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On-site Field Analysis of Hydraulic 

Fracturing Flowback and Produced Waters 

Scott Tucker, Application Scientist 

March 2012 

Hach Company 
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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 

training 
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Agenda 

• Importance of testing 

• Water analysis challenges 

• Advances in field testing 

• Herkimer Shale Case Study (field testing validation) 

• Summary 
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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 performance 
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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 3rd 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 
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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 water, fracturing

fluid, flowback water, and produced water.
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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 3rd 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 testing
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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 waters 
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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 

• Samples 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 3rd Party results showed strong 

correlation for electrochemical methods. 

*TDS = 0.64 x Conductivity 
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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 Sr2+ interference 

providing strong correlation between Hach 

and 3rd party Barium lab results. 
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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 

Hach 
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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 CaCO3. 
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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. 
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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) 
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Parameter Before (mg/L) After (mg/L)

Barium 2 to 100 2 to 8000

Chloride 10 to 8,000 100 to 200,000

Hardness 10 to 4,000 100 to 200,000

Sulfate 2 to 70 2 to 7000

Iron 0.02 to 3.0 0.1 to 300

Boron 0.2 to 14 2 to 50

Method adaptations for Hydraulic Fracturing

Extended ranges made easy for all key hydraulic fracturing parameters 

Development of Methods
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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. 
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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

SO4 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-chem
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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 kit 
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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 S2-/L. 

. 

• Hydrogen Sulfide (test kit): 

The H2S in the sample is effervesced and reacts with a 

CuSO4 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 H2S/L. 

HR Sulfide methods have recently are available and can easily be used in the field. 
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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. 
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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) 
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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 more 
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• Training encompasses everything 

necessary to train operators to complete a 

test 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 Center 
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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 minutes
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Thank you for your attention!