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1. INTRODUCTION CHLORINATION AS WATER TREATMENT. The most widely-used technique of water disinfection in aquatic facilities.First modern application:Disinfection in hospitals (1846). 2. CHLORINE AND ITS FORMS 2.1. THE CHLORINE .
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1. CHLORINATIONIN AQUARIA MÓNICA VALLS, NÚRIA GIL, PABLO AREITIO
Parques Reunidos Valencia, S.A. L’Oceanogràfic.
Junta de Murs i Valls, s/n
46013 Valencia, Spain.
ngil@oceanografic.org
2. 1. INTRODUCTION CHLORINATION AS WATER TREATMENT The most widely-used technique of water disinfection in aquatic facilities.
First modern application:
Disinfection in hospitals (1846)
3. 2. CHLORINE AND ITS FORMS2.1. THE CHLORINE “Chloros”: Greek translation of green
Atomic symbol: Cl2
Halogen family
Abundant element in nature (NaCl)
Strong oxidant: Disinfection applications The title on this slide and the next are different, yet both are designated 2.The title on this slide and the next are different, yet both are designated 2.
4. 2. DEFINITION OF CHLORINE & CHLORINATION2.2. COMMONLY USED FORMS OF CHLORINE
5. 3. CHLORINATION & ITS CHEMISTRY3.1. CONCEPT
CHLORINATION: CHLORINE + WATER
The most important reaction in the chlorination process is the formation of hypochlorous acid (HOCl), which is the most powerful disinfecting form
6. 3. CHLORINATION & ITS CHEMISTRY3.2. CHLORINE SUPPLY AND CHEMISTRY
7. 3. CHLORINATION & ITS CHEMISTRY 3.2. CHLORINE SUPPLY AND CHEMISTRY A. Ex situ:
iChlorine gas
iCalcium hypochlorite
iSodium hypochlorite
iChlorine dioxide
8. 3. CHLORINATION & ITS CHEMISTRY 3.2. CHLORINE SUPPLY AND CHEMISTRY A. Ex situ:
a - WITH INTERMEDIATION OF HYPOCHLOROUS ACID:
iCl2 + H 2O g HOCl + (H+ + Cl- ) n OCl- + H+
iCa (OCl) 2 + 2H2O g 2HOCl + Ca + OH
iNaOCl + H2O n HOCl + NaOH n H+ + OCl- + (OH- + Na+ )
b - WITHOUT INTERMEDIATION OF HYPOCHLOROUS ACID: Chlorine dioxide
i 2NaOCl2 + Cl 2 g 2ClO 2 + 2NaCl
9. B. In situ:
Principle: Electrolysis
2NaCl + 3H2O g NaOCl + HOCl + NaOH + 2H2
Generators
-Electrolytic battery using titanium anodes
-Dependent on electricity & water quality
12. 3. CHLORINATION & ITS CHEMISTRY3.3. FACTORS AFFECTING CHLORINATION 1.- Form : Chlorine dioxide > salt efficiency
2.- Temperature:
hTºC, hefficiency
iTºC, hstability
3.- Time of contact: htime, hefficiency
4.- Presence of organic substances: iefficiency
5.- pH: HOCl n OCl- + H+ / ipH, hefficiency
13. pH: Cl2 + H20 n HClO + H+ + Cl- n H+ + ClO- 3. CHLORINATION & ITS CHEMISTRY3.3. FACTORS AFFECTING CHLORINATION
14. 4. BIOLOGICAL EFFECTS 4.1. POSITIVE EFFECTS
DISINFECTION
ORGANIC MATTER OXIDATION
4.2. NEGATIVE EFFECTS
SHORT TERM EFFECTS
LONG TERM EFFECTS Is this one necessary?Is this one necessary?
15. 4. BIOLOGICAL EFFECTS4.1. POSITIVE EFFECTSDISINFECTION
Sterility of water: Neither feasible nor desirable
Control: (Thermotolerant) Coliforms (44.5ºC):
E. coli, Klebsiella sp., others.
Maximum acceptable concentracion of coliforms:
< 1000 CFU / 100 ml
Free Chlorine concentrations for MM tanks:
0,5 – 1,0 ppm (Depending on species, LSS, DOC, others)
Free Chlorine concentrations for Fish tanks:
<0,03 (UNCOMMON)
16. 4. BIOLOGICAL EFFECTS4.1. POSITIVE EFFECTSDISINFECTION
18. 4. BIOLOGICAL EFFECTS4.1. POSITIVE EFFECTSDISINFECTION
19. 4. BIOLOGICAL EFFECTS4.1. POSITIVE EFFECTSORGANIC MATTER OXIDATION Superchlorination: Breakpoint procedure
Use of a high concentration of chlorine (combined residual x10) to oxidize unwanted nitrogenous pollution (ammonia and chloramines) from water.
21. 4. BIOLOGICAL EFFECTS4.2. NEGATIVE EFFECTSSHORT TERM EFFECTS Oxidation of living tissues necrosis >> cell death
Highly irritant to eyes and respiratory system (chloramines in MM)
Chlorine poisoning causing hypoxia in fish
22. 4. BIOLOGICAL EFFECTS4.2. NEGATIVE EFFECTSLONG TERM EFFECTS A. CARCINOGENIC BYPRODUCTS:
Chloro-organic byproducts called trihalomethanes (THMs) like chloroform, bromoform, bromodichloromethane and hundreds of toxic DBPs are suspected carcinogens and not yet well understood
B. ENVIRONMENTAL IMPACT
Unknown accumulation in marine biota
23. 5. MEASUREMENT 5.1. Need of control:
Disinfection efficiency
Toxicity control
5.2. Factors affecting the choice of technique:
Range requirements
Accuracy of technique
Chemical forms of chlorine
On-site analysis or lab analysis
24. 5. MEASUREMENT 5.3. Analytical methods
A. Colorimetric Methods
N,N - diethyl - phenylenediamine method (DPD)
Photometry
Orthotolidine
Leucocrystal violet method
FACTS (Syringaldaxine)
Others: Chlorophenol Red CPR, Amaranth, Lissamine Green B
B. Titrimetric Methods and others
Amperometric titration
Spectrophotometry
Ion Chromatography (ClO2-,ClO3-)
DPD Ferrous titrimetric method
Iodometric titration and FIA Underlines and bolds correct on this page?Underlines and bolds correct on this page?
25. 5.3. Analytical methods
N,N – diethyl - phenylenediamine method (DPD)
Standard method * wide range * rapid *cheap * does not
require a high level of expertise.
Photometry: Accurancy > DPD but
similar characteristics
Amperometric titration:
Expensive * Accurate.
Spectrophotometry: Expensive *
Difficult calibration 5. MEASUREMENT
26. 6. CHLORINE REMOVAL 6.1. Importance
Prevention of toxicity of chlorine (overdosing)
Reduction of toxicity of DBPs
6.2. Techniques
Dilution
Evaporative techniques
Reduction (Sodium thiosulphate and others)
Adsorption
UV radiation Due to overdosing?Due to overdosing?
27. 7. ADVANTAGES AND DRAWBACKS OF CHLORINATION 7.1. ADVANTAGES
Well-known technology
Broad germicidal spectrum
Residual persistence (residual disinfection)
Biocompatibility (at certain dosages)
Easy and flexible application
Inexpensive
28. 7. ADVANTAGES AND DRAWBACKS OF CHLORINATION 7.2. DISADVANTAGES
Other procedures needed prior to chlorination
Toxicity of byproducts
Limited disinfection efficiency (viruses, cysts)
Adverse environmental impact
Safety and security regulations (transport, storage, and handling)
29. 8. CONCLUSIONS Chlorination is a well known, effective and versatile
technology for disinfection to be improved in conjunction with ozone and other water treatments in order to achieve safer and more comfortable environments for the aquatic species kept in Aquaria. 7. Could be conclusions, no?7. Could be conclusions, no?
30. 9.- BIBLIOGRAPHY Connell,G.F The chlorination/Chloramination handbook. AWWA,Denver,CO(1996).
Disinfectants and disinfectant By-Products. Proposed Rule.Fed.Reg(July 29,1994)
Fenner,bob.1999. Frequent Partial water changes.FAMA 5/99
Ibañez, Jorge G.; et.al. Microscale environmental chemistry: production of chlorine dioxide.
White, G.C. 1992 Handbook of chlorination, 4 rd.ed.
31. 10.- ACKNOWLEDGMENTS Akira Kanezaki, for translating this powerpoint presentation even though he doesn’t speak a lick of Spanish.
Allright… some other people at L’Oceanogràfic may have given us a little bit of help, too.