Aquatreat® Biocides

Cost-effective, broad-spectrum biocides

Aquatreat Biocides
Introduction

®

Effective against a broad spectrum of microorganisms
Product Chemistry Aquatreat Biocides are based on dithiocarbamate chemistry. Aquatreat SDM (Figure 1) and Aquatreat KM (Figure 2) are single-component biocides based on the sodium and potassium salts of dimethyldithiocarbamate. Aquatreat DNM-9, Aquatreat DNM-30 and Aquatreat DNM-360 are dualcomponent biocides based on a blend of sodium dimethyldithiocarbamate and disodium ethylene-bis-dithiocarbamate (Figure 3). Aquatreat Biocides are applicable for a wide range of industrial uses. Table 1 summarizes acceptable use patterns for these products. Toxicology Aquatreat Biocides have a low order of toxicity to humans. Tables 2 and 3 show comparative data for Aquatreat DNM-30 in eye and skin irritation studies. Figures 4 and 5 show comparative oral and dermal toxicity with Aquatreat DNM-30 and other commonly used biocides. Aquatreat Biocides are known to be toxic to fish and aquatic organisms. As with any biocide, care must be taken to eliminate the possibility of release of Aquatreat Biocides into natural waterways such as lakes, streams, rivers and oceans. Aquatreat products are not persistent biocides. Degradation of the products occurs as a result of oxidation, sunlight, lower pH and microbial action.

Aquatreat Biocides are EPA-registered, non-oxidizing dithiocarbamates that have a long history of proven performance. In cooling towers and airwashers, experience has shown that Aquatreat Biocides are effective in controlling both planktonic and sessile microorganisms. In paper mills, Aquatreat Biocides are known to be the most cost-effective materials available for the control of slime-forming bacteria and fungi in both virgin and recycle mills. For both beet and cane sugar mills, Aquatreat Biocides can be used to effectively control mesophilic and thermophilic bacteria that commonly foul the sugar production process. Aquatreat Biocides are especially effective in controlling sulfate-reducing bacteria in many applications, including drilling fluids and petroleum recovery waters. Additional uses for Aquatreat Biocides include sapstain control, fuel storage and in-flue gas desulfurization thickeners. Performance Features • EPA registered for a wide range of applications • Meet FDA requirements for use in paper and sugar applications • Cost effective • Effective against a broad spectrum of microorganisms, including bacteria, fungi and algae: - Aerobic and anaerobic bacteria - Sulfate-reducing bacteria (SRB) - Yeasts and molds - Legionella • Compatibility and strong performance in a wide range of environments/ conditions - Broad pH and temperature stability - Organic loading - Dissolved and suspended solids • Not persistent in discharge waters • Favorable handling and toxicity compared with competitive materials

2

N

S-+Na

H3C N

C S-+Na H 3C N C S-+K
S

CH3

Figure 1: Sodium Dimethyldithiocarbamate Aquatreat® SDM
S
S

Figure 2: CH3 Potassium Dimethyldithiocarbamate Aquatreat KM
S

Figure 3: Dual-Component Biocides
CH3

Aquatreat DNM-9, DNM-30, DNM-360
H 3C N C S-+K S

S H3C C N
S-+Na

H3 C
H3C

C N
N C

H3C S-+K N

C
CH3

H N S-+Na N H S

S-+Na

S-+Na

S-+Na

CH3 CH3 CH3
H3C N

S

S

CH3

C S-+Na S-+Na N H

H N

S-+Na

Table 1: Application use patterns
H3 C
H 3C N

S

S

S

S

1600
CH3

S

H3C
C
-+

1400
C N S-+ Na Pulp & Paper Mills
-+ S Na Cane Sugar Mills

C

N 1200 H mg/kg

H N

S-+Na

Beet
1600 1400

N Product

Cooling Air S K S-+K Towers Washers CH3 • • • • •
S-+Na

1000 Sugar

Mills
800

Drilling S Fluids • • • • •

HydroCarbon Fluids

Petroleum Recovery • • •

Sapstain Control •

Aquatreat SDM Aquatreat KM CH
3

• •
1600
S

CH3

600 1200
mg/kg

Aquatreat DNM-9 Aquatreat DNM-30 S Aquatreat DNM-360
H3C C

• • •
N H

• • •
H N
H N

• •
S-+Na

400 1000

200

S

1400 1200

S

• •

800 600 400 200


250 ISOTHIAZOLIN mg Chlorophyll/cm2


GLUTERALDEHYDE 200

0

H3C N

C N S-+Na

S-+Na

S-+Na

AQUATREAT DNM-30

mg/kg

1000
N H

S-+Na

CH3 Figure 4: 50 Oral Toxicity LD CH
3

800 600 400
S

S

Figure 5: AQUATREAT 3000 Toxicity - LDDNM-30 50 Dermal
2500 2000
mg/kg

0

ISOTHIAZOLIN

150

GLUTERALDEHYDE

Main 100 Slug Dosage

1600

200 0
AQUATREAT DNM-30

3000 2500
250

50

1600 1400 1200
mg/kg
mg/kg

1400 1200 1000 800

0 0 1 2 3 WEEK

ISOTHIAZOLIN

GLUTERALDEHYDE 1500 250 200

1000
mg Chlorophyll/cm
2

1000 800 600 400 200 0

mg/kg mg Chlorophyll/cm2

2000

150 200 1500 Maintenance Dose 100 1000 150

600 400 200 0
mg/kg
AQUATREAT DNM-30

3000 2500 2000
ISOTHIAZOLIN GLUTERALDEHYDE

500

0

100

50 500 AQUATREAT 0 0

50

1500
0

0 AQUATREAT 1 DNM-30

2

60 3 4 5 GLUTERALDEHYDE 6 7 ISOTHIAZOLIN WEEK 40 5 20 6 7

Dithiocarbamate

NaOCl

Dithiocarbamate

2500 2000

500 0

NaOCl

Dithiocarbamate

2500 2000
mg/kg

mg/kg

Biocide Aquatreat DNM-30
1000 Isothiazolin 1500

60 Biocide

Non-irritant Corrosive Severe Irritant Severe Irritant
mg Chlorophyll/cm
2

80

Aquatreat DNM-30 40 Isothiazolin Gluteraldehyde
20

Non-irritant Severe Irritant Severe Irritant

60

1500 1000 500

Gluteraldehyde 500 DBNPA
0
AQUATREAT DNM-30

40 0 DBNPA
0

20

40 DAYS

Severe Irritant
60

Dithiocarbamate

ISOTHIAZOLIN

GLUTERALDEHYDE

20

0

0
AQUATREAT DNM-30 ISOTHIAZOLIN GLUTERALDEHYDE

0

20

40 DAYS

60

NaOCl

Classification under AQUATREAT DNM-30 21 CFR 191.12

mg Chlorophyll/cm2

3000

80

0

0

NaOCl

Table 2: Eye Irritation in Rabbits

3000

AQUATREAT DNM-30

ISOTHIAZOLIN

1000

GLUTERALDEHYDE

0

1

2

3 WEEK

Table 3: 100 Skin Irritation in Rabbits
100 GLUTERALDEHYDE

mg Chlorophyll/cm2

DNM-30Slug Dosage

Maintenance Dose ISOTHIAZOLIN GLUTERALDEHYDE 80

4

Dithiocarbamate

20

NaOCl

Slug Dosage

100

40 DAYS

ISOTHIAZOLIN

Classification under 21 CFR 191.11

80

80

3

Cooling Water Applications
Cooling Towers and Air Washers Aquatreat® Biocides are particularly effective in controlling problematic organisms in both open recirculating and closed cooling water systems. In open recirculating systems, Aquatreat Biocides are effective against algae and bacteria commonly found in bulk water and in biofilms. In closed-loop systems, it is particularly important to control sulfate-reducing bacteria (SRB), denitrifying bacteria and other anaerobic bacteria. Due to their functionality and compatibility in reducing environments, Aquatreat Biocides are often the biocides of choice in closed-loop cooling systems. In air washers, Aquatreat Biocides offer the user broad functionality and a low order of toxicity relative to other commonly used materials. Algae Control Using Aquatreat DNM-30 Algae are organisms that use light energy and carbon dioxide from the air to produce organic biomass. They represent a broad range of unicellular and filamentous organisms. Most system operators also refer to the cyanobacteria (blue-green algae) as members of the algal group, although they are most closely related to bacteria. Algae cause a number of direct and indirect problems in water treatment systems. Directly, many algae grow in dense fibrous mats that plug distribution piping, accelerate corrosion and overall reduce system performance. These mats also provide areas for the growth of corrosioncausing anaerobic bacteria. Another important effect of algal growth is the continuous removal of carbon dioxide during the daylight hours. This can alter water chemistry and complicate normal scale control treatment programs. Indirectly, the consequence of algal growth can be even more severe and detrimental. Algae convert inorganic carbon (CO2) into organic biomass. As this biomass dies, it contributes nutrients that fuel the growth of other bacteria. These bacteria can foul heat exchanger surfaces and contribute to corrosion, e.g., sulfate-reducing bacteria. Laboratory Studies Laboratory studies are often used to obtain preliminary efficacy data and establish baseline dose response information. It is important that a biocide demonstrates a broad range of activity. Aquatreat DNM-30 has been tested against a number of pure and field-obtained enrichment cultures from a variety of sources as shown in Table 4. These data show that Aquatreat DNM-30 is effective at low-use concentrations against a wide variety of filamentous and unicellular algae.

Table 4: Aquatreat DNM-30 Efficacy Data

Algae Ulothrix spp. Heterocapsa pygmaea Euglena gracilis Chlorella pyrenoidosa Scenedesmus obliquus Phormidium spp. (mat) Oscillatoria prolifera Oscillatoria spp. Cooling tower enrichment Cooling tower enrichment Cooling tower enrichment

Type Filamentous green algae Slime-forming algae Unicellular flagellate Unicellular green algae Unicellular green algae Filamentous blue green Filamentous blue green Filamentous blue green Mixed culture of green and blue-green algae Mixed culture of green and blue-green algae Mixed culture of green and blue-green algae

Source Cooling tower effluent Estuary in-take water ATCC* 12894 ATCC 7516 ATCC 11457 Cooling tower isolate (Gulf coast) Unknown Carolina Biological Cooling tower (South Dakota) Cooling tower (southern Minnesota) Cooling tower (Montana)

MIC* 5-10 2.5-5 5-10 15-20 20-25 20-25 2.5-5 1-5 15-20 20-25 35-40

* The Minimum Inhibitory Concentration (MIC) tests were conducted in the medium specified by the source supplier (American Type Culture Collection, Rockville, MD; Carolina Biological Co., [CBC]) or in Alga Gro Medium (CBC) for pure cultures or in Alga Gro Medium reconstituted in filter-sterilized cooling tower basin water for cooling tower enrichments.

4

H3C N

S
C S-+Na

H 3C N

C S-+K

CH3

CH3

S

H 3C

S
N

C

S
S-+K

H3C N

C S-+Na
CH3

H N

S-+Na

S-+Na

N H S

CH3

S

S

Field Studies H S Na HC C N Aquatreat® dithiocarbamates have been used and evaluated in a number 1600 N N Natheir S efficacy Na of cooling water systems S for against planktonic and matH 1400 forming algae. Figures 6 and 7 (following page) document their ability S CHmat formation using alternating slug and maintenance to control algal 1200 dosages.
-+ 3 -+ -+ 3

Figure 6: Algal Biomass Reduction Using DNM-30

250

System Conditions 800 • Bulk water capacity—35,000 gallons 1600 • Bulk water temperature—80–100° F 600 • Bulk water 1400 pH—8.0–8.6 • Total dissolved solids—1,000–2,000 ppm 400
1200
mg/kg

mg Chlorophyll/cm2

mg/kg

1000

200

150 Maintenance Dose 100
250

Slug Dosage

mg Chlorophyll/cm2

Dithiocarbamate

NaOCl

Dithiocarbamate

2500

40
80 mg Chlorophyll/cm2

1000
2000

20

500 0

mg/kg

60

1500 1000 AQUATREAT
DNM-30

0

40 0 20

20

40 DAYS

60

NaOCl

200 Figure 6 1000 depicts data from a cooling tower deck in southern Minnesota. The deck had severe algal and cyanobacterial fouling problems, 0 tower 800 especially in the mid-summer cooling season. Replicate 5 cm2 coupons AQUATREAT ISOTHIAZOLIN GLUTERALDEHYDE DNM-30 600 on the deck early in the season, and algal growth was were installed monitored by removing coupons and measuring algal biomass by 400 chlorophyll determination. Without biocide treatment (Figure 6) greater 2 200 than 200 mg/cm , algal biomass accumulated on the coupons. Following 3000 an initial slug dosage (400 ppm) of Aquatreat DNM-30, the algal biomass 0 was reduced to about 50 mg/cm2 ISOTHIAZOLIN and was readilyGLUTERALDEHYDE maintained at less than AQUATREAT 100 mg/cm2 with aDNM-30 routine maintenance dosage of 20-40 ppm. Figure 7 2500 shows the alternating treatment of Aquatreat DNM-30 (20-40 ppm) and sodium hypochlorite in the same system. In this study, algal growth on 2000 the tower deck was more effectively controlled during Aquatreat DNM-30 3000 treatment than with sodium hypochlorite. 1500

50 200
mg Chlorophyll/cm2

150 0

0
100

1
Slug Dosage

2

3

WEEK

Maintenance Dose

4

5

6

7

50

Dithiocarbamate

Dithiocarbamate

NaOCl

0

1

2

3

4

5

6

WEEK Figure 7: 80 Algal Control: Aquatreat DNM-30 vs. Hypochlorite

mg/kg

60
100

NaOCl
7

100 0

80

ISOTHIAZOLIN

GLUTERALDEHYDE

500
0

0
AQUATREAT DNM-30 ISOTHIAZOLIN GLUTERALDEHYDE

0

20

40 DAYS

60

80

5

Problematic Bacterial Control Using Aquatreat® DNM-30 Bacteria pose various mechanical, economic and public health issues in cooling water systems. As a result, microbiologically influenced corrosion (MIC) is recognized as one of the most significant issues in industrial water treatment, resulting in equipment failure and economic loss. Bacterial accumulation in the form of biofilms contributes to significant mechanical problems, such as fouling of heat exchangers, restriction of flow and fouling of cooling tower fill. The formation of biofilm in heat exchangers or on cooling tower fill can have a significant impact on the costs associated with achieving desired cooling. The presence of bacteria such as Legionella spp. in cooling water systems has been recognized as a major public health issue. There is a large variety of aerobic and anaerobic bacteria that are found in industrial cooling water systems. Aquatreat DNM-30 has been demonstrated to be effective against a wide variety of bacteria. Table 5 shows the MIC, in parts per million, of Aquatreat DNM-30 necessary to control a number of different gram negative and gram positive bacteria. Figure 8 shows effectiveness of Aquatreat DNM-30 against aerobic heterotrophic bacteria in an industrial air washer. Gram negative bacteria such as the Pseudomonas species listed above are likely to be found in most cooling water systems and are among the most difficult to control with commercially available biocides. Pseudomonads are recognized as prolific biofilm-producing bacteria. Gram positive bacteria such as the spore-forming bacilli are also found in industrial water systems. These bacteria contribute to biofouling and other microbiological-related problems. Iron-oxidizing bacteria, including Sphaerotilus, form surface deposits and accelerate localized corrosion. Other bacteria, such as Escherichia and Salmonella, are among the common waterborne pathogens.

Table 5: Minimum Inhibitory Concentrations for Problematic Bacteria

Organism Gram Negative Bacteria Escherichia coli Escherichia coli

Source

Enrichment Medium

MIC* (ppm)

ATCC 29990 UM 0315

API-H (mod) API-H (mod) API-H (mod) API-H (mod) API-H (mod) API-H (mod)

55-60 60-65 85-90 60-65 35-40 55-60

Pseudomonas fluorescens ATCC 13525 Pseudomonas putida Enterobacter aerogenes Salmonella typhirmurium Gram Positive Bacteria Bacillus cereus Staphylococcus aureus Iron Oxidizing Bacteria Sphaerotilus natans ATCC 15291 ATCC 12633 UM 0298 ATCC 14028

NRRL B4278 API-H (mod) UM 0115 API-H (mod)

15-20 5-10

Iron isolation medium std.

1-5

Figure 8: Effectiveness of Aquatreat DNM-30 against Aerobic Heterotrophs in an Industrial Air Washer

1.00E+07 0 ppm 1.00E+06
CFU/mL

25 ppm 1.00E+05 91.8% 50 ppm 97.3%

1.00E+04

1.00E+03

1.00E+08 1.00E+07 1.00E+06
Control (pH 5) DNM-30 (pH 5) Control (pH 7) DNM-30 (pH 7) Control (pH 9) DNM-30 (pH 9)

6

CFU/mL

1.00E+05

While most cooling water systems are operated at alkaline pH, it is important for a biocide to exhibit activity over a broad pH range. Figure 9 shows the activity of Aquatreat® DNM-30 at pH 5, 7 and 9. The data 1.00E+07 demonstrate effectiveness over a broad pH range against aerobic 0 ppm bacteria in a cooling water sample. A current and especially serious public health problem found in industrial water systems is the occurrence of pneumophilia. Legionella 25 Legionella ppm is a relatively 1.00E+05 ubiquitous organism found 91.8%in water and soil. Because of the 50 ppm nature of industrial cooling tower systems, Legionella has the potential 1.00E+07 97.3% to accumulate and be distributed in tower aerosols. The organism is 0 ppm unusual in that it invades and multiplies within an amoeba. When outside 1.00E+04 1.00E+07 of the amoeba, the bacterium is relatively easy to control. 1.00E+06
CFU/mL

Figure 10: Reduction of unassociated Legionella pneumophila

400 350 300 250 200 400 150 350 400 100 300 350 50 250 300 0 200 250 SMB 150 200 MIC (ppm Active) 100 150 10,000 50 100 MIC (ppm Active)

1.00E+06

0 ppm

1.00E+04 1.00E+07 1.00E+03 1.00E+06 1.00E+03 Figure 9: 1.00E+05 Broad pH Performance of Aquatreat DNM-30 1.00E+04 1.00E+08 1.00E+03 1.00E+07 1.00E+08
CFU/mL CFU/mL

Control (pH 5) DNM-30 (pH 5) Control (pH 7) DNM-30 (pH 7) Control (pH 9) DNM-30 (pH 9)

Figure 11: 0 CFU/mL 1,000 50 Reduction of Amoeba-Grown Legionella exposure) SMB DBNPA DN-30 (6-hr DNM-30 Isothiazolin Quat using Aquatreat DNM-30
0 100 10,000 10,000 10 1,000 1,000 0 100 100 SMB DBNPA DN-30 DNM-30 Isothiazolin Quat

Control (pH 5) DNM-30 (pH 5) 5 10 15 Time (H) 20 25 Control (pH (pH 7) 5) Control DNM-30 7) 5) 30 (pH (pH DNM-30 Control (pH (pH 9) 7) Control DNM-30 (pH (pH 9) 7) DNM-30 Control (pH 9) DNM-30 (pH 9)

1.00E+02 1.00E+06 1.00E+07 0 1.00E+05 1.00E+06
CFU/mL

Legionella CFU/mL Legionella CFU/mL Legionella CFU/mL

MIC (ppm Active)

When present itsppm control is much more difficult. The 1.00E+03 1.00E+06inside the amoeba,25 conditions presented in Figure 10 show how the functionality of Aquatreat 1.00E+05 91.8% 50 ppm DNM-30 for control of unassociated25 Legionella compares with that of ppm 97.3% other available the efficacy of Aquatreat DNM1.00E+05biocides. Figure 11 shows 91.8% 50 ppm 30 for amoeba-associated bacteria. This study shows that DNM-30 has 1.00E+04 1.00E+08to penetrate amoeba and kill intracellular97.3% the capacity Legionella.
CFU/mL CFU/mL

DBNPA

DN-30

DNM-30 Isothiazolin Quat

CFU/mL CFU/mL 0 20 60 100

1.00E+04 1.00E+05 1.00E+03 1.00E+04 1.00E+07 1.00E+02 1.00E+03
0

ppm DNM-30 (active)

5 5

10 10

1.00E+02 1.00E+06
CFU/cm
2

15 Time (H)

20 20

25 25

30 30

10 10 0 0 0 20 60 100 100

0

15 Time (H)

1.00E+05 1.00E+07 1.00E+07 1.00E+04 1.00E+06

Control Control 100 ppm DNM-30 100 ppm DNM-30

0 1.00E+07 1.00E+06 1.00E+05

ppm DNM-30 (active) 20 60 ppm DNM-30 (active) Control

CFU/cm2

MPN SRB/g Sludge

CFU/cm2

1.00E+06 1.00E+03 1.00E+05 1.00E+05

Control
TOTAL ANAEROBES Control TOTAL SRB

1.00E+04 1.00E+07 1.00E+03 1.00E+06 1.00E+07 1.00E+02 1.00E+05 1.00E+06 1.00E+01 0 1.00E+04 1.00E+05 20

Control 100 ppm Control DNM-30 100 ppm DNM-30 100 ppm DNM-30 100 ppm

Dithiocarbamate at 120 ppm (as product) Control Control 100 120

1.00E+04 1.00E+04 1.00E+06 1.00E+03

40 60 80 Dithiocarbamate

ge

140

160

7

1.00E+08 1.00E+07 1.00E+06
CFU/mL Control (pH 5) DNM-30 (pH 5) Control (pH 7) DNM-30 (pH 7) Control (pH 9) DNM-30 (pH 9)

1.00E+05 1.00E+04 1.00E+03

400 350 300 250 200 MIC (ppm Active) 150 100 50

1.00E+02
0 5 10 15 Time (H) 20 25 30

1.00E+07

1.00E+06
CFU/cm2

SRB Data 0 The sulfate reducers are a group of anaerobic bacteria that produce SMB DBNPA DN-30 DNM-30 Isothiazolin Quat hydrogen sulfide from the reduction of sulfate and other sulfur species during their growth process. While difficult to detect, SRB are ubiquitous in most industrial water systems where anaerobic conditions exist. SRB 10,000 cause severe corrosion and odor problems in both open recirculating and closed cooling water systems. The economic implications of SRB in industrial water systems are significant due to the intensity of underCFU/mL 1,000 deposit and pitting corrosion that they often cause. Aquatreat® DNM-30 has been found to be especially effective in the control of SRB in both open recirculating and closed cooling water systems. Figure 12 shows data from a laboratory study in which Aquatreat DNM30 was used to treat cooling tower sludge. A sludge-in-water sample was treated with an initial dose of 120 ppm of Aquatreat DNM-30, 10 and the number of viable SRB was determined versus time, using an MPN technique. The data show that the initial dose produced a reduction 5 from 100 to 104 SRB/gram of sludge. A subsequent 120 ppm dose of Aquatreat DNM-30 effectively to less than 101 0 20 reduced the 60 population 100 SRB/gram of sludge. ppm DNM-30 (active)
Legionella CFU/mL
100

Figure 13 shows a field study in which Aquatreat DNM-30 was evaluated 1.00E+05 Control for efficacy against planktonic SRB in a closed, chilled-water loop. The number of SRB was counted for five weeks prior to the addition 100 ppm of Aquatreat DNM-30. During week five, a 120 ppm dose of Aquatreat DNM-30 1.00E+04 DNM-30 was added to the system. The number of SRB 100 was counted for ppm an additional five weeks after the biocide addition. TheDNM-30 data show that a single dosage of Aquatreat DNM-30 effectively lowered the total SRB from 1051.00E+03 SRB/mL to less than 101 SRB/mL.
TOTAL ANAEROBES TOTAL SRB

Control

Figure 13: Aquatreat DNM-30 Efficacy for Planktonic SRBs

1.00E+06

1.00E+05
120 ppm DNM-30 MPN SRB/mL

1.00E+04

1.00E+03

Figure 12: Reduction of SRB in Cooling Tower Sludge
1.00E+07 1.00E+06 1.00E+05 MPN SRB/g Sludge 1.00E+04 1.00E+03 1.00E+02 1.00E+01 0 20 40 60 80 Hours 100 120 140 160 Dithiocarbamate at 120 ppm (as product)

1.00E+02

1.00E+01
0 2 4 6 Time (Weeks) 8 10 12

Control

1.00E+06 Heterotrophs (0 ppm) CFU/mL or MPN/mL 1.00E+05 Denitrifiers (0 ppm) 1.00E+04 Heterotrophs (176 ppm)

1.00E+03

Denitrifiers (176 ppm)

8

1.00E+02

1.00E+07 1.00E+06
CFU/mL

Control (pH 5) DNM-30 (pH 5) Control (pH 7) DNM-30 (pH 7) Control (pH 9) DNM-30 (pH 9)

10,000

1,000

CFU/mL

1.00E+05 1.00E+04 1.00E+03 1.00E+02
0 5 10 15 Time (H) 20 25

Legionella CFU/mL

100

30

10 400 0 350 300

1.00E+07 0 ppm 1.00E+06 1.00E+07
CFU/mL

0

20

60

100

ppm DNM-30 (active)

25 ppm 1.00E+05 1.00E+06 1.00E+04 1.00E+05 Control 91.8% 50 ppm 97.3% Control MIC (ppm Active)

250 200 150 1.00E+07 100

CFU/cm2

1.00E+06

CFU/mL

DNM-30 (pH 7)

MPN SRB/g Sludge

In Figure 14, a Robbins biofilm-monitoring device was installed on a 1.00E+03 100 ppm closed, chilled-water loop. After a two-week fouling period, coupons DNM-30 1.00E+04 were removed and immersed in a 100 ppm solution of Aquatreat® DNM100 ppm 30 for six hours. Replicate coupons were removed and immersed in a DNM-30 solution containing no biocide for the same duration. After exposure, 1.00E+03 the 1.00E+08 coupons were scraped and evaluated for total aerobic bacteria, TOTAL SRB TOTAL ANAEROBES anaerobic bacteria and total SRB. The data indicate that Aquatreat DNMControl (pH 5) 1.00E+07 30 effectively lowered the total anaerobic population and was highly DNM-30 (pH 5) effective at killing the SRB contained in the biofilm. Control (pH 7)
Control (pH Another group of microorganisms that is often found in 9) closed-loop 1.00E+05 DNM-30 (pH 9) especially systems is denitrifying bacteria. These microorganisms are 1.00E+06 1.00E+04 prevalent where nitrite inhibitors are used for corrosion control. Their activity not only causes the typical microbial problems but also results in 1.00E+03 the1.00E+05 depletion of the nitrite inhibitor.

Figure 15 shows data from a closed-loop system where nitrite was used 50 1.00E+06 for corrosion control. The system pH was buffered to 10.2 using sodium Control 0 this system, nitrite was being depleted due to reduction by borate. In 1.00E+05 SMB Aquatreat DBNPA DNM-30 DN-30 was DNM-30 Isothiazolin Quat denitrifying bacteria. added to the system, and a significant reduction of total heterotrophic and denitrifying bacteria was 1.00E+04 Dithiocarbamate observed. The heterotrophic bacteria were enumerated on plate count at 120 ppm agar 1.00E+03 (Difco Laboratories) and denitrifying bacteria were quantified by 10,000 (as product) MPN technique. The data show the pronounced efficacy of Aquatreat 1.00E+02 DNM-30 for both the heterotrophic and denitrifying populations.
1,000 1.00E+01 0 20 40 60 80 Hours 100 CFU/mL 120 140 160

Figure 15: Aquatreat DNM-30 vs. Denitrifying Bacteria
10

1.00E+02
MPN SRB/mL 0 5 10 15 Time (H) 20

1.00E+04 Figure 14: Aquatreat DNM-30 Static Cell Death of Attached Bacteria in a Closed Chilled Water Loop (6-hr exposure) 1.00E+03

120 ppm DNM-30 25 30

Legionella CFU/mL

100

1.00E+06 0 Heterotrophs (0 ppm) 0 20 60 100

CFU/mL or MPN/mL

1.00E+05

1.00E+07 1.00E+02

ppm DNM-30 (active) Denitrifiers (0 ppm) Heterotrophs (176 ppm)

1.00E+04

1.00E+01 1.00E+06
0 CFU/cm2

2

4

6 Time (Weeks)

8

10

12

1.00E+03

Denitrifiers (176 ppm)

1.00E+05

Control Control 100 ppm DNM-30 100 ppm DNM-30

1.00E+02 1.00E+07 0 1.00E+06 1.00E+05 MPN SRB/g Sludge 1.00E+04 1.00E+03 1.00E+02 1.00E+01 0

5

10

15 Time (H)

20

25

30

1.00E+04

Control

1.00E+03
TOTAL ANAEROBES TOTAL SRB

Dithiocarbamate at 120 ppm (as product)

20

40

60

80 Hours

100

120

140

160

1.00E+06

1.00E+05
120 ppm DNM-30 MPN SRB/mL

1.00E+04 1.00E+06 1.00E+03 CFU/mL or MPN/mL 1.00E+05 Denitrifiers (0 ppm) 1.00E+04 Heterotrophs (176 ppm) Heterotrophs (0 ppm)

1.00E+02

1.00E+01
0 2 4 6 8 10 12

1.00E+03

9
Denitrifiers (176 ppm)

Another method of evaluating the efficacy of a treatment program is by quantification of cellular damage after exposure to a biocide. The percentage of cellular damage can be determined by epifluorescent microscopy using a combination of fluorescent dyes. Cells exhibiting a green fluorescence are relatively uninjured, while cells exhibiting an orange to red fluorescence are injured or dead. Using this technique, two chilled water samples from closed-loop systems were treated with Aquatreat® DNM-30. The sample labeled Chilled Water #1 consisted of primary chilled water from a commercial bank operating 24 hours per day. The sample labeled Chilled Water #2 was obtained from a central plant that supplied chilled water to 10 surrounding buildings. The chilled water from this system had not been drained for approximately 20 years and contained dozens of primary and secondary loops. The data in Figure 16 show that Aquatreat DNM-30 has good efficacy in both of these challenging systems after a 12-hour exposure.

Summary of Cooling Tower Data Aquatreat DNM-30 is a very effective biocide for problematic microorganisms in both open recirculating and closed cooling water systems. Aquatreat DNM-30 has proven especially effective for the control of anaerobic microorganisms such as SRB and denitrifying bacteria. Additionally, Aquatreat DNM-30 is effective in closed-loop systems because of its stability in reduced or non-oxidizing environments. All Aquatreat® Biocides are anionic reducing agents. These characteristics provide excellent compatibility with other common additives used for scale and corrosion control. Because of their reducing characteristics, Aquatreat Biocides should not be fed in close proximity to an oxidizing biocide or in systems where a continuous residual of oxidizing biocide is maintained. In systems where oxidizing biocides are used, Aquatreat Biocides can be an effective treatment on an alternating feed basis. Aquatreat Biocides are known to complex heavy metals that can be present in cooling water systems. The presence of low levels of heavy metals such as zinc (added for corrosion control) or iron in a cooling water can preclude the use of Aquatreat Biocides. Other additives such as phosphates, azoles, phosphonates and polymers may sufficiently stabilize 1.00E+08 heavy metals. Aquatreat Biocides are compatible with molybdate (MoO42-) containing treatments. Before use in any system, the compatibility of 1.00E+07 Aquatreat Biocides should be examined using samples from the system’s circulating water. See product label for dosage information.
CFU/g

Figure 16: Cellular Damage in Chilled Water Systems
50 45
% CELLULAR DAMAGE DNM-30 12-hr. Exposure

40 35 30 25 20 15 10 5 0
CHILLED WATER #1

1.00E+06 1.00E+05 1.00E+04

0 ppm

120 ppm

0 ppm

120 ppm

1.00E+03
Control DNM-30 Quat MBT DBNPA Isothiazolone

CHILLED WATER #2

Benefits of Aquatreat Biocides in Cooling Water Applications
1.00E+04 1.00E+03
CFU/g

• Effective control of problematic SRB and denitrifying bacteria
1.00E+05
CFU/g

1.00E+02 1.00E+01 1.00E+00
Control DNM-30 Quat MBT DBNPA Isothiazolone

• Excellent compatibility with additives used for scale and corrosion control 1.00E+04 • Inherent stability in reducing environments found in1.00E+03 closed-loop systems • Not a persistent biocide 1.00E+02 • Effective for a broad range of algae MBT and bacteria Control DNM-30 Quat DBNPA • Low order of toxicity to humans • Non-foaming
Isothiazolone

10
1.00E+07

Pulp and Paper Applications
In paper manufacture, large volumes of water are used in grinding and conveying pulp. The same water is also used as a medium for forming the paper web. This water is recycled throughout the papermaking process and is often a significant source of microbial contamination. The result of contamination can lead to significant problems, such as imperfections or loss of paper, mill downtime and equipment failure. One problem compounding microbial control issues is the use of recycled fiber, which contains a much higher microbial load. An effective biocide must have good microbial control across a range of pH and temperature conditions and exhibit functionality in applications, using both virgin and recycled fiber. Aquatreat® Biocides have proven effective in such systems and are widely used to control slime yeasts and fungi associated with paper mill applications.
% CELLULAR DAMAGE % CELLULAR DAMAGE
CFU/g CFU/g

Case Study 1 Aquatreat DNM-30 has proven cost effective for control of microorganisms associated with fouling in pulp and paper applications. Pulp is digested at relatively high 50 and these temperatures are maintained throughout the papermaking temperatures, 50 process. Therefore, a primary group of microorganisms that must be controlled is 45 DNM-30 12-hr. Exposure thermophilic 45°C) bacteria. A study was 45(grown optimally at temperatures above 12-hr. Exposure conducted40 with samples from a paper mill that wasDNM-30 experiencing serious microbial 40 problems. 35 The microbial problems included significant pH reductions in the primary 35 buffer and in the machine stock chest. Excessive slime formation on the wet end was 30 also observed. 30 To solve the problem, several biocides were evaluated in both the virgin 25 fiber at process temperature. The results are shown in Figures 17-22. and recycled

1 1

1 1

1 1

25 20 20 Note for Figures 17-22: Measurements taken after 8 hours of exposure to biocide. 15 chloride (Quat) was treated at 50 ppm, Aquatreat DMN-30 was Benzalkonium 15 treated at10 50 ppm, methylene-bis-thiocyanate (MBT) was treated at 20 ppm, 10 dibromonitrilopropionamide (DBNPA)120 was treated at 50 ppm and isothiazolone was 120 5 120 120 treated at 255ppm. 0 ppm ppm 0 ppm ppm 0 ppm ppm 0 ppm ppm 0 0
CHILLED WATER #1 CHILLED WATER #2 Figure 17: Virgin Fiber: Total Acid-Forming Anaerobic Bacteria

1 1

1 1

1 1

CHILLED WATER #1

CHILLED WATER #2

1.00E+04 1.00E+04 1.00E+03 1.00E+03
CFU/g CFU/g
CFU/g CFU/g

1

1.00E+02 1.00E+02 1.00E+01 1.00E+01 1.00E+00 1.00E+00
Control Control DNM-30 DNM-30 Quat Quat MBT DBNPA DBNPA Isothiazolone Isothiazolone

1

1

1

Figure 18: Virgin Fiber: Total Anaerobic Bacteria
1.00E+07 1.00E+07 1.00E+06 1.00E+06
CFU/g CFU/g
CFU/g CFU/g Control Control DNM-30 DNM-30 Quat Quat MBT MBT DBNPA DBNPA Isothiazolone Isothiazolone

1

1

1.00E+05 1.00E+05 1.00E+04 1.00E+04 1.00E+03 1.00E+03 1.00E+02 1.00E+02

1

1

1

11

50 45
%CELLULAR CELLULARDAMAGE DAMAGE % % CELLULAR DAMAGE

50 50 45 45 40 40 35 35 30 30
CFU/g DNM-30 DNM-30 12-hr. 12-hr. Exposure Exposure DNM-30 12-hr. Exposure

1.00E+08 1.00E+08 1.00E+08 1.00E+07 1.00E+07 1.00E+07
CFU/g CFU/g

40 35 30 25 20 15 10 5 0

25 25 20 20 15 15 10 10 5 5 0 0 0 0 ppm ppm 0 ppm 120 120 120 ppm ppm ppm 0 0 ppm ppm 0 ppm 120 120 120 ppm ppm ppm

1.00E+06 1.00E+06 1.00E+06 1.00E+05 1.00E+05 1.00E+05 1.00E+04 1.00E+04 1.00E+04 1.00E+03 1.00E+03 1.00E+03

Control DNM-30 Quat Control DNM-30 Quat Control DNM-30 Quat

MBT DBNPA MBT DBNPA Isothiazolone Isothiazolone MBT DBNPA Isothiazolone

CHILLED CHILLED WATER WATER #1 #1 CHILLED WATER #1

CHILLED CHILLED WATER WATER #2 #2 CHILLED WATER #2

The data in Figures 17-22 demonstrate that Aquatreat® DNM-30 is a cost-effective biocide in both virgin and recycled fiber. Aquatreat DNM-30 1.00E+04 1.00E+04 was particularly effective against thermophilic anaerobic bacteria, 1.00E+04 including those causing the pH reduction in the system. Case1.00E+02 History II 1.00E+02 A 650-ton-per-day mill producing clay-coated recycled paperboard was 1.00E+02 in the1.00E+01 process of closing its water system (increasing the use of recycled 1.00E+01 1.00E+01 water and reducing effluent volume). Excess machine whitewater was clarified with a disc saveall. The clarified water from the saveall was 1.00E+00 1.00E+00 1.00E+00 used as shower water on the paper machines. The microbial load of the Control DNM-30 Quat MBT DBNPA Isothiazolone Control DNM-30 Quat MBT basis DBNPA the Isothiazolone water system had been evaluated start of the Control DNM-30 Quaton a weekly MBT DBNPAfrom Isothiazolone recycled water program. Chlorine was applied to the influent water, paper machine stock system and saveall influent. Chlorine residuals were tested on each shift. Shortly after switching to recycled water, total bacterial counts increased 1,000 times and deposit problems began to occur on the paper machine. The deposits were especially prevalent on felt transfer rolls and suction boxes. Deposits periodically broke free and 1.00E+07 1.00E+07 caused sheet breaks. The deposits were analyzed and found to be 1.00E+07 over 90% microbiological, principally slime. Deposits were also found 1.00E+06 1.00E+06 on the showers that had been converted to recycled water. downstream 1.00E+06 It was determined that the most cost-effective program would be to treat 1.00E+05 1.00E+05 only the recycled shower water. A biocide evaluation was performed 1.00E+05 comparing a variety of biocides. Aquatreat DNM-30 was found to have 1.00E+04 1.00E+04 the highest bacterial kill activity in the system and was determined to be 1.00E+04 the most cost-effective biocide. 1.00E+03
CFU/g CFU/g CFU/g CFU/g

Figure 20: Recycled Fiber: Total Acid-Forming Anaerobic Bacteria
1.00E+05 1.00E+05 1.00E+05
CFU/g CFU/g CFU/g

1.00E+03 1.00E+03 1.00E+03

CFU/g

1.00E+04 1.00E+04 1.00E+04 1.00E+03 1.00E+03 1.00E+03 1.00E+02 1.00E+02 1.00E+02

Control DNM-30 Quat Control DNM-30 Quat Control DNM-30 Quat

MBT DBNPA MBT DBNPA Isothiazolone Isothiazolone MBT DBNPA Isothiazolone

Figure 21: Recycled Fiber: Total Aerobic Bacteria
1.00E+08 1.00E+08 1.00E+08 1.00E+07 1.00E+07 1.00E+07
CFU/g CFU/g CFU/g

CFU/g

1.00E+06 1.00E+06 1.00E+06 1.00E+05 1.00E+05 1.00E+05 1.00E+04 1.00E+04 1.00E+04

1.00E+03 1.00E+03 1.00E+02 1.00E+02 1.00E+02

Control DNM-30 Quat Control DNM-30 Quat Control DNM-30 Quat

MBT DBNPA MBT DBNPA Isothiazolone Isothiazolone MBT DBNPA Isothiazolone

Control DNM-30 Quat Control DNM-30 Quat Control DNM-30 Quat

MBT DBNPA MBT DBNPA Isothiazolone Isothiazolone MBT DBNPA Isothiazolone

Figure 19: Virgin Fiber: Total Aerobic Bacteria Figure 22: Recycled Fiber: Total Anaerobic Bacteria
1.00E+08 1.00E+07
CFU/g

1.00E+08 1.00E+08 1.00E+08 1.00E+07 1.00E+07 1.00E+07
CFU/g CFU/g

1.00E+06 1.00E+05 1.00E+04 1.00E+03
Control DNM-30 Quat MBT DBNPA Isothiazolone CFU/g

1.00E+06 1.00E+06 1.00E+06 1.00E+05 1.00E+05 1.00E+05 1.00E+04 1.00E+04 1.00E+04 1.00E+03 1.00E+03 1.00E+03

Control DNM-30 Quat Control DNM-30 Quat Control DNM-30 Quat

MBT DBNPA MBT DBNPA Isothiazolone Isothiazolone MBT DBNPA Isothiazolone

1.00E+05
FU/g

12

1.00E+04

After a system boil-out and cleanup, a biological control program using Aquatreat® DNM-30 was initiated. Aquatreat DNM-30 was fed to the discharge side of the shower water supply pump at an initial rate of 80 ppm and later reduced to 50 ppm. Total bacterial counts were reduced by 100 times. Another significant problem in pulp and paper systems is the growth of yeast and mold. Dithiocarbamates are well known as highly effective fungicides. In Figures 23 and 24, Aquatreat DNM-30 is compared to DBNPA and isothiazolone against mold and yeast. Similar results against fungi have been observed in other applications. Summary of Pulp and Paper Data Aquatreat Biocides should be fed as early as possible into the system at such points as the hydropulper, furnish chest or broke system. Aquatreat Biocides can be used to control slime on machines that make paper and paperboard for use in food packaging regulated under 21 CFR 176.300. Aquatreat Biocides offer the additional advantages of being non-foaming and non-corrosive to equipment. Special feed pumps, gaskets, line feeds and supply systems are not required. Aquatreat Biocides are supplied as aqueous solutions containing no organic solvents. Aquatreat Biocides are safe for systems supplying water to paper machine showers and are not irritating to mill personnel.

Figure 23: Aquatreat DNM–30 Antifungal Activity
1.00E+06

Mold ( Aspergillus niger ) Control

CFU/mL

1.00E+06 1.00E+05

Mold ( Aspergillus niger ) Control DBNPA (25 ppm) Isothiazolone (25 ppm)

CFU/mL

1.00E+05 1.00E+04
0 5 10

DNM-30 (60 ppm) DBNPA (25 ppm) Isothiazolone (25 ppm) 30 15 20 25 Time (H) DNM-30 (60 ppm)

1.00E+04
0 5 10 15 Time (H) Control 20 25 30

1.00E+06 Figure 24: Aquatreat DNM–30 Antifungal Activity 1.00E+05
CFU/mL

1.00E+06 1.00E+04 1.00E+05 1.00E+03 1.00E+04 1.00E+02 1.00E+03 1.00E+01
0 5

DBNPA (25 ppm) Control Yeast ( Candida spp. )

CFU/mL

DBNPA (25 ppm) DNM-30 (60 ppm) Yeast ( Candida spp. ) Isothiazolone (25 ppm) 10 15 DNM-30 (60 ppm) Time (H) 20 25 30

1.00E+02 1.00E+01
0 5

Isothiazolone (25 ppm) 10 15 Time (H) 20 25 30

Benefits of Aquatreat Biocides in Pulp and Paper Applications
• Effective over a wide pH range • Effective on slime-forming bacteria, fungi and yeasts • Meet FDA criteria for use on machines making paper or board for use in food packaging (21 CFR 176.300) • Non-irritating to personnel

13

Sugar Applications
Beet and Cane Sugar Dithiocarbamate biocides such as Aquatreat® DNM-30 are among the few products approved by both EPA and FDA for sugar production. 1.00E+06 Microorganisms account for significant product loss, prolific formation Mold ( Aspergillus ) niger 1.00E+06 of biofilms, organic acid formation, pH drops and Mold ( ) equipment corrosion. Aspergillus niger Control These problems are caused by both mesophillic (optimal growth between Control 1.00E+06 22° and 44°C) and thermophilic bacteria that enter with the beet or cane Mold ( Aspergillus niger ) stock and proliferate throughout the system. These bacteria are largely 1.00E+05 Control DBNPA ppm) comprised of spore-forming organisms such as (25 Bacillus and Clostridium 1.00E+05 spp. and a number of lactic acid DBNPA bacteria (i.e., Leuconostoc and (25 ppm) Isothiazolone (25 ppm) Lactobacillus). Aquatreat® Biocides have a long history of demonstrated Isothiazolone (25 ppm) 1.00E+05 DNM-30 (60 ppm) efficacy in both cane and beet sugar mills. DBNPA (25 ppm)
CFU/mL

Figure 26: Total Sugar Concentration

200

200
160
(g/L)

CFU/mL

160 200 120 120 160 80 80 120 40 40 80
40
0 20 Hours 40

DNM-30 (20 ppm)

CFU/mL

(g/L)

DNM-30 (20 ppm) Competitive Product A* Competitive DNM-30 (20 ppm) A* Product Control
Competitive ControlProduct A* 60 Control

CFU/mL

raw recirculating juice were incubated across time at 55°C. 0 5 10 15 20 25 30 During incubation, aliquots were taken and analyzed for total sugar, total Time (H) lactic acid and pH. Figures 26-28 show a comparison of Aquatreat DNM1.00E+06 30 with a competitive biocide Control for their relative ability to maintain total sugar content in circulating raw juice, limit pH reduction and suppress 1.00E+06 1.00E+05 lactic acid formation. Aquatreat DNM-30 shows superior efficacy relative Control DBNPA (25 ppm) 1.00E+06 to the competitive material. 1.00E+05 1.00E+04
CFU/mL

DNM-30 (60 ppm) Isothiazolone (25 ppm) Laboratory 0 Studies 5 10 15 20 25 30 Time functionality (H) 1.00E+04 Laboratory studies demonstrate the of Aquatreat DNM-30 DNM-30 (60 0 5 10 15 20 25 ppm) 30 for use in the treatment of a beet sugar system. In these studies, fresh Time (H)

1.00E+04

(g/L)

0 20 40 N-METHYLDITHIOCARBAMATE 60 *DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM Hours
*DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM N-METHYLDITHIOCARBAMATE

1.00E+04 samples of

0

20

Hours

40

60

Figure 27: System pH
7

*DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM N-METHYLDITHIOCARBAMATE

pH

1.00E+05 1.00E+03 1.00E+04
CFU/mL

Control Yeast ( Candida spp. ) DBNPA (25 ppm)

76
7 65 6 54 5 43

DNM-30 (20 ppm)

pH

1.00E+04 1.00E+02 1.00E+03 1.00E+03 1.00E+01 1.00E+02 1.00E+02 1.00E+01 1.00E+01
0

( Candida spp. ) Yeast DNM-30 (60 ppm) DBNPA (25 ppm)
Yeast Candida spp. ) Isothiazolone (25( ppm) DNM-30 (60 ppm)
0 5 10 15 20 DNM-30 (60 ppm) (25 Isothiazolone ppm) Time (H) 25 30

DNM-30 (20 ppm)
DNM-30 (20 ppm) Competitive Product A*
0 20 Competitive Hours 40

Control 60 Control

0

5
5

10
10

Isothiazolone 15 20 (25 ppm) 25

30
30

pH

Product A* 4 *DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM N-METHYLDITHIOCARBAMATE 3 Competitive Control 0

Time (H) 15
Time (H)

20

25

3

20 A* Product

Hours
Hours

40

60

0 20 40 60 *DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM N-METHYLDITHIOCARBAMATE
*DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM N-METHYLDITHIOCARBAMATE

Figure 28: Lactic Acid
Concentration (g/L) Concentration (g/L) Concentration (g/L)

0.5

0.4 0.5 0.3 0.5 0.4 0.2 0.4 0.3 0.1 0.3 0.2 0.0 0.2 0.1

Control

Competitive Product A*

Control
Control
DNM-30 (20 ppm)

Competitive Product A* Competitive Product A*
0 20 Hours

40 DNM-30 (20 ppm) 60

*DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM N-METHYLDITHIOCARBAMATE 0.1

DNM-30 (20 ppm)

0.0
0.0
0
0

20
20

Hours

40
40

60
60

Hours *DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM N-METHYLDITHIOCARBAMATE
*DISODIUM CYANODITHIOIMIDOCARBONATE + POTASSIUM N-METHYLDITHIOCARBAMATE

14

103
CFU/mL 66° C

Top

102 104 10 103
1

70° C 65° C

Middle

Bottom

CFU/mL

100 102 0 101 100

66° C 20 70° C

Top 40 Hours Middle 60 Bottom 80

0

20

40 Hours

60

80

250
Concentration (mg/L) Concentration (mg/L)

200 150 250 100 200 50 150 0
Middle Top Bottom Bottom

Field Studies Beet Sugar Field Study I A beet sugar production factory in California employs a 5,000-ton tower diffuser system. The normal chemical treatment before this trial was a shock dose of formaldehyde. No formaldehyde was added in the seven days prior to this trial. Six samples were selected for monitoring. These samples included: • Raw juice leaving cossette mixer • Circulation juice before heaters • Bottom of diffuser • Middle of diffuser • Top of diffuser • Pulp press water at the screens

0 20 40 the addition60 80 Initial sampling was conducted prior to of Aquatreat® DNM100 Hours 30 at a rate of 10 ppm/kg beets. In addition, the spray water at the Middle separator 50 rolls also received 8 pounds of Aquatreat DNM-30 per 1,000 Top tons of beets. Samples were collected at the indicated process points across a 72-hour period. The results of the testing are shown in Figures 0 0 sample points, 20 a clear reduction 40 80 29-32. At all in total 60 thermophilic bacteria was observed. Across the 72 hoursHours of the trial, a significant reduction in lactic acid formation was also observed.

1.00E+04
45° C

Figure 29: Thermophilic Bacteria Counts
104
65° C
4 103 10

Concentration (CFU/mL) Concentration (CFU/mL)

Raw Juice Figure 31: 1.00E+03 Thermophilic Bacteria Counts in Juice and Water Samples Press Water

1.00E+02 1.00E+04 1.00E+01 1.00E+03 1.00E+00 1.00E+02

1.00E+08
ClO2 Raw JuiceCirculating Juice 1.00E+07 66° C 1.00E+08 DNM-30 45° C 72° C (20 ppm) DNM-30 (20 ppm) 60 72° C 80 ClO2 ClO2

8 7.5 8 7 7.5 6.5 7 6 6.5 5.5 6 5 5.5 4.5 5 4 8 4.5 4
Days 8

CFU/mLCFU/mL

65° 66° C C 70° C 66° C 70° C

Top

Concentration Concentration CFU/g CFU/g

3 102 10

Top Middle

Bottom

1.00E+06 1.00E+07 1.00E+05
20

ClO2 Press Water 40 Circulating Juice Hours Mesophiles Thermophiles pH Mesophiles 40 Thermophiles pH Hours

2 101 10

Middle 40 Hours 40 Hours 60

Bottom

0 1.00E+06

1 10 100

1.00E+01 1.00E+00

1.00E+04 66° C 1.00E+05 1.00E+03 1.00E+04 1.00E+02

0

20

80

100

0

20

60

80

0 1.00E+03 20 0

Days

60

80

1.00E+02

0

Figure 30: Lactic Acid Concentration in Diffuser Samples
250
Concentration Concentration (mg/L) (mg/L)

Figure 32: Lactic Acid Concentration in Juice and Water Samples
300 250
Concentration (mg/L) Concentration (mg/L)

150 200 100 150 50 100 0 50 0
Top

200 150 300 100 250 50 200 0 150 100 50 0
0 0

Concentration (CFU/mL Concentration (CFU/mL x 106) x 106)

200 250

9 8 Percent Sugar 9 7 8 Total Bacteria Percent Sugar 6 Circulating Juice 7 5 Total Bacteria Raw Juice 6 4 Press Water 5 Leuconostoc 3 4 20 40 60 2 Circulating Juice Leuconostoc Hours 2 4 6 8 3 0 2
Hours 0 2 Press Water 20 4 40 Hours 6 Hours 60 8 Raw Juice

84 84 82
% Sugar % Sugar

Bottom Middle

82 80 80 78
80 10 12

Bottom

Middle 40 Hours 40 Hours 60 80

0

Top 20

78 76 76

0

20

60

80

10 80

12

15

Concentration CFU/g

Cane Sugar Study I This factory processes 3,000 tons of beets per day and alternates biocide use between chlorine dioxide and Aquatreat® DNM-30. Both 104 biocides were added alternately to the press pulp water prior to entering 65° C the diffuser. The biocides were applied at a concentration of 20 mg/ 3 kg beet. Over an eight-day period, the diffuser juice was monitored for 10 Top 66° thermophilic C totalmesophilic and bacteria. The results are presented in 2 Figure 33. The data show that Aquatreat DNM-30 provided an equal level 10 of control of total better control of total 70° C thermophiles and significantly Bottom Middle mesophiles throughout the duration of the trial. 1
10 100

Figure 33: Diffuser Samples

1.00E+08
ClO2

8
DNM-30 (20 ppm) ClO2

CFU/mL

1.00E+07 1.00E+06 1.00E+05 1.00E+04 1.00E+03 1.00E+02
Mesophiles Thermophiles pH 0

7.5 7 6.5 6 5.5 5 4.5 4

Cane Sugar Mill Study II This cane sugar mill processed 3,000 tons per day of sugar cane 80 0 20 40 60 using mill tandems. RawHours cane was washed to remove solids prior to crushing in the first two crushers. The extracted juice, known as “crusher juice,” contains upwards of 80% sucrose. Cane continues through the tandem mills where more sugar is extracted. The juice from each mill is recirculated to an earlier mill. All the juices were then combined to form the “dilute juice.” The troublesome organism in this system was Leuconostoc mesenteroides, which is responsible for significant sugar inversion and aggressive slime formation.

Days

8

Figure 34: Cane Sugar “Crusher Juice” DNM-30 (20 ppm)

250
Concentration (mg/L)

Concentration (CFU/mL x 106)

Aquatreat DNM-30 was applied to this system at a rate of 20 ppm or about 34 mL/min based on 3,000 tons/day. The effectiveness of control 200 was determined by measuring Leuconostoc counts in sucrose gelatin agar and by analysis of sucrose levels. The results presented in Figure 150 34 indicate that (at the concentration used) the Aquatreat DNM-30 at Bottom 20 ppm acts primarily as a bacteriostat preventing multiplication of the 100 bacteria. Middle
50
Top Summary of Sugar Data Laboratory and field studies have demonstrated that Aquatreat DNM-30 0 is bacteria associated and beet 0 effective in controlling 20 40 60 with both cane 80 Hours sugar manufacturing. In addition, the low relative cost of Aquatreat DNM30 and its ability to reduce sugar loss and control organic acid production and pH make it an excellent biocide for such applications.

9 8 7 6 5 4 3 2
0 2 4 Leuconostoc Total Bacteria Percent Sugar

84 82
% Sugar

80 78 76

6 Hours

8

10

12

1.00E+06
Controls CPU/mL or MPN SRB/mL

1.00E+05 1.00E+04
Heterotrophs

1.00E+04
45° C Concentration (CFU/mL) Raw Juice

1.00E+03
Press Water

1.00E+03 1.00E+02

{
60

60 ppm DNM-30 120 ppm DNM-30

Injection Water (pH = 6.3)+200 ppm Fe SRB (60 ppm) DNM-30

1.00E+02
72° C 66° C Circulating Juice

1.00E+01 1.00E+00
0

1.00E+01

0

20

40

80 100 Time (h)

120

140

160

180

16

20

40

60

80

Benefits of Aquatreat® Biocides in Sugar Applications
• EPA registered • Meet FDA criteria under 176.320 • Effective against difficult-to-treat thermophilic, spore-forming bacteria • Reduces sugar loss and organic acid formation • Cost effective at typical use levels

17

104
65° C

1.00E+08
ClO2 Top Concentration CFU/g

8
DNM-30 (20 ppm) ClO2

10
CFU/mL

3

66° C

1.00E+07
Bottom

7.5 7

102 101 100

70° C

1.00E+06 1.00E+05 1.00E+04 1.00E+03 1.00E+02
Mesophiles Thermophiles pH 0 Days 8

Middle

6.5 6 5.5 5 4.5 4

0

20

40 Hours

60

80

Oil Field Applications
250
Concentration (mg/L) Concentration (CFU/mL x 106)

200 Secondary

and Tertiary Oil Recovery In some oil recovery operations, water is injected into the ground under 150 high pressure to force residual crude oil toward a producing well. The Bottom water is forced through the very small pores of the core rock formation. 100 Any bacterial growth in this water will tend to block pores in the formation, Middle rendering the process far less efficient. Additionally, bacteria, such as 50 SRB, produce Top by-products that cause significant corrosion of pipe and equipment.
0

9 8 7 6 5 4 3 2
0 2 4 Leuconostoc Total Bacteria Percent Sugar

84 82
% Sugar

80 78 76

In these injection systems, Aquatreat® Biocides are highly effective for Hours enhanced oil recovery (EOR) and water floods. They are used in both secondary and tertiary recovery because of their stability in the presence of oxygen scavengers and their non-corrosive characteristics. Aquatreat Biocides are nonaldehyde products with broad activity against both aerobes and anaerobes yet have a low order of toxicity to humans. They are very cost effective when compared with isothiazolone compounds because they are more active, cost less per pound, are safer and exhibit control over a longer period. The activity of Aquatreat DNM-30 has been demonstrated using the American Petroleum Institute (API) RP-39 MIC test. The test was amended 1.00E+04 to include a broad spectrum of SRB, 45° including both cataloged strains and C Rawwater Juice isolates. Table 6 shows that Aquatreat DNM-30 is oil field injection 1.00E+03 very effective against many types of SRB at use concentrations. Aquatreat DNM-30 has been evaluated in a number of oil field injection waters. In Figure 35, a sample from a Wyoming flood project 72° secondary C Circulating Juice was treated with Aquatreat DNM-30, with a significantly high iron content 66° C 1.00E+01 and the total heterotrophic and SRB were followed across time. The data show good control over total heterotrophic bacteria and excellent activity against SRB. 1.00E+00
1.00E+02
0 20 40 Hours 60 80 Press Water

0

20

40

60

80

6 Hours

8

10

12

Figure 35: Aquatreat DNM-30 in Injection Water

1.00E+06
Controls CPU/mL or MPN SRB/mL

1.00E+05 1.00E+04
Heterotrophs

Concentration (CFU/mL)

1.00E+03 1.00E+02

{
60

60 ppm DNM-30 120 ppm DNM-30

Injection Water (pH = 6.3)+200 ppm Fe SRB (60 ppm) DNM-30

1.00E+01

0

20

40

80 100 Time (h)

120

140

160

180

Table 6: Sulfur-Reducing Bacteria—Laboratory Pure Cultures and Enrichments

Sulfate-reducer Desulfovibrio spp. Desulfovibrio spp.
300 250
Concentration (mg/L)

Source ATCC 7757 Oil field Injection Water (New Mexico) Oil field Injection Water (New Mexico) Oil field Injection Water (SW Texas) ATCC 43913 ATCC 49306 ATCC 33890

Enrichment System Med-42 Postgate E API-sulfate API-sulfate Med 1648 Med 1690 Med 1250

MIC (ppm) 20-25 65-70 15-20 55-60 45-50 20-25 120-130

Desulfovibrio spp. Desulfovibrio spp. Desulfobacter spp.
Raw Juice

200 150 100 50 0
0

Desulfomonile spp.
Circulating Juice spp. Desulfococcus

Press Water 20 40 Hours 60 80

18

In Figures 36 and 37, the activity of Aquatreat® DNM-30 is compared with a cocodiamine product in two additional injection waters. The control of aerobic heterotrophic bacteria was monitored across time. The data again show excellent activity of Aquatreat DNM-30 relative to the competitive biocide.

Aquatreat DNM-30 can be used in injection water systems where only short contact time is possible and where more rapid control must be established with slug doses, as opposed to continuous feed. In a study to demonstrate this effect, SRB levels were reduced significantly in the presence of a sulfite oxygen scavenger. Figure 38 shows the effect using 300 ppm of Aquatreat DNM-30. For such systems, Aquatreat DNM-30 should be added after sulfite addition.

Figure 36: Injection Water Samples: Sample 1

1.00E+06 Figure 38: Aquatreat DMN-30 in the Presence of Sulfite 1.00E+06 1.00E+05
Total SRB TotalCounts/mL SRB Counts/mL Total SRB Counts/mL

No Sulfite 100 ppm Sulfite No Sulfite 100 ppm Sulfite No Sulfite 100 ppm Sulfite

1.00E+07 1.00E+07 1.00E+06 1.00E+06 1.00E+05 1.00E+07 1.00E+05 1.00E+04 1.00E+06 1.00E+04 1.00E+03 1.00E+05 1.00E+03 1.00E+02 1.00E+04 1.00E+02 1.00E+01 1.00E+03 0 1.00E+01 1.00E+02 0 1.00E+01
0 10 10 20 20 30 30 40 Time (h) 40 Time (h) 40 Time (h) Control Control CDA (30) Control CDA (30) DNM-30 (120) CDA (30) DNM-30 (120) 70 50 60 50 60 70 DNM-30 (120) 50 60 70 80 80

1.00E+05 1.00E+04 1.00E+06 1.00E+04 1.00E+03 1.00E+05 1.00E+03 1.00E+02 1.00E+04 1.00E+02 1.00E+01 1.00E+03 1.00E+01 1.00E+00 1.00E+02 1.00E+00 1.00E+01 1.00E+00
0 0 2 2 4 4 6 8 Time in Hours 6 8 Time in Hours 6 8 Time in Hours

CFU/mL CFU/mL CFU/mL

12 12

24 24

0

2

4

12

24

Figure 37: Injection Water Samples: Sample 2
1.00E+07 1.00E+07 1.00E+06 1.00E+06 1.00E+05 1.00E+07 1.00E+05 1.00E+04 1.00E+06 1.00E+04 1.00E+03 1.00E+05 1.00E+03 1.00E+02 1.00E+04 1.00E+02 1.00E+01 1.00E+03 0 1.00E+01 1.00E+02 0 1.00E+01
0 10 10 20 20

10

20

30

80

1.00E+08 1.00E+07 1.00E+08 1.00E+06 1.00E+07 1.00E+08 1.00E+05 1.00E+06 1.00E+07 1.00E+04 1.00E+05 1.00E+06 1.00E+03 1.00E+04 1.00E+05 1.00E+02 1.00E+03 1.00E+04 1.00E+01 1.00E+02 0 1.00E+03 1.00E+01 1.00E+02 1.00E+01
0

Control 3.4% Control 3.4% Control 6.8% Control 6.8% Control 3.4% Control 6.8% DNM-30 in 3.4% DNM-30 in 3.4% DNM-30 in 6.8% 5 5 10 DNM-30 in 15 6.8% Time (h) 10 15 Time (h) DNM-30 in 6.8% 10 15 Time (h) 20 25 DNM-30 in 3.4% 20 25

CFU/mL CFU/mL CFU/mL

Control CDA (30) CDA (30)

Control

DNM-30 (120) CDA (30) 30 30 40 Time (h) 40 Time (h) 40 Time (h) 50 60 DNM-30 (120) 70 50 60 70 80 80

CFU/mL CFU/mL CFU/mL

Control

DNM-30 (120) 50 60 70 80

0

5

20

25

10

20

30

1.00E+07 1.00E+07 1.00E+06
Control in 3.4%

1.00E+06 1.00E+05 1.00E+07 1.00E+05 1.00E+04

B/mL

Control in 6.8%

Control in 3.4%

19

1.00E+06 1.00E+06 1.00E+05 1.00E+05
Total SRB Counts/mL Total SRB Counts/mL No Sulfite No Sulfite 100 ppm Sulfite 100 ppm Sulfite

1.00E+04 1.00E+04 1.00E+03 1.00E+03 1.00E+02 1.00E+02

Efficacy in Brines 1.00E+01 1.00E+01 Biocides are frequently used in oil field systems that contain brines and 1.00E+00 their activity under these conditions. As can be seen in must1.00E+00 maintain 12 24 00 22 ® 44 66 88 12 24 DNM-30 maintains its efficacy for both Figures 39 and 40, Aquatreat Time Hours Time inin Hours heterotrophic bacteria and SRB in seawater brine solutions.

Drilling and Well Completion Fluids Water-based drilling fluids are complex aqueous mixtures of specialty clays, starches, water retention agents, thinners and other ingredients. These fluids are subjected to extremes in pressure, shear and temperature as they are recirculated between the drill bit and surface. Water-based completion fluids are highly sophisticated systems based on organic polymers, sand and suspending and crosslinking agents. Like drilling fluids, they are subjected to extremes in pressure, shear and temperature. Recirculation and exposure of drilling and well completion fluids to subsurface conditions can promote bacterial growth. Unchecked, bacteria will degrade the fluids and generate corrosive agents and odors. To inhibit growth, a variety of biocides have been used. Aquatreat Biocides offer a safe and cost-effective choice for use in drilling and well completion fluids.

80 0

Figure 39: Aquatreat DMN-30 Efficacy in Brines: Heterotrophs

1.00E+08 1.00E+08 1.00E+07 1.00E+07 1.00E+06 1.00E+06
CFU/mL CFU/mL

Control 3.4% Control 3.4% Control 6.8% Control 6.8%

1.00E+05 1.00E+05 1.00E+04 1.00E+04 1.00E+03 1.00E+03 1.00E+02 1.00E+02 1.00E+01 1.00E+01
00 55 DNM-30 6.8% DNM-30 inin 6.8% 10 10 15 15 Time (h) Time (h) 20 20 25 25 DNM-30 3.4% DNM-30 inin 3.4%

Benefits of Aquatreat Biocides in Oil Applications
• Effective against anaerobic bacteria such as SRBs • Stable and effective in the presence of oxygen scavengers

80 0

Figure 40: Aquatreat DMN-30 Efficacy in Brines: Sulfate-Reducing Bacteria

• Non-corrosive • Low order of toxicity to humans • Cost effective at typical use levels • Exhibits effective control over a long use period

1.00E+07 1.00E+07 1.00E+06 1.00E+06
SRB/mL SRB/mL Control 3.4% Control inin 3.4% Control Control 6.8% inin 6.8%

1.00E+05 1.00E+05 1.00E+04 1.00E+04 1.00E+03 1.00E+03 1.00E+02 1.00E+02 1.00E+01 1.00E+01
00

DNM-30 3.4% DNM-30 inin 3.4% DNM-30 6.8% DNM-30 inin 6.8% 22 44 88 Time (h) Time (h) 12 12 24 24

20

Comparative Fluid Loss Test One of the most important functions of a drilling mud is to maintain fluid control. Aquatreat® DNM-30 and Aquatreat KM were compared with two different aldehyde-based biocides for API fluid loss control. A base mud was prepared by adding to tap water 7.5 pounds per barrel of bentonite clay while stirring, followed by 3.5 pounds per barrel of attapulgite clay. After the clays were hydrated, 4.0 pounds per barrel of starch were added to the slurry. The base mud was then divided into 350 cc aliquots, and biocide was added as indicated. The base muds were subjected to conditions that would simulate field conditions. The results in Table 7 show that both Aquatreat Biocides were effective throughout the 14-day test period.

Mud Rheology Characteristics Mud rheology is a critical property that must be maintained throughout the drilling process. Unchecked bacterial growth will significantly alter these properties and reduce mud effectiveness. Aquatreat DNM-30 has been demonstrated to effectively control bacteria that may impact rheological properties. This is demonstrated in Tables 8, 9 and 10 and compared with paraformaldehyde.

Table 7: Fluid Loss vs. Time

API FLUID LOSS (mL) Days Treatment Compound Blank Mud pH Aquatreat DNM-30 pH Aquatreat KM pH Paraformaldehyde (dry) pH Aldehyde-type (25%) pH Amount Pounds/bbl 0 1 6.1 8.3 6.8 8.2 6.9 8.3 5.0 8.3 6.4 8.3 3 8.3 10.1 7.3 10.4 7.5 10.3 6.2 10.1 7.4 10.1 5 13.7 8.2 7.9 8.5 7.9 8.4 8.7 8.2 10.5 8.1 7 28.0 8.1 9.8 8.3 10.1 8.4 9.1 8.1 11.5 8.0 9 37.0 8.0 12.0 8.2 13.1 8.3 10.1 8.0 12.9 8.0 14 45.0 7.9 17.1 8.2 19.2 8.2 14.0 8.0 21.0 8.0

.25 as is

.25 as is

.25 as is

1.0 as is

21

Table 8: Base Mud* — No Biocide

Days Fann Data 600 rpm 300 rpm AV. cps PV. cps YP. #/100 ft
2

Int.

1

2

4

6

7

8

12

15

19

12 8 6 4 4 2 4 8.5 10.5

10 7 4 3 4 2 3 8.5 10.5

11 7 5.5 4 3 3 4 8.2 13.0

10 8 5 2 6 3 5 7.7 44.0

11 8 5.5 3 5 5 5 7.6 55.0

12 9 6 3 6 5 5 7.0 55.0

13 9 6.5 4 5 5 4 6.6 56.5

12 8 6 4 4 3 4 6.5 58.5

11 8 5.5 3 5 4 4 6.3 59.1

9 5 4.5 4 1 1 2 5.7 60.0

10 Sec. Gel 10 Min. Gel pH API F.L.

Table 9: Aquatreat DNM-30 — .25#/bbl — 30% Solids

Days Fann Data 600 rpm 300 rpm AV. cps PV. cps YP. #/100 ft
2

Int.

1

2

3

6

7

8

9

13

12 8 6 4 4 2 5 8.5 9.0

12 9 6 3 6 2 4 8.5 9.0

12 9 6 3 6 3 3 8.5 9.0

11 8 5.5 3 5 2 4 8.6 9.0

11 8 5.5 3 5 2 4 8.5 9.0

10 7 5 3 4 2 4 8.6 9.4

11 8 5.5 3 5 3 4 8.5 9.6

10 8 5 2 6 3 4 8.2 9.8

11 8 5.5 3 5 4 4 8.1 15.2

10 Sec. Gel 10 Min. Gel pH API F.L.

Table 10: Paraformaldehyde — .25#/bbl

Days Fann Data 600 rpm 300 rpm AV. cps PV. cps YP. #/100 ft
2

Int.

1

2

3

6

7

8

9

13

16

13 9 6.5 4 5 4 5 8.5 9.5

12 8 6 4 4 3 5 8.5 10.0

11 8 5.5 3 5 4 3 8.6 10.0

11 8 5.5 3 5 3 3 8.7 10.5

10 8 5 2 6 2 3 8.5 11.0

10 7 5 3 4 3 4 8.6 10.8

10 7 5 3 4 2 4 8.5 11.0

10 7 5 3 4 2 3 8.5 12.0

10 7 5 3 4 3 4 8.2 14.0

10 7 5 3 4 3 4 8.3 16.0

10 Sec. Gel 10 Min. Gel pH API F.L.

* Base mud was prepared by adding to tap water 7.5 pounds per barrel of bentonite clay while stirring, followed by 3.5 pounds per barrel of attapulgite clay. After the clays were hydrated, 3.0 pounds per barrel of cornstarch were added. Two pounds per barrel of topsoil were added to each mud.

22

Storage and Handling
Aquatreat® products are available in bulk, intermediate bulk and 55-gallon drums. The standard drum is fiber with 525 pounds net. Plastic drums are also available. Aquatreat polymers have very low toxicity. Consult product MSDS for further information. Contact with the skin or eyes should be avoided. If an Aquatreat product contacts the eyes, flush with water. If redness or sensitivity occurs and persists, consult a physician. Aquatreat polymers should be shipped and stored in 304 stainless steel or better, fiberglass or plastic tanks. Certain phenolic linings are acceptable for use in drums and storage tanks. Mild steel, copper, brass and aluminum should not be used. The above materials of construction also apply to all pipes, valves and pumps used in the application or transport of Aquatreat polymers. Environmental Hazards This pesticide is toxic to fish. Do not apply (or use) in estuarine oil fields where drilling fluids (muds) are discharged in the surface water. Do not contaminate water by cleaning of equipment or disposal of wastes. Do not discharge effluent containing this product into lakes, streams, ponds, estuaries, oceans or other waters unless in accordance with the requirements of a National Pollutant Discharge Elimination System (NPDES) permit and the permitting authority has been notified in writing prior to discharge. Do not discharge effluent containing this product to sewer systems without previously notifying the local sewage treatment plant authority. For guidance, contact your State Water Board or Regional Office of the EPA. Storage and Disposal 1.  PROHIBITIONS: Do not contaminate water, food or feed by storage or disposal. Open dumping prohibited. 2.  PESTICIDE DISPOSAL: Pesticide wastes are toxic. Improper disposal of excess pesticide, spray mixture or rinsate is a violation of federal law. If these wastes cannot be disposed of by use according to label instructions, contact your state pesticide or environmental control agency, or the hazardous waste representative at the nearest EPA regional office for guidance. 3.  CONTAINER DISPOSAL: (a) Reseal container and offer for reconditioning, or (b)  Metal Containers: Triple rinse (or equivalent). Then offer for recycling or reconditioning, or puncture and dispose of in a sanitary landfill or by other approved state and local procedures. (c) Plastic containers: Triple rinse (or equivalent). Then offer for recycling or reconditioning, or puncture and dispose of in a sanitary landfill, or incineration, or if allowed by state and local authorities, by burning. If burned, stay out of smoke. 4.  GENERAL: Consult federal, state or local disposal authorities for approved alternative procedures.
23

Statement of Practical Treatment KEEP OUT OF REACH OF CHILDREN First Aid IF IN EYES - Hold eye open and rinse slowly and gently with water for 15–20 minutes. - Remove contact lenses, if present, after the first 5 minutes, then continue rinsing eye. - Call a poison control center or doctor for treatment advice. IF ON SKIN OR CLOTHING - Take off contaminated clothing. - Rinse skin immediately with plenty of water for 15–20 minutes. - Call a poison control center or doctor for treatment advice. IF SWALLOWED - Call a poison control center or doctor immediately for treatment advice. - Have person sip a glass of water if able to swallow. - Do not induce vomiting unless told to do so by the poison control center or doctor. - Do not give anything by mouth to an unconscious person. IF INHALED - Move person to fresh air. - If person is not breathing, call 911 or an ambulance, then give artificial respiration, preferably by mouth-to-mouth, if possible. - Call a poison control center or doctor for further treatment advice.

HOT LINE NUMBER Have the product container or label with you when calling a poison control center or doctor, or going for treatment. You may also call 1-888-456-6218 day or night for emergency medical treatment information.

For more information on our portfolio of technologies for industrial water treatment applications, visit our website at http://www.akzonobel.com/surface/markets/water_treatment/

Brazil and South America
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Europe, Africa and Middle East
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US, Canada and Mexico
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