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# On-site Field Analysis of Hydraulic Fracturing Flowback and Produced Waters Scott Tucker, Application Scientist March 2012 Hach Company2 

# Hach Company: A Global Leader in Water Analytics

• Over 75 years of analytics expertise in water

– 1933: Dr. Bruno Lange GmbH founded in Berlin

– 1947: Hach founded in Ames, Iowa

– 1999: Acquired by Danaher Corporation ($13B in Revenue, 2010)



### • Leader in laboratory and process monitoring for:

– Municipal drinking and wastewater

– Industrial wastewater and utilities



### • Commitment to customer value creation

– Strong investment in R&D and acquired technologies

– 527 patents covering 130 patent families



### – Highest quality products with reliable delivery

– Leadership in customer service, technical support, and training3 

# Agenda

• Importance of testing

• Water analysis challenges

• Advances in field testing

• Herkimer Shale Case Study (field testing validation)

• Summary4 

# Importance of Water Testing Type Key Questions Role of Water Quality Data Influent (source) • It costs $400K to $700K to transport water to site, how do I validate the product to avoid costly issues? • Provide selection/acceptance criteria of purchased water prior to a frac job • Maximize compatibility with fracturing additives and avoid interferences Reuse (flowback) • 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? • 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 Disposal (flowback/ produced) • How much will it cost to treat the water? • What are my disposal options? • Data for reuse vs. disposal decisions • Comply with regulations 

### Water quality information is key to avoiding costly issues and achieving long term well performance5 

# 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 Pa r a m e te r C o n c e n tr a ti o n R a n g e ( ppm ) Al ka l i n i t y 100 – 600 C a l ci u m 500 – 12,000 Ma g n e si u m 50 – 2,000 Ba ri u m 50 – 9,000 St ro n t i u m 5 0 -6 , 0 0 0 So d i u m 4,000 – 40,000 I ro n 50 – 300 Si l i ca 50 – 300 Su l f a t e 10 – 400 C h l o ri d e 5,000 – 80,000 TDS 1,000 – 150,000 T SS 1,000 – 7,000

* So u rce : Sh ra mko , An d re a . An a l yt i ca l C h a ra ct e ri za t i o n o f F l o w b a ck W a t e rs i n t h e F i e l d
. I PEC , H o u st o n , N o ve mb e r 3 -5 , 2 0 0 9
. A p p r o x i m a te F l o w b a c k W a te r C o n ta m i n a n t R a n g e s *



### W i t

h o u t a ccu ra t e , re l i

a b l e , a n d t i

me l y i n f o rma t i

o n , w a t e r w i

l

l b e co me t h e w e a k e s t l i

n k i n t h e p ro ce ss6 

# 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 Pa r a m e te r C u r r e n t m e th o d s ( ppm ) T a r g e t ( ppm ) Ba ri u m 2 – 100 2 – 9,000 C h l o ri d e 10 – 8,000 10 – 12,000 H a rd n e ss 10 – 4,000 10 – 14,000 Su l f a t e 2 – 70 2 – 400 I ro n 0.02 – 3.0 0.01 – 300 Bo ro n 0.2 – 14 0.2 – 50 

### Challenge : C re a t e me t h o d s t h a t ca n e a si l y b e co n d u ct e d b y o p e ra t o rs o n si t e , w h i ch co ve r t h e e n t i

re ra n g e n e e d e d t o t e st so u rce w a t e r , f ra ct u ri n g fluid, f l

o w b a ck w a t e r , a n d p ro d u ce d w a t e r .7 

# 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 testing8 

# 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

Samples chosen to reflect complex and variable nature of shale waters9 

# 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 : Hach and 3 rd 

### Party results showed strong correlation for electrochemical methods

. *TDS = 0.64 x Conductivity10 

# 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 Hach 

### Results : Modification overcomes Sr 2+ 

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

### party Barium lab results.11 

# 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



### Results : Key interferences commonly present in hydraulic fracturing water have been eliminated allowing for reliable onsite measurement of Iron. 0 5 10 15 20 25 30 35 40

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

Lab Hach12 

# Matrix Challenges for Total Hardness

Findings: • Iron’s contribution was very low, especially when using small sample volumes for titration. Plus, the addition of CDTA, the titration can accommodate up to 100 mg/L of iron.
• The total hardness value will include the divalent cations of barium, strontium, calcium and magnesium.



### Results : Hardness interferences with Iron can be eliminated and positive errors that may be caused by barium and/or strontium can be removed. Challenge: • Produced and flowback water can have elevated levels of barium, strontium and iron; causing a positive error.

Solution: • If the barium and strontium concentrations of the sample are known, these interfering cations can be subtracted from the total hardness value by performing a molecular weight conversion of both barium and strontium to CaCO 3 .13 

# Matrix Challenges for Conductivity

Findings: • Higher sample conductivities lead to larger positive errors (as high as 30%) when samples are diluted. It is recommended to avoid dilutions when measuring conductivity.



### Results : A metal enhanced 4-pole conductivity cell is ideal for sample matrices with high conductivity and eliminates dilution errors. Challenge: • Dilution of high conductivity samples can lead to positive errors in conductivity readings compared to un-diluted samples.

Solution: • A metal enhanced 4-pole conductivity cell can handle high sample concentrations without dilutions. It is recommended to calibrate using a calibration standard that approximates the range of conductivity values expected in the sample.14 

# 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)15 

### Pa r a m e te r B e fo r e (m g / L ) A fte r (m g / L ) Ba ri u m 2 to 100 2 to 8000 C h l o ri d e 10 to 8,000 100 to 200,000 H a rd n e ss 10 to 4,000 100 to 200,000 Su l f a t e 2 to 70 2 to 7000 I ro n 0.02 to 3.0 0.1 to 300 Bo ro n 0.2 to 14 2 to 50 

## Me th o d a d a p ta ti o n s fo r H y d r a u l i c F r a c tu r i n g

Ext e n d e d ra n g e s ma d e e a sy f o r a l l ke y h yd ra u l i

c f ra ct u ri n g p a ra me t e rs 

# D ev elopment of M et hods16 

# Herkimer Case Study

• Due to the interferences encountered in analyzing various types of waters, the Global Petroleum Research Institute (GPRI) was in need of modified methods to provide accurate and reliable results
.

• The purpose of this visit was to analyze and characterize produced water samples with Hach’s newly developed methods for flowback and produced waters.17 

# Herkimer Shale Produced Water Results

• “Hach’s hydraulic fracturing water analysis methods were easy to follow and provided accurate results
... Additionally, interferences noted for each method were simple to adjust for and all chemistries were properly explained.”

Keith McLeroy, Analytical Advisor GPRI at Texas A&M University-College Station
Hach’s modified procedures are effective and reliable for on-site analysis on these difficult matrices Parameter Result Notes Cl - (Titration) 230 g/L Silver nitrate titration Cl - (ISE) 255 g/L Ion Specific Electrode SO 4 137 mg/L SulfaVer method Ba 111 mg/L BariVer method Fe +2 200 mg/L Phenanthroline method Combined Fe 268 mg/L FerroVer method B 4 mg/L Carmine method (BoroVer) Conductivity 219 mS/cm E-chem18 

# Hydraulic Fracturing Water Analysis Kit

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

– Alkalinity

– Bacteria: Sulfate-reducing (SRB), Ironrelated (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 kit19 

# Hydrogen Sulfide

• Hydrogen Sulfide (photometric method): Hydrogen sulfide reacts with N,N- dimethyl -pphenylenediamine sulfate to from methylene blue. The intensity of the blue color is proportional to the sulfide concentration. Developed new HR method with concentration range 0 to 70 mg S 2- /L.

. 

### • Hydrogen Sulfide (test kit): The H 2 S in the sample is effervesced and reacts with a CuSO 4 disc, then perform a color comparison. Concentration steps: 0.0, 0.1, 0.3, 0.5, 0.7, 1.0 , 2.0 , 5.0 mg H 2 S/L.


### HR Sulfide methods have recently are available and can easily be used in the field.20 

# Total Petroleum (TPH)

• Total Petroleum Hydrocarbon: • This immunoassay method provides a semi-quantitative screening for TPH based on thresholds as diesel fuel in the following concentrations: Soil – 20, 50, 100, 200 ppm Water – 2, 5, 10, 20 ppm
• Immunoassay tests use antibody reactions to test for specific organic compounds in water. The antibodies selectively bind and remove the TPH from the sample.



### TPH results can be obtained in the field using this easy to use immunoassay method.21 

# Other Key Lab & Field Products Instruments
• 2100Q Portable Turbidimeter

• DR 2800 Portable Spectrophotometer

• DR 3900 Benchtop Spectrophotometer

• TSS Portable Probe

• MP-6 Meter HQd IntelliCALTM Probes
• Chloride ISE
• Dissolved Oxygen
• ORP Chemistries
• Boron
• Bromine
• Silica
• Chlorine / Chlorine Dioxide
• Manganese
• Phosphate
• Ferrous Iron
• BARTS (Heterotrophic Bacteria)22 

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

# Continuous Monitoring

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 more23 

### • Training encompasses everything necessary to train operators to complete atest and get a correct answer in lab or onsite
• 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 

# Hach Training

A commitment to educating our customers HTTC Hach Technical Training Center24 

# 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 www.hach.com/fracwater See how you can get real-time

results in the field in minutes25 

# Thank you for your attention!