Dow Microbial Control

Delivering Value with an Optimized Microbial Control

Program in Oil and Gas Operations
Protect Oil and Gas Operations with an Optimized Microbial Control Program

Bacteria will grow just about anywhere water can be found. In

hydrocarbon production and processes, the large volume of
associated water provides an environment in which bacteria
will thrive. Their presence impacts the quality and quantity of
production, asset integrity and the overall safety of operations.

Advanced stimulation techniques like hydraulic fracturing and

enhanced oil recovery (EOR) are more water-intensive processes
that are susceptible to bacterial contamination if not properly
controlled with an advanced and comprehensive biocides
treatment program. Left unchecked, the microbes will contribute
to reservoir souring, corrosion of pipelines and equipment, and
formation plugging.

Leaders in Microbial Control for Oil and Gas Operations

Dow Microbial Control has over 60 years of experience in developing
effective biocides and bringing microbial control solutions to the oil and
gas industry. Our leadership position is based on:
• The broadest portfolio of biocides for advanced sustainable microbial
control, including innovative formulations
• Technical expertise and advanced testing capabilities
• Regulatory expertise
• Industry expertise
• World-class manufacturing capabilities

2
Beyond Chemistry: Dow Offers Leading Solutions to Microbial Challenges

Dow Microbial Control, a business unit of The Dow Chemical Company (Dow), provides the broadest range of microbial control
solutions in the industry. We offer an unmatched combination of chemistries, delivery forms, technical expertise, reliability of supply,
and regulatory excellence by leveraging global capabilities with a local presence around the globe. At Dow, we believe that connecting
chemistry and innovation can generate innovative ways to solve global challenges at a local level. All of our advanced technologies offer
cost-effective and exceptional control of microorganisms to protect the integrity of topside assets, near well area and in the reservoir,
with low environmental impact and excellent safety profiles.

Over the years, we have successfully introduced new technologies and methodologies that have shaped the use of biocides in the
industry1. We are committed to science and dedicated to educating the market. Dow Microbial Control brings its technology to oil and
gas operators through a network of highly trained service companies.

Microbial Influenced
Souring Biofilm Control Sustainable Control
Corrosion (MIC)
Working with our customers Offering more effective products Helping to prevent microbially Developing solutions that provide
to develop better solutions and to help prevent or remove biofilm influenced corrosion to protect the sustainable microbial control and
treatment programs to control and driven by world-class laboratory integrity and service life of assets. meet regulatory needs.
protect against reservoir souring. test methodology simulating field
operating conditions.

Customer Application Centers

With an industry-leading breadth of knowledge and more than 60 years of experience in microbial control, our Customer Application
Centers offer advanced microbial control solutions both for today and the future. Our ongoing commitment to innovating new products,
actives and capabilities is supported by state-of-the-art, fully equipped microbiology, chemistry and analytical laboratories featuring a
world-class team of scientists.

Dow Microbial Control offers a uniquely focused service to our customers. This includes understanding customers’ specific application
performance requirements, environmental needs and today’s stringent regulatory requirements to ensure we develop effective,
optimized, sustainable solutions.

1
Recent publications include:
Co-authored by Dow Microbial Control and Multi-Chem Production Chemicals: Michael V. Enzien, Bei Yin, Donald Love, Michael Harless, Edward Corrin “Improved Microbial Control
Programs for Hydraulic Fracturing Fluids used during Unconventional Shale-Gas Exploration and Production,” paper no. 141409, Society of Petroleum Engineers 2011

Co-authored by Dow Microbial Control and Multi-Chem Production Chemicals: Edward Corrin, Terry M. Williams “A Case Study Evaluating a Co-Injection Biocide Treatment of
Hydraulic Fracturing Fluids Utilized in Oil and Gas Production,” paper no. 5998, Corrosion 2015

Co-authored by Dow Microbial Control, Baker Hughes Inc. and Encana Oil & Gas (USA) Inc.: Jon Raymond, Earl Parnell, Jennifer Fichter “Determining Effective Antimicrobial
Treatments for Long-Term Protection of Hydrocarbon Reservoirs,” paper no. 3879, Corrosion 2014

Co-authored by Dow Microbial Control and FTS International: Stephen N’Guessan, Jon Raymond, Reinaldo Navarrete “Environmentally-Conscious Biocides for Long-Term Protection
of the Fracture,” paper no. 173748, Society of Petroleum Engineers 2015

Co-authored by Dow Microbial Control and Delft TU: Michael V Enzien, Debora Takahashi , Bei Yin, Simona Bottero “Increase Oil and Gas Production Through Improved Microbial
Control Programs,” paper no. 2740_10, Brazilian Petroleum, Gas and Biofuels Institute

3
Protect Oil and Gas Operations with an Optimized Microbial Control Program
Registration* Efficacy†

CAS Number
Water Treatment Physical US Canada Speed Duration of
% Active Ingredient for Active
Microbiocide Form EPA PMRA of Kill Protection
Ingredient(s)

AQUCAR™ DB 100 97.6% 2,2-dibromo-3-nitrilopropionamide (DBNPA) Solid ✓ ✓

PREPARE

AQUCAR™ DB 20 20% 2,2-dibromo-3-nitrilopropionamide (DBNPA) Liquid 10222-01-2 ✓ ✓  

AQUCAR™ DB 5 5% 2,2-dibromo-3-nitrilopropionamide (DBNPA) Liquid ✓

42.5% Glutaraldehyde,
AQUCAR™ 742 ✓ ✓
7.5% alkyl dimethyl benzyl ammonium chloride (ADBAC) 111-30-8,
Liquid  
14% Glutaraldehyde, 68424-25-1
AQUCAR 714
™ ✓ ✓
2.5% alkyl dimethyl benzyl ammonium chloride (ADBAC)

AQUCAR™ 720 20% Glutaraldehyde (includes a non ionic surfactant) Liquid 111-30-8 ✓  

AQUCAR™ GA 50 50% Glutaraldehyde ✓ ✓

AQUCAR™ GA 30 LT 30% Glutaraldehyde (freeze-protected formulation) ✓ ✓

DECONTAMINATE

AQUCAR™ GA 25 25% Glutaraldehyde Liquid 111-30-8 ✓ ✓  

AQUCAR™ GA 15 15% Glutaraldehyde ✓ ✓

AQUCAR™ GA 4P0 4% Glutaraldehyde ✓

AQUCAR™ PS 75 75% tetrakis(hydroxymethyl)phosphonium sulfate (THPS) ✓

Liquid 55566-30-8  
AQUCAR™ PS 20 20% tetrakis(hydroxymethyl)phosphonium sulfate (THPS) ✓

AQUCAR™ BP 100 99% 2-bromo-2-nitropropane-1,3-diol (Bronopol) Solid ✓

AQUCAR™ BP 30 30% 2-bromo-2-nitropropane-1,3-diol (Bronopol) Liquid 52-51-7 ✓  

AQUCAR™ BP 10 10% 2-bromo-2-nitropropane-1,3-diol (Bronopol) Liquid ✓

AQUCAR™ A 78 78% dimethyloxazolidine (DMO) Liquid 52000-87-4 ✓  

PROTECT

64% 1-(3-chloroallyl)-3,5,7-triaza-
AQUCAR™ TA 64 Solid 4080-31-3 ✓  
1-azoniaadamantane chloride (CTAC)

AQUCAR™ TN 25 25% tris(hydroxymethyl)nitromethan (THNM) Liquid 16-11-4 ✓ ✓  

* Please check the registration details as they apply to your location in the US or Canada to verify the product is approved for your specific use.

4
†
Compatibility† Environmental Profile†
Efficacy on Friction Non-
Proppant Sour Performance Low
Oilfield Reducers/ Low Corrosive pH Range Bio- No AOX Aboitic
and Systems at High Temp. Aquatic
Organisms Anionic Foaming at Use- of Use degradation Formation Degradation
Formation (Sulfide) (>50°C) Toxicity
(SRBs, APBs) Additives level

       Up to 8.5    

       Up to 9.5    

       Up to 9.5    

       Up to 9.5    

       Up to 9.5    

       Up to 8.5    

       Up to 11    

       Up to 11    

       7 - 11    

† Characterization based on laboratory studies of active ingredients.

Generally, higher numbers of  represent more favorable characteristics. For speed

of kill and duration of protection, please find more detailed information below:

Speed of Kill
Minutes to about an hour 
Hours to about a day 
Multiple days 

Duration of Protection
Lasts weeks to months 
Lasts a few weeks 
Lasts for a few hours to few days 

5
Understanding the Needs of the Different Phases of Oil and Gas Exploration
and Production
Dow provides the world’s broadest range of microbial control actives for oil and gas applications as well as state-of-the-art diagnostic
techniques and expertise required for advanced sustainable microbial control. Dow collaborates with multiple stakeholders along the
hydrocarbon value chain to design and implement novel applications that can provide specific, yet extended, microbial control, all while
minimizing the impact on the environment.

Our advanced microbial control solutions are used in a broad range of oil and gas applications including: near wellbore treatment,
protection of the reservoir, hydraulic fracturing, water and polymer flooding, topside remediation of produced and recycled waters as
well as MIC and asset integrity.

Microbial control programs are necessary to optimize conventional as well as unconventional oil and gas production. To maximize
microbial control efficacy, the right technologies need to be applied in the different phases of the operation: preparing the water and
treating topside, decontaminating the well, as well as protecting the reservoir.

Treat topside, prepare the water Decontaminate the well Protect the reservoir
Produced water and oilfield waters can contain Native downhole populations and Throughout continuous water injection or after
bacteria that need to be treated. Treating microorganisms introduced during water the hydraulic fracturing process is complete, it is
the water with biocides will provide an initial injection leave wells infested with bacteria that critical to control microbial growth in the reservoir
reduction of bacteria, thereby helping to survive and thrive in subsurface conditions. environment. Biocides that remain effective
prevent corrosion of the assets, reduce souring, Inclusion of an effective biocide in injection under elevated temperature, pressure and
and enhancing the performance of biocides water and hydraulic fracturing fluid will provide salinity conditions for longer durations of time are
added in later stages of the process. initial control downhole. necessary to help prevent souring, corrosion of
assets and formation of in situ biofilm over time.

TREAT PREPARE
topside /
the water
ClO2/Oxidizers
DECONTAMINATE
the injection well
PROTECT
the reservoir
Quats/TTPC
DBNPA*
Glutaraldehyde*
Glutaraldehyde* + Quats
THPS*
Bronopol*
Dazomet
DMO*
CTAC*
THNM*
Nitrate (only for water flooding)

*Dow Technology
Duration of Effectiveness

Minutes Hours Days Weeks Months

Temperature
Ambient Downhole

Formation Compatibility
Poor Excellent
DBNPA: 2,2-dibromo-3-nitrilopropionamide
THPS: tetrakis(hydroxymethyl)phosphonium sulfate
DMO: dimethyloxazolidine
CTAC: 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride
THNM: Tris(hydroxymethyl)nitromethane

6
Compatibility
Hydrocarbon production involves many additives that can interfere with the activity of some biocides. It is critical to understand
potential incompatibilities and other properties of biocides that could negatively affect operations.

Friction Reducers Active levels required for 5-log kill of aerobic organisms
Many biocides have negative interactions in frac water with 500 ppm friction reducer
with friction-reducing polymers used for
hydraulic fracturing. Those interactions 500
can negatively influence the function of 450
both the biocide and the friction reducer. 400
350
Figure 1: Glutaraldehyde and Glut-Quat blends
300
ppm a.i.

retain antimicrobial performance in the presence of

friction reducers. 250
200
150
100 ■ Friction Reducer 1
■ Friction Reducer 2
50
0
Glut* Glut-Quat* DDAC TTPC ADBAC THPS*
*Dow Technology

Foaming Foam height measured at typical biocide usage levels

A biocide that foams can cause problems
15 Exceeded 15 cm
during application. Minimum foaming is a maximum measurable height
desirable parameter for a biocide.
12
Foam Height (cm)

Figure 2: Optimized Glut-Quat ratios minimize

foaming problems during application. When the 9
ratio is weighted more towards the glut component
as compared to the quat, the blends are less likely to
have foaming issues.
6

3
■ Dynamic
■ Stable
0
TTPC ADBAC 25.8% Glut* 42.5% Glut* Glutaraldehyde* THPS* DBNPA* Bronopol* Dazomet
(50 ppm a.i.) (20 ppm a.i.) 12.5% Quat* 7.5% Quat* (50 ppm a.i.) (70 ppm a.i.) (50 ppm a.i.) (200 ppm a.i.) (600 ppm a.i.)
(38 ppm a.i.) (43 ppm a.i.)

*Dow Technology

Proppant/Formation Compatibility
Surface-acting biocides (like quaternary amines and TTPC) can be adsorbed on high-surface area solids, like some proppants and silt
layers in the formation, thus reducing the availability of the biocide to kill microorganisms.

Use-Level Corrosion
Some biocides in their concentrated forms are corrosive to metals, including stainless steel. However, when diluted to their use
concentration (1000 ppm or less), most are essentially non-corrosive. The exceptions are oxidizing biocides, including chlorine dioxide,
which are strongly corrosive even at diluted use levels (1 ppm or less).

7
Efficacy
The biocide concentration required to reduce a microbial population by a specific logarithmic level (log kill) is commonly utilized to
assess antimicrobial performance in a given system (i.e. injection water, drilling mud, produced water, etc.). The concentration of biocide
required for effective microbial kill can vary across different applications and is dependent upon multiple factors including organism
type, microbial load, fluid/additive compatibility and system pH/temperature. Furthermore, the concentration and type of biocide
required for efficient microbial kill will depend on the particular performance needs such as speed of kill or length of protection.

Efficacy against Sulfate Rapid reduction of SRBs to treat topside/prepare the water and
Reducing Bacteria decontaminate the well
A laboratory study was performed in a 7

blended injection water matrix (seawater/

6
produced water), obtained from an active
oil and gas operation, to determine the 5
time-dependent performance of commonly
Log10 viable SRB

utilized oilfield biocide chemistries. 4

Samples of injection water were inoculated

3
with field-isolated Sulfate Reducing 0 mins
Bacteria (SRB) and then treated with 2 45 mins
different biocides, at two concentration 4 hours
levels. Viable organisms were measured 1

immediately following, 45 minutes and 4

0
hours after treatment. 100 250 100 250 100 250 10 25
ppm ppm ppm ppm ppm ppm ppm ppm
Figure 3: All biocides tested provide effective kill
against SRBs after four hours. Untreated Glutaraldehyde* Glut/ADBAC quat* THPS* DBNPA*

*Dow Technology

Efficacy against Acid

Producing Bacteria Rapid reduction of APBs to treat topside/prepare the water and
A lab study was performed with Acid decontaminate the well
Producing Bacteria (APBs) in a synthetic
9
injection water matrix. The samples were
inoculated with an isolated APB strain 8
and then treated with different biocides. 7
Viable organism levels were measured
6
immediately following, 45 minutes and 4
Log10 viable APB

hours after treatment. 5

4
Figure 4: All biocides tested provide effective kill 0 mins
against APBs after four hours. 3
45 mins
2
4 hours
1

0
100 250 100 250 100 250 10 25
ppm ppm ppm ppm ppm ppm ppm ppm

Untreated Glutaraldehyde* Glut/ADBAC quat* THPS* DBNPA*

*Dow Technology

8
Efficacy in Heat-Aged Systems Duration of protection in heat-aged systems
Providing protection not only against the organisms in
the injection water, but also against organisms native 100 ppm
to the formation, helps prevent souring. Extended
downhole protection is provided by biocides that are 200 ppm
able to retain efficacy in an environment with elevated
temperature and salinity. 300 ppm

High-temperature (75°C) antimicrobial efficacy studies 100 ppm

were performed for 64 days in three distinct fracturing
200 ppm
fluid systems utilizing CTAC, DMO and THNM
preservative chemistries ranging from 100 to 300 ppm
300 ppm
active ingredient. The number of days of protection
provided by the strongest performing preservative, 100 ppm
in each individual fracturing fluid system, following
repeated APB/SRB inoculations is represented in 200 ppm
Figure 5. Although all three preservative chemistries
work well in a variety of fracturing fluids, finding the 300 ppm
optimal preservative, dosage, and co-biocide requires
customized solutions, which Dow has the technical 0 10 20 30 40 50 60 70
expertise and capabilities to help develop.

Results can vary significantly between water samples,

dependent on additives used and water composition. *Dow Technology
Laboratory studies of biocide efficacy are highly
recommended for new operations in order to determine
the best biocide treatment program.

Figure 5: CTAC, DMO, and THNM provided long-term microbial control

of both SRB and APB in three fracturing fluid samples.

9
Sustainability
Sustainability, in the context of microbial control, is defined as a technology which is able to meet three needs:
1. Firstly, the microbial control solution must do its job effectively, meaning controlling and preventing the growth of microorganisms.
2. Secondly, the biocide treatments disappear after doing their job. They should be designed to be biodegradable, non-persistent,
and non-accumulative in the environment.
3. Finally, the biocides should do no harm to society, biodiversity, the environment, people, or processes.

Dow is dedicated to developing sustainable microbial control solutions and offers a leading portfolio of such products to the
industry today.

Hazard-Based Rating vs. Risk-Based Models Daphnia magna LC50 Rainbow Trout LC50
Individual data points for toxicity based solely upon the Active
(ppm) (ppm)
hazards of the concentrated product can give an incomplete
DBNPA 2.5 3.6
picture of the risk profile of any given biocide. Risk-
Glutaraldehyde 5 13
based models that take into account all factors (such as
toxicity, usage levels, and wastewater treatment processes, THPS 15-19 94-119
biodegradation, etc.) are more accurate and used by Bronopol 1.4 26
regulating authorities. DMO 48-51 93
CTAC 26 64
THNM 50-80 410
LC50: Concentration of a single dose lethal to 50% of laboratory test group. Though each
biocide will have a species that is most sensitive, Daphnia magna and Rainbow Trout are
common environment model organisms.
Degradation
Biodegradation and chemical degradation are important
aspects when considering the overall sustainability OECD 301 OECD 302
Active
of applying a biocide for oilfield applications. These “Readily Biodegradable” “Inherently Biodegradable”

degradation processes are taken into account by risk-based DBNPA •

models such as the OSPAR Commissions CHARM (Chemical Glutaraldehyde • •
Hazard and Risk Management) model for assessing
THPS •
chemicals used in offshore oil and gas operations, and other
Bronopol •
similar tools which assess margin of exposure associated
with specific biocide applications. DMO • •
CTAC • •
THNM •
OECD guidelines are intentionally agreed testing methods used by government, industry
and independent laboratories to identify and characterize potential hazards of chemicals.
OECD guidelines 301 and 302 assess the ability of microorganisms to degrade small doses
of biocide.

Absorbable Organic Halide (AOX) Formation

Most organic biocides do not contribute to AOX levels in water. Certain biocides, most specifically halogenated oxidizers
(chlorine, bromine, bleach, chlorine dioxide and “stabilized” versions thereof ), however, can react with residual hydrocarbons
found in oilfield waters to produce halogenated hydrocarbons. These products can often be difficult to biodegrade and many are
of concern for water discharge.

10
Genuine Glutaraldehyde
In the more than six decades since glutaraldehyde was introduced to the marketplace, it
has become known as a versatile molecule. Today, non-genuine products, mixed with less-
effective aldehydes such as formaldehyde or glyoxal, but labeled deceptively as glutaraldehyde,
are available in the marketplace all over the world. Risks are potentially high for workers
and the environment when mislabeled chemicals, especially ones containing carcinogens,
are unknowingly handled. GENUINE GLUTARALDEHYDE is not a carcinogen, mutagen, nor a
reproductive toxicant. It does not bio accumulate and is readily biodegradable. It’s critical for
companies to ensure they are using GENUINE GLUTARALDEHYDE to comply with approved
safe handling guidelines. Non-genuine products may have significantly different toxicological
properties that can harm workers and the environment and have been proven to fall short in
efficacy and sustainability.

The Dow Chemical Company has developed and validated new analytical methods to help customers distinguish GENUINE
GLUTARALDEHYDE from non-genuine products that are labeled incorrectly as “glutaraldehyde”. These methods include an
innovative, field-deployable, and easy to use test-kit that provides a rapid detection method.

For more information, visit www.glutaraldehyde.com.

Product Stewardship
Dow has a fundamental concern for all who make, distribute, and use its products, and for the environment in which we live. This
concern is the basis for our product stewardship philosophy by which we assess the safety, health, and environmental information
on our products and then take appropriate steps to protect employee and public health and the environment. The success of our
product stewardship program rests with each and every individual involved with Dow—products from the initial concept and
research, to manufacture, use, sale, disposal, and recycle of each product.

Dow strongly encourages its customers to review both their manufacturing processes and their applications of Dow products
from the standpoint of human health and environmental quality to ensure that Dow products are not used in ways for which
they are not intended or tested. When considering the use of any Dow product in a particular application, review the latest Safety
Data Sheet (SDS) and country-specific product label to ensure the intended use is within the scope of approved uses and can be
accomplished safely. Dow personnel are available to answer your questions and to provide reasonable technical support. Dow
product literature, including SDS’s, should be consulted prior to use of Dow products. Current SDS’s are available from Dow.

Use biocides safely. Always read the label and product information before use.

Dow Beyond Microbial Control

In addition to the broad portfolio of microbial control technologies, Dow is uniquely positioned to address local and regional
hydrocarbon industry challenges worldwide.

Familiar with individual company and local needs, Dow’s oil and gas experts draw upon global R&D resources and decades of
experience for customizing solutions and services tailored to the evolving needs of our customers. And Dow’s experts routinely
leverage a first-class toolbox of technologies for addressing customer challenges:
• Dow’s branded systems and solutions for cost-effective, sustainable operations relating to exploration, production, enhanced oil
recovery, transportation, refining, gas processing and distribution are industry standards.
• With a broad portfolio of ion exchange resins, reverse osmosis membranes, ultrafiltration membranes and electrode ionization
products – Dow spearheads the development of sustainable technologies that integrate water and energy requirements to help
oil and gas customers optimize all phases of their water usage.

11
For more information contact us: From North America From Asia Pacific
www.dowmicrobialcontrol.com Toll-free 800-447-4369 Toll call + 60-3-7965-3392
Toll call 989-832-1560 Toll fax + 60-3-7958-5598
Fax 989-832-1465
From Latin America
From Europe, India, Africa and the Middle East Toll call + 55-11-5188-9555
Toll-free 800-3-694-6367 Fax + 55-11-5188-9400
Toll call + 32-3-450-2240
Fax + 32-3-450-2815 Global + 1-989-832-1560
Fax + 1-989-832-1465

Notice: No freedom from infringement of any patent owned by Dow or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer
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