# RPSEA

Characterization of Flowback Waters from
the Marcellus and the Barnett Shale Region s

Report No. 08122

- 05.0 9



# Barnett and Appalachian Shale

Water Management and Reuse
Technologies

Contract 08122

- 05

March 1 6 , 201 2

Principal Investigator Pr incipal Investigator

Thomas D. Hayes, Ph.D.

Coordinator, Environmental
Engineering Solutions

Gas Technology Institute
1700 S. Mount Prospect Rd.

Des Plaines, IL Blaine F. Severin, Ph.D., P.E.
Senior Process Engineer

Environmental Process Dynamics, Inc.

4117 Spinnaker Ln.

Okemos, MI

## LEGAL NOTICE

This report was prepared by the Gas Technology Institute as an account of
work sponsored by the Research Partnership to Secure Energy for

America, RPSEA. Neither RPSEA members of RPSEA, the National Energy
Technology Laboratory, the U.S. Department of Energy, nor any person
acting on behalf of any of the entities:

a. MAKES ANY WARRANTY OR REPRESENTATION, EXPRESS OR

IMPLIED WITH RESPECT TO ACCURACY, COMPLETENESS, OR

USEFULNESS OF THE INFORMATION CONTAINED IN THIS

DOCUMENT, OR THAT THE USE OF ANY INFORMATION,

APPARATUS, METHOD, OR PROCESS DISCLOSED IN THIS

DOCUMENT MAY NOT INFRINGE PRIVATELY OWNED RIGHTS,

OR

b. ASSUMES ANY LIABILITY WITH RESPECT TO THE USE OF, OR

FOR ANY AND ALL DAMAGES R ESULTING FROM THE USE OF,

ANY INFORMATION, APPARATUS, METHOD, OR PROCESS

DISCLOSED IN THIS DOCUMENT.

THIS IS AN INTERIM REPORT. THEREFORE, ANY DATA, CALCULATIONS,

OR CONCLUSIONS REPORTED HEREIN SHOULD BE TREATED AS

PRELIMINARY.

REFERENCE TO TRADE NAM ES OR SPECIFIC COMMERCIAL PRODUCTS,

COMMODITIES, OR SERVICES IN THIS REPORT DOES NOT REPRESENT

OR CONSTIITUTE AND ENDORSEMENT, RECOMMENDATION, OR

FAVORING BY RPSEA OR ITS CONTRACTORS OF THE SPECIFIC

COMMERCIAL PRODUCT, COMMODITY, OR SERVICE.

# THIS PAGE INTENTIONALLY LEFT BLANK

### iv TABLE OF CONTENTS

Table of Contents

................................ ................................ ................................ ............ iv

List of Tables

................................ ................................ ................................ ................... v List of Figures

................................ ................................ ................................ .................. vi
List of Acronyms and Abbreviations

................................ ................................ ............... vii
Executive Summary

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

Introduction

................................ ................................ ................................ ..................... 3

Methods and Procedures

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

Results fr om the Marcellus

................................ ................................ ............................ 10

Flowback Water Collection Characteristics

................................ ................................ 11 General Chemistry

................................ ................................ ................................ ..... 12 Organic Compounds

................................ ................................ ................................ .. 20 Volatile Compounds

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

Semi volatile Compounds

................................ ................................ ....................... 24

Pesticides

................................ ................................ ................................ ............... 28 Polychlorinated Biphenyls (PCBs)

................................ ................................ .......... 28

Metals

................................ ................................ ................................ ........................ 28

Results From The Barnett

................................ ................................ ............................. 32

Flowback Water Collection Volumes

................................ ................................ ......... 32 General Chemistry

................................ ................................ ................................ ..... 33 Organic Compounds

................................ ................................ ................................ .. 38 Volatile Compounds

................................ ................................ ............................... 39

Semi volatile Compounds

................................ ................................ ....................... 41

Pesticides

................................ ................................ ................................ ............... 43 Polychlorinated Biphenyls (PCBs)

................................ ................................ .......... 45

Metals

................................ ................................ ................................ ........................ 45

Discussion

................................ ................................ ................................ ..................... 48
Heavy Metals

................................ ................................ ................................ ............. 50 Total Dissolved Solids, Major Cations and Anions

................................ .................... 50
Implications for Fate and Transport

................................ ................................ ........... 54

Conclusions

................................ ................................ ................................ ................... 57

References Cited

................................ ................................ ................................ .......... 59
Acknowledgements

................................ ................................ ................................ ....... 61 Appendix A: Field Sampling and Analysis Plan (FSAP)

................................ ............... 62 Appendix B: Quality Assurance Project Plan (QAPP)

................................ .................. 63

### v LIST OF TABLES

Table 1. Measurements and Determinations. General Chemistry 7

Table 2 . Summary of Methods 9
Table 3: Water Use and Flowback Water Collection Associated with Hydraulic
Fracturing Completion of Shale Gas Wells 11

Table 4. Summary of Chemical Characteristics of Water Used for Hyd raulic

Fracture 14

Table 5: Range of Results from 1 and 5 Day Samples 15
Table 6: Range of Results from 14 and 90 Day Samples 16

Table 7: Concentration of Total Dissolved Solids in Flowback Water at 19
Locations (mg/l) 17

Table 8: Total Organic Carbon TOC (mg/l) 19
Table 9: Biochemical Oxygen Demand (BOD mg/l) 20
Table 10: Influent Water Day 0 (minus sand) 22
Table 11: Number of Observations of 70 Volatile Compounds in All 60 Marcellus
Samples 23

Table 12: Semi

- Volatile Content in 19 Marcellus Influent Samples 25

Table 13: Number of Observations of 116 Semi

- Volatile Compounds in all 60
Marcellus Samples 27

Table 14: Metals Data in Raw Water and Source Water with Additives 29
Table 15: Metals Data for Marcellus Flowback Days 1 and 5 30
Table 16: Metals Data for Marcellus Flowback Days 14 and 90 31
Table 17: Sample Dates (Days after Fracture) for 5 Sites in the Barnett 32
Table 18: Cumulative Flow (BBL) for 5 Sites in the Barnett 33
Table 19. Summary of Chemical Characteristics of Influent Water Used for
Hydraulic Fracturing after Additives were Blended 34

Table 20 General Chemical Parameters, Barnett Day 1 and Day 3 35
Table 21: Summary of General Chemistry of Flowback Water Days 5

- 6 and 10

- 12 36
Table 22: Salt Concentrations (T DS, mg/l) 37
Table 23: Total Dissolved Carbon Concentrations (TDS, mg/l) 37
Table 24: BOD (TDS, mg/l) 38
Table 25: COD (TDS, mg/l) 38
Table 26: Volatile Organics in the Influent Water Samples 39
Table 27: Summary Volatiles Data; All Site Samples (Days 1

- 12, Total = 16
Samples) 40

Table 28: Semi Volatile Compounds in the Influent Water 41

Table 29:Semi

- volatiles Data from 16 Site Samples (Days 1

- 23) All Five Sites 43
Table 30: Summary Pesticide Data 44

Table 31; PCB Data 45

Table 32: Total Metals in Influent Water Samples 46
Table 33: Metals Data in the Barnett Samples 47

Table 34: Total Metals Data Days 5

- 6 and 10

- 12 48
Table 35. Comparisons of Median Metals Levels in Shale Gas Waters with
Municipal Biosolids (Sewage Sludge) 50

### vi LIST OF FIGURES

Figure 1 . Salt Concentration and Flowback Water Flow Versus Time from

Location 

### B 18

Figure 2: Distribution of Observations for 70 Volatile Organics from 60 Samples

from the Marcellus 24

Figure 3: Distribution of Observation of Semi Volitales in 60 Marchellus
FLowback Samples from 19 Sites 26

Figure 4: Number of Detectable and Non

- Detectable Tests for Volatile
Compounds 40

Figure 5: Distribution of Observations of Semi volatile Organics in 16 Site
Samples 42

Figure 6: Median Common Components of Flowback Water from the Marcellus
Samples 49

Figure 7: Median Observations of Common Contaminants in the Barnett Samples 49
Figure 8: Relative Abundance of Cations in Flowback Waters 52

Figure 9: Relative Abundance of Anions in Flowback Waters 53

### vii LIST OF ACRONYMS AND ABBREVIATIONS

Acronym Definition Acronym Definition



### ASWCMC Appalachian Shale Water

Conservation and
Management Coalition PPM Part per million (≈mg/l)

BBL/bbl Barrel (42 gallons) PA

- DEP Pennsylvania Department of

Environmental Protection

BCF Billion Cubic Feet PPB Part per billion (≈μg/l)

BTEX Benzene, Toluene,

Ethylbenzene, Xylenes POGAM Pennsylvania Oil & Gas

Association

Flowback

Water The water stream that

flows from a well in the
weeks following hydraulic
fracturing completion QAPP Quality Assurance Project Plan

Frac k Hydraulic Fracture TCF Trillion Cubic Feet

Frac Job Well completion event

involving hydraulic
fracturing TDS Total Dissolved Solids

FSAP Field Sampling and

Analysis Plan TPH Total Petroleum Hydrocarbons

mg/l Milligrams per liter PCB Polychlorinated Biphenyl
Compound

μg/l Micrograms per liter POTW Publicly Owned Treatment
Works (a Sewage Treatment
Facility)

MSC Marcellus Shale Coalition WV

DEP West Virginia Department of

Environmental Protection

### 1



## EXECUTIVE SUMMARY

The hydraulic fracturing of shale for the development of unconventional natural gas

sources has such great potential that it is often touted as an energy revolution. With all

the positive economic upside to the development of this resource, detractors to the

industry question the potential environmental impact of the process. Good water

management is essenti al to the economic sustainability of the industry. Unfortunately,

the public literature is replete with anecdotal evidence. There remains a dearth of

sound scientific publications on which rational decisions may be made. The purpose of

this report is he lp address water management issues by elucidating the chemical nature

of flowback waters. Hopefully, this knowledge may be used to help develop sustainable

water management plans.

This report covers recent sampling of flowback water from 19 sites in the Marcellus

region of Pennsylvania and West Virginia and 5 sites from the Barnett region of northern

Texas. The database includes flowback rates, volumes, and chemical analyses of the

injected water and the recovered flowback water. Chemical analyses inclu de general

chemical information typically used for drinking water analyses. Additionally, the waters

were tested for 70 volatile organics, 116 semi

- volatile organics, 22 pesticides, PCB’s,

and 27 metals. The list of chemicals evaluated for this project w as co

- developed by

industrial partners, and state environmental agency representatives.

The data are of interest for a couple of discernable trends, such as increased salts

(total dissolved solids) and decreased flow with time. The main salt compositio n

appears to be sodium chloride. Chloride accounts for more than 9 3 % of the available

anionic content. Some sulfate (500

- 1000 ppm range) is present in the Barnett samples,

but is very low in the Marcellus samples (<100 ppm). Carbonate alkalinity, the ma in pH

buffering system in natural waters is quite low (<150 ppm). The commonly observed

cations are sodium, calcium, barium, strontium, and iron. The low alkalinity and sulfate

concentrations are keys to understanding the relative abundance of the variou s cation

species. They are also keys to understanding the range and capability of

treatment/reuse options for the prevention of scale build

- up. Heavy metals (other than

iron) are generally either not detected, or in very trace concentrations, and genera lly far

less concentrated than levels present in municipal wastewater sludge.

### 2 Other components, such as the aromatics such as benzene, toluene, ethyl

benzene, and toluene (BTEX) and other organic compounds, such as naphthalene, that

are commonly asso ciated with petroleum sites tend to be present only in low to trace

concentrations (ug/l to ppm) without a discernable pattern with time. Heavier

polynuclear aromatic hydrocarbon compounds (PAH’s)

--- such as commonly seen in

petroleum wastewater

--- are generally not present in the flowback water, and occur

occasionally in only very trace concentrations. These compounds are considered by

the wastewater treatment industry to be highly treatable. Several standard treatment

methods are available to handle these types of compounds at these low levels.

Compounds that can originate from human sources, such as pyridine and the

general class of phthalate esters

, are found in less than 50% of the samples.

Methylated phenols are more commonly encountered, but only in concentrations

between 10 to 100 ppb. Halogenated compounds are rarely encountered. One

pesticide was detected (<0.05 ppb) in one sample (out of 79 ) and was likely an error.

PCB’s were not detected in any samples.

Most of the organic chemical analyses performed resulted in “non

- detects.” These

non

- observations are vital to begin the discussion of what “not to look for” when

performing analyses on shale gas waters. It is important to focus engineering and

planning resources on the chemistry that is present, and to avoid effort in fruitless

areas.

### 3



## INTRODUCTION

The Marcellus shale formation is the largest known shale deposit in the world. It

o verlies much of the Appalachian Basin from West Virginia in the south, to Upstate New

York in the north, and Ohio to the west. The recoverable reserves of natural gas in the

Marcellus shale have been estimated at more than 489 trillion cubic feet (Engelde r,

2008). Recent advances in horizontal drilling and multi

- stage hydraulic fracturing

technologies have made sustainable natural gas production viable from otherwise

uneconomical, unconventional shale reservoirs such as the Barnett, Haynesville,

Fayettevi lle, Woodford, et al. These tools and technologies have been successfully

applied and currently enable the ongoing and the future development of these shales.

Many of the logistical challenges associated with the development of shale gas

stem from the l arge amounts of water associated with the completion and operation of

shale gas wells that must be transported, stored and disposed of in a manner that is

protective of human health and the environment. In the course of developing shale gas

in the Barnett and the Marcellus Shale, thousands of wells will be drilled and completed.

Hydraulic fracturing (“ fracking” ) is a necessary step for the completion of each of these

wells in order to achieve economic well performance in terms of natural gas production.

This step requires between 1 and 4 million gallons (23,800 and 95,200 bbl) of water for

successful completion of each well; vertical wells require approximately 1 million gallons

(23,800 bbl) and horizontal wells require 3

- 4 million gallons (71,400 to 95,2 00 bbl)

(Gaudlip, et al., 2008).

During a typical “frac K job,” water is pumped downhole while chemicals such as

friction reducers and various grades of sand are introduced to ensure a successful

fracture of the shale. Following hydraulic fracturing, a f raction of the water

(approximately 25%) that was injected is collected over several days resulting in the

collection of a “flowback” water stream that contains salts, oils and greases, and soluble

organics (volatile and semi volatile ) that accumulated in the water downhole. Flowback

water also contains low concentrations of chemicals that are introduced during the frac k

job which normally include friction reducing polymers, corrosion inhibitors, scale

inhibitors, and biocides. These additives facilitate the hydraulic fracturing process and

prevent problems with well operation.

### 4 The first steps in identifying effective water management alternatives include an

effective analysis of the characteristics of the water streams involved in shale gas

development

. The overall objective of this project is to develop an information base on

the nature and composition of influent water and flowback waters associated with

completions of shale gas wells in the Marcellus and Barnett Shales.



## METHODS AND PROCEDUR ES

Upon request to the Marcellus Shale Coalition (MSC), 17 member companies of the

MSC volunteered 19 locations for the sampling of influent and effluent water streams.

Two companies provided access to five sites in the Barnett. At each location, a well

comple tion was conducted using hydraulic fracturing procedures that involved the

injection of an influent stream of water and the subsequent collection of flowback water.

Standard procedures were used to conduct sampling and analysis needed for the

development of water characterization data. All sampling was performed by the GTI

subcontractor, URS, following the same standard procedures. All sample analyses

were performed by a single laboratory, Test America of Pittsburgh, PA. Test America,

an independent ana lytical laboratory, provided the appropriate sample containers,

preservatives and completed the analytical analyses. Test America is certified in West

Virginia and Pennsylvania. Data tabulation, analysis and information base development

was provided by t he Gas Technology Institute for this effort.

Details of the methods and procedures used for the collection and analysis of

samples obtained from each of the 19 locations are found in the Field Sampling and

Analysis Plan (FSAP) which is located in Appendi x A. The Field Sampling and Analysis

Plan (FSAP) was developed to ensure that the data and information gathered for the

flowback characterization study was properly collected and documented.

A major aim of the characterization study was to generate technically sound data.

To meet this objective a Quality Assurance Project Plan (QAPP) was used to generate

accurate, precise, representative and complete data; this document is provided in

Appendi x B. The QAPP provided the specific quality assurance/quality control (QA/QC)

procedures executed during the flowback Characterization Study.

### 5 Together

, the FSAP and QAPP comprise the Sampling and Analysis Plan (SAP).

The SAP was designed to meet the fo llowing informational goals:

Identify specific constituents of interest (COI) associated with flowback water;

Determine whether hydraulic fracturing additives are a source of COI in the

management of water associated with shale gas development; and,

Prov ide sufficient information for the selection of proper water management and

disposal techniques.

Prior to initiating the characterization study, the SAP was reviewed by regulatory

officials from the Pennsylvania Department of Environmental Protection (PAD EP) and

the West Virginia Department of Environmental Protection (WVDEP).

The original SAP proposed that four (4) grab samples from six (6) vertical or

horizontal well locations be collected throughout West Virginia and Pennsylvania. The

following grab samples were proposed:

One baseline fracturing water sample that includes the fracturing chemicals,

excluding the sand;

Flowback water samples will be collected on days 1, 5 and 14 of the following the

fracturing process; and

Water from an existing prod ucing well at 90 days following hydraulic fracturing.

A similar plan was developed for sites in the Barnett with projected collection on

days 1, 3, 5, and 10.

The list of constituents recommended for the characterization study was developed

from comments received from the PADEP, the WVDEP and members of the

Appalachian Shale Water Conservation and Management Committee (ASWCMC).

Because the recommended list of constituents was extremely extensive, it was decided

that one sample from each site would be comp leted for the full list of recommended

constituents. All other samples were collected and analyzed for a subset of these

constituents, which was designed based on generator knowledge.

The constituents analyzed also include the 56 parameters currently included on the

PA

- DEP Form 26R instructions. This list of parameters is currently undergoing review

and changes are being considered given that much has learned since that list was

initia lly included on the instruction form. Also, it may be appropriate to address

### 6

concerns on a media and program specific basis in lieu of the approach suggested by

the Form 26R instructions.

To be consistent with this form, the ASWCMC and MSC modified th e sampling

program to include additional constituents. More locations were also included to assist

operators meet disposal requirements in newly developed areas.

Following the first few rounds of sampling, industry identified a data gap with

respect to c haracterizing the supply water used for fracturing. Supply water is identified

as the water used for fracturing prior to introducing the frac k ing additives.

The updated protocol characterization study called for the collection of five (5) grab

samples f rom the each of the locations and expanded the sampling effort to encompass

19 well locations volunteered by 17 member companies of the Marcellus Shale

Coalition. The plan for the Barnett samples called for collection of four (4) samples at

five sites. Ta ble 1 presents the list of all of the constituents of interest (by category) that

formed the basis for sample analysis. Analytical methods used to perform the various

determinations are listed in Table 2.

### 7

Table 1. Measurements and Determinations.

General Chemistry

pH
Acidity
Total Alkalinity

Hardness as CaCO3
Total Suspended Solids

Turbidity

Chloride

Total Dissolved Solids
Specific Conductance Total Kjeldahl Nitrogen
Ammonia Nitrogen

Nitrate

- Nitrite

Nitrite as N
Biochemical Oxygen

Demand
Chemical Oxygen

Demand Total Organic Carbon (TOC)
Dissolved Organic Carbon Oil & Grease (HEM)
Cyanide, Total
Amenable Cyanide

Bromide

Fluoride

Total Sulfide

Sulfate

Total Phosphorus

Total Recoverable

Phenolics

Volatile Compounds

1, 4

- Dichlorobenzene

1, 3

- Dichloropropane

2, 2

- Dichloropropane

1, 1

- Dichloropropene

p

- Isopropyltoluene
Naphthalene

n

- Propylbenzene

1, 2, 3

- Trichlorobenzene

1, 2, 4

- Trichlorobenzene

1, 2, 4

- Trimethylbenzene

1, 3, 5

- Trimethylbenzene
Benzyl chloride
Isopropylben zene

2

– Butanone
Methyl tert

- butyl ether
(MTBE)
Xylenes (total)

2

- Chloroethyl vinyl ether

cis

- 1, 2

- Dichloroethene

Bromobenzene

n

- Butylbenzene

sec

- Butylbenzene

tert

- Butylbenzene

4

- Chlorotoluene

1, 2

- Dichlorobenzene 1, 3

– Dichlorobenzene

Acetone

Acrolein
Acrylonitrile

Benzene

Bromodichloromethane

Bromoform

Bromomethane

Carbon disulfide

Carbon tetrachloride

Chlorobenzene

Chloroethane

Chloroform

Chloromethane

Dibromochloromethane

1, 2

- Dibromo

- 3

– chloropropane

1, 2

- Dibromoethane (EDB)

Dibromomethane

Dichlorodifluoromethane

1, 1

– Dichloroethane

1, 2

– Dichloroethane

1, 1

– Dichloroethene

trans

- 1, 2

- Dichloroethene

1, 2

- Dichloropropane cis

- 1, 3

- Dichloropropene

trans

- 1, 3

- Dichloropropene

1, 4

– Dioxane
Ethylbenzene
Ethylene Glycol

2

- Hexanone
Methylene chloride

4

- Methyl

- 2

- pentanone (MIBK)
Styrene

1, 1, 1, 2

- Tetrachloroethane

1, 1, 2, 2

- Tetrachloroethane

Tetrachloroethene

Toluene

1, 1, 1

- Trichloroethane

1, 1, 2

- Trichloroethane

Trichloroethene

Trichlorofluorometh ane 1, 2, 3

- Trichloropropane
Vinyl acetate
Vinyl chloride

Tert

- butyl acetate
tetrahydrofuran

1

- chloro

- 4

- trifluoromethylbenz

Semi volatile Compounds

Diphenylamine

Benzidine
bis (2

- Chloroisopropyl) ether

1, 4

– Dioxane

1, 2

– Diphenylhydrazine

Acenaphthene
Acenaphthylene

Acetophenone

2

– Acetylaminofluorene

4

– Aminobiphenyl

Aniline
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) fluoranthene
Benzo (ghi) perylene
Benzo (k) fluoranthene

Benzyl alcohol Diethyl phthalate

Dimethoate

p

- Dimethylaminoazobenzene

7, 12

- Dimet hylbenz (a)

– anthracene

2, 4

– Dimethylphenol
Dimethyl phthalate

Di

- n

- octyl phthalate

1, 3

– Dinitrobenzene

4, 6

- Dinitro

- 2

– methylphenol

2, 4

– Dinitrophenol

2, 4

– Dinitrotoluene

2, 6

– Dinitrotoluene

Dinoseb

Disulfoton
Ethyl methanesulfonate

Fl uoranthene

Fluorene Nitrobenzene

2

- Nitrophenol

4

- Nitrophenol

N

- Nitrosodi

- n

- butylamine

N

- Nitros odiethylamine

N

- Nitrosodimethylamine

N

- Nitrosodi

- n

- propylamine

N

- Nitrosodiphenylamine

N

– Nitrosomethylethylamine

N

– Nitrosomorpholine

N

– Nitrosopiperidine

N

– Nitrosopyrrolidine

5

- Nitro

- o

– Toluidine

Parathion

Pentachlorobenzene

Pentachloroethane

Pentachloronitrobenzene

### 8

bis (2

- Chloroethoxy) methane
bis (2

- Chlor oethyl)

– ether
bis (2

- Ethylhexyl) phthalate

4

- Bromophenyl phenyl ether
Butyl benzyl phthalate

4

– Chloroaniline

4

- Chloro

- 3

– methylphenol

2

– Chloronaphthalene

2

– Chlorophenol

4

- Chlorophenyl phenyl ether
Chrysene

Diallate
Dibenz (a, h) anthracene

Dibenzofuran

Di

- n butyl phthalate

1, 2

– Dichlorobenzene

1, 3

– Dichlorobenzene

1, 4

– Dichlorobenzene

3, 3'

– Dichlorobenzidine

2, 4

– Dichlorophenol

2, 6

– Dichlorophenol Hexachlorobenzene

Hexachlorobutadiene
Hexachlorocyclopentadiene

Hexachloroethane
Hexachloropropene
Indeno (1, 2, 3

- cd) pyrene

Isodrin

Isophorone

Isosafrole

3

- Methylcholanthrene
Methyl methanesulfonate

2

- Methylnaphthalene

2

– Methylphenol

3

- Methylphenol & 4

– Methylphenol

Naphthalene

1, 4

- Naphthoquinone

1

– Naphthylamine

2

– Naphthylamine

2

– Nitroaniline

3

– Nitroaniline

4

– Nitroaniline Pentachlorophenol

Phenanthrene

Phenol

Phorate

2

– Picoline

Pronamide
Pyrene
Pyridine

Safrole

1, 2, 4, 5

– Tetrachlorobenzene
2, 3, 4, 6 Tetrachlorophenol

Thionazin

o

– Toluidine

1, 2, 4

– Trichlorobenzene

2, 4, 5

– Trichlorophenol

2, 4, 6

– Trichlorophenol

O, O, O

– Triethylphosphorothioate

Chlorobenzilate

Aramite

Metals

Aluminum
Antimony

Arsenic

Barium
Beryllium

Boron

Calcium

Cadmium

Cobalt Chromium

Trivalent Chromium
Copper

Iron

Lead

Lithium
Magnesiium
Manganese
Molybdenum Nickel

Potassium

Sodium

Selenium

Tin

Strontium

Titanium

Thallium

Zinc

Pesticides

Chlordane (Technical)

alpha

– BHC

beta

– BHC

delta

– BHC

gamma

- BHC (Lindane)

Heptachlor

Aldrin Heptachlor epoxide

Endosulfan I

Dieldrin

4, 4'

– DDE

Endrin

Endrin ketone
Endrin aldehyde Endosulfan II

4, 4'

– DDD

Endosulfan sulfate

4, 4'

– DDT
Methoxychlor
Toxaphene

Organophosphorus Pesticides

Thionazin Ethyl parathion Tetraethyldithiopyro

- phosphate

Polychlorinated Biphenyls (PCBs)

Arochlor 1016

Arochlor 1221

Arochlor 1232 Arochlor 1242

Arochlor 1248 Arochlor 1254

Arochlor 1260

### 9

Table 2 . Summary of Methods

Parameter Analytical Method Preparation Method

pH SW846 9040 SW846 9040

Acidity (Titrimetric) SM20 2310 B (4a)

Alkalinity, Total SM18 2320 B SM18 2320 B

Amenable Cyanide SM18 4500

- CN E SM18 4500

- CN E

Biochemical Oxygen Demand SM18 5210 B SM18 5210 B

Bromide MCAWW 300.1A MCAWW 300.1A

Chemical Oxygen Demand MCAWW 410.4 MCAWW 410.4

Chloride MCAWW 300.1A MCAWW 300.1A

Cyanide, Total SW846 9012A SW846 9012A

Dissolved Organic Carbon SW846 7196A SW846 7196A

Fluoride MCAWW 300.1A MCAWW 300.1A

Hexavalent Chromium EPA 901.1 MOD

Hardness, Total SM20 2340C

Mercury in Liquid Waste SW846 7470A SW846 7470A

N

- Hexane Extractable Material CFR136A 1664A H EPA 1664A

Nitrate as N MCAWW 300.1A MCAWW 300.1A

Nitrite

- Nitrate MCAWW 353.2 MCAWW 353.2

Nitrite as N MCAWW 300.1A MCAWW 300.1A

Nitrogen, Ammonia MCAWW 350.1 MCAWW 350.1

Organochlorine Pesticide SW846 8081A SW846 3510C

Organophosphorus Compounds SW846 8141A SW846 3510

Phenolics SW846 9066 SW846 9066

Polychlorinated Biphenyls SW846 8082 SW846 3510C

Semi volatile Organic Compounds SW846 8270C SW846 3520C

Specific Conductance MCAWW 120.1 MCAWW 120.1

Sulfate MCAWW 300.0A MCAWW 300.0A

Sulfides, Total SW846 9030B/903 SW846 9030B/903

Total Phosphorus MCAWW 365.2 MCAWW 365.2

Total Dissolved Solids SM18 2540 C

Total Kjeldahl Nitrogen MCAWW 351.3 MCAWW 351.3

Total Organic Carbon SM20 5310B

Total Suspended Solids SM20 2540D

Trace Inductively Coupled Plasma SW846 6010B SW846 3005A

### 10

Table 2 . Summary of Methods

Parameter Analytical Method Preparation Method

Metals SW846 6010B SW846 3010A

Trivalent Chromium SW846 6010B Wet None

Turbidity (Nephelometric) MCAWW 180.1 MCAWW 180.1

Volatile Organics by GC/MS SW846 8260B SW846 5030B

Ethylene Glycol SW846 8015 SW846 8015

Methylene Blue Activated Substances

(MBAS) SM5540C SM5540C



### Under the updated sampling plan, the following grab samples were collected at

each of the volunteered locations:

A supply water sample (before the blending of additives);

One influent water sample following blending with fracturing additives, excluding

sand;

Flowback water samples collected on 1, 5 and 14 days after hydraulic fracturing;

and

Water from the producing well at 90 days after completion.

Following the collection of the samples and the performance of all of the

determinations, the data was organized, qualified and tabulated by GTI.



## RESULTS FROM THE MAR CELLUS

Throughout the performance of the flowback water sampling program, natural gas

development companies of the Marcellus Shale provided a high level of access to all of

the host sites that was necessary to obtain the critical flowback water samples at the

sta ndardized times of 0, 1, 5, and 14 days following the hydraulic fracturing event of

each host site well. About a third of the companies assisted with the collection of a 90

day sampling of the flowback water, as well. In total, 17 shale gas companies ena bled

the sampling of 19 locations within the Marcellus Shale Region, including 3 locations in

West Virginia and 16 locations in Pennsylvania.

### 11



## Flowback Water Collection Characteristics

Water volumes associated with 12 of the 19 wells sampled in this pr oject are shown

in Table 3. Of the 12 wells reporting water volume information, five wells were vertical

wells and seven wells were of horizontal configuration. Of the vertical wells, an average

of approximately 40,000 bbls of influent water were used to achieve fracturing, and

about 15,000 bbls on average were collected within a 90 day period. Of the horizontal

wells, an average of approximately 90,000 bbls of influent water were used to achieve

fracturing, followed by a collection of about 16,000 bbls of effluent water (flowback).

Cumulative volumes of water collected over time for these 12 completed wells are

shown in Table 3.

Table 3: Water Use and Flowback Water Collection Associated with Hydraulic

Fracturing Completion of Shale Gas Wells

Locatio n Well Type Total Vol.

Frac Fluid

Used,

bbls Cumulative Volume of

Flowback Water, BBL

Percent

Collected 1 Day* 5 Days 14 Days 90 Days

A Vertical 40,046 3,950 10,456 15,023 37.5

B Vertical 94,216 1,095 10,782 13,718 17,890 19.0

C Horizontal 146,226 3,308 9,652 15,991 10.9

D Horizontal 21,144 2,854 8,077 9,938 11,185 52.9

E Horizontal 53,500 8,560 20,330 24,610 25,680 48.0

F Horizontal 77,995 3,272 10,830 12,331 17,413 22.3

G Horizontal 123,921 1,219 7,493 12,471 18,677 15.1

H Vertical 36,035 3,988 16,369 21,282 31,735 88.0

K Horizontal 70,774 5,751 8,016 9,473 13.4

M Horizontal 99,195 16,419 17,935 19,723 19.9

N Vertical 11,435 2,432 2,759 3,043 3,535 30.9

O Horizontal 96,706 5,131 19,202 19.8

Q Vertical 23,593 1,315 3,577 5,090 21.6

S Vertical 16,460 2,094 7,832 9,345 10,723 65.1

Weighted Average % Collected  24.3

* Days from the hydraulic fracturing event.

### 12



## General Chemistry

A summary of the general chemical characteristics of the water influent streams and

the flowback water effluents associated with the initiation of the fracing process are

presented in Table 4. Raw Source water is compared against blended water containing

conditioning chemicals (minus sand). Dissolved solids measurements for the influent

waters used for hydraulic fracturing (with additives) had a median value of 735 mg/l,

which is considered in the range of fresh surface water supplies. O il and grease

me asurements had a median value of almost 30 mg/l with a range of 0.5 to 255 mg/l

.

T otal organic carbon had a range of 5.6 to 1,260 mg/l with a median of 226 mg/l;

elevated values in these measurements may be due to various degrees of blending of

reused bri ne waters into frac job influent water supplies.

A summary of the same characteristics is tabulated for water supplies from 7

locations (F, H, I, J, L, M, S) in Table 5 ; information in this table provides an indication of

the quality of influent water be fore the blending of additives. The data in this table

indicates that water supplies had very low total organic carbon content (< 4 ppm), low

biochemical oxygen demand (< 2 ppm) and non

- detect levels of oils and greases; the

values for these parameters a re well within the ranges expected for normal surface

waters and groundwater. Total dissolved solids ranged from 50 to 5,500 mg/l with a

median value around 390 mg/l; the upper end of the range may be due to the varied

degree of flowback water reuse that is employed at these sites.

The water is of relatively modest alkalinity with a median values of 85

– 120 mg/l,

reflecting low carbonate concentrations which allow for very high levels of soluble

calcium. High levels of calcium confer a very high hardn ess on the water as evidenced

by median hardness values of 17,700 and 34,000 mg/l for the 5

- day and 14

- day sample

sets, respectively. Cations are dominated by sodium and calcium in this water; anions

are dominated by chloride. Levels of total organic ca rbon (TOC) in the flowback water

samples at 5 and 14 days (with median values of 63 and 39 mg/l) are substantially

lower (by about 75%) than the TOC of the blended influent water with additives; a

possible reason for this is that the polyacrylamide frictio n reducers exert a TOC in the

influent stream and are removed as water resides in the down

- hole environment. The

same observation is made in comparing biochemical oxygen demand (BOD) values in

### 13

flowback water with the BOD of the influent water streams; in general, the BOD levels of

the 5

- day and 14

- day flowback waters are less than half the influent BOD

concentrations. The moderate levels of BOD in the influent waters may have resulted

from carbonaceous algae growth in the source water or resulted from the biodegradable

nature of the additives (e.g. polyacrylamide friction reducing compounds). The loss of

friction reducing compounds due to adherence to surfaces downhole may be

responsible for the lower BOD concentrations in flowback waters.

Results from Day 1 and Day 5 are presented in Table 5. Day 1 results, in general,

show a huge range of values, indicating the rapid change in concentrations with

initiation of flowback. By Day 5, most sites are demonstrating concentrations trending

toward the maximu m seen by Day 10 or 90. Two interesting observations concern TOC

and BOD, both of which show a slight decrease from the initial blended water, to Day 1,

to Day 5.

Results from Day 14 and Day 90 are presented in Table 6. Day 14 results, in

general, sho w a large range of values, based on one sample from Site K that was

generally less concentrated than the 5 Day sample. Day 90 results are from five sites

only, and reflect the deviations associated with a relatively small sample size.

Salt concentration s in influent water and in flowback water generated over time from

the 19 sampling locations are tabulated in Table 7. As shown in Table 7, influent water

usually contains moderate to low concentrations of salts. Following the use of this

water for hydra ulic fracturing, a flowback water stream that is collected from the well

exhibits increasing concentrations of salts with time.

### 14 Table 4. Summary of Chemical Characteristics of Water Used for Hydraulic Fracture

Parameter Raw Source 1 Water Blended 4 Frac Water

Units Range Median Range Median

pH 6.7

- 7.3 7.1 6.0

- 8.9 7.2 No Units

Acidity < 5

– 5.5 < 5 < 5

- 1230 < 5 mg/l

Total Alkalinity 6.2

– 88.8 71.4 < 1

– 308 81.8 mg/l

Hardness as CaCO3 18

- 1,080 140 26

- 9,500 130.0 mg/l

Total Suspended Solids <2

– 24 9.6 < 2

- 5,290 155.0 mg/l

Turbidity 1.3

– 33.7 4.3 2.7

– 715 249.0 NTU

Chloride 4.1

– 3,000 42.3 18

- 10,700 90.2 mg/l

Total Dissolved Solids 2 51

– 5,510 390 221

- 27,800 735.0 mg/l

Specific Conductance 54.8

– 10,100 466 177

- 34,600 726.0 umhos/cm

Total Kjeldahl Nitrogen < 2.3

– 56.4 2.2 2.3

– 400 33.5 mg/l

Ammonia Nitrogen < 0.24

– 20.8 0.52 0.58

– 441 5.9 mg/l

Nitrate

- Nitrite < 0.01

– 3.0 0.51 < 0.032

- 0.34 0.1 mg/l

Nitrite as N < 0.0032

– 4.9 < 0.0032 < 2.0

– 1740 271.0 mg/l

Biochemical Oxygen

Demand < 2.0

– 110 < 2.0 < 4.3

- 47,400 1730.0 mg/l

Chemical Oxygen Demand < 4.3

– 924 18.4 5.6

- 1,260 226.0 mg/l

Total Organic Carbon (TOC) 1.8

– 202 3.8 5

- 1,270 301.0 mg/l

Dissolved Organic

Carbon 1.4

– 222 3.2 < 0.49

– 255 29.2 mg/l

Oil & Grease (HEM)

- < 0.5 < 1.7

– 680 4.6 mg/l

Cyanide, Total < 1.7

– 625 < 1.7 < 0.005

- 0.87 < 0.005 μg/l

Amenable Cyanide < 0.005

- 0.3 < 0.005 < 0.014

– 107 0.9 mg/l

Bromide < 0.0014

– 1.9 0.14 < 0.004

- 58.3 0.004 mg/l

Fluoride < 0.004

- 1.2 < 0.004 < 1.2

- 8.8 < 1.2 mg/l

Total Sulfide 1.2

- 5.6 1.6 < 0.031

– 2920 50.3 mg/l

Sulfate 3.8

– 139 43.7 < 0.03

– 16 0.14 mg/l

Total Phosphorus < 0.03

– 0.1 0.044 < 0.0057

- 0.77 0.033 mg/l

Total Recoverable

Phenolics 0.0057

- 0.14 0.0065 0.05

– 0.50 0.05 mg/l

Methylene Blue Active

Substances (MBAS) 3 0.05

– 0.50 0.05 6.0

- 8.9 7.2 mg/l

1 Water Supplies at 7 Locations: F, H, I, J, L, M, S. 2 Upper end concentrations in the TDS range may be due to
implementation of flowback water reuse and blending into the influent stream. 3 Data analysis for 8 Locations: D, F,

H, I, J, M, N, S. 4 Additives included corrosion inhibitors, scale inhibitors , friction reducers, biocides, and oxygen

scavengers. Blended water samples were taken before the addition of sand.

### 15 Table 5: Range of Results from 1 and 5 Day Samples

General Chemistry Day 1 Day 5

Range Median Range Median Units

pH 5.9

- 7.9 7.4 5.8

- 7.2 6.6 No Units

Acidity ND 5

- 447 48.7 mg/l

Total Alkalinity 107

- 577 251 48.8

- 327 135 mg/l

Hardness as CaCO3 156

- 25,000 4,150 5,100

- 55,000 20,000 mg/l

Total Suspended Solids 6.8

- 522 71 10.8

- 3220 102 mg/l

Turbidity 10

- 461 52.1 14

- 1540 92 NTU

Chloride 64.2

- 151,000 9,890 26,400

- 148,000 43,900 mg/l

Total Dissolved Solids 680

- 122,000 18,900 38,500

- 238,000 72,700 mg/l

Specific Conductance 479 645,000 37,750 79,500

- 470,000 175,000 umhos/cm

Total Kjeldahl Nitrogen 14.2

- 158 52.9 38

- 204 89.5 mg/l

Ammonia Nitrogen 2.8

- 173 32 29.4

- 242 90 mg/l

Nitrate

- Nitrite 0.01

- 2.8 0.5 0.049

- 1.2 0.36 mg/l

Nitrite as N ND

- 6.7 3.1 4.8

- 25.9 11.8 mg/l

Biochemical Oxygen

Demand 27.6

- 1,440 327.5 37.1

- 1,950 141 mg/l

Chemical Oxygen

Demand 397

- 10,700 1,660 195

- 17,700 4,845 mg/l

Total Organic Carbon 2.2

- 672 142 3.7

- 388 61.8 mg/l

Dissolved Organic

Carbon 20.2

- 657 253 30.7

- 501 88.3 mg/l

Oil & Grease (HEM) 5.7

- 53.9 13.7 0

- 655 16.2 mg/l

Cyanide, Total 6.6

- 177 21.5 5.2

- 72.1 13.6 ug/L

Bromide 35.5

- 376 120 0

- 1190 445 mg/l

Fluoride 0.077

- 32.9 0.975 0.045

- 17.3 2.4 mg/l

Total Sulfide 1.6

- 3.2 1.6 1.6

- 5.6 2.4 mg/l

Sulfate 10.7

- 348 46 2.4

- 106 37.8 mg/l

Total Phosphorus 0.037

- 21.8 0.18 0.053

- 2.3 0.305 mg/l

Total Recoverable

Phenolics 0.007

- 0.064 0.027 0.0076

- 0.31 0.024 mg/l

### 16 Table 6: Range of Results from 14 and 90 Day Samples

Day 14 (17 Sites Reporting) Day 90 (5 Sites Reporting)

General Chemistry Range Median Range Median Units

pH 4.9

- 6.8 6.2 5.2

- 6.2 5.9 No Units

Acidity 19.4

- 473 114 162

- 925 220 mg/l

Total Alkalinity 26.1

- 121 85.2 7.5

- 75.2 41.4 mg/l

Hardness as CaCO3 630

- 95,000 34,000 40,000

- 85,000 77,000 mg/l

Total Suspended Solids 17

- 1150 209 150

- 446 201 mg/l

Turbidity 10.5

- 1090 233 106

- 277 174 NTU

Chloride 1,670

- 181,000 78,100 78,300

- 185,000 122,000 mg/l

Total Dissolved Solids 3,010

- 261,000 120,000 155,000

- 345,000 216,000 mg/l

Specific Conductance 6,800

- 570,000 256,000 249,000

- 600,000 385,000 umhos/cm

Total Kjeldahl Nitrogen 5.6

- 261 116 92.8

- 312 136 mg/l

Ammonia Nitrogen 3.7

- 359 121 96

- 416 259 mg/l

Nitrate

- Nitrite 0.025

- 0.92 0.25 ND

- 0.029 0.0145 mg/l

Nitrite as N 1.7

- 77.4 18.75 42.8

- 42.8 42.8 mg/l

Biochemical Oxygen

Demand 2.8

- 2070 39.8 4.1

- 1080 33.6 mg/l

Chemical Oxygen

Demand 228

- 21,900 8530 2,630

- 36,600 16,200 mg/l

Total Organic Carbon 1.2

- 509 38.7 4

- 5,680 117 mg/l

Dissolved Organic

Carbon 5

- 695 43 3.3

- 5,960 117 mg/l

Oil & Grease (HEM) 7.4

- 103 30.8 14.7

- 62.6 21.3 0

Cyanide, Total 1.9

- 7.4 5 42.6

- 42.6 42.6 ug/L

Bromide 15.8

- 1,600 704 766

- 1,990 1,260 mg/l

Fluoride ND 2 ND

- mg/l

Total Sulfide 1.6

- 3.2 2 2.4

- 4 3.2 mg/l

Sulfate 0.078

- 89.3 40 83.8

- 83.8 83.8 mg/l

Total Phosphorus 0.035

- 2.2 0.115 ND mg/l

Total Recoverable

Phenolics 0.006

- 0.31 0.016 0.0091

- 0.23 0.0295 mg/l

### 17 Table 7: Concentration of Total Dissolved Solids in Flowback Water at 19 Locations,

(mg/l)

Location Day 0* Day 1 Day 5 Day 14 Day 90

A 990 15,400 54,800 105,000 216,000

B 27,800 22,400 87,800 112,000 194,000

C 719 24,700 61,900 110,000 267,000

D 1,410 9,020 40,700 155,000

E 5,910 28,900 55,100 124,000

F 462 61,200 116,000 157,000

G 1,920 74,600 125,000 169,000

H 7,080 19,200 150,000 206,000 345,000

I 265 122,000 238,000 261,000

J 4,840 5,090 48,700 19,100

K 804 18,600 39,400 3,010

L 221 20,400 72,700 109,000

M 371 228,000

N 735 31,800 116,000

O 2,670 17,400 125,000 186,000

P 401 11,600 78,600 63,900

Q 311 16,600 38,500 120,000

R 481 15,100 46,900 20,900

S 280 680 58,300 124,000

*Day 0 sample was taken of the influent water plus additives without sand.



### A typical profile of salt concentrations (such as Location B) measured in flowback

water with time is shown in Figure 1. Early flowback water emerging soon after the frac

job is relatively low in TDS content. Following the initial day, the concentration of total

dissolved solids increases with time from low salt concentrations to a plateau of

elevated salt levels as measur ed at 14 and 90 days. Also shown in this diagram is the

marked concomitant d e crease in flowback brine flow with time, exhibiting a high initial

flow rate of over 2,400 bbls/day, then decreasing to a minimal flow rate of less than 55

bbls/day after the ini tial few weeks following completion, a 98% reduction of daily flow

.

The lowest flow rate bar shown on the chart in Figure 1 was calculated from

### 18

cumulative water data between 14 and 90 days; actual flows in the 60 to 90 day period

are significantly less th an 55 bbls/day. The diagram, however, demonstrates that

although the TDS levels in the flowback water emerging between 14 and 90 days

almost doubles to nearly reach 200,000 mg/l. The daily brine volumes produced by the

well decrease to a low rate that c an be easily managed as a typical produced water

stream.

Figure 1 . Salt Concentration and Flowback Water Flow Versus Time from Location B



### General characteristics of the samples tested in this project appear very consistent with

the ranges of values reported in the literature for normal produced waters (USGS,

2004). The l arge database collected by the USGS indicates that salinities for produ ced

waters generated among all basins can vary widely from approximately 5,000 to greater

than 350,000 mg/l of total dissolved solids. Chloride is the dominant anion in nearly all

formation waters associated with petroleum and with most conventional natur al gas

### 19

(Kharaka and Rice, 2004). Sodium is the most dominant cation in most producing fields

and constitutes 70 to more than 90% of total cations (USGS, 2004). General

characterization data from the waters tested at the 19 locations of this project appea r

consistent with much of the available compositional information available from the

USGS database. The USGS database containing produced water characterization data

from more than 60,000 wells is accessible from the Internet at:

http://energy.cr.usgs.gov/prov/prodwat/intro.htm

. Total organic carbon reflects a trend generally opposite that of the total dissolved

solids. Table 8 shows that the TOC in the flowback water typically decreases o ver time.

The BOD (Table 9) is more erratic. Some wells remain constant over time, while other

wells increase; still others decrease in measured BOD with time.

Table 8: Total Organic Carbon TOC (mg/l)

Site Day 0 Day 1 Day 5 Day 14

A 350 260 NS 38.7

B 168 207 50.6 34.2

C 167 82.5 32.9 14.4

D 741 342 161 NS

E 226 108 46.2 5.9

F 205 43.5 62.8 44

G 123 60.8 42.2 NS

H 78.3 1260 443 119

I 607 610 48 12.8

J 569 56.6 27.5 23.6

K 949 124 103 7.2

L 202 155 115 80.5

M 86.6 2.2 3.7 1.2

N 208 28.1 37.8 NS

O 575 308 237 509

P 5.6 292 287 226

Q 410 142 46.5 24

R 173 604 388 323

S 931 672 104 150

Median 208 155 57 36

Average 357 282 124 101

### 20 Table 9: Biochemical Oxygen Demand (BOD mg/l)

Site Day 0 Day 1 Day 5 Day 14

A 794 353 3

B ND 132 1,950 149

C 5 132 63.7 39.8

D 438 656 721 NS

E 788 158 106 32.4

F 154 75.4 64.8 120

G 302 144 7.3 NS

H 110 1,740 737 138

I 578 399 99 10.4

J 47 43 48 20.3

K 430 650 214 30.5

L ND ND 27.6 37

M 137 36.3 103 10

N 166 73.2 70.9 NS

O 924 606 1,520 725

P 4 391 1,260 752

Q 121 184 144 98.1

R 271 692 1250 6

S 2,220 1,440 218 990

Median 271 269 106 38

Average 441 439 453 198



## Organic Compounds

The organic compounds included in the characterization of water samples included

the categories of volatile organics, semi volatile organics, chlorinated pesticides,

organophosphorus pesticides, and polychlorinated biphenyls. Most of the compounds

in the first two categories and all compounds in the last three categories were included

on the list of analyses in response to recommendations from PA

- DEP and WV

- DEP.

The following sections summarize the results among all five of the categories of

analysis.

### 21



## V olatile Compounds

S amples collected from Locations A through S were analyzed for 70 volatile

compounds of highly varied chemical characteristics, including the volatile hydrocarbon

constituents that are normally found in produced water (such as benzene, to luene,

ethylbenzene, and xylenes

– or BTEX, and naphthalene) as well as constituents not

known to be associated with conventional produced water such as chlorinated solvents

and halogenated aromatics.

Source water data (Day 0 minus sand) are presented in Table 10. Of 1330

measurements, only 92 observations of volatile compounds were made. Acetone was

measured in 12 samples, representing the use of acetone as a component of the

additives. BTEX and alkylated benzene isomers likely represent a component of water

reuse from previous sites. Traces of halogenated solvents occasionally occur at the

part per billion level. Apparently, the additives used in the fracking process do not

manifest themselves amongst the most problematic volatile components.

As n oted before, the organic components, unlike total salts, do not follow a timed

based profile. In general, their appearance in the flowback waters appears anywhere

from low and constant or intermittent and random. As such, the best means of

presenting the volatile data for the 19 sites is to present tablulated distributions, ie., the

number of observations within a stated concentration range. Table 11 shows the

distribution of observations for all 60 samples. As an example, p

- Isopropyltoluene was

observ ed once at a concentration between 50

- 99 μg/l, twice between 10

- 49 μg/l, once

between 1

- 4.9 μg/l, and undetected (ND) in 56 samples. Many of the compounds were

observed only once in sixty samples, making them either incidental or mistaken. No

compound wa s encountered in all sixty samples. The chemical most likely to be

observed was acetone in 48 of sixty samples. Thirty five of the compounds from the

voilatiles list were never observed. In total, 4200 measurements were taken and 3710

of them were “non

- detects.”

### 22

Table 10: Influent Water Day 0 (minus sand)

Volatiles Observations Range

, μg/l Median

, μg/l

Naphthalene 7 0.55

- 820 3.8

n

– Propylbenzene 1 ND

- 2

1, 2, 4

– Trimethylbenzene 10 0.72

- 140 9.15

1, 3, 5

– Trimethylbenzene 7 2.8

- 100 7.7

Isopropylbenzene 2 0.95

- 0.95 0.95

2

– Butanone 2 3.6

- 7.5 5.55

Xylenes (total) 11 2.6

- 210 18

sec

– Butylbenzene 2 3.2

- 84 43.6

Acetone 12 5.4

- 170 17.5

Benzene 4 2.2

- 6.7 6.7

Bromodichloromethane 1 ND

- 2

Bromoform 4 7.8

- 9.3 8.55

Carbon disulfide 4 1.6

- 54,000 12,250

Chloroform 1 ND

- 2.4

Dibromochloromethane 1 ND

- 2.1

1, 2

– Dichloroethane 1 ND 2.6

Ethylbenzene 5 0.81

- 19 1.7

Methylene chloride 1 ND

- 13

Tetrachloroethene 2 1.3

- 1.4

Toluene 13 0.93

- 81 5.6

Trichloroethene 1 ND

- 0.81

Total Observations 92 

### of 1330 Measurements



### Constituents that exceeded 100 ppb included components that are commonly

present in conventional produced water, such as naphthalene, BTEX, several

methylated benzene compounds and an alkylated toluene (p

- isopropyltoluene). Few

determinations of these com pounds exceeded 1 ppm and only one occurrence was

above 2 ppm. In the locations where BTEX was measured at levels above 100 ppb,

BTEX levels in the 5

- day and 14

- day flowback waters that were in contact with the

natural gas producing formation were general ly higher than BTEX concentrations in the

influent water streams, indicating that these compounds are naturally occurring and not

the result of additives. Levels of BTEX and methylated aromatics vary from location to

location. Determination of factors t hat control levels of these compounds could

### 23

potentially be determined through a correlation of the composition of volatiles and other

flowback water characteristics with the key shale gas development parameters of

geographic area, depth of wells, completio n methods, etc. For a distribution of all

volatile organic concentration observations, see Figure 2.

Table 11: Number of Observations of 70 Volatile Compounds in All 60 Marcellus Samples

Number of Observations

>1000 500

-

999 100

-

499 50

-

99 10

-

49 5

-

9.9 1

-

4.9 ND

1 ND Between Limits in μg/l

p

– Isopropyltoluene 0 0 0 1 2 0 1 0 56

Naphthalene 0 2 1 0 2 0 8 3 44

n

– Propylbenzene 0 0 0 1 0 0 1 0 58

1, 2, 3

– Trichlorobenzene 0 0 0 0 1 1 0 0 58

1, 2, 4

– Trichlorobenzene 0 0 0 0 0 0 1 0 59

1, 2, 4

– Trimethylbenzene 0 4 1 5 8 2 14 5 21

1, 3, 5

– Trimethylbenzene 0 3 2 1 7 6 7 2 32

Isopropylbenzene 0 0 2 1 0 0 2 2 53

2

– Butanone 0 0 0 0 2 2 1 0 55

Xylenes (total) 4 1 8 0 8 7 7 0 25

n

- Butylbenzene 0 0 0 0 0 0 1 0 59

sec

- Butylbenzene 0 0 0 2 0 0 0 0 58

Acetone 4 1 9 2 26 5 0 0 12

Acrylonitrile 0 0 0 0 0 1 0 0 59

Benzene 3 1 7 1 2 7 7 1 31

Bromoform 0 0 0 0 0 1 0 0 59

Bromomethane 0 0 1 0 0 0 0 0 59

Carbon disulfide 2 0 2 0 1 0 0 0 55

Chloroform 0 0 0 0 1 0 1 0 58

Chloromethane 0 0 1 0 0 1 1 0 57

Ethylbenzene 0 1 4 1 6 1 5 3 39

Methylene chloride 0 0 0 0 0 1 2 0 57

4

- Methyl

- 2

- pentanone (MIBK) 0 0 0 0 0 0 0 1 59

Styrene 0 0 0 0 0 0 1 0 59

Tetrachloroethene 0 0 0 0 0 1 0 0 59

Toluene 5 4 4 2 3 2 19 2 19

All 35 Others (See Table 1) 0 0 0 0 0 0 0 0 2450

Total 18 17 42 17 69 38 79 19 3710

### 24



## Semi volatile Compounds

A total of 112 semi volatile organic compounds (as listed in Table 1) were included

in the analysis of influent water and in flowback water samples. A summary of the

results of semi volatile determinations in these samples the day 0 source water

(chemical additives minus sand) is pr esented in Table 12. The most commonly

encountered semi volatile s belong to the phthalate ester group, probably representing

introduced plasticizers. Pyridine is commonly encountered and possibly represents a

residue from some of the manufacture of some of the additives. Occasional traces of

PAH’s are present, likely from water reuse in some of the input waters. In a total of 19

samples, a total of 2204 chemical tests were performed. Only 76 samples were above

appears to not appreciably influence the concentrations of the 116 listed semi volatile

organics. Figure 2: Distribution of Observations for 70 Volatile Organics from 60 Samples from

the Marcellus

### 25 For all sample times, semi

- volatile compound determinations that were detectable

are listed in Table 13. As seen in this table, only four constituents were measured in

any of the samples at levels exceeding 10 ppb. Acetophenone and aniline are

commonly a ssociated with fossil fuels, as are the methylated phenols. The only

compound that was measured above 1 ppm was pyridine. Pyridine is a nucleophile Table 12: Semi

- Volatile Content in 19 Marcellus Influent Samples

Source Water Day 0 Observations

In 19 Samples Range

, μg/l Median of

Observation

Acetophenone 1 ND

- 0.97

Benzo (a) anthracene 1 ND

- 1.1

Benzo (a) pyrene 1 ND

- 6.9

Benzo (b) fluoranthene 1 ND

- 11

Benzo (ghi) perylene 1 ND

- 7.4

Benzo (k) fluoranthene 1 ND

- 6.7 6.7

Benzyl alcohol 2 74

- 74 74

bis (2

- Chloroethyl)

- ether 1 ND

- 4300

bis (2

- Ethylhexyl) phthalate 11 2

- 21 9.4

Butyl benzyl phthalate 1 ND

- 5.1

Chrysene 1 1.7

- 1.7 1.7

Dibenz (a, h) anthracene 1 ND

- 12 12

Di

- n butyl phthalate 9 0.29

- 1.7 0.6

1, 2

- Dichlorobenzene 1 ND

- 0.68

1, 4

- Dichlorobenzene 1 ND

- 0.6

2, 6

- Dichlorophenol 1 ND

- 2

Diethyl phthalate 2 0.49

- 1.8 1.145

2, 4

- Dimethylphenol 1 ND

- 0.39

Fluoranthene 1 ND

- 5.5

Fluorene 2 0.83

- 1.2 1.015

Indeno (1, 2, 3

- cd) pyrene 2 10

- 10 10

2

- Methylnaphthalene 7 1.3

- 300 7.5

Naphthalene 6 0.61

- 1800 4.3

Phenanthrene 7 0.28

- 24 1.3

2

- Picoline 1 ND

- 5.3

Pyrene 3 0.19

- 0.54 0.22

Pyridine 9 0.91

- 510 17

All 89 Other Chemicals (Table 1) 0 ND ND

### 26

used widely in the manufacture of certain chemicals and pharmaceuticals . I ts presence

may be due to its u se as a precursor in the manufacture of one of the hydraulic

fracturing additives. Most the semi volatile determinations were either non

- detect (>

96% of the measurements) or at low trace levels (Figure 3). Most of the chemicals in

Table 13 appeared as chance encounters, ie., detection in one or two of sixty samples.

### 27

Table 13: Number of Observations of 116 Semi

- Volatile Compounds in all 60 Marcellus

Samples

Number of Observations

>1000 500

-

999 100

-

499 50

-

99 10

-

49 5

-

9.9 1

-

4.9 ND

0.99 ND Between Limits in μg/l

Diphenylamine 0 0 0 0 0 0 2 0 58

1, 4

– Dioxane 1 0 0 0 15 9 4 2 29

Acenaphthene 0 0 0 0 0 0 0 3 57

Acenaphthylene 0 0 0 0 0 0 0 1 59

Acetophenone 0 0 0 0 6 3 6 9 36

Aniline 0 0 0 0 0 0 2 0 58

Benzo (a) anthracene 0 0 0 0 0 0 2 0 58

Benzo (a) pyrene 0 0 0 0 0 0 2 0 58

Benzo (b) fluoranthene 0 0 0 0 0 0 2 0 58

Benzo (ghi) perylene 0 0 0 0 0 0 3 0 57

Benzo (k) fluoranthene 0 0 0 0 0 0 1 1 58

Benzyl alcohol 0 0 1 0 2 3 1 0 53

bis (2

- Chloroethyl)

- ether 0 0 0 0 1 0 0 0 59

bis (2

- Ethylhexyl) phthalate 0 2 0 0 8 9 15 1 25

Butyl benzyl phthalate 0 0 0 0 1 3 0 0 56

Chrysene 0 0 0 0 0 0 2 0 58

Dibenz (a, h) anthracene 0 0 0 0 0 0 2 0 58

Di

- n butyl phthalate 0 0 1 1 3 2 5 10 38

1, 2

- Dichlorobenzene 0 0 0 0 0 0 0 2 58

1, 3

- Dichlorobenzene 0 0 0 0 0 0 0 1 59

1, 4

- Dichlorobenzene 0 0 0 0 0 0 0 2 58

Diethyl phthalate 0 0 0 0 1 0 8 4 47

2, 4

- Dimethylphenol 0 0 0 0 3 4 1 2 50

Dimethyl phthalate 0 0 0 0 0 1 0 0 59

Di

- n

- octyl phthalate 0 0 0 0 2 3 3 0 52

Disulfoton 0 0 0 0 0 0 1 0 59

Ethyl methanesulfonate 0 0 0 0 0 0 0 0 60

Fluoranthene 0 0 0 0 0 5 2 0 53

Fluorene 0 0 0 0 0 2 2 8 48

Hexachlorobenzene 0 0 0 0 0 0 1 1 58

Indeno (1, 2, 3

- cd) pyrene 0 0 0 0 0 0 2 0 58

2

- Methylnaphthalene 0 0 3 2 0 0 9 6 40

2

– Methylphenol 0 0 0 0 3 6 2 3 46

3

- Methylphenol & 4

- Methylphenol 0 0 0 0 7 3 3 13 34

Naphthalene 1 1 0 0 3 1 5 5 44

4

– Nitroaniline 0 0 0 0 0 0 1 0 59

N

- Nitrosodiphenylamine 0 0 0 0 0 0 1 0 59

Phenanthrene 0 0 0 0 2 0 5 7 46

Phenol 0 0 0 0 5 0 4 2 49

2

– Picoline 0 0 0 0 1 0 1 0 58

Pyrene 0 0 0 0 1 0 3 5 51

Pyridine 2 2 21 4 5 3 6 0 17

1, 2, 4

- Trichlorobenzene 0 0 0 0 0 0 0 2 58

All 74 Others (See Table 1) 0 0 0 0 0 0 0 0 4440

Total 4 5 26 7 69 57 109 90 6593

### 28



## Pesticides

Determinations of the 20 chlorinated pesticides and three organophosphorus

pesticides listed in Table 1 were conducted on the influent and 14

- day flowback water

streams. None of these pesticides were detected. This would suggest that no

chlorinated pesticides were introduced wit h the additives with the influent water during

well completions.



## Polychlorinated Biphenyls (PCBs)

Determinations of the 7 polychlorinated biphenyl compounds (arochlors) listed in

Table 1 were conducted on the influent and 14

- day flowback water streams. Results

from the measurements of organophosphorus pesticides in all samples of the influent

water and in the 14

- day flowback water are summarized in Figures 16 and 17,

respectively. As seen from these graphs, all determinations for PCBs were measured

as non

- detect. This would suggest that no PCBs were introduced with the additives

with the influent water during well completions.



## Metals

Total metals data for the six raw water samples and the 19 influent water samples

with additives are presented in Table 14. For the most part, the differences in the

ranges of concentration between the two sample sets can be explained by the

differences expected for the different population (6 vs 19 samples). There is an added

unknown statistical bias in the subset of the number of samples in the influent utilizing

blended (reused) water versus the number of raw water sources utilizing reused water.

### 29 T able 14: Metals Data in Raw Water and Source Water with Additives

All units m g/l Raw Water day 0

6 Samples Influent with Additives

19 Samples

Obs Range Median Obs Range Median

Aluminum 4 0.122

- 0.264 0.213 5 0.177

- 2 0.4

Antimony 2 0.0146

- 0.0154 0.015 1 0.015

- 0.0154 0.0154

Arsenic 0 0

Barium 6 0.243

- 5.48 0.589 6 0.108

- 87.1 1.005

Beryllium 0 0

Boron 5 0.0189

- 2.45 0.0343 5 0.019

- 2.58 0.0433

Calcium 6 4.88

- 40.1 31.75 6 6.69

- 241 32.2

Cadmium 1 0.0017

- 0.0017 0.0017 1 0.002

- 0.0017 0.0017

Cobalt 0 ND 0 ND

Chromium 0 ND 0 ND

Trivalent

Chromium 0 ND

0 ND

Copper 0 ND 1 0.045

- 0.0445 0.0445

Iron 6 0.192

- 4.31 0.4995 6 0.137

- 3.56 0.4455

Lead 0 ND 0 ND

Lithium 3 0.0338

- 2.24 0.0422 3 0.03

- 2.34 2.05

Magnesiium 6 1.08

- 183 5.845 6 1.25

- 183 13.87

Manganese 6 0.0087

- 0.237 0.0817 5 0.008

- 0.395 0.127

Molybdenum 0 ND 0 ND

Nickel 1 ND

- 0.0111 0.0111 1 0.02

- 0.0195 0.0195

Potassium 4 2.36

- 53.6 2.89 4 2.25

- 57.4 7.265

Sodium 6 4.2

- 1380 31.05 6 32.6

- 1460 59.5

Selenium 0 ND

- 1 0.035

- 0.0353 0.0353

Tin 0 ND

- 0 ND

Strontium 6 0.352

- 76.2 0.6785 6 0.206

- 78.5 0.919

Titanium 1 ND

- 0.0299 0.0299 2 0.019

- 0.0271 0.0233

Thallium 0 ND 0 ND

Zinc 6 0.0257

- 0.172 0.0486 6 0.035

- 0.176 0.0635

Mercury 3 5E

- 05

- 0.00061 5E

- 05 3 4E

- 05

- 6E

- 05 5E

- 05



### Metals data, especially the top five cations, sodum, barium, iron, strontium and

magnesium, tend to follow a timed profile. These data are presented by collection day

to better show the trends. Summary data for days 1 and 5 are presented in Table 15.

Summary data for days 14 and 90 are presented in Table 16. The 90 day data present

a much smaller database (5 sites compared to 17

- 19 samples in the other sets). The

top six metal ions in flowback water are sodium, calcium, magnesium, strontium and

iron and potassium. These ions, and most others listed, increase from day 1 to day 90

and represent a significant increase over the raw water and influent water data in the

Table 14.

### 30 Table 15: Metals Dat a for Marcellus Flowback Days 1 and 5

Day 1 (19 Samples) Day 5 (18 Samples)

Metals (mg/l) Obs Range Median Obs Range Median

Aluminum 17 0.165

- 4.03 0.507 17 0.111

- 47.2 0.378

Antimony 13 0.0089

- 0.0378 0.0247 10 0.017

- 0.0472 0.0325

Arsenic 12 0.0133

- 0.0551 0.0333 11 0.014

- 0.124 0.043

Barium 19 0.332

- 1450 37.6 18 21.4

- 13900 736.5

Beryllium 0 0

Boron 19 0.0181

- 13.1 6.68 18 3.14

- 97.9 12.05

Calcium 19 35.2

- 19700 833 18 1440

- 23500 5555

Cadmium 4 0.0002

- 0.0029 0.00235 7 0.002

- 0.0096 0.0038

Cobalt 3 0.0045

- 0.0105 0.0057 0

Chromium 16 0.0075

- 0.359 0.0318 14 0.008

- 0.152 0.0271

Trivalent

Chromium 6 0.0075

- 0.0491 0.0293 9 0.0075

- 0.0924 0.0272

Copper 11 0.0096

- 0.255 0.0571 9 0.029

- 4.15 0.0789

Iron 19 2.68

- 67.2 13.9 18 20.4

- 180 41.25

Lead 12 0.0017

- 0.0709 0.02565 8 0.021

- 0.606 0.05605

Lithium 18 4.06

- 129 14.05 18 10.6

- 153 42.75

Magnesiium 19 16

- 1320 89 18 135

- 1550 581.5

Manganese 19 0.146

- 5.96 0.782 18 0.881

- 7.04 2.64

Molybdenum 19 0.0089

- 0.372 0.0356 15 0.009

- 0.147 0.0317

Nickel 17 0.0106

- 0.203 0.0286 6 0.011

- 0.187 0.02275

Potassium 19 2.69

- 923 109 18 48.9

- 2430 300.5

Sodium 19 63.8

- 34700 6290 18 10700

- 65100 18100

Selenium 1 ND

- 0.0043 0.0043 0

Tin 3 0.0038

- 0.007 0.0051 1 ND

- 0.02 6 0.0257

Strontium 19 0.58

- 4330 167 18 345

- 4830 1160

Titanium 11 0.0151

- 0.092 0.0385 9 0.024

- 0.313 0.107

Thallium 3 0.0049

- 0.0272 0.0054 3 0.019

- 0.0246 0.0194

Zinc 18 0.0561

- 0.665 0.191 18 0.068

- 1.23 0.164

Mercury 6 4E

- 05

- 0.000074 5.05E

- 05 5 2E

- 05

- 0.00024 0.000043

### 31 Table 16: Metals Data for Marcellus Flowback Days 14 and 90

Day 14 with 17 S ites Report ing Day 90 with 5 S ites Report ing

Metals ( m g/l) Obs Range Median Obs Range Median

Aluminum 15 0.158

- 4.68 0.835 5 0.173

- 1.04 0.37

Antimony 8 0.0092

- 0.0491 0.02645 0

Arsenic 12 0.0126

- 0.135 0.07695 4 0.0462

- 0.114 0.0726

Barium 17 0.0631

- 12500 589 5 133

- 4220 1440

Beryllium 2 0.00021

- 0.0022 0.001205 0

Boron 17 0.464

- 114 13.6 5 13

- 145 25.3

Calcium 17 14.3

- 140000 9600 5 8500

- 24000 18300

Cadmium 12 0.0014

- 0.0124 0.00385 4 0.0025

- 0.0077 0.00255

Cobalt 2 0.0109

- 0.0278 0.01935 0

Chromium 15 0.0012

- 0.567 0.0312 3 0.0135

- 0.0209 0.0177

Trivalent

Chromium 10 0 .0012

- 0.0942 0.01335 1 ND

- 0.0175 0.0175

Copper 11 0.0077

- 0.518 0.079 2 0.0272

- 0.0515 0.03935

Iron 17 0.439

- 574 73.2 5 69.7

- 158 93

Lead 10 0.0033

- 0.596 0.092 3 0.0456

- 0.97 0.068

Lithium 17 0.0077

- 201 73.7 5 44.5

- 137 88.6

Magnesiium 17 2.83

- 1800 794 5 933

- 1790 1710

Manganese 17 0.0587

- 18.6 4.79 5 2.13

- 9.77 4.72

Molybdenum 11 0.0066

- 0.188 0.0324 1 0.017

- 0.017 0.017

Nickel 8 0.0013

- 0.769 0.05795 0

Potassium 17 8.23

- 2820 368 5 191

- 3950 548

Sodium 17 70.7

- 85600 31500 5 26900

- 75800 39700

Selenium 4 0.0301

- 0.0956 0.0367 1 ND

- 0.044

Tin 4 0.0039

- 0.0235 0.02185 0

Strontium 17 0.103

- 5570 1850 5 1220

- 8020 3480

Titanium 10 0.0636

- 0.247 0.1435 4 0.13

- 0.242 0.173

Thallium 2 0.0339

- 0.151 0.09245 1 0.168

- 0.168 0.168

Zinc 16 0.0117

- 2.29 0.226 5 0.0293

- 0.811 0.178

Mercury 2 0.000049

- 0.00029 0.00017 1 ND

- 0.000068

### 32



## RESULTS FROM THE BARNETT

Using the same protocols employed in the Marcellus, f ive sites were sampled in the

Barnett. Flowback water samples were collected at the time intervals indicated in Table

1 7 . Initial raw water for Sites LPG1 and LPG2 was from the same source and is

represented by a single sample. Initial raw water for Sites LPG 3, LPG 4, and LPG 5

was from the same source and is represent ed as a single sample. Four of five sites

reported data on Day 1. Three sites reported on Day 5 and one site reported on Day 6.

These four samples dates are treated together in discussions of Day 5

- 6 events. Three

sites reported on Day 10 and one site reported on Day 12. These sample dates are

treated together in discussions of Day 10

- 12 events. Sampling and assurance plans

followed those developed for the Marcellus in Appendices A and B. Chemical results

were collected and treated as described in Ta bles 1 and 2. Results from all samples

taken from Sites LPG 1

- 5 are presented with the analysis results from the Marcellus in

the GTI Flowback Water Information Base in Excel Format that was submitted by GTI to

RPSEA.



## Flowback Water Collection Volumes

Flowback volumes for Sites LPG1

- 4 were recorded on a daily basis. Selected

points are presented in Table 1 8 to correspond with the chemical data presented the

following sections. Data are similar in form to those presented for the Marcellus in

Table 3. Like the Marcellus, water recovery is rapid during the first few days, with

recovery rates slowing by day 10

- 12 after fracture. Table 17: Sample Dates (Days after Fracture) for 5 Sites in the Barnett

Day 0 Day1 Day 3 Day 5 Day 6 Day 7 Day 10 Day 12

LPG1 X X X X

LPG2 X X X X

LPG3 X X X X

LPG4 X X X

LPG 5 X

### 33



## General Chemistry

A summary of the general chemical characteristics of the two water influent samples

and the flowback water effluents associated with the completion and operation of wells

of the 5 sampling locations are presented in Tables 19

- 2 2 . Characteristics of the two

samples of raw influent water are shown in Table 19 . The pH of these streams ranging

from 7.7 to 8.5 seems to be normal for surface waters. Dissolved solids measurements

for the influent waters used for hydraulic fracturi ng (with additives) had a range of 200

-

800 mg/l, which is considered in the range of fresh surface water supplies.

Interestingly, oil and grease measurements had a range of 17

- 22 mg/l and total organic

carbon had a range of 124

- 143 mg/l; elevated values i n these measurements may be

due to various degrees of blending of reused waters into frac job influent water supplies.

Table 18: Cumulative Flow (BBL) for 5 Sites in the Barnett

Initial Fracture (BBL) Recovered Volumes (Cumulative) BBL

Day1 Day 3 Day 5 Day 6 Day 7 Day 10 Day 12

LPG1 129,336 2,402 7,566 11,806 12,752 14,154 20,346 23,082

LPG2 127,076 957 3,256 5,175 6,171 7,146 10,031 11,878

LPG3 100,611 4,117 8,071 13,735 14,827 15,972 19,021 20,960

LPG4 155,362 873 2,878 3,986 4,274 4,522 5,209 5,745

LPG 5 X X X X X X X X

### 34

Table 19. Summary of Chemical Characteristics of Influent Water Used for

Hydraulic Fracturing after Additives were Blended

General Chemistry LPG 3,4, 5 LPG 1,2 Average Units

pH 7.7 8.5 No Units

Acidity ND ND ND mg/L

Total Alkalinity 251 236 243.5 mg/L

Hardness as CaCO3 28 100 64 mg/L

Total Suspended Solids 360 80 220 mg/L

Turbidity 265 116 190.5 NTU

Chloride 151 21.6 86.3 mg/L

Total Dissolved Solids 800 203 501.5 mg/L

Specific Conductance 1550 484 1017 umhos/cm

Total Kjeldahl Nitrogen 36 21.9 28.95 mg/L

Ammonia Nitrogen 3.9 8 5.95 mg/L

Nitrate

- Nitrite 0.048 0.036 0.042 mg/L

Nitrite as N 0.57 0.14 0.355 mg/L

Biochemical Oxygen Demand 130 245 187.5 mg/L

Chemical Oxygen Demand 829 559 694 mg/L

Total Organic Carbon (TOC) 143 124 133.5 mg/L

Dissolved Organic Carbon 84.3 281 182.65 mg/L

Oil & Grease (HEM) 22.2 17 19.6 mg/L

Cyanide, Total ND 1.9 1.9 mg/L

Amenable Cyanide ND ND ND mg/L

Bromide 0.7 ND 0.7 mg/L

Fluoride 1.00 0.096 0.548 mg/L

Total Sulfide ND ND ND mg/L

Sulfate 107 28 67.5 mg/L

Total Phosphorus 3 0.11 1.555 mg/L

Total Recoverable Phenolics ND 0.014 0.014 mg/L



### Characteristics of flowback water sampled at 1 day, 3 days, 5

- 6 days, and 10

- 12

days following the hydraulic fracturing event are presented in Tables 2 0 and 2 1 . The

water is elevated in alkalinity with median values ranging from 725

- 1,200 mg/l. The

water remains imbalanced with high levels of calcium and magnesium. Cations are

dominated by sodium and calcium in this water. Anions are dominated by chloride.

However, there is a fairly large sulfate component to the anionic balance, which has

### 35

importance in the relative value of barium and strontium in the water. This topic is

evaluated further in the discussion section.

Table 20 General Chemical Parameters, Ba rnett Day 1 and Day 3

LPG1,2,3, 5 LPG 1,2,4

General Chemistry Day 1 Day 3

Parameter Range Median Range Median Units

pH 6.7

- 8 7.2 6.5

- 7.2 6.6 No Units

Acidity ND

- ND ND ND

- ND ND mg/L

Total Alkalinity 482

- 1,590 980 236

- 1,550 1,340 mg/L

Hardness as CaCO3 840

- 2,800 2,200 3,000

- 24,000 4,600 mg/L

Total Suspended Solids 48

- 237 153 59

- 120 89 mg/L

Turbidity 37

- 266 130 104

- 371 154 NTU

Chloride 3,330

- 17,900 11,405 17,500

- 49,000 21,400 mg/L

Total Dissolved Solids 5,850

- 31,400 25,050 33,500

- 96,900 37,200 mg/L

Specific Conductance 11,300

- 59,000 55,550 71,400

- 174,000 82,600 umhos/cm

Total Kjeldahl Nitrogen 16

- 203 155 74

- 239 215 mg/L

Ammonia Nitrogen 9

- 223 186 143

- 309 251 mg/L

Nitrate

- Nitrite 0.024

- 0.024 0.024 0.051

- 0.051 0.051 mg/L

Nitrite as N 81.9

- 107 94.45 85.7

- 96.8 91.25 mg/L

Biochemical Oxygen Demand 89

- 1,480 311 94

- 290 244 mg/L

Chemical Oxygen Demand 850

- 4,280 1,485 1,900

- 5,850 2,290 mg/L

Total Organic Carbon (TOC) 34.7

- 99.1 47.5 15.4

- 19 17.4 mg/L

Dissolved Organic Carbon 30.6

- 91.3 53.55 9.7

- 23.2 17.6 mg/L

Oil & Grease (HEM) 5.6

- 1720 862.8 26.7

- 26.7 26.7 mg/L

Cyanide, Total 15.6

- 15.6 15.6 ND

- ND ND ug/L

Amenable Cyanide ND

- ND ND ND

- ND ND mg/L

Hexavalent Chromium 0.014

- 0.16 0.0165 0.011

- 0.042 0.02 mg/L

Dissolved Hexavalent Chromium 0.01

- 0.08 0.03 ND

- 0.15 0.08 mg/L

Bromide 34.3

- 532 303.5 270

- 448 399 mg/L

Fluoride 1.6

- 30.6 4.75 4

- 4.9 4.45 mg/L

Total Sulfide ND

- ND ND ND

- ND ND mg/L

Sulfate 259

- 972 669 277

- 1,010 585 mg/L

Total Phosphorus 0.37

- 3.4 0.79 0.39

- 0.66 0.525 mg/L

Total Recoverable Phenolics 0.034

- 0.45 0.08 0.046

- 0.13 0.088 mg/L

### 36

Table 21: Summary of General Chemistry of Flowback Water Days 5

- 6 and 10

- 12

General Chemistry LPG 1,2,3,4

Day 5

- 6 LPG 1,2,3,4

Day 10

- 12

Parameter Range Median Range Median Units

pH 6.6

- 7.2 7 6.5 7.2 7.05 No Units

Acidity ND

- ND ND ND ND ND mg/L

Total Alkalinity 238

- 1,630 1,007 215 1,240 725 mg/L

Hardness as CaCO3 3,400

- 24,000 4,300 3,500 21,000 5,800 mg/L

Total Suspended Solids 37

- 253 95 120 535 242 mg/L

Turbidity 2

- 400 9 144 314 239 NTU

Chloride 16,700

- 72,400 23,150 9,600 60,800 34,700 mg/L

Total Dissolved Solids 25,000

- 98,900 37,800 16,400 97,800 50,550 mg/L

Specific Conductance 53,000 174,000 87,900 34,800 179,000 111,500 umhos/cm

Total Kjeldahl Nitrogen 28

- 251 163 26 298 171 mg/L

Ammonia Nitrogen 30

- 302 209 18 486 303 mg/L

Nitrate

- Nitrite ND 0.023 0.0115 0.018 0.035 0.0265 mg/L

Nitrite as N 4.5

- 96.3 50.4 3.5 38.1 4.7 mg/L

Biochemical Oxygen Demand 93

- 323 207 101 2,120 582 mg/L

Chemical Oxygen Demand 2,440

- 3,610 2,690 927 3,150 2,945 mg/L

Total Organic Carbon (TOC) 9.5

- 26.7 15.5 6.2 36.2 9.75 mg/L

Dissolved Organic Carbon 6.6

- 27.8 12.95 5.5 65.3 11.2 mg/L

Oil & Grease (HEM) 110

- 110 110 88.2 1430 163.5 mg/L

Cyanide, Total 2.2

- 17.9 10.05 6 6 6 mg/L

Amenable Cyanide ND

- ND ND ND ND ND mg/L

Bromide 218

- 690 571 117 798 589 mg/L

Fluoride 0

- 5.3 2.55 3.5 12.8 3.8 mg/L

Total Sulfide ND

- 0.8 NA ND ND ND mg/L

Sulfate 145

- 1,300 1,055 120 1,260 709 mg/L

Total Phosphorus 0.41

- 2.3 0.48 0.19 0.7 0.395 mg/L

Total Recoverable Phenolics 0.0075

- 0.0081 0.0078 0.0093 0.23 0.11965 mg/L

### 37 Salt concentrations (TDS) in influent water and in flowback water generated over

time from the 5 sampling Sites from the Barnett are tabulated in Table 2 2 . As shown in

Table 15, influent water contains moderate to low concentrations of salts. Following the

use of this water for hydraulic fracturing, a flowback water stream that is collected from

the well exhibits increasing concentrations of salts with ti me. These profiles of salt

concentrations are similar to Figure 1. As expected, early flowback water emerging

soon after the frac job is relatively low in TDS content; following the initial day, the

concentration of total dissolved solids increases with time from low salt concentrations

to a plateau of elevated salt levels as measured at 10 and 12 days.

Table 22: Salt Concentrations (TDS, mg/l)

Day 0 Day 1 Day 3 Day 5 Day 6 Day 7 Day 10 Day 12

LPG 1 203** 31,400 33,500 39,500 48,900

LPG 2 203** 26,500 37,200 36,100 52,200

LPG 3 800* 5,850 25,000 30,000 16,400

LPG 4 800* 96,900 98,900 97,800

LPG 5 800* 23,600

* One Sample,** One Sample



### Levels of total organic carbon (TOC) in the flowback water samples at 5

- 6 and 10

-

12 days are lower than the TOC of the raw water. Organic components, as represented

by Total Organic Carbon, remain fairly constant or decrease over time (Table 23 . The

TO C of the Barnett samples is generally lower than that of the Marcellus samples.

Table 23: Total Dissolved Carbon Concentrations (TDS, mg/l)

Day 0 Day 1 Day 3 Day 5 Day 6 Day 7 Day 10 Day 12

LPG 1 124** 34 17 13 7

LPG 2 124** 36 15 10 6

LPG 3 143* 59 27 28 36

LPG 4 143* 19 18 12

LPG 5 143* 99

* One Sample,** One Sample

### 38 The same observation cannot be made in comparing biochemical oxygen demand

(BOD) values in flowback water with the BOD of the influent water streams (Table 2 4 ).

The BOD data are quite erratic, with sudden spikes to values exceeding 645

- 2000 mg/l.

The moderate levels of BOD in the influent waters may have been due to recycling of

recovered water from other frac jobs.

Table 24: BOD (TDS, mg/l)

Day 0 Day 1 Day 3 Day 5 Day 6 Day 7 Day 10 Day 12

LPG 1 245** 243 290 319 2120

LPG 2 245** 374 244 323 928

LPG 3 130* 90 94 645 101

LPG 4 130* 94 92 236

LPG 5 130* 1480

* One Sample,** One Sample



### COD data (Table 2 5 ) show s steady increase with time, roughly following the total

salts concentration, indicating that much of the COD may be associated with inorganic

matter in the water.

Table 25: COD (TDS, mg/l)

Day 0 Day 1 Day 3 Day 5 Day 6 Day 7 Day 10 Day 12

LPG 1 559** 1610 1900 2620 2920

LPG 2 559** 1360 2290 2440 3070

LPG 3 829* 850 2760 7870 927

LPG 4 829* 5850 360 3150

LPG 5 829* 4280

* One Sample,** One Sample



## Organic Compounds

As with the Marcellus characterization, organic compounds determined in the

characterization of water samples fell into the categories of volatile organics, semi

volatile organics, chlorinated pesticides, organophosphorus pesticides, and

### 39

polychlorinated biphenyls. The following sections summarize the results amo ng all five

of the categories of analysis.



## Volatile Compounds

As presented in Table 1, samples collected from Sites 1

- 5 were analyzed for 70

volatile compounds of highly varied chemical characteristics, including the volatile

hydrocarbon constituents tha t are normally found in produced water (such as benzene,

toluene, ethylbenzene, and xylenes

– or BTEX, and naphthalene) as well as

constituents not known to be associated with conventional produced water such as

chlorinated solvents and halogenated aromati cs. The volatile organic content from the

two raw water samples are presented in Table 2 6 . Only traces of napthlene, toluene,

and benzene were identified in the sample for Sites LPG 1 and LPG2.

Table 26: Volatile Organics in the Influent Water Samples

Volatiles (μg/L) LPG 3,4, 5 LPG 1,2 

### Average Units

Naphthalene ND 1.3 NA μg/L

Benzene ND 2 NA μg/L

Toluene ND 3 NA μg/L

A summary of the results for volatile compound determinations performed

recovered flowback water is shown in Table 2 7 . Traces of benzene and other alkylated

benzyl isomers were present in the recovered water. The relative concentrations did

not appear to change with time after fracture and appeared to fluctuate fairly randomly.

All data were, therefore, consolidated to present the range of results encountered in all

16 samples. It is important to note that of all the components measured in the test

protocol, only 8 compounds common to waters generated from petroleum and gas sites

were detected. No compound was obser ved in all 16 samples. The most commonly

encountered constituents were the BTEX and similarly related alkyl

- benzene isomers.

Traces of acetone, a commonly used cleaning fluid, were also found at measurable

concentrations.

### 40

Table 27: Summary Volatiles Data; All Site Samples (Days 1

- 12, Total = 16

Samples)

Volatiles Data (μg/L) Number of

Observations Range Median Average

Isopropylbenzene 2 0.8

- 69 35 35

Acetone 9 27

- 540 110 145

Naphthalene 12 8.3

- 84 22 27

1, 3, 5

- Trimethylbenzene 12 6.4

- 300 15 59

1, 2, 4

- Trimethylbenzene 13 6.9

– 1,200 37 173

Xylenes (total) 14 43

– 1,400 360 425

Benzene 15 49

– 5,300 680 1,198

Ethylbenzene 15 2.2

- 670 29 74

Toluene 15 79

– 8,100 760 1,246

The concentrations of 70 compounds were evaluated in the 16 test samples for a

total of 1120 evaluations. Most tests were reported as non

- detectable (1013

evaluations). Ninety

- two observations were below 1 ppm and only 15 observations

were above 1 ppm. Chlorinated, brominated, or other man

- made compounds were not

detected. More than 90 percent of all constituent determinations, on average, were at

Figure 4: Number of Detectable and Non

- Detectable Tests for Volatile

Compounds.

### 41

non

- detectable levels and less than 1.5 percent of all constituent determin ations were

above 1 ppm (Figure 4 above ).



## Semi volatile Compounds

A total of 112 semi volatile organic compounds (as listed in Table 1) were included

in the analysis of influent water and in flowback water samples. A summary of the

results of semi volatile determinations in the two raw water samples is presented in

Table 2 8 . The sample from Sites LPG 3,4,and 5 had traces of PAH, and traces of two

phthalate esters and two chlorinated hydrocarbons. Water from Site LPG 1 and 2

water had only a sing le report of pyridine.

Table 28: Semi volatile Compounds in the Influent Water

Semi

- Volatiles (μg/l) LPG 3,4, 5 LPG 1,2 

### Average

Benzo (a) anthracene 1.3 ND NA

Benzo (a) pyrene 1.1 ND NA

Benzo (b) fluoranthene 1.3 ND NA

Benzo (ghi) perylene 1.1 ND NA

Benzo (k) fluoranthene 0.95 ND NA

bis (2

- Ethylhexyl) phthalate 36 ND NA

Butyl benzyl phthalate 2 ND NA

Chrysene 1.2 ND NA

Dibenz (a, h) anthracene 0.98 ND NA

Di

- n butyl phthalate 1.9 ND NA

2, 6

- Dichlorophenol 2 ND NA

Fluoranthene 1 ND NA

Hexachlorobenzene 0.8 ND NA

Indeno (1, 2, 3

- cd) pyrene 0.91 ND NA

Pentachlorophenol 0.69 ND NA

Phenanthrene 1.2 ND NA

Pyrene 1 ND NA

Pyridine 0.96 40 20.5

### 42 A summary of the results for semi

- volatile compound determinations performed on

the 16 site samples is shown in Table 29 . Of the 112 compounds in the sample set,

about 70% were not detected in any sample. Of the 32 compounds observed, about 1/3

of these were incidental detections in one of the 16 samples. All compounds detected

are naturally occurring in petroleum. Pyridine is a nucleophile that is used widely in the

manufacture of certain types of chemicals and pharmaceuticals and its presence may

be due to its use as a precursor in the manufacture of one of the hydraulic fracturing

additives. In general, nearly all of the semi volatile determinations were either non

detect (> 96% of the measurements) or at low trace levels (Figure 5 above ). Figure 5: Distribution of Observations of Semi volatile Organics in 16 Site Samp les

### 43 Table 29:Semi

- volatiles Data from 16 Site Samples (Days 1

- 23) All Five Sites

Semi

- volatiles (μg/l) Number of

Observations Range Median Average

Diphenylamine 2 0.6

- 10.0 5.3

Benzidine 1 ND

- 35

1, 4

- Dioxane 7 3.1

- 12 5.4 6.5

1, 2

- Diphenylhydrazine 2 0.5

- 7.8 4.2

Acetophenone 1 ND

- 4.6

Benzo (a) anthracene 1 ND

- 17.0

Benzo (a) pyrene 1 ND

- 130.0

Benzo (b) fluoranthene 2 0.5

- 84.0 42.2

Benzo (ghi) perylene 2 0.7

- 84.0 42.3

Benzo (k) fluoranthene 2 0.6

- 65.0 32.8

Benzyl alcohol 8 14.0

- 200 27.0 81.5

bis (2

- Ethylhexyl) phthalate 5 4.8

- 490 33 210

Butyl benzyl phthalate 4 1.9

- 110 12.6 34.3

Chrysene 2 0.57

- 240 120

Dibenz (a, h) anthracene 2 3.2

- 150 77

Di

- n butyl phthalate 4 1.5

- 120 22 41

2, 4

- Dichlorophenol 1 ND

- 15

2, 4

- Dimethylphenol 8 8.3

- 21 15.5 14.5

Di

- n

- octyl phthalate 1 ND

- 270

Fluoranthene 1 ND

- 0.18

Fluorene 6 0.46

- 1.3 0.725 0.8

Indeno (1, 2, 3

- cd) pyrene 2 2.9

- 140 71

2

- Methylnaphthalene 16 5.4

- 20,000 22.5 1362

2

- Methylphenol 15 5.8

- 76 31 28.3

3

- Methylphenol & 4

- Methylphenol 15 7.8

- 100 44 41

Naphthalene 16 4.8

- 3100 22 238

N

- Nitrosodiphenylamine 2 7.8

- 10 8.9

N

- Nitrosomethylethylamine 1 ND

- 410

Phenanthrene 14 0.52

- 1400 1.3 107

Phenol 7 17

- 93 68 63

Pyrene 1 ND

- 0.18 0.2

Pyridine 15 100

- 670 500 413



## Pesticides

Determinations of the 20 chlorinated pesticides and 3 organophosphorus pesticides

on 5 site samples and two source waters (Day 0) are listed in Table 3 0 . A single

incidental measurement of less than 0.1 ppb was detected on day 1 from LPG 1. All

other determinations for chlorinated pesticid es were measured as non

- detect. This

### 44

would suggest that no chlorinated pesticides were introduced with the additives with the

influent water during well completions.

Table 30: Summary Pesticide Data

Site LPG1 LPG2 LPG3 LPG4 LPG 5

Sample Day Day 1 Day 0 Day 0 Day 7 Day 1 Day 5 Day 0

Chlorinated Pesticides

Chlordane (Technical) ND ND ND ND ND ND ND

alpha

- BHC ND ND ND ND ND ND ND

beta

- BHC 0.073 ND ND ND ND ND ND

delta

- BHC ND ND ND ND ND ND ND

gamma

- BHC (Lindane) ND ND ND ND ND ND ND

Heptachlor ND ND ND ND ND ND ND

Aldrin ND ND ND ND ND ND ND

Heptachlor epoxide ND ND ND 0.43 ND ND ND

Endosulfan I ND ND ND ND ND ND ND

Dieldrin ND ND ND ND ND ND ND

4, 4'

- DDE ND ND ND ND ND ND ND

Endrin ND ND ND ND ND ND ND

Endrin ketone ND ND ND ND ND ND ND

Endrin aldehyde ND ND ND ND ND ND ND

Endosulfan II ND ND ND ND ND ND ND

4, 4'

- DDD ND ND ND ND ND ND ND

Endosulfan sulfate ND ND ND ND ND ND ND

4, 4'

- DDT ND ND ND ND ND ND ND

Methoxychlor ND ND ND ND ND ND ND

Toxaphene ND ND ND ND ND ND ND

Organophospates

Thionazin ND ND ND ND ND ND ND

Ethyl parathion ND ND ND ND ND ND ND

Tetraethyldithiopyrophosphate ND ND ND ND ND ND ND

### 45



## Polychlorinated Biphenyls (PCBs)

Determinations of the 7 polychlorinated biphenyl compounds (arochlors) listed in Table

1 were conducted on the two influent waters and Sites 2,4, and 5. As seen from these

graphs, all determinations for PCBs were measured as non

- detect. This would sugges t

that no PCBs were introduced with the additives with the influent water during well

completions.

Table 31 : PCB Data

Source Water

Day 0 LPG1

Day LPG2

Day LPG3

Day

LPG 3,4, 5 LPG 1,2 1 5 1 5 1 7

Arochlor 1 016 ND ND ND ND ND ND ND ND

Arochlor 1221 ND ND ND ND ND ND ND ND

Arochlor 1232 ND ND ND ND ND ND ND ND

Arochlor 1242 ND ND ND ND ND ND ND ND

Arochlor 1248 ND ND ND ND ND ND ND ND

Arochlor 1254 ND ND ND ND ND ND ND ND

Arochlor 1260 ND ND ND ND ND ND ND ND



## Metals

Unlike the organic constituents that do not change much with time, the metals

concentrations tend to increase with time from fracture and follow the general trend for

TDS. A summary of metal concentrations in the two influent water samples is

presented in Table 3 2

. The total metals content of the Day 1 and Day 3 samples are summarized in Table

34. As seen in this table, sodium is the major cation in all of the samples, followed by

concentrations in some samples of calcium, magnesium and barium that will need to be

monitored for purposes of scale control in some locations.

The total metal content of the Day 5

- 6 and Day 10

- 12 samples are presented in

Table 35. Since strontium is present in flowback waters at concentrations between 345

to 4,830 mg/l in the 5

- day flowback samples, it will be important for operators to

implement procedures to prevent the formation of strontium

- bearing scale. Iron level s in

### 46

the range of 10 to 180 mg/l may also need to be watched and mitigated in order to

prevent operational difficulties at a number of well completion locations.

Heavy metals of toxicological concern that are often associated with urban industrial

activity (including chromium, copper, nickel, zinc, lead, cadmium, mercury and arsenic)

are at very low levels in all of the shale gas water samples.

Table 32: Total M etals in Influent Water Samples

Total Metals LPG 3,4, 5 LPG 1,2 

### Average Units

Aluminum 0.525 0.604 0.564 mg/L

Antimony ND ND mg/L

Arsenic ND ND mg/L

Barium 0.0527 2.66 1.356 mg/L

Beryllium ND ND mg/L

Boron 0.509 0.124 0.317 mg/L

Calcium 13.1 17.1 15.1 mg/L

Cadmium ND ND mg/L

Cobalt ND ND mg/L

Chromium ND 0.0064 0.0064 mg/L

Trivalent Chromium ND 0.0026 0.0026 mg/L

Copper ND ND mg/L

Iron 1.68 1.18 1.43 mg/L

Lead 0.0127 ND mg/L

Lithium 0.0464 ND mg/L

Magnesium 1.57 11.5 6.535 mg/L

Manganese 0.0359 0.0478 0.042 mg/L

Molybdenum ND ND mg/L

Nickel ND ND mg/L

Potassium 3.5 4.46 4 mg/L

Sodium 278 81.3 179.6 mg/L

Selenium ND ND mg/L

Tin ND ND mg/L

Strontium 0.244 1.3 0.77 mg/L

Titanium ND ND mg/L

Thallium ND ND mg/L

Zinc 0.0281 ND mg/L

Mercury ND ND mg/L

### 47 Table 33: Metals Data in the Barnett Samples

Metals Data (mg/l) 

### LPG1,2,3, 5 / Day 1 LPG 1,2,4 Day 3

Range Median Range Median

Aluminum 0.114

- 0.572 0.495 0.34

- 0.49 0.34

Antimony ND ND ND ND

Arsenic ND ND ND 0.03

Barium 0.053

- 3.31 1.50 1.63

- 15.0 2.86

Beryllium ND ND ND

Boron 0.51

- 39.1 23.5 25.6

- 29.6 29.3

Calcium 13

- 768 564 753

- 6,290 1,270

Cadmium ND

- 0.000 0.00

- 0.00 0.00

Cobalt 0.006

- 0.028 0.014 0.01

- 0.01 0.01

Chromium 0.011

- 0.066 0.030 0.02

- 0.06 0.04

Trivalent Chromium 0.003

- 0.014 0.008 0.02

- 0.02 0.02

Copper 0.087

- 0.131 0.109 0.04

- 0.04 0.04

Iron ND 18.9

- 43.6 37.4

Lead 0.013

- 0.034 0.013 ND

Lithium 0.046

- 10.8 9.01 10.7

- 32.3 13.1

Magnesiium 2

- 116 89 113

- 713 199

Manganese 0.036

- 1.98 0.711 0.35

- 1.63 0.66

Molybdenum 0.015

- 0.066 0.043 0.02

- 0.08 0.07

Nickel 0.029

- 0.036 0.033 0.02

- 0.02 0.02

Potassium 4

- 216 111 192

- 662 247

Sodium 278

- 12,200 7805 11,800

- 23,700 14,100

Selenium ND 0.03

- 0.03 0.03

Tin 0.004

- 0.004 0.004 0.03

- 0.03 0.03

Strontium ND

- 206 132 220

- 1170 282

Titanium ND ND 0.00

Thallium ND 0.05

- 0.05 0.05

Zinc 0.028

- 0.560 0.202 0.14

- 0.18 0.15

Mercury ND ND

### 48 Table 34: Total Metals Data Days 5

- 6 and 10

- 12

LPG 1,2,3,4 / Day 5

- 6 LPG 1,2,3,4 Day 10

- 12

Range Median Range Median

Aluminum 0.37

- 1.64 0.39 0.37

- 2.21 0.43

Antimony ND ND ND

Arsenic ND ND ND

Barium 1.48

- 16.8 2.19 0.93

- 17.9 3.6

Beryllium ND

- ND ND ND

Boron 18.0

- 37.1 31.2 7.0

- 31.9 30.3

Calcium 944

- 6,680 1,290 1,110

- 6,730 1,600

Cadmium ND ND

Cobalt 0.01

- 0.01 0.01 0.01

- 0.01 0.01

Chromium 0.01

- 0.11 0.03 0.01

- 0.12 0.03

Trivalent Chromium 0.03

- 0.11 0.07 ND 0.03 0.01

Copper 0.37

- 0.37 0.37 0.06

- 0.52 0.29

Iron 11.8

- 76.7 17.25 12.1

- 93.8 24.9

Lead ND ND 0.01

- 0.02 0.02

Lithium 5.10

- 35.6 14.80 2.56

- 37.4 19.0

Magnesiium 145

- 757 182 149

- 755 255

Manganese 0.32

- 1.93 0.42 0.25

- 2.20 0.86

Molybdenum 0.02

- 0.04 0.04 0.02

- 0.03 0.02

Nickel 0.02

- 0.03 0.02 0.03

- 0.05 0.04

Potassium 85

- 725 284 80

- 750 316

Sodium 7,540

- 25,300 15,950 4,370

- 28,200 18,850

Selenium ND 0.03

- 0.04 0.03

Tin ND ND

Strontium 67

- 1,320 330 48

- 1,550 529

Titanium 0.02

- 0.02 0.02 0.02

- 0.03 0.02

Thallium ND ND ND

- 0.14

Zinc 0.09

- 0.31 0.11 0.10

- 0.36 0.15

Mercury ND ND



## DISCUSSION

This report brings to light compositional features of flowback water that are

important when considering the possible common and uncommon impacts for this

wastewater. Common consideration for treatment considers parameters such as

biological oxygen demand, total carbon, to tal kjdehal nitrogen, oil and greases, etc. It is

useful to present a quick summary of these parameters. The following two plots show

the median observed common pollutants for the Marcellus samples (Figure 6) and for

the Barnett samples (Figure 7).

### 49 Figure 6: Median Common Components of Flowback Water from the

Marcellus Samples

Figure 7: Median Observations of Common Contaminants in the

Barnett Samples

### 50



## Heavy Metals

Heavy metals of toxicological concern that are often associated with urban indu strial

activity (including chromium, copper, nickel, zinc, lead, cadmium, mercury and arsenic)

are at very low levels in all of the shale gas water samples compared to levels reported

for municipal wastewaters. Table 35 presents median values from the 5

- D ay Flowback

samples which are compared to median heavy metals concentrations measured in

sewage sludges (biosolids) generated by Penn State for the State of Pennsylvania

( Steinhouwer , 2000). The comparison shows that the levels of heavy metals of concern

are 100 to 10,000 times higher in municipal biosolids (sewage sludges that are routinely

transported across communities to disposal sites) than the levels measured in shale gas

waters.

Table 35. Comparisons of Median Metals Levels in Shale Gas Waters wi th Municipal

Biosolids (Sewage Sludge)



### Metal 5

- day Flowback Sewage Sludge* Units

Chromium 0.015 35 mg/l

Copper 0.029 511 mg/l

Nickel < 0.0004 22.6 mg/l

Zinc 0.156 705 mg/l

Lead < 0.0021 65 mg/l

Cadmium < 0.0001 2.3 mg/l

Mercury <0.0002 1.5 mg/l

Arsenic 0.029 3.6 mg/l

* Penn State study reporting median heavy metal content values for Pennsylvania publicly owned

treatment works (POTW) biosolids. Stehauwer, et al., 2000.



## Total Dissolved Solids, Major Cations and Anions

The tendency for the flow rate of flowback water to decrease, and the total

dissolved solids content to increase with time, provides opportunity to capture and reuse

early flowback for reuse. The major challenge to the realization of this opportunity is the

ultra

- hig h concentration of divalent cations, which have tendencies to cause precipitates

and scale in process equipment.

The seven major cations encountered in the flowback waters are sodium, calcium,

### 51

strontium, potassium, magnesium, iron, barium, and lithium. Of these cations; calcium,

barium, strontium, magnesium, and iron are notorious scale formers. The seven major

anions measured in these waters are chloride, bicarbonate, bromide, fluoride, sulfide,

sulfate, and phosphate. Of these anions, carbonate spec ies, sulfate, and phosphate

are known to be potential scale formers.

Figure 8 is a distribution profile of the relative abundance of the major cations in all

samples from the Marcellus and the Barnett. Figure 9 is a distribution of the relative

abundance of the anions. The calculation for these figures was as follows. Each

sample (60 from Marcellus, 19 from Barnett) was treated individually. The value of the

each cation species in the individual was compared to the sodium content of the

sample, based on the equivalent weight of each cation. The value of the individual

anion species was compared to the chloride content. (Note: this presentation considers

phosphorous measurements to represent P as phosphate). The equivalent ratio of an

ion (example cal cium to sodium) from each sample was pooled (60 samples from

Marcellus and 19 from the Barnett). The data in the figures represents the median ratio

from each pool.

Most of the cation charge is carried by sodium. The proportion of sodium (87% of

cation equivalents) in the Barnet samples is somewhat higher than the Marcellus

samples (74% of cation equivalents). Chloride is the most common anion, representing

more than 93% of the anionic content in the Barnett and 99% in the Marcellus samples.

Sodium a nd Chloride are not shown in Figures 8 and 9 in order to better observe the

trends in the less concentrated species.

Calcium is the second most abundant cation, representing about 22% of the

cationic charge in the Marcellus and about 9% in the Barnett samp les. This difference

may, in part be due to the relatively higher content of carbonate alkalinity in the Barnett

than in the Marcellus. Calcium also precipitates as a sulfate. The relative sulfate

concentration in the Barnett 30 times greater than in th e Marcellus. This also suggests a

reasonable expectation why the calcium in the Barnett is less abundant than in the

Marcellus samples. Calcium is stable at pH< 6. One potential means of handling

calcium is by addition of acid to stabilize the calcium. The modest bicarbonate

concentration in both sample bases indicates that there is a relatively low buffering

### 52

capacity. A small acid addition should be sufficient to perform this procedure ;

therefore, the use of acidification would be very economical for the stabilization (i.e.

solubilization) of calcium in the flowback waters of the Barnett and Marcellus Shale

Plays

.

Strontium carries 1

- 2 % of the cationic charge in the flowback waters. St rontium is

known to co

- precipitate with calcium and barium, either as a carbonate or a phosphate,

or a sulfate. Any pretreatment or reuse option should be designed to handle strontium.

Potassium is the fourth most abundant cation, but should not pose any treatment

problems. In advanced separation processing, potassium is expected to behave much

like sodium.

Magnesium is about as abundant as potassium. Magnesium precipitates at high pH

(>11) as a hydroxide, or in phosphate and ammonia rich waters as str uvite. These

conditions will not likely be found in these waters.

Iron (calculated herein as the ferrous form) will precipitate at pH 5 as a hydroxide.

With oxygen present, iron will convert to the ferric form and more readily precipitate at

lower pH. A standard means of controlling iron is aeration followed by causti c addition

Figure 8: Relative Abundance of Cations in Flowback Waters

### 53

and settling. Iron is also biologically active, inviting many different types of surface

active bacteria that catalyze many redox reactions. These reactions may involve

oxygen, carbonate, organic carbon, sulfate, sulfur, and sulfide.

Lithium is present in these waters, but should not interfere with any treatment

process. In advanced separation processing, this light metal is expected to behave

much like sodium and potassium.

Barium readily precipitates as a sulfate. It is interesting to note that the Barnett

water contains much more sulfate than the Marcellus water. This may be one reason

why the barium content of the Barnett water has relatively less barium than the

Marcellus water.

Figure 9: Relative Abundance of Anions in Flow back Waters

### 54



## Implications for Fate and Transport

As seen in Table 1, the list of measurements and determinations that were pursued

in this study were very exhaustive but highly useful in establishing an information base

to define a chemical fingerprint associated with flowback waters from these geologic

formations. Much of the expense and time required for water characterization has

arisen from the extensive effort to analyze the samples for large numbers of volatile and

semi volatile organic compounds (including chlorinated pesticides, organophosphorus

pesticides and polychlorinated biphenyls); the information base developed in this

project strongly suggests that this level of water characterization in the future is not

necessary and that monitoring should be focused on measuring constituents that are

l ikely to be present.

A number of observations that are relevant to fingerprinting and to the fate and

transport of constituents can be made from consideration of the information base

assembled from the first 19 locations in the Marcellus and the first fi ve locations in the

Barnett. First, there is clear indication that halogenated hydrocarbon compounds

(among volatile, semi volatile , pesticides and PCB categories) and nearly all of the

polynuclear aromatic hydrocarbons (of 3 rings and above) are not a pa rt of detectable

components in flowback waters. Volatile and semi volatile organic constituents that are

normally found in conventional produced waters, such as BTEX, methylated benzenes,

naphthalene, naphthenic acids, volatile acids, simple alkanes, etc. , are also found in

flowback waters and in influent waters for frac jobs that utilize flowback water reuse.

However, in terms of fate and transport in the environment, many volatile and semi

volatile organics present in shale gas waters are at modest conc entrations (most

compounds are below 1 ppm). The challenge, therefore, is to choose an alternate

parameter that can be used to quickly detect any small release of flowback water that

may occur in the course of storage or handling.

A more practical appr oach might be to use chloride analyses of samples to monitor

fate and transport of flowback/produced waters. Chloride has been used as a

conservative tracer in hydrogeochemical studies for decades and is well documented in

the literature (Clement et al., 2000; Farrell et al., 1994; L amontagne et al., 2005; Negrel

and Lachassagne, 2000; Nelson et al., 2001; Paine, 2003; van Breukelen et al., 1998)

.

### 55

A general overview of the processes controlling the movement of solutes in the

subsurface is provided below.

Fate and transport of co nstituents in the soil/rock/water system is governed by four

fundamental processes: advection, dispersion, retardation, and decay. Advection is

simply the mass movement of a solute along with groundwater and is modeled by

Darcy’s Law. Dispersion is a mathe matical description of diffusion and mechanical

mixing of a solute in a system. Diffusion is modeled using Fick’s first and second law.

Dispersion is an empirical correction factor controlled by the physical properties of the

soil/rock matrix (porosity, gr ain size, sorting, etc) and scale of the system. Retardation is

the process by which non conservative solutes interact with the soil/rock and their

movement downgradient is subsequently slowed. It is modeled by a linear equation that

is a function of poros ity, moisture content, bulk density, and the humic organic matter

content. Examples of retardation reactions are adsorption

- desorption, ion exchange,

precipitation

- dissolution, and oxidation

- reduction reactions. Decay is the process by

which a solute is re moved from the system due to chemical reactions, biological

reactions, and/or radioactive decay and is modeled using the appropriate equation for

the reaction occurring in the system.

Conservative solutes are ones that can be modeled using only advecti on and

dispersion. Common examples are chloride and bromide, but bromide levels in the

samples collected as part of this study were several orders of magnitude lower than

chloride levels. Non

- conservative solutes can only be modeled using advection,

dispe rsion, retardation, and/or decay. Examples of non

- conservative solutes are

volatile/ semi volatile organics (e.g. benzene, toluene, PAHs, PCBs, etc.), sulfate, iron,

and many others. Non

- conservative species subsequently migrate slower throughout

the subsu rface than do conservative tracers and therefore are inappropriate to use as

indicators of Marcellus Shale flowback water impact to a system. Nearly all classes of

volatile and semi volatile organics discussed in this report have been shown to be

sequeste red to various types of soils, thereby significantly retarding their mobility in the

environment (Linz and Nakles, 1997).

Chloride, on the other hand, is more mobile and has considerable potential as an

early sentinel indicator of flowback water impacts due to a number of advantages. In

### 56

addition to being conservative (by virtue of its non

- volatile, non

- sequestering, non

reactive property), chloride is usually present in relatively high concentrations ranging

from 10,000 to 200,000 mg/l, ten to a hundred times the concentration of most

inorganics and more than a million times the levels of most volatile and semi volatile

organic constituents. Chloride is also easily measured with field kits that can determine

the presence of this anion with small samples, and verified in its presence with simple

conductivity instruments. Due to its high concentration and its ubiquitous presence in

flowback waters, chloride anion is an excellent monitoring tool for even the smallest

leaks of flowback water into the environ ment.

### 57



## CONCLUSIONS

With the completion of this sampling and analysis effort, the following conclusions

can be drawn from the results:

1. General chemistry characterization of flowback water indicates that values for

pH, alkalinity, total dissolved solids , total organic carbon, oils and greases and

other parameters from general water characterization are well within the normal

ranges reported for conventional produced waters. Flowback water appears

similar in composition to conventional produced water, ev en in the presence of

additives employed for performing hydraulic fracturing.

2. Shale gas flowback water cations are dominated by sodium and calcium; anions

are dominated by chloride.

3. Metals in flowback water are well within the ranges for normal produced waters.

Industrial heavy metals (e.g. chromium, copper, nickel, zinc, lead, cadmium,

arsenic and mercury) are a small fraction (less than 1 percent) of the heavy

metals content found in municipal biosolids generated from POTW’s.

4. Among volatile organic compounds , more than 93% of these constituents were

found at non

- detectable levels and less than 1% were above 1 ppm for any of the

5 sampling events among 19 locations. The data indic ate that the constituents

above 1 ppm are those that are a normal part of produced waters associated with

natural gas operations (such as xylenes, toluene and naphthalene).

5. Among semi volatile organic constituents, more than 96% of all determinations

wer e at nondetectable levels and less than 0.1% of these constituents were

above 1 ppm.

6. All chlorinated pesticides, organophosphorus pesticides and polychlorinated

biphenyls were determined to be at non

- detect levels for all tested samples of

influent water and flowback waters.

7. Virtually, all man

- made halogenated organic compounds were at non

- detect

levels; the same was true for organophosphorus pesticides. This strongly

suggests that additives that are blended with influent waters do not contain

concent rations of man

- made organic chemicals of concern.

### 58 8. The results of this shale gas water characterization effort indicate that pesticides,

PCBs, a large fraction of the volatile and semi volatile constituents should be

considered to be unnecessary for the s ampling and analysis of flowback waters

in the future.

9. Determination of factors that affect levels of organic and inorganic compounds

could potentially be determined through a correlation of flowback water

composition with the key shale gas development parameters of geographic area,

depth of wells, completion methods, etc.

### 59 REFERENCES CITED

APHA. 1992. “Standard Methods for the Examination of Water and Wastewater”, 18 th



### Edition (SM18).

APHA. 1999. “Standard Methods for the Examination of Water and W astewater”, 20 th



### Edition (SM20).

Clark, C.E. and J.A. Veil. 2009. Produced Water Volumes and Management Practices
in the U.S. USDOE/Argonne Laboratories Report No. ANL/EVS/R

- 09/1.

Clement, T.P., Johnson, C.D., Sun, Y., Klecka, G.M., and Bartlett, C. , 2000, Natural
attenuation of chlorinated ethene compounds; model development and field

- scale application at the Dover site: Journal of Contaminant Hydrology, v. 42, p. 113

- 140.

Engelder, T., and G.G. Lash. 2008. Marcellus Shale Play’s Vast Resource Pot ential Creating a Stir in Appalachia. The American Oil & Gas Reporter, May.

Farrell, D.A., Woodbury, A.D., and Sudicky, E.A., 1994, The 1978 Borden tracer
experiment; analysis of the spatial moments: Water Resources Research, v. 30, p.

3213

- 3223.

Gaudli p, A.W., L.O. Paugh, and T.D. Hayes. 2008. Marcellus Shale Water
Management Challenges in Pennsylvania. SPE Paper No. SPE

– 119898

- PP, Society of
Petroleum Engineers.

Hayes, T.D. 2009. Sampling and Analysis of Water Streams Associated with the

Developmen t of Marcellus Shale Gas, Final Report to the Marcellus Shale Coalition.
Gas Technology Institute, Des Plaines, Il

. Kharaka, Y.K. and C.A. Rice. 2004. “Organic and Inorganic Species in Produced
Water: Implications for Water Reuse”, Proceedings of the Na tural Gas Technologies

Conference, Phoenix, Feb 8

- 10. Available fro m the Gas Technology Institute

Lamontagne, S., Leaney, F.W., and Herczeg, A.L., 2005, Groundwater

- surface water
interactions in a large semi

- arid floodplain; implications for salinity mana gement: Hydrological Processes, v. 19, p. 3063

- 3080.

Linz, D.G. and D.V. Nakles. 1997. Environmentally Acceptable Endpoints in Soil.
American Academy of Environmental Engineers, United Book Press, Inc., Baltimore,

MD.

Negrel, P., and Lachassagne, P ., 2000, Geochemistry of the Maroni River (French
Guiana) during the low water stage; implications for water

- rock interaction and
groundwater characteristics: Journal of Hydrology, v. 237, p. 212

- 233.

Nelson, M.D., Parker, B.L., Al, T.A., Cherry, J.A., and Loomer, D., 2001, Geochemical
reactions resulting from in situ oxidation of PCE

- DNAPL by KMnO (sub 4) in a sandy
aquifer: Environmental Science & Technology, v. 35, p. 1266

- 1275.

Paine, J., 2003, Determining salinization extent, identifying salinity sourc es, and
estimating chloride mass using surface, borehole, and airborne electromagnetic

induction methods: Water Resources Research, v. 39, p. 10.

### 60

Stehouwer, R.C., A.M. Wolf, and W.T. Doty. 2000. “Chemical Monitoring of Sewage
Sludge in Pennsylvania: Vari ability and Application Uncertainty.” J. Environ. Qual. 29:

1686

– 1695.

USEPA. 1984. “Methods for Organic Chemical Analysis of Municipal and Industrial
Wastewater”, 40CFR, Part 136, Appendix A, October 26.

USEPA. 1983. “Methods for Chemical Analysis of Water and Wastes”, EPA

- 600/4

- 79

- 020, March.

USEPA. 1986. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods”,
Third Edition, November (SW846).

USGS. 2009. USGS Produced Water Database. Available at: http://energy.cr.usgs.gov/prov/prodwat/intro.htm

. van Breukelen, B.M., Appelo, C.A.J., and Olsthoorn, T.N., 1998, Hydrogeochemical
transport modelling of 24 years of Rhine wa ter infiltration in the dunes of the Amsterdam
water supply: Journal of Hydrology, v. 209, p. 281

- 296.

### 61



## ACKNOWLEDGEMENTS

The data presented in this report from the Marcellus Shale was generated from a

project conducted in 2009 under the funding of the Ma rcellus Shale Coalition. A

summary of the report is available from Gas Technology Institute upon request (Hayes,

2009).

### 62



## APPENDIX A : FIELD SAMPLING AND A NALYSIS PLAN (FSAP)

# Appendix A

Field Sampling and Analysis Plan (FSAP)

# FIELD SAMPLING AND ANALYSIS PLAN

DEVONIAN SHALE FLOW BACK WATER

CHARACTERIZATION STUDY

Prepared by

Appalachian Shale Water C onservation and Management Committee

December 2008

### TABLE OF CONTENTS

1.0 INTRODUCTION

................................ ................................ ................................ ... 3

1.1 PURPOSE

................................ ................................ ................................ ............ 3

1.2 DATA OBJECTIVES

................................ ................................ .......................... 3

1.3 BACKGROUND

................................ ................................ ................................ .. 3

2.0 CHARACTERIZATION STUDY OF FLOW BACK WATER

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

2.1 Sampling and Analyses

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

3.0 SAMPLING PROTOCOLS

................................ ................................ ..................... 7

3.1 PROJECT INITIATION

................................ ................................ ...................... 7

3.2 DOCUMENTATION

................................ ................................ ........................... 7

3.2.1 Field Logbook

................................ ................................ ............................... 7

3.2.2 Chain

- of

- Custody Form

................................ ................................ ................ 8

3.3 SAMPLE DESIGNATION AND IDENTIFICA TION

................................ ....... 8

3.4 SAMPLE MANAGEMENT AND SHIPMENT

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

4.0 SAMPLING EQUIPMENT AND PROCEDURES

................................ .............. 10

5.0 INVESTIGATION DERIVED WASTE

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

5.1 MANAGEMENT OF HAZARDOUS IDW

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

6.0 REFERENCES

................................ ................................ ................................ ...... 12

Tables

1 Summary of Extensive List of Constituents of Interest, EPA Methods, Reporting

Limits and Holding Times.

2 Summary of List of Constituents Based on Generator Knowledge, EPA Methods,

Reporting Limits and Holding Times

### 1.0 INTRODU CTION

This Field Sampling and Analysis Plan (SAP) details the procedures for sampling and

field documentation to be utilized for the characterization study of the fracturing and flow

back fluid s associated with the Devonian shale. The FSAP has been prepar ed to ensure

that all data and information gathered are properly sampled, documented, and technically

sound. The FSAP and Quality Assurance Project Plan (QAPP) together comprise the

Sampling and Analysis Plan (SAP).

1.1 PURPOSE

The FSAP includes a detail ed description of field sampling procedures to be conducted.

The procedures described are consistent with the RCRA Technical Enforcement

Guidance Document (TEGD), U.S. EPA, 1989; RCRA Facility Investigation Guidance

Document (U.S. EPA, May 1989); RCRA Gro und Water Monitoring; Draft technical

Guidance (U.S. EPA, 1992); Data Quality Objectives for Remedial Response Activities

(U.S. EPA, 1987).

The SAP consists of 5 sections. Section 1.0 includes a brief description of the data

objectives and a brief discus sion of the project. 2.0 provides information regarding

documentation, quality assurance/quality control (QA/QC) requirements, and reporting.

Section 3.0 addresses the sampling procedures. Section 4.0 describes the proper handling

requirements of any in vestigative derived waste generated. Reference documents are

provided in Section 5.0

1.2 DATA OBJECTIVES

The data objectives will address characteriz ation of the fracturing and flow back fluids

associated with the development of the Devonian shale. This characterization study will:

Identify the specific constit uents of interest (COI) associated with flow back

water;

Reduce/eliminate the allegations that the chemicals used for fracturing will

contaminate groundwater; and

Provide sufficient information fo r the selection of proper disposal techniques.

Achieving these data objectives will require obtaining data of acceptable levels of

certainty. Therefore, it is essential that the field and sampling procedures be completed

under stringent and appropriate methods.

1.3 BACKGROUND

The process of developing Devonian Shale wells requires i ncreasing the number of

fractures and extending the existing fractures

. Fracturing is necessary to obtain a greater

volume of natural gas from the Devonian Shale at in a cost

- efficient manner. F racturing

uses high volumes and high

- pressure chemically treated water or a gel to induce fractures

### in the shale surrounding the well bore. Most applications require between 500 and 10,000

psi.

Fracturing is done by isolating of f a portion of the well and injecting chemically treated

water or gel and sand with cement, perforating, under very high pressure into the isolated

portion of the well bore. Generally, 1.5 to 5 million gallons of water is pumped into the

formation of a ver tical or horizontal well, respectively. The high pressure fractures the

shale and sand keeps the fractures open. A drop in pressure indicates that the formation

has accepted water.

To prevent the fractures from closing when the pressure is reduced seve ral hundred tons of sand or other propant is pumped down the well and into the pressurized portion of the

well. When the fracturing occurs the sand is forced into the fractures. If enough sand is

trapped in the fractures it will prop the fractures open whe n the pressure is reduced. The

propped fractures provide an increase in the permeability for gas flow.

Approximately 25 to 30 percent of the water used in frac turing is recovered. This flow

back water is currently a concern because there is a limited am ount data. The ASMCWC

is conducting this study in an effort to characterize the flow back water associated with

the Devonian Shale.

The flow back water will be collected in either an on

- site off

- stream temporary impoundment or a series of frac tanks.

### 2.0 CHARACTERIZATION STUDY OF FLOW BACK WATER

Fracturing is completed over several days depending on the geological formation.

Because the flow back water is under pressure, initially the flowback water is recovered

at a faster rate in the beginning of fr acturing and significantly declines as facturing

continues and the well is released to production. T he initial concentrations at the start of

fracturing (high yields of flow back water) should yield lower concentrations of

constituents of interest (COI). It is assumed that the concentration of the frac turing

chemicals remain constant throughout the flow back regardless of the rate of return.

However, the increase concentration of in the COI is due to a longer residence time in the

applicable formation an d not associated to the additives of the fracing fluids.

Therefore, t o obtain representative samples of the flow back water samples will be

collected on three separate days (i.e., days 1, 5 and 14). The data obtained from day 14

should represent the chem ical characteristics of the natural formation fluid.

Additionally, a ba seline sample of the fracturing fluid will be collected prior to injection.

The baseline sample will contain the materials (e.g., water and chemicals) used in the

fracturing process

. A sample will also be collected from a well in Devonian shale that

has been in production for a period of time (i.e., a well that has been in production fo r more than 3 months)

. The data obtained from this well should represent the chemical

characteris tics of the natural formation fluid. The analytical results associated with these

samples will assist in the data interpretation.

2.1 Sampling and Analyses

In general, several frac tanks are connected in

- line and filled simultaneously with the

flow back w ater. This is completed to avoid back pressure when shutting one frac tank

and opening another tank for additional capacity. This filling process will provide a

composite sample of the flow back water over time. To minimize volatilization, a

representat ive composite sample of the flow back water samples will be collected from

the top of a frac tank or flow back impoundment

.

The flow back water is either pumped into the frac tanks for storage until the water is

disposed o f proper ly . If a project does have an impoundment that stores flow back water

on site in an impoundment, a grab sample will be collected from the impoundment

following day 1, 5 and 14 of fracturing.

The base fracturing fluid will be collected prior to going down hole. The base fra cturing

fluid will be collected from either the sampling lines built into the blenders or as a grab

sample from the blending containers. In either case a representative sample of the fluid

will be collected.

Numerous flow back water samples will be col lected from several unique locations.

Phase one of this characterization study will include the sampling of six flow back water

samples from six unique locations.

### The list of constituents recommended for the characterization study was developed from

comments received from the Pennsylvania Department of Environmental Protection

(PADEP), the West Virginia Department of Environmental Protection (WVDEP) and

members of the ASWCMC. Because the recommended list of constituents is extremely

extensive, it was decided that one sample from each site will be completed for the full list

of recommended constituents (Table 1 ). All other samples will be sampled for a subset

of these constituents (Table 2 ), which are based on generator knowledge and Group 1 and

Group 2

. T he analytical results of phase one of the characterization study will determine

the list of constituents of subsequent sampling events

.

### 3.0 SAMPLING PROTOCOLS

This section identifies the protocols to be implemented during field sampling.

Specific ally this section describes the preparation, documentation, and reporting

procedures to be used that will assure quality assurance and quality control.

3.1 PROJECT INITIATION

Following acceptance of this plan by the ASWCMC and the state agencies, Gas

Tech nology Institute (GTI) will authorize Test America an independent a credited

analytical laboratory to provide the appropriate sample containers and preservatives; and

URS, an independent environmental consulting company has been retained to collect the

flo w back water. Furthermore, Test America will complete the analytical analyses. Test

America is certified by WVDEP and PADEP.

The regulatory agencies are invited to collect split samples. The samples will be

collected at the discretion of the agency. Al l agency sampling must be approved and

coordinated with the appropriate gas company.

3.2 DOCUMENTATION

A field logbook and chain

- of

- custody form will be utilized during the field activities.

3.2.1 Field Logbook

During field activities, a site

- specific logbook will be used for documentation of all notes.

It is recommended that each page of the logbook be numbered and dated. The entries

should be legible and contain accurate and inclusive documentation of the project

activities. Once completed, the log book becomes an accountable document and is

maintained as part of the project file. The logbook should include, at a minimum, the

following information:

Identification of logbook ownership and telephone number on the inside front

cover;

Well location and identifying number;

Names of field personnel at the site;

Weather information (general);

Sample locations and activities;

Sample collection equipment;

Date and time of monitoring of sampling;

Water quality measurements (field pH, specific conductance, wat er temperature);

Field instrument calibration information;

Visual observations;

Collection of field quality assurance samples (i.e., blanks or duplicates);

Regulatory agency personnel observing sampling;

### Enter agency, collector’s name, samples splits, etc ., i f a regulatory agency splits

samples ; and

Documentation of sample shipment dates, time, and carrier tracking (air bill)

number, if necessary.

Copies of the field book pages will become part of the sample data package.

3.2.2 Chain

- of

- Custody Form

The c hain

- of

- custody form is used to record the custody of all samples collected. This

chain

- of

- custody form documents transfer of the custody from the sampling personnel to

another person, to the laboratory, or to another party, such a s a courier delivery ser vice.

The chain

- of

- custody form also serves as a sample logging mechanism for the laboratory

sample custodian.

When the field personnel sends samples to the analytical laboratory, each cooler chest

containing samples must be accompanied by a chain

- of

- cus tody form. These forms

contain the following information pertaining to the samples:

Project Name

Name(s) and signature(s) of the individual(s) collection the samples;

Sample location;

Date and time of sample collection;

Total number of sample containers per sample location;

Type of sample preservation used (e.g., HNO 3 

### , HCl, etc.)

Analytical parameters of interest for each sample and number of containers per

analytical parameter;

Remarks or observations;

Signature(s) of all individual(s) relinquishing and receiving custody of the

samples;

Name of the carrier shipping the samples; and

Air bill number under which sample containers(s) was sent, if applicable;

The chain

- of

- custody forms are multi

- colored carbon copy forms. The original copy

(white) is submit ted to the laboratory with the samples, the second copy (pink) is sent to

GTI, and the third (yellow) is kept for the project files.

3.3 SAMPLE DESIGNATION AND IDENTIFICATION

Each sample collected for this characterization study will be assigned a uniqu e sample

tracking number. The identification of the well location and participating gas company

will not be identified. All well locations will be blind. GTI will assign each well a

project identifier. The project identifier will be a unique single alp hanumeric letter that

will identify the Devonian Shale well location and company. This unique alphanumeric

letter will be provided to the third party environmental consultants to be used in the

sample designation.

### 3.4 SAMPLE MANAGEMENT AND SHIPMENT

The possession of samples or other physical evidence shall be traceable from the time the

samples are obtained until they have been submitted to the analytical laboratory. To

simplify the documentation of possession that is maintained on the chain

- of

- custody

form, the number of people who handle the sample during the investigation should be

minimized. All samples will be documented in the field logbook, on the chain

- of

custody form and on the sample container labels. Field documentation procedures are

provid ed above in Section 2.3 and the in the QAPP.

Sample labels shall be completed for each sample using waterproof non

- erasable ink. All

samples are to be sealed immediately upon collection and are to be immediately place on

ice in a cooler.

Samples are to be properly packaged for shipment and delivery to the laboratory. To

ensure that the samples are kept cold for preservation requirements, the samples are to be

shipped in iced coolers for overnight delivery. Samples collected during the

characterization study are to be classified as environmental samples.

Shipping containers are to be secured with tape and use of security seal method to ensure

that the cooler may not be opened without evidence of the seal being tampered.

Ice used to keep the samples coo led must be secured in plastic bags (e.g., Zip

- Lock®

plastic bags) to ensure that melted ice does not cross contaminate the samples pr leak

from the coolers.

Samples will be either hand delivered to the laboratory or shipped via priority service to

the laboratory or the air bill retained for the project file.

### 4.0 SAMPLING EQUIPMENT AND PROCEDURES

Grab samples will be conducted using a new PVC bailer from the top of the frac tank.

The order, in which the grab samples are collected, as prioritized to the sensitivity to

volatilization, is as follows:

Volatile Organics

Purgeable Organics

Purgeable Organic Halogens

Total Organic Halogens

Total Organic Carbon

Extractable Organics

Total Metals

Dissolved Metals

Phenols

Cyanide

Sulfate and Chloride

Turbidity

Ni trate and Ammonia

There is not an order of preference for the collection of the remaining conventional

parameters.

Temperature, pH, dissolve oxygen, and specific conductance measurements will be

completed in the field

### 5.0 INVESTIGATION DERIVED WASTE

Mater ials which may be investigation derived waste (IDW) are:

Personnel protective equipment (PPE), including disposable gloves, coveralls,

booties, etc.;

Disposable equipment, including plastic ground and equipment covers, aluminum

foil, Composite liquid wast e samplers (COLIWASAs), used sample containers,

tape, etc.;

5.1 MANAGEMENT OF HAZARDOUS IDW

If wastes are suspected to be hazardous, appropriate analysis must be performed to make

that determination. The analytical testing should meet the requirements of the potential

disposal characterization requirements. If the IDW is determined to be hazardous wastes

either through testing of characteristics or as a listed waste, they must be properly

container and labeled. They may be stored on site for a maximum o f 90 days before they

must be manifested and shipped to a permitted treatment of disposal facility.

Care should be taken to keep non

- hazardous materials segregated from hazardous waste

contaminated materials.

### 6.0 REFERENCES

Kitrell, F.W. 1990. A Pra ctical Guide to Water Quality Studies.

U.S. EPA, 1986. Test Methods for Evaluating Solid Waste, Volume II; Field Manual,

Physical/Chemical Methods. Office of Solid Waste and Emergency Response, SW

- 846,

November 1986

U.S. EPA 1987. Data Quality Objectiv es for Remedial response Activities. Oswer

Directive 935507B, Office of Emergency and Remedial Response, Washington DC.

EPA/5406/6=87/100 and 004.

U.S. EPA, 1986. RCRA Ground

- Water Technical Enforcement Guidance Document.

Office of Waste Programs Enfor cement, Washington DC, Oswer Directive 99501.

U.S. EPA, 1992. RCRA Groundwater Monitoring: Draft Technical Guidance. Office of

Solid Waste, Washington DC. EPA/530/R

- 93/001.

U.S. EPA, 1998. Environmental Investigations Standard Operating Procedures a nd

Quality Assurance Manual. U.S. EPA Region 4, Athens, GA, May 1996.

### 63



## APPENDIX B : QUALITY ASSURANCE PR OJECT PLAN (QAPP)

# Appendix B

Quality Assurance Project Plan (QAPP)

# QUALITY ASSURANCE PROJECT PLAN

DEVONIAN SHALE FLOWBACK WATER

CHARACTERIZATION STUDY

Prepared by

Appalachian Shale Water Conservation and Management Committee

November 2008

### TABLE CONTENTS

1.0 PURPOSE 3

2.0 PROJECT DESCRIPTION 4

2.1 SCOPE OF WORK 4

3.0 QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA 5

3.1 DATA QUALITY LEVELS 5

3.2 QUALITY CONTROL PARAMETERS 6

4.0 SAMPLING PROCEDURES 8

4.1 SAMPLE IDENTIFICATION 8

4.2 SAMPLE CONTAINERS 9

4.3 FIELD QA/QC SAMPLES 9

4.3.1 Trip Blanks 9

4.3.2 Equipment Blanks 10

4.4 DOCUMENTATION 10

5.0 SAMPLE CUSTODY 11

6.0 ANALYTICAL PROCEDURES 12

7.0 CALIBRATION PROCEDURES AND FREQUENCY 13

7.1 PREP ARATION OF STANDARDS 13

7.2 CORRECTIVE ACTION 13

8.0 DATA EVALUATION/VALIDATION 15

8.1 FIELD DATA VALIDATION 15

8.2 LABORATORY DATA VALIDATION 15

8.3 INDEPENDENT DATA VALIDATION 16

8.4 DATA REPORTING 16

8.4.1 LEVEL I REPORTING 17

8.4.2 LEVEL II REPORTI NG 17

8.4.3 LEVEL III REPORTING 17

9.0 QUALITY CONTROL PROCEDURES 19

9.1 FIELD QC CHECKS 19

9.1.1 EQUIPMENT BLANKS 19

9.1.2 TRIP BLANKS 19

### 9.2 INTERNAL LABORATORY QC CHECKS 20

9.2.2 Preparation/Method Blanks 20

9.2.3 Matrix Spike And Duplicate (Or Matrix Spike Duplicate) Analysis 21

9.2.4 Surrogate Spike Standard Performance Evaluation 21

9.2.5 Calibration Check Compounds And Rea gent Blanks 21

10.0 PERFORMANCE AND SYSTEM AUDITS 22

10.1 PERFORMANCE AUDITS 22

10.1.1 Laboratory Performance Audits 22

10.2 SYSTEM AUDITS 22

10.2.1 Laboratory System Audits 22

11.0 ASSESSMENT PROCEDURES FOR DATA ACCEPTABILITY 23

11.1 PRECISION 23

11.2 ACCURACY 23

11.3 COMPLETENESS 23

11.4 QUALITY CONTROL CHARTS 24

12.0 PREVENTIVE MAINTENANCE 25

12.1 FIELD 25

12.2 LABORATORY 25

13.0 CORRECTIVE ACTION 26

14.0 QA REPORTS TO MANAGEMENT 27

FIGURE

1 Chain of Custody Record

TABLES

1 Summary of Extensive List of Constituents of Intere st, Reporting Limits, and Holding

Times

2 Summary of List of Constituents Based on Generator Knowledge, Reporting Limits, and

Holding Times

### This document is the Quality Assurance Project Plan (QAPP), which provides specific quality

assuran ce/quality control (QA/QC) procedures to be executed and supported for the

Characterization Study of the flow back water associated with the well fracturing of the

Devonian Shale

.

Data generated for environmental purposes must be technically sound and legally defensible, and

supported by defined and verified limits of confidence. Therefore, the objective of this QAPP is

to ensure the generation of accurate, precise, representative and complete data. The QAPP sets

forth the data collection procedures a nd data evaluation processes, which will ensure that

appropriate levels of data quality are obtained

.

Analyses must meet the QA/QC requirements associated with this QAPP and the following

documents:

SW

- 846, Third Edition (September 1986), as amended by updates 1 (July 1992), II (September

1994), IIA (August 1993), and IIB (January 1995), or the most current SW

- 846 update;

EPA's "Handbook for Analytical Quality Control in Water and Wastewater Laboratories" (EPA

600/1

- 79

- 019);

Standard Methods for the Ex amination of Water and Wastewater.

Only U.S. EPA

- approved methods will be used for chemical analyses. Any omission in this

QAPP of relevant requirements, tasks and other items found in the referenced methods does not

constitute a waiver of the omitted requirement, task, or item. It is the responsibility of all

personnel involved in the various site investigation activities to perform and document the

required procedures designated herein.

### The Appalachian Shale Water Conser vation and Management Committee (ASWCMC) is

conducting a study to characterize the fracturing and flow back water generated from

development of Devonian Shale wells

.

Samples will be collected from both vertical and horizontal Devonian Shall gas wells. Numerous

samples will be collected from several locations. Phase one of the characterization study will

include 4 grab samples from 6 well sites. A sample will also be collected from a well that has

been in production for at least three months. The following grab samples will be collected from

each site:

One baseline fracturing water sample that includes the frac turing chemicals, excluding

the sand;

Flowback water samples will be collected on days 1, 5 and 14 of the following the

fract uring process; and

Water from an existing producing well.

The list of constituents recommended for the characterization study was developed from

comments received from the Pennsylvania Department of Environmental Protection (PADEP),

the West Virginia Dep artment of Environmental Protection (WVDEP) and members of the

ASWCMC. Because the recommended list of constituents is extremely extensive, it was decided

that one sample from each site will be completed for the full list of recommended constituents

(Tabl e 2). All other samples will be sampled for a subset of these constituents (Table 3), which

are based on generator knowledge. The analytical results of phase one of the characterization

study will determine the list of constituents of subsequent sampling events.

In addition, field measurements of pH, specific conductance, temperature, dissolved oxygen, and

turbidity will be taken of flow back aqueous samples.

### Data Quality Objectives (DQOs) are qualitative and quantitative statements to ensure that data of

known and appropriate quality are obtained during the characterization study (sampling and

analysis).

The data objectives will address characterization of the flow back fluids associated wi th well

fracturing generated from Devonian shale. This characterization study will:

Identify the specific constituents of interest (COI) associated with flow back water;

Reduce/eliminate the allegations that the chemicals used for fracturing will contami nate groundwater; and

Provide sufficient information for the selection of proper disposal techniques.

Achieving these data objectives will require obtaining data of acceptable levels of

certainty. Therefore, it is essential that the field and sampling p rocedures be completed

under stringent and appropriate methods

There are typically five analytical levels of data quality available to accomplish the objectives of

investigations of this type. These levels are typically desig nated as follows:

Level I: field screening or analysis using portable instruments, calibrated to non

compound specific standards;

Level II: field analysis using portable instruments, calibrated to specific compounds;

Level III: non

- Contract Laboratory P rogram (non

- CLP) laboratory methods;

Level IV: CLP Routine Analytical Services (RAS) methods; and

Level V: non

- standard analytical methods.

DQO Levels I and III will be used to characterize the Devonian Shale F rac turing Flowback

sampling activities. The following sections describe the use of the analytical procedural levels

that will be used during the project.

Field Screening Methods

- Level I

Field determinations of pH, specific conductance, temperature, dissolved oxygen, and turbidity

### will be m ade during characteristic sampling as part of a field screening procedure. These

analytical methods are used to determine stabil ity of the well and they are typically designated as

Level I data quality.

In addition, as part of the health and safety progr am, worker safety may be monitored via one or

more of a variety of field screening tests such as a photoionization detector (PID) or flame

ionization detector (FID) to test for volatile organic vapors, or a combustible gas indicator to test

for explosivity potential. These tests, which are semi

- quantitative, are classified as field

screening evaluations, even though they typically are not used for site characterization purposes.

Non

- CLP Laboratory Methods

- Level III

Level III analytical procedures prov ide precise, accurate and defensible data for the intended data

uses, with a less formal documentation and reporting nomenclature at reduced analytical costs

over Level IV data quality procedures. Data Quality Level III will be used during this

characteri zation study. Table 1 , summarizes analyses that will be conducted to characterize and

quantify constituent concentrations.

The exact quantitative criteria used to evaluate data quality from the laboratory's precision and

accuracy perspective for the aqueous and solid sampling media will be presented in the selected

laboratory Quality Assurance Manual(s) (Appendix QAPP

- 1 and following). The following is a

description of terms that appear in the QAM.

Reference : The referen ce of the U.S. EPA standard analytical methodology used for each

procedure.

Precision : A measure of the mutual agreement among individual measurements of the same

property under prescribed similar conditions. Precision is evaluated based on the relative percent difference (RPD) between duplicate matrix spike results or duplicate sample results, as

appropriate. The matrix spike duplicate RPD limits are parameter and method

- specific,

MS/MSD RPD QC limits will be presented in the laboratory QAMs. Laborator y duplicate

sample RPD limits are typically 20 percent for aqueous media and 35 percent for solid media

(exceptions may apply for solid media whose samples may be nonhomogeneous). Field

duplicates are also evaluated by calculating the RPDs between field d uplicate sample results.

However, evaluations of field duplicate RPDs are used as advisory determinations since

numerous factors in sampling and analysis may cause variances between field duplicate results.

Accuracy : The degree of agreement of a measur ement with an accepted reference or true

value. Accuracy is evaluated based on the percent recovery of spiked samples. The matrix spike

recoveries for organic analyses are method and parameter specific and are typically used as an

advisory QA/QC measure due to the difficulty associated with recovering spiked organic

### parameters. Organic parameter percent recovery QC limits will be presented in the laboratory’s

QAM. The matrix spike recoveries for inorganic and most conventional parameters are typically

a range of ±25 percent.

Completeness : A measure of the amount of valid data obtained from a measurement system

compared to the amount expected to be obtained under normal conditions. The method of

calculation for percent completeness is defined in Sectio n 12.3. Completeness can be evaluated

in two ways: 1) by comparing the number of samples actually collected to the expected number

of samples to be collected; and 2) by comparing the number of valid analyses received from the

laboratory to the number of actual samples collected. The results of any Level III analyses to be

performed is typically used for characterization studies and as such will have a minimum

completeness of 95 percent for both evaluations of completeness.

Exact QA/QC criteria the labor atory will use to evaluate its data's precision and accuracy will be

provided following selection of the analytical laboratory, if the criteria are not method

- specific.

Table 1 summarizes the individual parameters and associated reporting limits.

The re are also qualitative criteria that are adhered to ensure that data of known and appropriate

quality are obtained during investigation activities. These criteria include representativeness and

comparability.

The sampling and analysis programs are desig ned to ensure that analytical data obtained during

the characterization study represent current conditions found at the site and produce data of

comparable quality. The sampling frequency was selected to ensure data are suitable for their

intended use and adequately characterize the flow back water. Additionally, standard recognized

analytical methodologies will be utilized to ensure comparability. These designs are instituted to

ensure appropriate sample representativeness and data comparability.

### This section outlines the procedures to be used for the preparation of sampling equipment and

containers and for sample preservation. It also provides some of the quality control and

operating procedures to be followed for sampling. Detailed field sampling details including the

number of samples to be collected, the rationale for sampling, and QC requirements are

described in the Field Sampling and Analysis Plan.

Each sample collected for this charact erization study will be assigned a unique sample tracking

number. The identification of the well location and participating gas company will not be

identified. All well locations will be blind. GTI will assign each well a project identifier. The

projec t identifier will be a unique single alphanumeric letter that will identify the Devonian Shale

well location and company. This unique alphanumeric letter will be provided to the third party

environmental consultants to be used in the sample designation.

Flow back Sampling

Fracturing is completed over several days depending on the geological formation. The flow back

water is initially removed at a faster rate at the start of production and significantly declines as

production continues. It is believe d that the volume of water is relative to the concentration. It is

assumed that the concentration of the fracturing chemicals remain constant throughout the flow

back regardless of the rate of return. However, the increase of in the COI is due to a longe r residence time in the applicable formation and not associated to the additives of the fracturing

fluids. Therefore, t o obtain representative samples of the flow back water samples will be

collected on three separate days (i.e., days 1, 5 and 14)

.

Addi tionally, a baseline sample of the fracturing fluid will be collected prior to injection. The

baseline sample will contain the materials (e.g., water and chemicals) used in the fracturing

process. A sample will also be collected from a well in Devonian s hale that has been in

production for a period of time (i.e., I production fro more than 3 months). The analytical results

associated with these samples will assist in the data interpretation.

Quality Assurance

The quality assurance field will only be use d to indicate a sample collected for quality assurance

purposes.

Quality Assurance/Quality Control Samples will be identified as follows:

EB

- Equipment Blank

TB

- Trip Blank

### The following are sample identification samples.

A05V Sample collected fr om company X on day 5 from a vertical well

.

CEH Sample collected from company Y from an existing horizontal well.

TB Trip Blank

.

Each sample container will be marked with a label identifying the specific parameters of interest.

The label will rec ord the date of sample collection, alphanumeric identification, parameters to be

analyzed, and preservatives, if applicable. Sample bottles should be prelabeled by the laboratory

to avoid unnecessary delays.

The specific information for each sample will be documented in the field logbook and on a

chain

- of

- custody form. The sample identification will be correlated in the logbook and chain

- of

custody by sample designation, sampling date, time, and location. The analytical parameters for

which the sample i s to be analyzed and the respective number of sample bottles will be provided

on the chain

- of

- custody sheet.

All new pre

- cleaned sample bottles with screw

- type Teflon

- lined lids will be used for holding

and shipping samples. These sample bottles will be supplied by the analytical laboratory, and

pre

- preserved by the laboratory as necessary.

Two types of field QA/QC samples will be collected (i.e., trip blanks and equipment blanks).

The following provides a description of the essential field QA/QC samples.

Trip blanks are collected only for volatile organic samples. The trip blank is prepared by the

laboratory by filling a batch of pre

- cleaned 40

- ml vials with laboratory

- grade water. T he vials

are transported to the site and returned to the laboratory in the same manner as the environmental

sample containers. Any constituents found in the trip blank could be attributed to: a) interaction

between the sample and the container, b) contam inated laboratory

- grade water, or c) a storage or

handling procedure which alters the sample. One trip blank should accompany VOC samples for

each sampling event . The trip blank is placed in the cooler that contains samples for volatile

organics. At no time after the preparation are trip blanks to be opened before they are returned to

the laboratory.

### To verify that no constituents are introduced from sampling equipment, equipment blanks are

collected by pouring distilled water th rough the representative sampling device and analyzing for

all constituents of interest. One equipment blank will be collected during the characterization

study.

A number of documents will be used during the characterization study. These documents

include: chain

- of

- custody forms and field data sheets.

Chain

- of

- custody Forms

The field chain

- of

- custody form is used to record the custody of all samples collected. This

chain

- of

- custody form documents the transfer of the custody from the sampling personnel to

another person, to the laboratory, or another party, such as a courier delivery service.

When the field team sends samples to an analytical laboratory, each shipping cooler containing

samples, which are sent under one shipping d ocument, must be accompanied by a chain

- of

custody form (Figure 1 ) . These forms document information regarding the origination of

samples and those parties having subsequent possession of samples. They also contain

information pertaining to these samples , such as project name, name of the individuals collecting

the samples, sample identification number, the date and time of collection, the number of sample

containers for each parameter of interest for each sample, remarks or observations of samples, if

ap propriate, the signature of the person relinquishing control of the samples and the person

receiving the samples, and the name of the overnight carrier shipping the samples to the

laboratory. The original chain

- of

- custody sheet is sent with the samples. One copy will be

submitted to Gas Technology Institute (GTI), and the other copy is stored in the field team files.

### The primary objective of sample custody is to create an accurate written verified record, which

can be used to tra ce the possession and handling of the samples from the moment of collection

through data analysis and reporting.

The field sampler will be personally responsible for the care and custody of the samples collected

until they are properly transferred. Sampl es will be accompanied by a Chain

- of

- Custody Record.

Upon arrival at the laboratory, samples will be checked in using laboratory custody procedures

outlined in the laboratory QAM. The laboratory is required to verif y that all samples were

received and i n good condition. The laboratory should assign a laboratory

- specific sample

identification. This unique identification guarantees sample anonymity to the analyst of the

sample's site.

Once samples have been logged

- in and transferred to the proper storag e areas, the laboratory

department manager is responsible for their proper storage and condition. Copies of the

completed Chain

- of

- Custody Records and an analysis narrative presenting laboratory sample

identifications and their correlating field assigned sample identifications should be included in

the data package for delivery to the data user.

### All analyses will be performed using U.S. EPA analytical methods procedures from the

following:

Third Edition (September 1986), as amended by updates 1 (July 1992), II (September

1994), IIA (August 1993), and IIB (January 1995), or the most current SW

- 846 update;

EPA's "Handbook for Analytical Quality Control in Water and Wastewater Laboratories"

(EPA 600/1

- 79

- 019);

Standard Met hods for the Examination of Water and Wastewater.

Tab le 1 and Table 2

, summarize the list the constituents of interest (COIs) associated with the

characterization study for the flow back water from the wells of the Devonian shale and the

required reportin g limits to be reported by the laboratory. Method selection w as based on the

following factors: reliability in identification and quantifications, and comparability of sample

results and best achievability of the lower of federal Maximum Contaminant Leve ls (MCLs).

All procedures for environmental sample handling, storage, and documentation while in the

laboratory's custody and deliverable requirements upon delivery of the data to the user are stated

in the laboratory QAMs.

### All field and laboratory equipment are calibrated before use to ensure proper operating

conditions. Laboratory instrument calibration procedures are presented in the laboratory QAMs.

Field calibration procedures and frequencies should b e followed in accordance with the

manufactures specifications. Field calibrations must be completed each day at a minimum. pH

meters are required to be calibrated or verified every two hours at a minimum.

All analytical met hods must be validated at some point by the use of calibration standards. A

calibration standard is made by the appropriate dilution of a pure substance, the purity of which

is traceable to an NBS or U.S. EPA standard. Because of the high sensitivity of many analytical

instruments, the calibration standard is an extremely dilute version of the pure compound.

Because of the high dilution required to be within the linear range of the instrument, the

preparation of the calibration standard is frequently mad e by serial dilution rather than in a single

step. In order to provide standard solutions at sufficiently low concentrations, a minuscule

amount of the pure substance will be required, the measurement of which is subject to extreme

error. Thus, it is pre ferable to deal with potential dilution errors, rather than with the large error

associated with the measurement of a very small amount of the pure substance.

The initial standard is usually obtained either as a pure material or as a prepared certified so lution

of a given concentration of the pure compound or compounds. In preparing the stock solution of

the calibration standard, great care must be exercised in measuring weights and volumes as

accurately as possible, since all of the analyses following th e calibration will be based on the

accuracy of the calibration, and the accuracy of the analytical data is dependent on the calibration

curve. It is the analyst's responsibility to assure that all standards used are within the standard

solution holding ti me, and to prepare fresh standard solutions whenever necessary. In preparing

working solutions, or using working solutions, the analyst must check for signs of deterioration

of the standard, such as cloudiness, precipitation, or discoloration. The standa rd must also be

periodically compared with previous runs of standards, and with independently prepared

standards to assure that response factors fall within a historically accepted range.

There are many laboratory functions that ma y require corrective action. The decision to

undertake corrective action, and the ensuing action must be documented so that traceability can

be maintained. The point of originating the corrective action varies, depending upon the mode of

detection that s uch action is necessary. It is generally the role of either the Laboratory QA

Officer or the Laboratory Department Manager to initiate such action. Those actions that affect

the quality of the data will be recorded and the record maintained by the Labora tory QA Officer.

### The general procedures for appropriate laboratory corrective actions and identification of

potential problems are presented in the analytical laboratory QAM.

### Data are typically validated by the laboratory and field personnel. First, during the field

operations, field measures will be validated at the time of collection by the field sampler by

verifying the use of standard operating procedures for the sampling effort and using field QC

checks. Second, lab oratory analytical results will be validated by the Laboratory Department

Manager or the analyst who is the specific analytical task leader.

Validation of field obtained data, as well as ongoing QA/QC checks of environmental sam ples

being taken, is performed on field data. All field data are reviewed during the time of collection

and second, all data are reviewed by secondary field personnel if multiple personnel are present.

Corrections in the field logbooks will be removed by placing a single line through the entry,

initialing and dating the correction. If information is added without a correction being necessary

that entry will be initialed and dated to indicate that it was not entered at the original time of data

entry. En tries should never be “whited out” or made in pencil.

The individual Laboratory Department Managers should validate all laboratory data, prior to

reporting. Some of the following QA/QC measures are reviewed or procedures are typically

used:

A standard curve is prepared prior to sample analysis;

The standard regression coefficient is within the acceptable range;

Standard reference materials are analyzed at the proper frequencies and acceptable results

are obtained;

The re agent blanks are analyzed at the proper frequency;

Precision requirements of this plan are met;

Accuracy requirements of this plan are met;

Completeness requirements of this plan are met;

Samples are analyzed within the proper sample holding times;

All cal culations are verified as correct;

Proper units are reported; and

The proper methodologies were used.

Besides this review of analytical results and project specific precision, accuracy, and

completeness requirements, the Laboratory Department Manager shou ld perform unannounced

audits of report forms and other data sheets as well as regular reviews of instrument logs,
performance test results, and analysts’ performance. Any review of analytical results or internal

QA/QC checks that indicate problems, immed iate corrective actions should be taken and all data

collected since the previous approved QC audits should be reviewed for validity. Specific

### laboratory procedures for validation of the analytical data generated are described in the

laboratory QAMs.

The laboratory will provide DQO Level 3 (i.e., CLP Like) data packages. However, the data

packages will not be validated at this time. D ata validation procedures following the applicable

guidance from the current U. S. EPA 's Contract Laboratory Program, National Functional

Guidelines for Organic Data Review and the U. S. EPA's Contract Laboratory Program,

National Functional Guidelines for Inorganic Data Review will be performed

, if required.

Analytical Laboratory

Once the data have been validated internally by the laboratory, all of the results are electronically

or automatically entered into the laboratory's data management system where they are stored

prior to reporting. When all analyses are complet ed for data storage, the Laboratory Director (or

his/her designee) will issue a final data report including a descriptive case narrative. He or she

will then issue the report to the data user. All applicable QC data should be included with the

final repo rt.

The data reports generated for this project should contain all pertinent information for the data

user to determine the applicability and usability of the data for its intended purposes. For this

reason, a specified and uniform data reporting format should be implemented. For this project,

DQO levels III data packages will be reported as a Level IV (CLP

- like) deliverable to facilitate

data validation, if needed. The following criteria and information should be supplied, at a

minimum, for data report s generated for this project:

1. A descriptive case narrative identifying any problems encountered during internal data

validation (as described above);

2. Completed and legible chain

- of

- custodies for all analyses contained within each

submitted data package;

3. A lab sample chronicle indicating which analyses were requested and performed for the

samples contained in the data package;

4. A summary of the laboratory sample identifications and the correlating field sample

identifications;

5. A summary of all applicable analytical results reported in the correct number of

significant figures, reporting units; and

### 6. Included in the individual sample reporting results should be the complete sample

identifications, the sample dilutions (if necessary), and the individual samp le analysis

dates.

Summary reporting only will be provided. Bulleted items above are required under this DQL.

Summary reporting only will be provided. The data package reporting requirements are the same

as Level I except legible and calculated QA/QC summaries for laboratory blanks, surrogate

recoveries (if applicable), laboratory control sample recoveries, and matrix spike/matrix spike

duplicate recoveries (or matrix spike recovery and laboratory duplicate results) must also be

supplied under this DQL.

The following summary forms and raw data deliverable requirements will apply for Data Quality

Level III.

The following forms are required for all analyses using Gas Chromatography/Mass Spectroscopy

methods.

Narrative and sample identification cross reference;

Copies of Chain

- of

- Custody documentation;

Laboratory chronicle;

Method summaries and references;

O rganic analysis data sheet for samples and blanks (with TICs a s required);

System monitoring compound/surrogate recoveries summary;

Matrix spike/Matrix spike duplicate summary or any lab duplicate;

QC Check Sample summary;

Method blank summary and results;

Instrument performance check summary;

Initial calibration sum mary for all constituents of interest;

Continuing calibration check summary for all constituents of interest;

Internal standard area and RT summary;

Extraction/preparation logs;

The handwritten calculation for at least one positive result in one sample at a rate of one

calculation per twenty samples or per data package (whichever is greater) per fraction

(e.g., VOC or SVOC); and

Raw data including run logs, mass spectra, quantitation reports and chromatograms for

### samples, as well as any raw data used to com plete the hand written calculation.

The following forms are required for all total metal analyses.

Narrative and sample identification cross reference;

Copies of Chain

- of

- Custody documentation;

Laboratory chronicle;

Method summaries and references;

Inorg anic analysis data sheets;

Initial and continuing calibration verification;

Initial and continuing calibration blanks and preparation blank summary;

I CP interference check sample summary;

Spike sample recovery;

Duplicate results summary;

Laboratory Control Sample summary;

Standard addition results summary, when applicable;

ICP serial dilutions;

Instrument detection limits;

ICP inter

- element correction factors summary;

P reparation log;

Analysis run log;

The hand

- written calculation for at least one positive result in one sample at a rate of one

calculation per twenty samples or per data package (whichever is greater) per method

(e.g., GFAA/ICP/CU); and

Raw data.

The following data and summary forms will be submitted by the laboratory for inorganic non

metal s analyses or other analyses not discussed above:

Narrative and sample identification cross reference;

C opies of Chain

- of

- Custody documentation;

Laboratory chronicle;

Method summaries and references;

Analysis data sheets;

Calibration summaries; and

Calibr ation equation and curve plot;

Blank results summary;

Sample spike recovery, where applicable;

Duplicate sample results, where applicable; and

Laboratory control sample summary where applicable.

### Quality control (QC) pro cedures and checks are used to verify the accuracy of investigation data.

Field QC checks are used to identify potential problems with sampling procedures such as the

inconsistent use of sampling standard operating procedures or field introduced sample or water supply contamination and/or problems with sample homogeneity or representativeness.

Laboratory QC checks are used to identify potential problems with analytical procedures such as

the misapplication of required analytical methodologies or other labo ratory related problems

which could result in inaccurate or imprecise data reported. The laboratory QC checks and

procedures presented in this section are required for most of the applicable methods, but the

frequency of the QC checks should follow proced ures outlined in the laboratory QAMs.

To check the quality of data from field sampling efforts, field blanks and field duplicate samples

will be collected for analysis. These samples will be treated as separate samples for

identif ication, logging, and shipping. Analytical results on blanks and duplicates will be reported

with the appropriate field sample data. The number of these samples, when required, and their

use was described in Section 5.0.

The equi pment blank provides a check on possible sources of sample contamination. The

equipment blanks should be collected in the worst

- case scenario. The reason for performing

equipment blanks in the most impacted area is to attempt to simulate a worst

- case sc enario

regarding contributions from site condition or from improperly cleaned sampling equipment to

sample contamination. One equipment blank will be for this project . Equipment blanks should

be handled, transported, and analyzed in the same manner as th e samples with which they are

associated.

The equipment blank water must be maintained at 4 (±2) C following collection and during

shipment. Holding times for individual parameters are dictated by the specific analytical method

being used. The holding

- time clock begins at the time of sample collection of the equipment

blank.

Trip blanks are used to check for sample contamination introduced by the sample containers, by

the sampling equipment, or by the sampling environment. Trip bla nks travel to the site with the

empty sample bottles and return from the site with the collected samples in an effort to simulate

sample handling conditions. Trip blanks are collected in association with samples that are to be

analyzed for volatile organi c compounds. Potential sources of sample contamination are from

### the laboratory

- grade reagent water, sample containers, field or laboratory ambient air, laboratory

reagents, or cross contamination during shipping, handling, preparation or analysis. A t ri p blank

should accompany VOC samples for each sampling event

.

The trip blank water must be maintained at 4 (±2) C through sample collection activities and

during shipment. Holding times for individual parameters are dictated by the specific analytical

me thod being used. The holding

- time clock begins at the time of sample collection of the oldest

sample in the sampling container.

The QC check frequencies and requirements specified in the following sections is a general

description only. The laboratory will follow the internal QC checks specified in its QAM for

each analysis type employed. However, these QC checks must meet, at a minimum, the

requirements specified in the respective U.S. EPA analytical methods.

The f ollowing internal laboratory QC checks are performed for most analyses, whenever

applicable, to ensure the measurement systems are under control:

Initial and continuing calibrations;

Preparation/method blanks;

Matrix spike and matrix spike duplicate or ma trix spike and laboratory duplicate analysis,

as appropriate;

Surrogate spike standard performance evaluation (for organic analyses only); and

Calibration check compounds and reagent blanks (for organic analyses only).

Additional internal laboratory QC ch ecks are typically performed for most analyses, as required

by the associated analytical method. Only the most common QC checks are generally described

below.

9 .2.1 INITIAL AND CONTINUING CALIBRATION

Each measurement system must be calibrated immediate ly prior to use and be shown to maintain

the calibration throughout the course of the analysis. For the organic parameter methods, all

target compounds will be checked during initial and continuing calibrations. Calibration

procedures and frequencies is discussed for the various analysis types in the laboratory QAMs.

An initial calibration will be performed prior to WSC sample analyses. Continuing calibrations

will be typically analyzed at a minimum frequency of one every ten samples. For CLP GC/MS

ana lysis, calibration checks are only required once every 12 hours of analysis.

A preparation or method blank is run with each batch of samples received for analysis.

Compound or analyte responses observed in the blank at levels above the reportable detection

### limit are reviewed for possible laboratory contamination. If high blank values are observed,

laboratory glassware and reagents may need to be checked for contamination and the analysis of

future samples halted until t he system can be brought under control. A high blank value is

typically defined as a value greater than the method detection limit. A preparation and/or method

blank will be prepared at a frequency of one per 20 samples or one per day, whichever is great er.

For all analyses where matrix spiking is possible, 1 in 20 samples is analyzed as matrix spikes

and matrix spike duplicates or 1 in 20 samples is analyzed as matrix spikes and du plicates. Field

personnel must provide additional volume for the laboratory to complete a MS/MSD. The

percent recovery for spiked samples is calculated using the equations given in Section 12.0 and

compared to the accuracy criteria specified in the QAM f or the associated analytical method.

The relative percent difference of replicate spikes or replicate analytical results are calculated

using the equations given in Section 12.0 and compared to the precision criteria specified in the

laboratory QAMs (Appe ndix QAPP

- 1 and following) for the associated analytical method.

Surrogate standards are defined as nonpriority pollutant compounds used to monitor the percent

recovery efficiencies of the analytica l procedures on a sample

- by

- sample basis. Surrogate

standard determinations are performed on all samples and blanks for organic analyses. All

samples are fortified with surrogate spiking compounds before purging or extraction to monitor

the preparation a nd analysis of samples.

Surrogate compounds and recovery levels for the associated analyses are presented in the

laboratory QAM (surrogate recovery limits are method

- and media

- specific and are either

specified in the method or are calculated annually by the analytical laboratory as described in the

analytical method). When the surrogate recovery level is outside of the control limits on the

initial analysis, the laboratory must take the following actions for all organic analyses for

samples:

Check calcul ations to assure there are no errors, check internal standard and surrogate

spiking solutions for degradation or contamination and check instrument performance;

and

Recalculate or reinject/repurge the sample or re

- extract and reanalyze the sample.

These calibration check compounds and reagent blanks are analyzed periodically throughout the

course of the analysis, depending on the required analysis. The exact frequencies and methods of

use are presente d in the laboratory QAM.

### Two types of audit procedures may be conducted during any environmental investigation:

performance audits and system audits. These audits may be performed on the laboratory as well

as field activities. A description of the laboratory's specific guidance for Performance and

System Audits will be presented in laboratory QAMs. General procedures for laboratory

performance and system audits are presented below.

Laboratory performance audits are typically conducted by the Laboratory QA Officer on a regular

basis. Each laboratory analyst is given a performance evaluation sample containing analytes for

the parameters which he/she u sually performs. These audit samples are used to identify

problems in sample preparation or analysis techniques or methodologies which could lead to

future analytical problems.

Additionally, the laboratory performance audits include verification of each analyst's record

keeping, proper use and understanding of procedures, and performance documentation.

Corrective action will be taken for any deficiencies noted during the audit.

Laboratory system audi ts are typically conducted by the Laboratory QA Officer. These audits are

used to ensure that all aspects of the Laboratory's QAM are operative. This involves a thorough

review of all laboratory methods performed and documentation to confirm that work i s performed according to project specifications.

In some cases, outside certification agencies conduct performance and system audits to verify

contract compliance or the laboratories' ability to meet certification requirements on methods of

analysis and d ocumentation. Results of these outside certification audits may be reviewed at any
time as a check on the laboratory’s internal auditing procedures.

### The following discussion describes the procedures that will be employed to evaluate the

precision, accuracy, and completeness of the generated data.

Precision is a measure of agreement among individual measurements of the same property under

prescribed similar conditions. Precision is assessed by calculating the relative percent difference

(RPD) of replicate spike samples or replicate sample analyses according to, the following

equation:

RPD = R1

- R2 x 100 where R1 = result 1

(R1 + R2)/2 R2 = result 2

Accuracy is a measure of the closeness of an individual measurement to the true value. Accuracy

is measured by calculating the percent recovery (%R) of known levels of spike compounds as

follows:

concentration of spike sample

- concentration of unspiked

sample

%R = ____________________________________________________

_ x 100

concentration of spike added

Completeness is a measure of the a mount of valid data obtained from a measurement system,

expressed as a percentage of the number of valid measurements that should have been collected.

As is specified in Section 4.2, more than one completeness check can be evaluated. It is

calculated as follows:

number of valid samples reported

Completeness (%) =

_______________________________ x 100

total number of samples analyzed

### Quality control charts can be prepared after e very 20 analytical determinations to graphically

evaluate precision and accuracy criteria. The charts are prepared by calculating the mean value

of the determinations and setting control limits at + 3 standard deviations from that mean. The

following equ ations are used:

The control limits should be within acceptance limits or ranges presented in the as yet unselected

laboratory's QAM. If the values are found to be outside these limits or rang es, the measurement

system is examined to determine if possible problems exist.

### Periodic preventive maintenance is required for equipment whose performance can affect results.

Instrument manuals are kept on file for refer ence if equipment needs repair. Troubleshooting

sections of manuals are often useful in assisting personnel in performing maintenance tasks.

Field sampling personnel will be responsible for preventive maintenance of all field instruments.

Th e field sampling personnel will protect the instruments by placing them in portable boxes

a nd/or protective cases.

All field equipment will be subject to a routine maintenance program, prior to and after each use.

The routine maintenance program for each piece of equipment will be in accordance with the

manufacturer's operations and maintenance manual. All equipment will be cleaned and checked

for integrity before and after each use. Necessary repairs will be performed immediately after

any defects are observed, and before the item of equipment is used again.

Equipment parts with a limited life (such as batteries, membranes and some electronic

components) will be periodically checked and replaced or recharged as necessary according to

the manufacturer 's specifications.

Preventive maintenance is important since it provides for a longer useful life of the equipment

and helps to ensure a successful field sampling and testing program. Each piece of field

equipment will have its own log sheet which contai ns the equipment identification and the type

of maintenance performed. Since most equipment is used on an irregular basis, all equipment

will be properly stored when not in use.

All major laboratory instruments should normally be under service contract so that trained

professionals are available on call to minimize instrument downtime. Other preventive

maintenance schedules and/or procedures for laboratory equipment is presented in the laboratory

QAMs (Appendix QAPP

- 1 and following).

### Corrective action procedures are divided into two subgroups: m ethods corrective action and

sy s tems corrective action. These corrective actions are implemented whenever system or

performance audits note deficiencies or when QC procedures indicate a potential analytical

problem. The laboratory guidance on Corrective Action procedures is presented in the laboratory

QAMs.

### This QAPP provides a documentable mechanism for the assurance of quality w ork performed at

for the characterization study. Audit reports will be provided by the Laboratory Director (or

his/her designee) as a means of tracking program performance, as applicable, or if needed.

Additionally, periodic assessments of measurement da ta accuracy, precision, and completeness

and significant QA/QC problems will be performed and reported to laboratory and/or project

management, if needed.

Field QA reports will not be necessary considering the expected size and length of any individual

sa mple collection activities. Any problems noted during sampling will be immediately

communicated to GTI, so GTI can take whatever corrective actions necessary.

Upon completion of the project

- specific Work Plans, a final QA/QC report will be issued,

assess ing the overall degree of project conformance to specifications and the impact of any non

conformances that may affect management decisions.

The final storage location of the files will be maintained at GTI’s office in Chicago. The files

will be main tained for a period of at least three years.