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Product Information

AQUCAR™ GA 50 Water Treatment Microbiocide


For Use in Industrial Water Treatment, Papermaking and Gas and Oilfield Systems

General AQUCAR™ GA 50 Water Treatment Microbiocide is a high performing microbicide based on


glutaraldehyde (CAS Reg. No. 111-30-8). It is effective against the bacteria and fungi
present in papermaking systems and useful in preventing slime formation in all areas of the
papermaking process. It is especially effective in controlling bacterial growth in aqueous
pigments and filler slurries.

Structure O O

H H

Physical The following are typical properties of AQUCAR™ GA 50 Water Treatment Microbiocide;
Properties they are not to be considered product specifications.
Appearance: ....................................................................................... Transparent colorless
Active, % glutaraldehyde (w/w): ....................................................................................... 50
pH @ 25°C: ........................................................................................................... 3.1 to 4.5
Solubility in water, 20°C: ......................................................................................... Miscible
Boiling point: ................................................................................................. 100.5°C/213°F
Freezing point: ..................................................................................................... -21°C/-6°F
Specific gravity, @ 20/20°C: ....................................................................................... 1.129
Vapor pressure @ 20°C: .......................... 0.2 mm Hg based on glutaraldehyde (0.27 hPa)

Applications/ Water Flood Injection Water


Directions for Use Glutaraldehyde exhibits excellent stability in oilfield injection waters, which ensures that its
antimicrobial activity will not be diminished in long pipelines. Hard waters or brines do not
adversely affect its biocidal efficacy, and glutaraldehyde is non-ionic so it won’t interfere
with the action of demulsifiers, corrosion inhibitors, or surfactants. AQUCAR™ GA water
treatment microbiocides are typically slug dosed into the injection water on a daily or weekly
basis at 50 to 2500 ppm active for up to 4 hours, although the exact treatment regimen will
depend on the condition of the system, the amount of water being treated, etc.

Drilling, Completion, Workover, and Fracturing Fluids


Glutaraldehyde functions as a biocide over a broad pH range and its efficacy is much faster
at neutral to alkaline pH’s than at acidic pH’s. Therefore, the AQUCAR™ GA water treatment
microbiocide products are excellent choices for use in preserving drilling muds and other
oilfield fluids that are typically alkaline in pH. The combination of rapid alkaline efficacy at the
typical use rates of 25 to 500 ppm as active, and proven stability and effectiveness in high
salinity matrices ensures microbial protection of these important fluids.

Produced Waters
Most oilfield systems contain sulfate reducing bacteria (SRB’s) and acid producing bacteria
(APB’s). The presence of SRB’s and APB’s presents a serious challenge for effective
control of microbial contamination in a production system. For a biocide to be effective
against these problematic organisms, it must be stable in the presence of sulfides or organic
acids that are produced by these organisms. Glutaraldehyde, unlike some other biocides
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(formaldehyde, acrolein, and isthiazoione) does not react with, and is not deactivated by,
H2S or other organic acids. This ensures that all of the glutaraldehyde added is available
to act as a biocide. Like its use in waterflood inection systems, glutaraldehyde is typically
added in slug doses on a daily to weekly basis at concentration of 50 to 2500 ppm as active.

Oil and Gas Transmission lines


Biofilms are a major problems in oil and gas production systems and pipelines are often
afflicted with biofilm-related problems. Microbiologically Influenced Corrosion (MIC) is often
associated with the presence of a biofilm. The control of biofilms is therefore crucial to
ensuring that corrosion events, due to microorganisms, are minimized. Glutaraldehyde has
been shown to penetrate a biofilm and kill the microorganisms that are contained within it.
The penetrating ability of glutaraldehyde, along with its long-term stability in oilfield waters,
makes it an effective product to control established biofilms in pipelines and prevents the
formation of new ones.

Gas Storage Wells and Hydrocarbon Storage Facilities


The water bottoms in hydrocarbon storage tanks and gas storage wells can often be
contaminated with SRB’s and serve as hosts to biofilms. This, in turn, can lead to the
formation of H2S in the gas storage facility and the corrosion of hydrocarbon storage tanks.
Glutaraldehyde preferentially partitions into the water phase in a mixed hydrocarbon/water
system and so would attack any microorganisms that are present in these water bottoms.

Production Wells
The injection of scale and corrosion inhibitors into production wells can introduce
microorganisms into the production equipment and the formation. The addition of
glutaraldehyde during these injections (squeeze treatments) can help to control these
microorganisms and may help reduce the occurrence of MIC in production equipment.

Food Additive Regulations


The product meets the requirements of the listed below. Uses are subject to good
manufacturing practices and any limitations which are part of the regulations. The
information given here is for use as a general guideline. The regulations should be consulted
for complete details. In some cases a product formulation may meet an FDA clearance and
the use is not on the product label.

21 CFR 172.230(a)(3) Cleared for use as a cross-linking agent

21 CFR 173.320(b)(6) Chemicals for Controlling Microorganisms in Beet-Sugar Mills (max.


250 ppm active)

21 CFR 173.357(a)(2) Fixing agent in the immobilization of glucose isomerase enzyme


preparations for use in manufacture of high fructose corn syrup.

21 CFR 175.105 (c)(5) Adhesives

21 CFR 176.170 (a)(5) Cleared for use as antimicrobial agent in pigment and filler slurries
used in manufacture of paper and paperboard (max. 300 ppm active)

21 CFR 176.180 (b)(1) Components of Paper and Paperboard in Contact with Dry Food
(max. 300 ppm active)

21 CFR 176.300 Slimicides

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Special Features • Very effective in alkaline papermaking processes
and Benefits • Broad spectrum biocide: controls bacteria, yeast and mold
• Functional over a broad pH and temperature range
• Fast-acting
• Non-surface active and non-foaming
• Effective against aerobic and anaerobic microorganisms, including sulfate-reducing
bacteria
• Does not contain or release formaldehyde
• Compatible with commonly used “wet-end” additives
• Compatible with anionic, nonionic and cationic dispersants
• Not affected by the presence of hard water
• Non-corrosive to metals at recommended use levels
• Low in toxicity and easy to handle relative to other slimicides
• Can be diluted or deactivated easily
• Non-halogenated materials
• Contain no heavy metals

AQUCAR™ GA 50 Water Treatment Microbiocide has BfR XXXVI approval with the following
restriction: max. use allowed = 5.0% based on dry fibres weight. The residual level of
glutaraldehyde must not be detectable in the finished product (limit of detection 2 mg/kg).
In addition, the use of the substance must not result in the finished dispersion film having a
preserving effect on foodstuffs.

Product Effect of Papermaking Additives


Performance A wide range of additives are used in the papermaking process to impart specific properties
to the finished product. A majority of these chemicals, including slimicides, are added to the
wet stock and are referred to as “wet-end” additives. While it is important that the slimicide
not interfere with the function of the additives, it is equally important that the additives have
no deleterious effect on the efficacy of the slimicide.

A series of laboratory experiments was conducted to determine if commonly used wet-end


additives would adversely affect the performance of AQUCAR™ GA 50 Water Treatment
Microbiocide. Table 1 shows the effect of alum, calcium carbonate, kaolin clay, rosin, starch,
sulfite and titanium dioxide on the biocidal efficacy of 25 parts per million (ppm) active slimi-
cide. All additives were tested at a concentration of 0.5 percent, with the exception of calcium
carbonate (0.1 percent), and sulfite (0.005 percent). The experiments were conducted at pH
7, using a pure strain of Pseudomonas aeruginosa. The results compare the efficacy of the
active slimicide in the presence of the additives with a sample that contained slimicide alone.
After one hour, all samples showed a greater than 99% reduction in microorganism levels.
After three hours, the reduction was essentially complete, demonstrating the effectiveness of
AQUCAR GA 50 in the presence of these chemicals.

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Table 1 Chemical Additive Microorganism Level, CFU/mL2
Effect of Chemical Sample 1
1 hr. 3 hr.
Additives on the Control 6.7 x 10 6
7.2 x 106
Efficacy of AQUCAR GA 50 WTM alone

5.0 x 10 1
ND
AQUCAR™ GA 50 AQUCAR GA 50 WTM + Alum ND ND
Water Treatment AQUCAR GA 50 WTM + Calcium Carbonate 1.4 x 104 3.6 x 102
Microbiocide AQUCAR GA 50 WTM + Kaolin 3.1 x 103 ND
AQUCAR GA 50 WTM + Rosin ND ND
AQUCAR GA 50 WTM + Starch 1.1 x 10 2
ND
AQUCAR GA 50 WTM + Sulfite ND ND
AQUCAR GA 50 WTM + Titanium Dioxide ND ND
(1) All samples contained 25 ppm active ingredient, except for “Control” which contained no slimicide
(2) ND = None Detectable

Efficacy Many types of microorganisms, such as bacteria, mold and yeast, can be found in a paper
mill. When uncontrolled, the growth of microorganisms can lead to serious process and
quality problems, including offensive odors, corrosion of equipment, and spots and breaks in
the paper. The following experiments demonstrate the effectiveness of AQUCAR™ GA 50
Water Treatment Microbiocide against the many types of microorganisms found in
papermaking systems.

The activity of AQUCAR GA 50 was determined in samples of white water obtained from
two individual paper mills that had been experiencing microbiological problems. The
alkaline samples consisted mainly of Pseudomonas, Bacillus, and Klebsiella species, while
Klebsiella and Rhodotorula predominated in the acidic sample. The contaminated water
samples were diluted (1:4) with deionized water and treated with various concentrations of
the slimicide. The results of these experiments are shown in Table 2. As the results show,
AQUCAR GA 50 greatly reduced the level of microorganisms in both acidic (pH 5.3) and
alkaline (pH 8.1) systems.

Table 2 Microorganism Level, CFU/mL1, After:†


Effect of Active
AQUCAR™ GA 50 pH Ingredient (ppm) 1 hr. 3 hr. 7 hr. 24 hr.
Water Treatment 8.1 0 (control) 2.0 x 105 5.0 x 105 3.0 x 105 3.0 x 105
Microbiocide on 50 1.5 x 104 5.9 x 103 2.5 x 102 ND
Microorganisms in 100 ND ND ND ND
Whitewater 5.3 0 (control) 3.0 x 10 5
3.0 x 10 5
2.0 x 10 5
2.0 x 105
50 1.8 x 10 4
4.0 x 10 3
5.0 x 10 2
1.3 x 101
100 1.0 x 102 7.0 x 101 ND ND
(1) ND = None Detectable

The American Society for Testing Materials (ASTM) has developed a test method to
determine the efficacy of slimicides. This method involves the use of an aqueous buffered
solution contaminated with pulp and rosin and inoculated with a test organism (Enterobacter
aerogenes or Pseudomonas aeruginosa). The contact time of the slimicide is three hours
from the time the pulp culture is inoculated. The results shown in Table 3 demonstrate the
excellent performance of AQUCAR™ GA 50 Water Treatment Microbiocide in this standard
test protocol. Although 80 percent reductions in microorganism populations are considered
effective by the ASTM, AQUCAR GA 50 provided a greater than 90 percent reduction at
25 ppm and essentially complete kill at 50 ppm.

Page 4 of 11 ® ™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Form No. 253-02362-10/16/12 PS
Table 3 AQUCAR™ GA 50 WTM
ASTM Paper (ppm, a.i.) P. aeruginosa, CFU/mL1 % Reduction
Slimicide Test 0 (control) 3.7 x 10 –
6

25 7.5 x 104 97.9


50 3.5 x 10 1
99.9
100 ND 100.0
AQUCAR GA 50 WTM
(ppm, a.i.) E. aerogenes, CFU/mL1 % Reduction
0 (control) 2.0 x 108 –
25 2.8 x 10 6
98.6
50 ND 100.0
100 ND 100.0
(1) ND = None Detectable

Product Efficacy in Pigment Slurries


Performance AQUCAR™ GA 50 Water Treatment Microbiocide can effectively control the level of
microorganisms in pigment slurries. Table 4 shows that between 100-200 ppm of
AQUCAR GA 50 will kill challenges of 1 x 105 CFU/mL of organisms in a kaolin slurry
within 24 hours. This level of efficacy is maintained for at least 28 days and growth of
microorganisms is suppressed for a minimum of 4 months. Somewhat higher initial levels of
AQUCAR GA 50 will control additional challenges of bacteria after 100 days have passed.

Table 4
Efficacy of
AQUCAR™ GA 50
Water Treatment
Microbiocide
in a Kaolin Slurry
Challenge: Escheria coli + Citrobacter freundii (~106 CFU/mL) at Day 0, 28, 112, 119
Efficacy
AQUCAR™ GA 50 WTM (ppm) Initial* 1 Day 29 Days 112 Days 119 Days
100 2.5 x 106 + + - -
200 2.9 x 106 + + + -
500 2.3 x 106 + + + +
1000 8.1 x 105 + + + +
Challenge: Bacillus subtilus, Micrococcus luteus, P. aeruginosa (~106 CFU/mL) at Day 0, 28, 111
Efficacy
AQUCAR GA 50 WTM (ppm) Initial* 1 Day 29 Days 106 Days 112 Days
100 2.8 x 105 + - + -
200 2.5 x 105 + + + -
500 2.4 x 105 + + + -
1000 4.0 x 104 + + + +
+ = Effective as preservative
- = not effective as preservative
* = microorganism count (CFU/mL) determined <2 hours after challenge

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Efficacy against Legionella pneumophila, also known as Legionnaire’s Disease Bacteria (LDB), is the
Legionella causative agent of Legionnaire’s Disease. It was discovered following an outbreak of
pneumophila this often fatal disease at the American Legion Convention in Philadelphia in 1976. The
bacterium, a Gram-negative rod, has since been found in many sources of water, including
both natural waterways and industrial cooling water. Its presence in cooling towers has on
several occasions, been linked to disease outbreak, and its control is of critical importance
to the success of any cooling water biocide program.

The effectiveness of glutaraldehyde in killing Legionella pneumophila was evaluated under


laboratory conditions at pH 6.7 and 8.0. In all cases, the biocides completely killed the
test organisms at both pH 6.7 and 8.0, even at the lowest concentration tested (25 parts
per million active). In addition, this activity was achieved extremely rapidly, with all of the
organisms destroyed in less than one hour. This speed of kill is critical in evaporative
cooling towers where biocide depletion, because of blowdown and low cycles, may result in
relatively low biocide residence times in the system.

In preliminary laboratory tests, glutaraldehyde have been shown to inactivate pure cultures
of LDB. However, the ability of these formulations to control the growth or inactivate LDB
in operating cooling towers exposed to ultraviolet light, organic material, other microbial
contamination and aeration, has not been studied. These findings also do not address
the problem of long-term preventative maintenance of water cooling towers. Even in the
absence of complete knowledge about LDB levels and the disease outbreak, it is prudent
to minimize slime growth and excessive bacterial contamination in cooling towers. This
precaution is supported by limited ecological studies on LDB that have shown the presence
of the organism is usually associated with heavy fouling of the cooling systems.

AQUCAR™ GA 50 Water Treatment Microbiocide is an aqueous solution of glutaraldehyde


50% active ingredient. This product is effective over a wide range of pH and temperature
conditions and are well suited for use in the following applications.

Compatibility with AQUCAR™ water treatment microbiocides have been used successfully to treat systems
Water Treatment containing phosphonate, phosphate, chromate, nitrite, molybdate and many other scale and
Chemicals corrosion inhibitors. Because of glutaraldehyde’s non-ionic nature, it is also compatible with
dispersants, surfactants and most other water treatment chemicals. In addition, glutaraldehyde
is fully compatible with halogens and may be used to treat chlorinated systems.

Compatibility with Ammonia


Concentrated solutions of glutaraldehyde are known to react very quickly with concentrated
solutions of ammonia. In cooling water applications, AQUCAR™ water treatment microbiocides
are typically added at relatively low concentrations, usually <100 ppm active ingredient.
Cooling systems heavily contaminated with ammonia rarely contain more than 100 ppm
ammonia and frequently contain 25-50 ppm. Because of the low concentration of these two
potential reactants, the rate of reaction is slowed dramatically. In addition, because of their
relatively quick biocidal action, AQUCAR water treatment microbiocides only require chemical
stability of approximately six hours to be effective.

The data in Table 5 is representative of the effect of ammonia and pH on the stability of
use-level concentrations of AQUCAR water treatment microbiocides.

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As expected, as the pH and/or ammonia concentrations of the solutions increased,
the stability of the AQUCAR™ water treatment microbiocides decreased. However, if a
20 percent loss in eight hours is acceptable, the following can be concluded: at pH 7 or
8, 50 or 100 ppm active concentration of AQUCAR water treatment microbiocide could
be used to treat a cooling water system that contains up to 100 ppm ammonia. At pH 9,
50 ppm AQUCAR water treatment microbiocide could be used in the presence of up to 50
ppm ammonia; while 100 ppm AQUCAR water treatment microbiocide could be used if the
concentration of ammonia were between 25 and 50 ppm.

These data indicate that AQUCAR water treatment microbiocides are useful in treating
cooling systems containing appreciable concentrations of ammonia. It should be noted that
their stability may vary under actual field conditions and should be monitored to confirm
chemical compatibility.

Table 5 Initial Concentration


AQUCAR™ Microbiocide, % remaining
Effect of Ammonia
pH Ammonia, ppm ppm active ingredient after 8 hours
Concentration and
7.0 25 50 100
pH on AQUCAR
7.0 50 50 100
Water Treatment
7.0 100 50 99
Microbiocide
7.0 25 100 98
Stability
7.0 50 100 94
7.0 100 100 92
8.0 25 50 100
8.0 50 50 100
8.0 100 50 96
8.0 25 100 98
8.0 50 100 90
9.0 25 50 88
9.0 50 50 80
9.0 100 50 65
9.0 25 100 80
9.0 50 100 75
9.0 100 100 50
All stability experiments were conducted at 30°C/86°F

Efficacy of The efficacy of glutaraldehyde is demonstrated by the following experiments. Field isolates
AQUCAR™ GA 50 of seawater and produced water SRBs were grown to high levels in the laboratory and then
Water Treatment challenged with glutaraldehyde. The following results were obtained.
Microbiocide

Efficacy of Log Reduction (hours)


Glutaraldehyde vs. Biocide (ppm a.i.) 1 2 4
Seawater SRB’s GA, 25 4 4 7
GA, 50 6 7 8
GA, 100 8 8 8
Control 108 108 108

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Efficacy of Log Reduction (hours)
Produced Water Biocide (ppm a.i.) 1 2 4
SRB’s
GA, 25 4 6 5
GA, 50 5 6 5
GA, 100 5 8 8
Control 108 108 108

The experimental protocol allowed for the growth of both high populations of SRB’s as
well as the accumulation of bacterial metabolites such as sulfide. As these results show,
glutaraldehyde was effective against these field isolates.

Efficacy vs. Algae Algae, relatively simple organisms which utilize sunlight for growth, can be found on
distribution decks, sidewalls, louvers and other exposed areas of a cooling tower.
When larger masses of algae break free they can plug screens and pipes and also coat
the packing material, leading to a reduction in the cooling efficiency of the tower. As
demonstrated, the biocide was able to reduce algal growth against all species, even at the
lowest concentration tested. (25 ppm a.i.)

The algae was grown in Bolds Basic Media at pH 7.0 in a psychrotherm at 21°C/70°F for
seven days. Biocide was then added to the flasks and after the desired contact time (5 and
24 hrs.) a portion of the solution was subcultured into fresh growth media. Algal growth in
each sample was examined after seven days. The extent of growth was determined by
comparison to a control and quantitated by use of a Klett Summerson Colorimeter.

Effectiveness AQUCAR™ GA 50 Water Treatment Microbiocide is compatible with the following materials
on Materials of of construction:
Construction
Stainless steel, nickel, and polyethylene.

AQUCAR GA 50 is compatible with the following gasketing materials:

Silicone, Kalrez,1 Teflon2 and Grafoil.3

Glutaraldehyde Many studies have been performed on glutaraldehyde to determine its potential to
and the biodegrade in the environment. Glutaraldehyde is readily biodegradable compound that
Environment has little environmental impact when handled properly. Due to its rapid decomposition both,
aerobically and anaerobically it has a favorable ecotoxicology profile. The details of two of
the many biodegradation studies that have been performed on glutaraldehyde are detailed
below.

The OECD (Organization for Economic Cooperation and Development) 301 series of
biodegradation protocols are designed to determine the biodegradation potential of
substances under stringent conditions. In one such biodegradation test, glutaraldehyde met
and exceeded the OECD ready biodegradability classification criteria and thus was found to
be readily biodegradable.

1Kalrez, 2Teflon and 3Grafoil are registered trademarks of E.I. du Pont de Nemours and Company.

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% Biodegradation
100
of Glutaraldehyde
(GA) in OECD 301A
Test 80

% Biodegradation
70% Threshold
60

Sodium Benzoate Control


40 GA Biodegradation

20

0
0 2 4 6 8 10
Day

Complete details on the biodegradation tests mentioned, as well as many other


environmental fate and ecotoxicology tests performed on glutaraldehyde, are summarized in
a Dow publication entitled “Ecotoxicology of Glutaraldehyde” (Form No. 253-01418).

Aerobic Aquatic Metabolism


T1/2 in river water - 10.6 hr. Carbon dioxide was the major metabolite, with glutaric acid
as intermediate
O O O O
CO2
H H HO OH
Glutaraldehyde Glutaric Acid Carbon
Dioxide

Anaerobic Aquatic Metabolism


T1/2 in river water - 7.7 hr. 1,5-Pentanediol was the major metabolite
O O O

H H H OH HO OH
Glutaraldehyde 5-Hydroxypentanal 1,5-Pentanediol

Toxicology For product safety information, refer to Safety Data Sheet (SDS).

Storage, Product Handling


Handling and Handle AQUCAR™ GA 50 Water Treatment Microbiocide in well ventilated areas and wear
Disposal appropriate protective equipment for the task. At a minimum, this includes proper gloves,
splash-proof monogoggles (chemical goggles) or both safety glasses with side shields and a
wrap-around full-face shield, coveralls and boots. Atmospheric levels should be maintained
below the exposure guideline. When respiratory protection is required for certain operations,
use an approved air-purifying respirator.

Disposal of AQUCAR™ GA 50 Water Treatment Microbiocide


If excess product cannot be used according to use directions, it must be sent to an approved
waste disposal facility. Because disposal regulations can vary by location, contact the
regulatory authority for waste disposal guidance in your location. This product should never

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be disposed of by dumping into lakes, streams, ponds, estuaries, oceans, sewers, ditches,
or into soil at any time.

Disposal of Product Containers


Empty containers of AQUCAR™ GA 50 Water Treatment Microbiocide should be triple
rinsed with water to remove excess product promptly after emptying. The rinse water should
be collected and sent to an approved waste handling facility. If allowed by your location,
offer empty product containers for recycling or reconditioning or puncture and dispose of
according to local regulations.

In the United States, refer to the product label for specific precautions and use directions.
Further information and precautions regarding the handling, storage, and disposal of
AQUCAR GA 50 can be obtained by consulting the latest Safety Data Sheet (SDS) for this
product and the “Gutaraldehyde Safe Handling and Storage Guide” (Form No. 253-01338),
available from your Dow representative.

Summary At recommended dose levels, AQUCAR™ GA 50 Water Treatment Microbiocide is useful


in controlling many bacterial and slime problems typically encountered in the papermaking
process. (Please refer to the product label for specific use directions.) They are compatible
with most common papermaking additives and display excellent biodegradation in the
environment.

Product Dow has a fundamental concern for all who make, distribute, and use its products, and for
Stewardship 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
our 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.

Customer Notice 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. Dow personnel are available to answer your questions and to provide reasonable
technical support. Dow product literature, including Safety Data Sheets (SDS), should be
consulted prior to use of Dow products. Current Safety Data Sheets are available from Dow.

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For further information visit our website:
www.dowmicrobialcontrol.com
or call:

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