# EVALUATING CHARACTERISTICS OF SOURCE, FLOWBACK , & PRODUCED WATER FOR EFFECTIVE WATER TREATMENT Scott Tucker May 29, 2014 Hach Company

# HOW DO WATER CHARACTERISTICS



# IMPACT TREATMENT?

Improved Performance Time Savings Cost Savings 

### Risk Management

Understanding what’s in your water adds up to improved

performance and significant savings

# HYDRAULIC FRACTURING WATER ANALYSIS

A comprehensive, on
- site water analysis program is critical to a successful frac job

# SOURCE WATER MONITORING

• Key Questions

– It costs $400K to $700K to transport water to site, how do I validate the product to avoid costly issues?

– How is my source water quality changing over time?



### • Role of Water Quality

– Provide selection/acceptance criteria of purchased water prior to a frac job

– Maximize compatibility with fracturing additives and avoid interferences Understanding source water quality in real
- time can help ensure that you are meeting spec and mitigating issues early in the processUse of a biocide prior to injection may be necessary
– most popular methods include UV, chlorine dioxide, or ozone 

# EXAMPLE: BACTERIOLOGICAL EFFECTS

• Source water may contain large 

### populations of microorganisms

• Injecting this water can cause:

• Microbiologically influenced corrosion (MIC)



### • Well souring due to hydrogen sulfide

- producing bacteria

• Clogging due to slime
- forming bacteria

# BEFORE AND AFTER BLENDING

• Key Questions

– How consistent is the water quality in my working/storage tanks?

– How do I combine multiple sources of water in a way that allows me to still meet spec?

– How do I verify that the blending process is working correctly



### • Role of Water Quality

– Early warning system to potential issues with the frac fluid

– Optimize blending of multiple sources of water prior to the blender to meet specifications

– Provide traceability to root cause performance issues Understanding the make up of the water in your storage tanks and final blend can help

identify and protect yourself from potential formulation issuesUnderstanding calcium and iron levels prior to frac fluid formulation is critical to optimal performance 

# EXAMPLE: CATION EFFECTS

• Fluids that are crosslinked are gels that are used to carry the proppant (sand) downhole

• Elevated levels of naturally occurring calcium inhibit the 

### crosslinking from occurring.

• Iron in the formation can prevent the crosslinking breakers from working after transporting the 

### sand downhole
.

# REUSE & TREATMENT DECISIONS

• Key Questions

– How do I determine if the water is acceptable for reuse?

– What is the best method for treating the water?

– How do I avoid over/under treating?

– When should I try to treat vs. dispose and what are my disposal options



### • Role of Water Quality

– Optimize blending and onsite treatment

– Avoid interferences with friction reducers
– TDS (Chloride)

– Prevent down hole plugging
– TSS, Bacteria

– Minimize formation of precipitates
– Barium, Iron, Hardness, Silica, Strontium, Sulfates

– Protect capital equipment from corrosion
– Bacteria, Dissolved Oxygen Measuring before and after the treatment process allows you to make important economic determinations that save time, chemicals, and energy

# EXAMPLE: SCALING AND CORROSION EFFECTS

• Scaling Agents

– Ba , Ca, Sr

, SO 4 can produce fouling precipitates of BaSO 4 , SrSO 4 and CaSO 4 . These ions are naturally occurring from shale formation reservoirs



### • Corrosive Agents

– Iron oxides
– naturally occurring; Acids ( HCl )
– by product of the drilling process, helps dissolve minerals and initiate cracks in the rocks



### BaSO 4 

### Scale

A knowledge about the ions in your water is needed to judge risk level

# WATER ANALYSIS CHALLENGES

• Flowback and produced water properties vary

– From region
- to - region & within regions



### • Challenging sample matrix

– Suspended solids, dissolved solids, color, bacteria, oil, polymers, etc



### • Delays, complexity, and cost in obtaining reliable results

– Significant time delay to receive results from 3 rd party lab, plus hassle to collect, preserve, and ship sample Parameter Concentration Range ( ppm ) Alkalinity 100 – 600 Calcium 500 – 12,000 Magnesium 50 – 2,000 Barium 50 – 9,000 Strontium 50
- 6,000 Sodium 4,000 – 40,000 Iron 50 – 300 Silica 50 – 300 Sulfate 10 – 400 Chloride 5,000 – 80,000 TDS 1,000 – 150,000 TSS 1,000 – 7,000

*Source: Shramko , Andrea. Analytical Characterization of Flowback Waters in the Field. IPEC, Houston, November 3
- 5, 2009. Approximate Flowback Water Contaminant Ranges*

Without accurate, reliable, and timely information, water will become the weakest link in the process

# PROBLEM STATEMENT

• Existing methods only cover ranges adequate for source water

• Limited number of viable portable parameters available (i.e. pH, conductivity, etc)

• No easy, portable methods for the other key parameters of interest in hydraulic fracturing waters Parameter Current methods ( ppm ) Target

( ppm )
Barium 2 – 100 2 – 9,000 Chloride 10 – 8,000 10 – 12,000 Hardness 10 – 4,000 10 – 14,000 Sulfate 2 – 70 2 – 400 Iron 0.02 – 3.0 0.01 – 300 Boron 0.2 – 14 0.2 – 50
Challenge: Create methods that can easily be conducted by operators onsite, which cover the entire range needed to test source, fracturing fluid, flowback , and produced water.

# OUR APPROACH

Sample & Screen Identify Issues
Modify
Simplify

Validate for Field Use • Collect representative samples from key shale plays

• Characterize samples with electrochemical parameters

• Create laboratory experiments to identify interferences with existing field methods

• Explore opportunities to overcome interferences through method modification
• Validate test results against 3 rd party laboratory results

• Explore opportunities to simplify procedures for easier field use
• Create step
- by
- step procedures that can be performed by an operator

• Confirm performance through field testingSamples chosen to reflect complex and variable nature of shale waters



# SAMPLE SELECTION

• Five flowback and produced samples collected across three major shale plays:

– 2 Eagle Ford = EF
- 1 and EF
- 2

– 2 Marcellus = M
- PA (Pennsylvania) and M

- OH (Ohio)

– 1 Barnett = B

## Results : Hach and 3 rd 

## Party results showed 

## strong correlation for electrochemical methods. 

# PRELIMINARY SCREENING

0 1 2 3 4 5 6 7 8

EF-1 M-PA EF-2 B M-OH

pH Measurement

Lab Hach

0 100,000 200,000 300,000 400,000

EF-1 M-PA EF-2 B M-OH

TDS Measurement

Lab Hach 

## • S amples were tested using two key electrochemical methods

– pH varied from 4 to 7

– TDS (via conductivity*) varied from 25,000 to 370,000

• Variability of pH and TDS across samples illustrates variable nature of shale water

### Results : Modification overcomes Sr 2+ 

### interference providing strong correlation between Hach and 3 rd 

### party Barium lab results. 

# OVERCOMING INTERFERENCES FOR BARIUM Challenge:
• Strontium will interfere with barium, but unclear at what level and to what extent Findings:
• At less than 20 mg/L, the interference from Strontium becomes negligible Solution:
• Overcome Strontium interference by diluting sample, so that Strontium and Barium are below the 20 mg/L threshold

0 500 1,000 1,500 2,000 2,500 3,000 3,500

EF-1 M-PA EF-2 B M-OH

Barium Measurement

Lab HachResults : Key interferences commonly present in hydraulic fracturing water have been eliminated allowing for reliable onsite measurement of Iron. 

# OVERCOMING INTERFERENCES FOR IRON Challenge:
• At combined concentrations over 50 mg/L Barium and Strontium will interfere Iron causing a precipitate Findings : • EDTA ( Ethylenediaminetetraacetic acid) chelates the Barium and Strontium making them unavailable to react with the iron reagent Solution:
• Add 2 drops of 1M EDTA solution directly to the sample cell to overcome the interference with Barium and Strontium in hydraulic fracturing waters

0 5 10 15 20 25 30 35 40

EF-1 M-PA EF-2 B M-OH

Iron Measurement

Lab Hach

### Parameter Impact Before (mg/L) After (mg/L) Barium Scaling 2 to 100 2 to 8000 Chloride Scaling/Corrosion/

Interferences 10 to 8,000 100 to 200,000 Hardness Scaling/Corrosion 10 to 4,000 100 to 200,000 Sulfate Scaling 2 to 70 2 to 7000 Iron Corrosion 0.02 to 3.0 0.1 to 300 Boron Crosslinking 0.2 to 14 2 to 50 Hydrogen Sulfide Corrosion/

Biofouling 0.005 to 0.7 0.005 to 70
Extended ranges made easy for all key hydraulic fracturing parameters 

# METHOD ADAPTATIONS FOR HYDRAULIC FRACTURING

# METHODS MADE EASY

• Step
- by
- step procedures and detailed explanations for the non - technical user in a “Hydraulic Fracturing Water Analysis Handbook”

Methods can now be performed quickly and easily in the

field by non

- technical operators

• Dilutions that are “invisible” to the user and are performed directly in sample cell:

– User selects low range (LR), mid

- range (MR), or high range (HR) by pressing the ‘ conc ’ key

– Adds corresponding sample volume: LR = 10 mL , MR = 1.0 mL , or HR = 0.1 mL

– Dilution factors calculated automatically by colorimeter

• Titration methods are simplified through:

– An expanded concentration range using smaller sample volumes

– A digital titrator (i.e. no glass pipettes )

# HYDRAULIC FRACTURING WATER ANALYSIS KIT

• Includes instruments, reagents, and methods to support parameters critical to hydraulic fracturing applications:

– Alkalinity

– Bacteria: Sulfate

- reducing (SRB), Iron

related (IRB), Slime

- forming (SLYM)

– Barium

– Chloride

– Conductivity

– Hardness

– Iron

– pH

– Sulfate 

### • Provides real
- time, on
- site results No need to spend the time and money to send samples to a regional lab!


### • Supports analysis of:

– Source water

– Produced water

– Frac fluid

– Flowback water

– Water treatment

– Drilling fluids

– Enhanced oil recovery

• Additional parameters may be added as needed The newly developed methods can provide real
- time field results for key hydraulic fracturing waters via a portable kit

# OTHER KEY LAB & FIELD PRODUCTS Instruments

• 2100Q Portable Turbidimeter

• DR 1900 Portable Spectrophotometer

• DR 3900 Benchtop Spectrophotometer

• TSS Portable Probe

• MP
- 6 Meter HQd IntelliCAL TM Probes

• Chloride ISE

• Dissolved Oxygen



### • ORP Chemistries

• Boron



### • Hydrogen Sulfide

• Bromine

• TPH



### • Chlorine / Chlorine Dioxide

• Manganese

• Ferrous Iron

• LuminUltra ® ATP

### TPH Monitoring of Mobile Treatment System

– Issue :
• Hydrocarbons cause performance issues with gel formulations

• C ompany struggled to get reliable and consistent TPH results from third party lab

• Long wait times to receive information and wanted to “get out of the business of sending samples out”

– Solution:

• On
- site monitoring using an immunoassay method providing a semi
- quantitative screening for TPH

– Results :
• Produced consistent and reliable results with the new testing procedures

• Reduced information delay from several weeks to minutes

• Reduced third party lab expenses by $30K per year 

# APPLICATION SPOTLIGHT

Obtaining TPH results in the field improved reliability, minimized

information delay, and saved money

### Microorganism Analysis with LuminUltra’s ® ATP technology

– Issue :
• A lack of effective microbiological control can lead to upstream and downstream problems

– Solution:

• On
- site monitoring using ATP (Adenosine Triphosphate) testing provides results within minutes

– Results :
• Rapid microbiological results allow operators to avoid costly issues

• Reduced information delay from several weeks to minutes

• Reduced third party lab expenses 

# APPLICATION SPOTLIGHT

Microbiological threats are many, and are best mitigated at their earliest

stages to minimize cost impacts

### Robust Online Analyzers



### • Mount directly into the treatment process for continuous analysis of :

Monitor continuously and adjust processes in real
- time to optimize

treatment effectiveness and reduce costs 

### – Chlorine
– Suspended Solids

– Conductivity
– Total Organic Carbon



### – Dissolved Oxygen
– Turbidity

– Oil in water
– UV transmittance

– pH – And many more 

# CONTINUOUS MONITORING

### • Training encompasses everything necessary to train operators to complete a test and get a correct answer in lab or on
- site

• Hands
- on training, small class sizes, combine 

### technical discussion with practical exercises

• Experienced trainers available globally

• Customized classes
– field or lab setting
– 

### HTTC brings the class to you

A commitment to educating our customers HTTC Hach Technical Training Center 

# TRAINING

# ADDITIONAL RESOURCES Additional information is available at the Hach website:

• Watch the methods in action

• Request your electronic copy of the ‘Hydraulic Fracturing Water Analysis Handbook’

• Access application notes and datasheets



### • Order products and services hach.com/fracwater