it is less than 100 cm 2 in area.
4.5. The disc smear shall be placed in a sample holder such that individual smears are separated from each other to prevent cross contamination.
4.6. A sample number that uniquely identifies the smear shall be doc umented on the sample holder
and on the radiation survey form

. 4.7. Each smear may be submitted to an analytical laboratory for determination of gross alpha and/or gross beta activity ( in units of dpm ) as described in Table 8.3.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 33 of 3 8



## Appendix **C Sampling Protocol**  **for Conventional & Unconventional**  **O il or**  **Gas Drill Cuttings**

Sampling and analysis will be completed for every 1000 cubic yards of material (cuttings) or per well, whichever is more frequent and at least four discreet samples per well. Unconventional (Sha le

Formations) gas wells shall be divided into two distinct sections for sampling and analysis. Unconventional (Shale

- Formations) vertical drill cuttings are to include material encountered from the
surface to the kick

- off

- point or above the shale formatio n. Horizontal drill cutting will include material
from the kick

- off

- point or once the vertical drill encounters the shale formation to the end of the horizontal drilling. Separate or discrete samples will be taken to represent Brine, Pyritic, or Petroleum formations encountered within to drilling process.

a. The Driller will take discreet samples and place in 1 liter wide mouth amber bottles filled to within one inch of the top, after the material is dewatered or stabilized for transportation or handling. A minimum of four discreet samples per well / well section shall be collected.

i. Estimate volume of cuttings from the well prior to drilling based on depth and diameter

ii. If the well is expected to produce less than 1000 cubic yards of cuttings divide the depth of the well by four (4) to determine the four section of the well to be sampled.

iii. A discrete sample shall be obtained from a similar area of each section

– preferably the
middle of each section.

iv. If the well is expected to produce greater than 1000 cubic yards of cuttings

– perform the sampling for the first 1000 cubic yards, then repeat the process for the remainder of the cuttings. It is unlikely that a single well would produce more than 2000 cubic yards of cuttings.

b. The 1 liter wide mouth amber bottles shall be labeled with proper id and a complete Chain of Custody filled out for the sample.

c. The following information must accompany the sample:

i. Listed on the Chain of Custody

1. Drilling Company Name

2. CountyPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 34 of 3 8

3. Latitude and Lon gitude

4. Type of cuttings (Conventional well, Unconventional (Shale

- Formations) Vertical or Horizontal)

5. Depth of well at time of sampling

6. Date and time of sampling

ii. Drilling Additives (This may be disclosed prior to sampling)

d. The sample bottl es are to be stored on ice and shipped directly to the laboratory after sampling of well drill cuttings or section of the well, if the well in Unconventional (Shale formations), with completed Chain of Custody.

e. Non

- typical Discrete Samples will also be taken to represent any non typical materials encountered during the drilling process. These samples are in addition to the four discreet samples based on sampling plan. Such non typical cutting materials are the product of:

• Brine

• Pyritic

• Petrole um bearing formationsPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 35 of 3 8



## Appendix **D Sampling Protocol for**  **Conventional & Unconventional Cuttings from**  **a Pit**

Sampling and analysis will be completed for every 1000 cubic yards of material (cuttings) or per well, whichever is more frequent and at least fo ur discreet samples per well. The cuttings will be sampled
from the on

- site pit. Separate or discrete samples will be taken to represent Brine, Pyritic, or Petroleum formations encountered within the drilling process. If possible, sampling of the pit s hould be completed prior to adding cuttings that contain product.

a. After cuttings have settled in the pit, water shall be removed as per normal procedures using a
vacuum truck.

b. A backhoe or excavator will be used to sample the pit.

i. The Driller wil l take discreet samples and place in 1 liter wide mouth amber bottles filled to within one inch of the top. Samples should be dewatered as much as possible prior to filling glass sample jar. A minimum of four discreet samples per well shall be collected after all material is placed in the pit

ii. Divide the pit into four equal sections using imaginary lines. Create a small hand drawn diagram of the pit and sections

– make sure the area the blow

- off enters the pit is marked on the diagram. Number the se ction in numerical order

– use number 1 for the section the blow enters the pit.

iii. Using a backhoe or excavator obtain 1 sample per imaginary quarter of the pit.

1. One sample must be taken from the course cuttings in the quarter where the
blow

- off ente rs the pit

2. The remaining three samples shall be taken from the other three quarters

3. Samples can be taken at various depths from the pit

iv. If the well is expected to produce greater than 1000 cubic yards of cuttings

– divide the pit into eight secti ons and sample each section. It is unlikely that a single well would produce more than 2000 cubic yards of cuttings.

c. The 1 liter wide mouth amber bottles shall be labeled with proper id and a complete Chain of Custody filled out for the sample.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 36 of 3 8

d. The following information must accompany the sample:

i. Listed on the Chain of Custody

1. Drilling Company Name

2. County

3. Latitude and Longitude

4. Type of cuttings (Conventional well, Unconventional (Shale

- Formations) Vertical or Horizontal)

5. Depth of we ll at time of sampling

- section of the on

- site pit relating to the diagram on the COC.

6. Date and time of sampling

ii. Drilling Additives (This may be disclosed prior to sampling)

e. The sample bottles are to be shipped directly to the laboratory after sampling of well drill cuttings with completed Chain of Custody.

f. Non

- typical Discrete Samples will also be taken to represent any non typical materials encountered during the drilling process. These samples are in addition to the four discreet samples based on sampling plan. Such non typical cutting materials are the product of:

• Brine

• Pyritic

• Petroleum bearing formationsPIOGA / MSC Field Sampling Plan November 4 , 2013 Page 37 of 3 8



## Appendix E Characterize LPG Processing Equipment

1. Surveying LPG processing equipment that potentially contains TENORM inside the equipment will be performed by personnel specifically for alpha contamination surveys so as to provide a consistent and complete survey

. 2. Fixed and removable survey measurements will be performed to identify activity that can be
removed versus ac tivity that is fixed on the surface of the contaminated item and cannot be easily
removed.
3. Radiation surveys will be performed with radiation survey equipment that have been calibrated
within 12 months of the survey . Daily operational checks will be per formed on survey equipment to

ensure proper accuracy (as specified in Appendix B)

. 4. G amma scintillation detector s will used to measure the gamma radiation levels (in cpm) in contact with the surfaces being characterized.
5. Surfaces that exhibit more than 2 ti mes the background gamma count rate will be characterized
further.
6. An alpha particle survey instrument will be used to survey all accessible locations of the surface being characterized

. 7. Surfaces that exhibit an alpha count rate of more than 1 0 cpm will b e characterized further

. 8. LPG processing equipment suspected of being impacted with TENORM (primarily Pb

- 210 and Po

- 210 inside propane separation and storage components ) will be opened, if possible, to perform alpha
radiation measurements of inner surfaces and to collect samples of solids (if present) on inner
surfaces.
8.1. The inner surface of small diameter piping or other LPG processing components will be surveyed for the presence of alpha and beta radiation using the procedure described in Appendix B.
8.2. A sa mple for removable material from the inner surfaces will be collected, if possible. using the procedure as described in Appendix B.
8.3. The survey procedures noted above will be repeated at other locations, if possible, inside the pipe and equipment.
8.4. The indi vidual performing the survey shall sign and date the completed radiation survey form.PIOGA / MSC Field Sampling Plan November 4 , 2013 Page 38 of 3 8



## Appendix **F Example of Chain of Custody** QSP

- 010

- F286 Rev 000 CHAIN OF CUSTODY SAMPLE SUBMISSION RECORD

Customer No.___________________ Work Order No._______________________

Drilling Company ID #

_______________________________ Phone Number

__________________________ County

__________________________ Latitude and Longitude

____________ ______________ Type of Cuttings: Conventional Unconventional (Shale

- Formatio ns) Vertical Horizontal

Type of Drilling: Air Foamer Air mist Mud Aqueous Non aqueous (oil) Synthetic Grab #1 Samplers Initials Time

___________ __________ Depth of well

___________

Grab #2 Samplers Initials Time

___________ __________ Depth of well

_________ __

Grab #3 Samplers Initials Time

___________ __________ Depth of well

___________

Grab #4 Samplers Initials Time

___________ __________ Depth of well

___________ Drilling Additives (Please include a copy of MSDS

– unless previously supplied )

___________________________________________________________________________

RELINQUISHED BY: (SIGNATURE) DATE TIME RECEIVED BY: (SIGNATURE) DATE TIME

RELINQUISHED BY: (SIGNATURE) DATE TIME RECEIVED BY: (SIGNATURE) DATE TIME

LOGGED IN BY: (SIGNATURE) DATE TIME