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 process 
Use 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 issues
Understanding 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, SO4can produce fouling precipitates of BaSO4, SrSO4and CaSO4. 

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

BaSO4 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 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
Samples 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 3rd 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

• 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: 

Modification overcomes Sr2+ 

interference providing strong 

correlation between Hach and 3rd

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

Hach
Results: 

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), 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
OTHER KEY LAB & FIELD PRODUCTS

Instruments

• 2100Q Portable 

Turbidimeter

• DR 1900 Portable 

Spectrophotometer

• DR 3900 Benchtop

Spectrophotometer

• TSS Portable Probe

• MP-6 Meter

HQd IntelliCALTM 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

• Company 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