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GENUINE GLUTARALDEHYDE Efficacy. Safety. Purity.

About Dow Microbial Control

The leading provider of biocide and antimicrobial technologies that helps control and prevent growth of nuisance and dangerous microorganisms

Driven to take action

• We predict microbial problems

• We diagnose microbial problems

• We solve microbial problems

Our Advanced Sustainable Microbial Control technology does its job, goes away and does no harm to products, people or the environment

A business unit of The Dow Chemical Company

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Innovative Science and Technology

One of the Broadest Portfolio of Active Ingredients Offering well-known and respected products:

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Dow Microbial Control is the leading registrant in active ingredients, including several chemistries unique to Dow

Global Resources – Personalized, Local Approach 12 Customer Application Centers: Laboratory Facilities

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12 Customer Application Centers: Laboratory Facilities

DMC Customer Application Center

DMC Center of Excellence

Buffalo Grove Illinois, USA

DMC Center of Excellence

Querétaro Mexico

Spring House Pennsylvania, USA

DMC Center of Excellence

Horgen Switzerland

DMC Center of Excellence

Warsaw Poland

Dubai United Arab Emirates

Mumbai India

Singapore

Shangai China

Soma Japan

Melbourne Australia

São Paulo Brazil

Customer Application Center

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Advanced microbiological and analytical testing facility for optimization of biocides in:

Oil and gas application

Industrial water treatment

Paint and coatings

Industrial water-based products

The Importance of a Microbial Control Program

Microorganisms are found everywhere in our environment.

Left uncontrolled, microbes can cause: • Diseases in animals and humans • Spoilage in products • Disruption in industrial process

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Virus Bacteria

Fungus Algae

FPO FPO

FPO FPO

Why Are Biocides Used in Oil and Gas Production?

• Reduce corrosion

• Combat souring

• Promote optimum production rates

• Protect functional fluids from spoilage

Use of Glutaraldehyde in Oil and Gas Applications

Glutaraldehyde is widely used to control microbial growth in oil and gas systems: • Water flood injection water • Drilling, completion, workover and fracturing fluids • Produced waters • Pipelines

Excellent choice for use in preserving drilling muds and other oil field fluids that are typically alkaline in pH.

Dosage: 50-2500 ppm Active, ~4 hrs contact time, daily/weekly basis, slug dose

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Use of Glutaraldehyde in Oil and Gas Applications

• Proven successful for more than 40 years

• Highly effective against aerobes, SRBs, APBs

• Synergistic with quaternary amines

• Incompatible with amines

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Use of Glutaraldehyde in Oil and Gas Applications

Glutaraldehyde is highly effective against a broad range of sulfate reducing bacteria (SRBs) and acid producing bacteria (APBs).

The table below shows the efficacy of glutaraldehyde (50 ppm a.i.) against oil- and gas-related microorganisms.

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Microorganisms

Time required for:

99% Kill Complete Kill

Thiobacillus novellus < 1 hr 3 hrs

Leptothrix discophora < 1 hr 1 hr

Clostridium sporogenes < 1 hr 3 hrs

Nitrobacter agilis < 1 hr 1 hr

Desulfovibrio desulfuricans < 3 hrs 7 hrs

Glutaraldehyde Mechanisms

• Formation of highly reactive intermediate with primary amines

• Crosslinking of cellular components

The Many Benefits of GENUINE GLUTARALDEHYDE

Does its job Test results confirm that under many application conditions, GENUINE GLUTARALDEHYDE performs more effectively than products that use formaldehyde, glyoxal or other materials.

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The Many Benefits of GENUINE GLUTARALDEHYDE

Goes away GENUINE GLUTARALDEHYDE is more sustainable than non-genuine products. It is readily biodegradable, formaldehyde free, non-carcinogenic, non-persistent and non-bioaccumulative.

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The Many Benefits of GENUINE GLUTARALDEHYDE

Does no harm to products, people or the environment GENUINE GLUTARALDEHYDE has a long safety record and its proper use is well documented. Non-genuine glutaraldehyde blends that contain blended materials may place products, workers, processes, equipment and the environment in harm’s way.

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Not All Products Labeled Glutaraldehyde Are GENUINE GLUTARALDEHYDE • Some unscrupulous dealers are selling blends of

formaldehyde, glyoxal and other impurities.

• This poses serious performance, health, safety, financial, legal and ethical issues.

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Non-Genuine Glutaraldehyde

Early 2011, Dow Microbial Control launched a campaign to warn consumers against non-genuine glutaraldehyde products sold mainly by Chinese traders.

In 2012, the Customer Application detected excessive amounts of formaldehyde in non-genuine glutaraldehyde products sold in the global market.

Of the non-genuine products tested, the laboratory detected the presence of 21-22% glutaraldehyde, 17.3-17.5% formaldehyde and 0.1-1.3% glyoxal.

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21-22% Glutaral-dehyde

17.3-17.5%

Formaldehyde

0.1-1.3% Glyoxal

Non-Genuine Glutaraldehyde Product

50% Glutaraldehyde

0%

Dow’s Genuine 50% Glutaraldehyde Product

Non-Genuine Glutaraldehyde Occupational health hazard

Formaldehyde is known to be a human carcinogen (cancer-causing agent). Effects of excessive and prolonged exposure to formaldehyde is associated with irritation of the respiratory tract, skin and eyes, and possibly naso/pharyngeal cancers.

Without a proper understanding of the product, workers can be exposed unknowingly to the formaldehyde present in the non-genuine product. This presents serious health risks to the workers.

By using non-genuine glutaraldehyde, businesses are putting workers, processes, products and equipment at risk of possible health/mechanical damage by these high concentrations of formaldehyde in the non-genuine formulation.

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Non-Genuine Glutaraldehyde Workplace Safety and Health

Employers are legally obligated to ensure safety of their workers, according to the Workplace Safety and Health Act in their respective country.

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“It shall be the duty of every employer to take, so far as is reasonably practicable, such measures as are necessary to ensure the safety and health of his employees at work.” “Ensuring that those persons are not exposed to hazards arising out of the arrangement, disposal, manipulation, organisation, processing, storage, transport, working or use of things.” “Ensuring that those persons at work have adequate instruction, information, training and supervision as is necessary for them to perform their work.”

Non-Genuine Glutaraldehyde Overpaying for non-genuine product

Purchase of “cheap” non-genuine products does not equate to cost savings. Unknowingly, customers are overpaying for non-genuine material.

Unscrupulous formulators are making a quick and substantial profit at the expense of customers.

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Non-Genuine Glutaraldehyde Cost comparison

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AQUCAR™ IG 50 Water Treatment Biocide

China Non-Genuine

% Glutaraldehyde 50 22

% Formaldehyde - 17.5

% Glyoxal - 1.3

Product price/kg 3.8 USD/Kg DDP 2.25 USD/Kg DDP 100% Glut Price/kg 7.6 USD/Kg DDP 10.22 USD/Kg DDP

Overpaying - 2.62 USD/Kg

Therefore, at 100 MT 100% glutaraldehyde per year, the customer overpays by USD $262,000

Non-Genuine Glutaraldehyde Reduced efficacy against microorganisms

Formaldehyde is not as efficacious as glutaraldehyde in killing microorganisms commonly found in industrial environments.

Glutaraldehyde rapidly kills microorganisms, requiring only a short contact time to react.

Figure on the right shows that glutaraldehyde can inhibit bacteria even when used at a lower ppm concentration.

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Non-Genuine Glutaraldehyde Reduced efficacy against microorganisms

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0

50

100

150

200

250

Genuine Glut Product A Product D FA

ppm

pro

duct

Dose needed to achieve 2-log kill of SRB in 2 hours in the presence of 100 ppm SBS

Product A: 28.7% glutaraldehyde + 14.3% formaldehyde Product D: 20.8% glutaraldehyde + 18.0% formaldehyde

The True Cost of Using Non-GenuineGlutaraldehyde

Environmental, health and safety Non-genuine glutaraldehye is a health hazard to workers who unknowingly handle high levels of formaldehyde, which is a known carcinogen. Human ethics and legal complications Farm managers/formulators fail to protect workers from danger. Loss of money From cost computation, customers are overpaying for non-genuine materials. Compromised O&G application protection Reduced efficacy to protect equipment from prevailing spoilage microorganisms.

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Ensure You Get Only GENUINE GLUTARALDEHYDE

Buy from a reputable source The Dow Chemical Company is one of only two known companies that has the process technology and capabilities to manufacture glutaraldehyde on a commercial scale.

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Ensure You Get Only GENUINE GLUTARALDEHYDE

Look for the special “FORMALDEHYDE FREE” tamper-proof seal on product

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Ensure You Get Only GENUINE GLUTARALDEHYDE

When in doubt, test the product Dow Microbial Control has developed a simple test to detect non-genuine glutaraldehyde.

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Seeing Is Believing

Using a colorimetric method, Dow’s Customer Application Center is able to distinguish non-genuine from genuine glutaraldehyde product within 1 hour.

Can you see the difference?

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1 ppm Formaldehyde

5 ppm Formaldehyde

10 ppm Formaldehyde

Non-Genuine Glutaraldehyde 10,000X dilution

Distilled Water GENUINE GLUTARALDEHYDE

10,000X dilution

Detection using the NASH Reagent

Advanced Analytical Testing for Quantitation of Adulterants High Performance Liquid Chromatography (HPLC) is a sophisticated technique used to separate and analyze the individual components in a product.

On the right, we compare a mini HPLC profile of a non-genuine glutaraldehyde product (top) versus the profile of a sample of genuine glutaraldehyde (below).

Between the retention time of 15 –16 minutes (shown on the right), we would expect a sharp peak at 15.26 minutes if formaldehyde is present.

What do you see?

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NO formaldehyde detected

Dow Chemical’s Genuine Glutaraldehyde

Significant level of formaldehyde detected via HPLC analysis

Counterfeit Product

There’s No Substitute for GENUINE GLUTARALDEHYDE

Get all the facts at www.glutaraldehyde.com

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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 is responsible for determining whether products and the information in this document are appropriate for Customer's use and for ensuring that Customer's workplace and disposal practices are in compliance with applicable laws and other government enactments. The product shown in this literature may not be available for sale and/or available in all geographies where Dow is represented. The claims made may not have been approved for use in all countries. Dow assumes no obligation or liability for the information in this document. References to “Dow” or the “Company” mean the Dow legal entity selling the products to Customer unless otherwise expressly noted. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED. ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow

Thank You

Appendix

Common Non-Genuine Glutaraldehyde Combinations De-mystifying the Missing Aldehydes Value

Common Non-Genuine Glutaraldehyde Combinations

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Glutaraldehyde Formaldehyde Glyoxal Misleading Comments

A 22% 17 – 18 % <1% “Glutaraldehyde with impurity”

B 35 – 43% 2 – 4% – “More expensive grade of

glutaraldehyde that contains less impurity”

C 35.5% – 7% Formaldehyde-free Glutaraldehyde.

Note: • If formaldehyde or glyoxal are detected in glutaraldehyde product, it is plausible that the former have been deliberately included.

GENUINE GLUTARALDEHYDE does not contain any of these adulterant chemicals. • Never assume “formaldehyde-free” glutaraldehyde to be GENUINE GLUTARALDEHYDE. Glyoxal may be used as the sole adulterant

and escape detection. Submit your samples to your local Dow Contact for verification by HPLC.

De-mystifying the Missing Aldehydes Value

For every 1% formaldehyde detected by HPLC, the same amount of formaldehyde gives a value of 1.667% when titration is performed. This gives an excess of 0.667% value to the reading.

Glyoxal 1% (HPLC) gives 1.726% when titration is performed. This gives an excess of 0.726% value to the reading.

These excessive values are exploited by counterfeiters to cheat customers by giving false values to the supposed “glutaraldehyde” product.

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De-mystifying the Missing Aldehydes Value

Case Study: (date 17 Sept, 2012)

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Analysis by High Performance Liquid Chromatography Analysis by

Titration

Serial No. Sample Description % GA % FA % Glyoxal % Total aldehyde % Total aldehyde

1 China Glut sample (P-451, 12042101)

21.1 17.3 0.1 38.5 51.5

2 AQUCARTM IG 50 (Batch:

ZI2255S4D1) 50.0 ND ND 50.0 50.5

Similar to results obtained from titration

From the table above: Although only 21.1% glutaraldehyde was detected by HPLC in the non-genuine sample, a total of 51.5% aldehyde was detected by titration.

How did this happen? This artificially inflated value can be explained by calculation:

21.1% (GA) + 17.3 x 1.667 % (FA) + 0.1 x 1.726 % (Glyoxal) = Approx. 50.1%

De-mystifying the Missing Aldehydes Value

Learning point: The addition of formaldehyde and glyoxal artificially inflate the total aldehydes value, giving a false perception of quantity.

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