www.anadarko.com | NYSE: APC



# ANADARKO PETROLEUM CORPORATIONwww.anadarko.com | NYSE: APC



# Will Discuss

Impact of make

- up water composition on fracturing fluid

design, considerations

Make

- up water constituents which are critical for fracturing

fluid formulation

Matching of frac chemicals to make

- up water compositions

Impact of blending flowback /production water with fresher

make

- up waters

Treatment of flowback /produced water for re

- use

2www.anadarko.com | NYSE: APC



# Water Cycle in Shale Gas Plays

3www.anadarko.com | NYSE: APC



# F ormulation of completion package

Reservoir souring

Scale formation during pumping

Incompatibility with formation brine/formation rock in

reservoir

Scaling during flowback and production in near wellbore, production tubing, flowlines and facilities 

# Impact of Make

- up Water C ompositionwww.anadarko.com | NYSE: APC



# MAKE

- UP AND FLOWBACK WATERSwww.anadarko.com | NYSE: APC



# Problematic ions are Ba, Ca , Fe, HCO 3 

# and SO

4 

# (Causes of scales,

incompatibilities and performance limits)

Reservoir is primary source for Ba and Ca , mostly for HCO 3 

# also

Formation and/or corrosion can be sources for Fe

W ells, ponds, creeks, rivers and some formations are sources for SO

4



# In general, reservoirs do not contribute both high Ba and SO

4 

# unless

brines from multiple zones are produced

This may be a problem in some areas where fluids from new

developments are mixed with existing streams

G ood elemental analysis map of wells/flow lines is critical to water

reuse as well as water management 

# Problematic Elementswww.anadarko.com | NYSE: APC 

# Range of Key Elements in

Fresher Make

- up Water Sources

Water from W. Texas Lake

Elements mg/l

Bicarbonate 110

Chloride 4072

Sulfate 2830

Barium 0

Calcium 850

Magnesium 360

Sodium 2410

Chloride 4070 TYPICAL RANGE OF KEY ELEMENTS IN

FRESHER MAKE

- UP WATERS

- ALL AREAS

ELEMENTS Concentration

mg/l

Ba++ 0

- 10

Ca ++ 7

- 400

Fe++ 0

- 20

SO4

-- 0

- 1000

HCO3

- 0

- 350 FRESH WATER SOURCES in AREA 1

Primary

Elements, mg/l Municipal

Waters Creek/River

Streams AMD Brines

Bicarbonate 97

- 207 12

- 30 0

Chloride 30

- 60 3

- 20 8

- 22

Sulfate 10

- 25 6

- 144 125

- 156

Barium 0 <0.03 <0.05

Calcium 12

- 35 7

- 38 21

- 35

Iron 0 0.1

- 1 2

- 3

Magnesium 4

- 7 1

- 15 13

- 17

Sodium 31

- 67 2

- 36 9

- 13

Strontium 0 0

- 0.2 0.10

pH 6.5

- 7.4 6

- 8 3

- 5www.anadarko.com | NYSE: APC



# Range of Key Elements in

Flowback /Formation Brine

RANGE OF KEY ELEMENTS IN FLOWBACK/FORMATION BRINES

ELEMENTS Area 1 Area 2 Area 3 Area 4

Ba++ 0

- 12,340 0

- 35 0

- 110 0

- 1,200

Ca++ 7

- 50,000 65

- 6,000 10

- 1,100 15

- 17,000

Fe++ 0

- 230 1

- 250 1

- 300 0

- 320

SO4

-- 0

- 150 0

- 500 0

- 300 0

- 960

HCO3

- 0

- 470 150

- 450 50

- 1,500 50

- 800

Estimated Flowback

Volume, % of Pumped 15

- 20 <30 <30 <25www.anadarko.com | NYSE: APC



# DESIGN/FORMULATION

OF

FRACTURING FLUIDSwww.anadarko.com | NYSE: APC 

# Fracturing Fluid Design/Formulation

10 

# Fracturing Fluid Design Decision

• Slick Water

• Hybrid System

• Gel



# Water Sources

• Fresher make

- up

• Flowback /Produced

• Blends



# Fracturing Fluid Formulation

• Friction reduction

• Bacteria control

• Scale control ?

• Others ?www.anadarko.com | NYSE: APC



# Friction reduction / proppant transport

Slickwater : polymers

Hybrid (gel + slickwater ) & Gel: Polymers , X

- linkers, gel breakers, pH control, etc.

Bacteria control

Scale management

– to be evaluated case by case

Clay control

– as needed

Surfactants

– as needed

Others 

# Fracturing Fluid Formulation

- Functionalitywww.anadarko.com | NYSE: APC



# Flexibility in water and product selection

Almost all flowback waters can be used

Both anionic and cationic polymer packages are utilized

Tolerance to high salt and divalent ions can be accomplished by controlling % of ionic charges on polymer and/or molecular modification with more salt tolerant polar groups such as

sulfonate

Flexibility in selection of bacteria control products

Less prone to scale formation but some constraints in scale

inhibitor selection if cationic FR is used

Anionic FR constrains use certain organic clay control products

Compatible surfactants are available for anionic and cationic FRs 

# Slickwater Formulationwww.anadarko.com | NYSE: APC



# Friction Reduction Results for High Salinity Brine,

Fresher W ater and Blends

– 2 Vendor P roducts

November 14, 2012 13 % FRICTION REDUCTION @ VARYING DOSAGE RATES ( gpt )

in DIFFERENT BRINES

FR DOSAGE

RATES, gpt

MAKE

- UP WATER TDS,

ppm VENDOR 1 1.5 2

Fresh Water 0.7K Vendor A Product 70

Vendor B Product 77 77 76

Blend Vendor A Product 70

3 FW+1FBW 38K Vendor B Product 49 70 70

Blend Vendor A Product

1 FW+1FBW 76K Vendor B Product 60 72 70

Blend Vendor A Product 70 69

1 FW+3FBW 114K Vendor B Product 57 67 68

High Salinity Brine 152K Vendor A Product 69

Vendor B Product 45 51 37 WATER DATA

Fresh

Water High

Salinity

Brine

Elements mg/l mg/l

Bicarbonate 112 230

Chloride 100 90000

Sulfate 200 X

Barium X 7000

Calcium 65 11400

Magnesium 15 800

Iron X 100

Potassium 15 200

Sodium 100 40000

Strontium X 2500

TDS, mg/l 0.7K 152Kwww.anadarko.com | NYSE: APC



# Friction Reduction Results in Area 2 Flowback

Brine, Fresher W ater and Blends

% FRICTION REDUCTION WITH VENDOR C PRODUCT

IN AREA 2 BRINES @ 2 Reynolds Numbers

63000 41000

FR Dosage Rates, gpt FR Dosage Rates, gpt

MAKE

- UP WATER 0.75 1.0 1.5 0.75 1.0 1.5

Fresh Water W

- 1 75 75 73 58 68 67

Blend W

- 2 73 75 75 59 57 64

Flowback Brine W

- 3 73 75 74 54 63 61www.anadarko.com | NYSE: APC 

# Hybrid System Formulation

• 

# Hybrid gel

– 

# Slickwater & guar, or SW & CMC

– 

# Variations in % of SW, linear gel and cross

- linked gel



# Guar and CMC gel systems

Linear guar and/or its derivatives or CMC and/or its derivatives

pH adjustments: Guar (pH=8

- 10); CMC (pH = 5

- 7)

Cross linkers, breakers, pH adjustment products, biocides, scale

inhibitors, surfactants



# Gel systems are impacted by multivalent ions in particular

by cations:

Fe, Mg and Ca are likely to drop out as carbonates/hydroxides in

order to increase pH to 8

- 10 for Guar system

pH of flowback /produced water is more favorable for CMC system

however CMC gel system is impacted by multivalent cations which

compete for negatively charged segments of polymers

November 14, 2012 15www.anadarko.com | NYSE: APC



# Use of Flowback Brine for Gel Boragel System:

pH Adjustment in Area 3 Flowback Brine

November 14, 2012 16 

### AREA 3 Flowback Brine

Elements mg/l

Bicarbonate 735

Chloride 18,000

Sulfate 60

Barium 35

Calcium 450

Magnesium 70

Iron 30

Potassium 200

Sodium 10,000www.anadarko.com | NYSE: APC 

# Bacteria Control

November 14, 2012 17 

# Second most important element of fracturing fluid package

P roduct requirements

Compatible with completion package/reservoir conditions

Effective initial kill and prolonged protection

Meet/Exceed Environmental, Health and Safety requirements

Cost effective

Options

Non

- oxidizing biocides

Oxidizers

Non chemical means

Combinations of above

Recommendations

Select products/methods to meet criteria and test

products/methods using actual fracturing packages

Employ aggressive performance monitoring program

More and more on the fly applicationwww.anadarko.com | NYSE: APC



## Establish scale control needs

Initially, we do not have sufficient data on reservoir/reservoir and

flowback fluids to determine if scale control is needed

Carry out very rigorous flow back monitoring programs to learn about the

reservoir/reservoir fluids

Determine where and how much scale will form?

Use data on fluids and conditions to examine scaling issues for all

potential scenarios from blending stage to a time in the future that

production is stabilized

Can you do anything about it?

Driving forces for scale formation may be too strong to prevent scale

formation

Do you want to control scale partially/completely and where?

During blending/pumping, in reservoir, near wellbore, downhole in

tubing, flowlines , facilities

S creen SI products under realistic conditions

Implement monitoring program to verify product effectiveness/optimize SI 

# Scale Management/Control Decisionwww.anadarko.com | NYSE: APC 

# Potential Solids Upon Injection of Area 3 Flowback Brinewww.anadarko.com | NYSE: APC



# Potential Scales from W. Texas Lake Water if it is Injected

(Based on 1 STB of Water)

November 14, 2012 20 Water from W. Texas Lake

Elements mg/l

Bicarbonate 110

Chloride 4072

Sulfate 2830

Barium 0

Calcium 850

Magnesium 360

Sodium 2410

Chloride 4070www.anadarko.com | NYSE: APC 

# Total Calcite from a Daily Well Stream

( 4 bbl of formation water, 600 Mcf gas and 140 bbl of Oil)www.anadarko.com | NYSE: APC 

# Scale Tendency of Calcite for a Daily Well Stream

( 4 bbl of formation water, 600 MCf gas and 140 bbl of Oil)www.anadarko.com | NYSE: APC



# Scaling Tendency of Area 1 Flowback Water

and Fresh Water Mixture (97% Fresh/3% Flowback )www.anadarko.com | NYSE: APC

0 20 40 60 80 100 120

0 25 50 75 100 125 150 175 200 225SI InhibitorEfficiency (%)

SO4 Concentration (mg/L) 

### SI Efficiency With Slick Water Additive Package @ 140F

Fixed Ba @ 7000 mg/l, vary SO4

2000ppm SI

1500ppm SI

1250ppm SI

1000ppm SI

750ppm SI

500ppm SI

250ppm SI 

# Scale Inhibitor Evaluation for Area 1 Completion Fluid

Package: Ba fixed @ 7000 ppm, SO4 Variedwww.anadarko.com | NYSE: APC



# IMPACT OF MIXING FLOWBACK BRINES

WITH

FRESH MAKE

- UP WATERSwww.anadarko.com | NYSE: APC



# Impact of Mixing Reclaimed Area 1 Flowback Brine

with Various Fresh Make

- up Waters from Area 1

0 2000 4000 6000 8000 10000 12000 14000

0 0.2 0.4 0.6 0.8 1 1.2Solids (BaSO4 & CaCO3), lb//100K STBW

Fraction of Area 1 Flowback Water Solids Can be Generated per 100K STBW Frac Job upon Mixing of

Area 1 Flowback Water with Different Fresher Brines @ 150F & 3000 psia

BaSO4 Ave Ions AMD Brine with A1 FlowBack Water

BaSO4 Max Ions Creek Water with A1 FlowBack Water

CaCO3 Max Ions Utility Water with A1 FlowBack Water

BaSO4 Max Ions Utility Water with A1 FlowBack Water

CaCO3 Max Ions Creek Water with A1 FlowBack Water AREA 1 WATER DATA

Flowback

Brine

Elements mg/l

Bicarbonate 25

Chloride 65000

Sulfate 0

Barium 2650

Calcium 9650

Magnesium 660

Iron 17

Potassium 250

Sodium 22470

Strontium 3230

pH 9.1www.anadarko.com | NYSE: APC



# Water Treatment For Reuse

Water coming from formation is most compatible with the formation

No or minimal treatment of flowback /produced water is needed

Remediation of flowback /produced water primarily depends on fracturing system used and conditions at target zone but should include

Bacteria control

Removal of organics, total suspended solids (TSS) and Fe

A typical Effluent Specifications:

Fe <10 ppm

TSS <50 ppm

Hydrocarbon content <40 ppm

100% bacterial control

pH = 6.5

- 7.5

27www.anadarko.com | NYSE: APC



# Broad range of products are available to formulate a well performing

fracturing fluid in most brines

Minimize the number of chemicals and quantities utilized (2

- 3

essential chemicals)

Friction reducer

Bacteria control products

Sale Inhibitor

– valid assessment is needed

Clay Stabilizer

– generally not needed if flowback water is used

Surfactants

– Fit for purpose application

Reuse of reclaimed flowback brines and produced waters offer technical advantage for controlling scale and preventing clay swelling

Hybrid systems may require removal of some of the cations such as Fe, Mg and Ca since they impact product performance

However , reclaim water can be used for acid or in slickwater stages

while fresher make

- up waters can be used for gels 

# Summarywww.anadarko.com | NYSE: APC



## Adjustments to completion packages are not well managed in a timely

manner due to insufficient information on make

- up water and formation

fluids, short lead

- time, limited product lines of fracturing company/vendor,

lack of knowledge, etc.

Aggressive fluid sampling/analysis programs should be implemented in new

developments until the area is fully understood

Aggressive product evaluation program, with vendors and potential product

suppliers

, should be in place to continuously improve product performance,

economics and environmental acceptability.

Even though in wells certain salinity ranges are reached, it is difficult to

define formation brine unless amount of flowback and/or produced water

exceeds total injected fluid. Equilibrium values will change with time. 

# Summary (cont.)www.anadarko.com | NYSE: APC



# QUESTIONS/COMMENTS