Oxidizing Biocide with function

of slime prevention & removal

Jan 2013 Acculab

☞ Free HOBr generation mechanism of Justeq07

NaOCl + Stabilizer

HOBr Bacteria NaBr

- Steady conversion of Stabilized Chlorine and Bromide to free HOBr in process waters - Oxidation of bromide only occurs in situ (pH 5-9)

Stabilized chlorine + Br- → HOBr

Justeq 07

Oxidizing (NaOCl)

Non-oxidizing

Remark

(A) Air/water pollution

No

5~20% emission of input amount (at pH 8.0~8.5)

No Justeq 07: Odor free (Suitable for factories in the urban areas) AOX ~2/100 less than NaOCl

(B) Bio-fouling Excellent Poor Good ①Justeq 07: prevent biofilm formation at 2nd stage & remove aged bio-film within about 1 month ②increment of U value: energy saving

(C) Resistance (against microbes)

No No Yes

①Mists of non-oxidized biocide solutions have risk of skin irritation & other sensitive issues (Humidifier disinfectant) ②Non-oxidizing biocides are generally using in the paper mill

Biocides for Cooling Water

General biocide usage of standard cooling tower NaOCl solution (~12%) is used as oxidizing biocide for cooling water. In order to complement NaOCl, non-oxidizing biocide may be used every two week.

Justeq 07: stabilized chlorine/bromide ion

(A-1) Chlorine emission: Hypohalous acid and haloamine flashoff in industrial evaporative cooling systems

(A-1-1) Speciation of Cl2, HOCl and OCl- as a function of pH

(A-1-2) The speciation as a function of pH using values for K1 = 3.9x10-4 & K2= 2.9x10-8 at 25℃

(A-2) Case studies : Amounts of hypochlorous acid flushoff by using standard cooling water systems at pH 8.5

Spec of standard cooling water system

Biocides Input (ppm)

Amount (Kg)/month

Amount of NaOCl flushoff

(Kg)/month

Remark

RR ㎥/hr 10,000 NaOCl (ppm/RR) 1 7,200 720 Not good due to the formation of slime δT

℃ 5 Non-oxidized

(ppm/HV/week)

EV ㎥/hr

86.2 NaOCl (ppm/RR) 1

7,200 720 Use non-oxidizing biocide to prevent & reduce the slime growth COC 7 Non-oxidized

(ppm/HV/3 month) 100 600

TBD ㎥/hr

14.4 Justeq 07 (ppm/HV/day)

30 1,800 - No emission. Amount of biocide depends on water quality HV

㎥ 2,000 Justeq 07

(ppm/HV/day) 40 2,400 -

☞ Total usage of halogen can be reduced up to 1/5~1/10

(A-3) Relative AOX formation in cooling tower by halogen biocides

NaOCl (Un-stabilized chlorine)

Stabilized bromine

Justeq 07 (Stabilized chlorine)

Remark

100 % 50% ~20% Based on the chorine consumption rate

100% 40% ~10% Relative AOX formation at same halogen conc (USP 5,683,654 table II)

100% 20% ~2% Final relative AOX formation by Justeq07

AOX: Absorbable Organic Halides: For environmental protection reasons, the AOX value must be monitored at all times. A cooling cycle operating with Justeq07 shows much lower AOX values than a cycle operated with chlorine or bromine

(B-1) Steps in biofilm development

1) Surface conditioning

- Almost immediately a organic layer deposits on the water/solid interface - Conditioning layers neutralize excessive surface charge & surface free energy -The absorbed organic molecules often serve as a nutrient source for bacteria

2) Adhesion of pioneer bacteria

-Some of the planktonic (free-floating) bacteria will approach the wall & become entrained within the boundary layer -Initial attachment is based on electrostatic attraction & physical force

-Some of the reversibly adsorbed cells become irreversibly adsorbed. -Stabilized chlorine/ bromide ion works in stage 2 ☞ No adhesion or removal of pioneer bacteria by killing planktonic microorganism or hindering bacteria attachment

3) Slime formation

- Adsorbed bacteria excrete extracellular substance

- These polymeric substance, or glycocalyx, consists of charged & neutral polysaccharides groups - These substance facilitate attachment & act as an ion-exchange system for trapping & concentrating trace nutrients - In a mature biofilm, more of the volume is occupied by the loosely organized glycocalyx matrix (75~95%) than by bacteria cells (5~25%)

4) Secondary colonizers

- As well as trapping nutrient molecules, the glycocalyx net also snares other types of microbial cells through physical restraint and electrostatic interaction -These secondary colonizers metabolize waste from the primary colonizer as well as produce their own waste which other cell then use in turn

5) Fully functioning biofilm

-The mature, fully functioning biofilm is like a living tissue on the wall surface Mature biofim are imaginatively described in the article “Slime City” -As stabilized chlorine & bromide ion has outstanding penetration properties it overcomes the protective barrier of the aged bio-film and then disintegrate. HOBr by reaction of stabilized chlorine & bromide ion detach the slime structures in addition to the biocidal effect.

penetration time (min.)

chloride ion 5

chlorosulfamate 6

hypochlorite 48

•The mean penetration time into ~1mm thick biofilm

P.S.Stewart et al.

Center for Biofilm Engineering and Department of Chemical Engineering, Montana State University

Journal of Applied Microbiology 2001,91,525-532

(B-2) Penetration rate of chlorine-based biocides into biofilm

(B-3) Increment of U (overall heat transfer coefficient for condenser) by biofilm

Biofilm thickness

(㎛)

U (Btu/ft2*hr*℉)

☞Additional surface area

(%)

0 870 0

100 510 71

120 469 86

243 318 174 0%

20%

40%

60%

80%

100%

120%

140%

160%

180%

200%

- 100 200 300

% o

f a

dditio

nal

surf

ace

area

biofim thickness (㎛)

biofim thickness vs enegy loss

☞ Additional surface area required for compensating water side biofouling

(B-4) Easier cleaning: reduce the cleaning effort - Cleaning works may be hazardous to health w/o the use of protective equipment (dispersed & inhaled germ aerosols, legionella, sick building syndrome, etc)

(B-5) Fountain Application (Everland Youngin Korea)

⇒

⇒

w/o biocide with Justeq 07 after 1 week

No odor

(C-1) Mechanism of action of industrial biocide

Biocide

Electrophiles Membrane active

Oxidant Electrophiles Protonophores Lytic

Chlorine Bromine Ozone Peroxides

Isothiazolones Aldehydes Carbamates DBNPA BNPD

Quats Biguanides Phenols Alchols

Week acids Parabens Pyrithiones

Humidifier disinfectant: PHMG, PGH, CMIT/MIT,

DBNPA: 2,2-dibromo-2-cyanoacetamide BNPD: 2-bromo-2-nitropropane-1,3-diol

Technical brochure of PPChem The mechanism of action of Isothiazolone Biocides Terry M. Williams

(C-2) Humidifier Disinfectants

Methylisothiazolinone, A Neurotoxic Biocide, Disrupts the Association of Src Family Tyrosine Kinases with Focal Adhesion Kinase in Developing Cortical Neurons

1. Journal of Pharmacology and Experimental Therapeuticsjpet.aspetjournals.org Published online before print March 17, 2006, doi: 10.1124/jpet.106.103044 JPET June 2006 vol. 317 no. 3 1320-1329 Dr. Elias Aizenman, Department of Neurobiology, University of Pittsburgh School of Medicine; E1456 BST, Pittsburgh, PA 15261. E-mail: redox@pitt.edu 2. From Wikipedia, the free encyclopedia: Key word (methylisothiazolinone)

1. MIT(methylisothiazolinone) and its closely related analog, chloromethylisothiazolineone or CMIT, affect the ability of young or

developing neurons to grow processes (axons and dendrites) in tissue culture 2. The toxic actions of MIT on developing neurons occurs at much lower

concentrations than those inducing lethal injury (1-3 micromolar). CMIT is even more potent, working at concentrations as low as 0.1 micromolar

☞ One micromolar is approximately 0.115 parts per million.

(C-3) Toxicities of MIT & CMIT

(C-4) Physico-Chemical Properties of Sodium hypochlorite solution

Melting Point: -6°C (21 deg F) (5% solution) Boiling Point: Decomposes above 40°C (104 deg F) pH value: Approx. 11 Odour chlorine (bleach) odour Odour Threshold: Not applicable. Odour is due to breakdown products such as chlorine. Stability: Sodium hypochlorite solution decomposes slowly. Decomposition is speeded up by heat (temperatures above 40 deg C) and light. Hazardous Decomposition Products: Chlorine, oxygen, sodium chlorate.

Corrosion: Test results of Metal corrosion (40℃)

① de-ionized water ② stabilized chlorine/bromide ion：100 ppm ③ 12% NaOCl：60ppm ④ competitor：40ppm + NaOCl：60ppm

Nail 1day Brass 3 days Sus 304 1 month

① ② ③ ④ ① ② ③ ④ ① ② ③ ④

interface

Due to corrosive gas, corrosion occur above interface of ③ & ④

Certification 1 : U.S.A - EPA Reg #: 84024-1 (Oct 18 2007) California EPA Reg (May 25, 2012)

※ Justeq 07: Brand name in U.S.A

Certification 2 : Japan (Dec 22 2011)

☞ Chromosomal aberration test ※ Ecocide 100: Brand name in Japan

-

Certification 3 : Japan (Sept 3 2010)

- 微生物を用いる變異原性試驗 (Ames 試驗)

※ Ecocide 100: Brand name in Japan

# Registered Product Name Distributor Name

1 Cite 8570 Cite corporation

2 Biotrol 409 U.s. water services

3 Alg-715 Aquatech

4 Qwt 2133 Quality water treatment, inc.

5 7407 Power engineering co.

6 Mitco cc-7l microbiocide Mitco inc

7 Justeq07 R2j chemical services

8 Cwt 2190 Masters chemical co inc

9 Busan 1735 Buckman laboratories inc.

10 American #818 industrial microbiocide American water treatment inc

11 United 339 cycle smart stabilized bromine treatment United laboratories, inc.

12 A-207 Chemco products inc.

13 Ml-719 Gehrke technology group

14 Jbc 22 biocide Jentek water treatment, inc.

15 Cesco act 2020 Cesco solutions, inc.

16 Aq4113 Aqualine water treatment products inc

17 Waterchem 2030 Water chemical service, inc.

18 Al-7015 Barclay water management inc

19 Oxy-brom Walling water management

20 Justeq07 Chemtreat inc

21 Mg-3610 Algoma products inc.

22 Justeq07 Pacific standard specialties

☞ U.S.EPA Reg No. : 84024-1

Manufactureer Name: Justeq LLC ☞: Source

http://www.pesticideinfo.org/List_Products.jsp?ProdFormulation=&ChemClassList=&SiteName=&ProdStatus=All&CompName=&PestName=&ChemToxList=&ChooseSearchType=Begin&select2=&ProdTox=&ProdName=&NameType=Both&ProdRegYear=&ChemRegList=&ProdUseList=

Bacteriocide&ChemToxBool=Is&offset=4000

Sub-registration in U.S.A

Summery of Justeq 07

1) Excellent biofilm penetration

2) Not be consumed by the EPS(exo polysaccharides) contained in the slime layer NaOCl(strong oxidizer) react and are consumed by EPS 3) Penetrate to kill the bacteria within the slime layer, leading to removal of

existing slime deposits

4) Easy installation of supply systems (Pump & tank)

5) Protect the operating personnel - No damage by Justeq 07 (no chemical burning & skin irritation)