Formation of chlorination by-products in drinking water treatment plants using breakpoint chlorination

Dávid Stefán, Norbert Erdélyi, Bálint Izsák, G. Záray, Márta Vargha

Research output: Contribution to journalArticle

Abstract

In drinking water treatment plants generally chlorination is applied for disinfection using Cl2, ClO2, or NaOCl reagents. In Hungary due to the relatively high ammonium ion concentration of source water originating from deep aquifiers, not only the disinfection but simultaneously the ammonium ion removal is also a crucial task to prevent the nitrite formation. For this purposes the breakpoint chlorination is used which needs approximately 10 times more chlorine than the disinfection resulting in enhanced formation of organic and inorganic by-products. Chlorination by-product formation was investigated in twelve drinking water treatment plants applying breakpoint chlorination. Trihalomethanes were detected in the highest concentration (14.7 μg/L to 143 μg/L), followed by haloacetic acids and haloacetonitriles. In 50% of the investigated water treatment plants, the concentration of trihalomethanes in finished water exceeded the Hungarian parametric value, but it was the same range as in water supplies using chlorine for disinfection. The concentration of trihalomethanes, haloacetic acids, haloacetonitriles and adsorbable organic halides in finished water was found to correlate with residual free chlorine (r > 0.5) and raw water temperature (r > 0.48). At high bromide concentration (cBr- > 0.2 mg/L) of the raw water the proportion of brominated by-products (trihalomethanes and haloacetic acids) increased up to 50%. Chlorate concentration was particularly high at drinking water treatment plants using hypochlorite (0.66–2.0 mg/L). By-products are mostly generated at breakpoint chlorination, but their additional formation within the water distribution system is also significant, especially where the concentration of free chlorine is high and the residence time is long. Elimination (potentially biodegradation) of haloacetic acids and haloacetonitriles was observed at several sampling sites. The efficiency of the granulated activated carbon filters in removing adsorbable organic halides, trihalomethanes and haloacetic acids amounted generally under 25%.

Original languageEnglish
Article number104008
JournalMicrochemical Journal
Volume149
DOIs
Publication statusPublished - Sep 1 2019

Fingerprint

Trihalomethanes
Water treatment plants
Chlorination
Drinking Water
Disinfection
Chlorine
Byproducts
Acids
Water
Ammonium Compounds
Chlorates
Ions
Hypochlorous Acid
Water distribution systems
Nitrites
Biodegradation
Bromides
Water supply
Activated carbon
Sampling

Keywords

  • Breakpoint chlorination
  • Chlorination by-products
  • Drinking water treatment plants
  • Haloacetic acids
  • Haloacetonitriles
  • Trihalomethanes

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy

Cite this

Formation of chlorination by-products in drinking water treatment plants using breakpoint chlorination. / Stefán, Dávid; Erdélyi, Norbert; Izsák, Bálint; Záray, G.; Vargha, Márta.

In: Microchemical Journal, Vol. 149, 104008, 01.09.2019.

Research output: Contribution to journalArticle

Stefán, Dávid ; Erdélyi, Norbert ; Izsák, Bálint ; Záray, G. ; Vargha, Márta. / Formation of chlorination by-products in drinking water treatment plants using breakpoint chlorination. In: Microchemical Journal. 2019 ; Vol. 149.
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AB - In drinking water treatment plants generally chlorination is applied for disinfection using Cl2, ClO2, or NaOCl reagents. In Hungary due to the relatively high ammonium ion concentration of source water originating from deep aquifiers, not only the disinfection but simultaneously the ammonium ion removal is also a crucial task to prevent the nitrite formation. For this purposes the breakpoint chlorination is used which needs approximately 10 times more chlorine than the disinfection resulting in enhanced formation of organic and inorganic by-products. Chlorination by-product formation was investigated in twelve drinking water treatment plants applying breakpoint chlorination. Trihalomethanes were detected in the highest concentration (14.7 μg/L to 143 μg/L), followed by haloacetic acids and haloacetonitriles. In 50% of the investigated water treatment plants, the concentration of trihalomethanes in finished water exceeded the Hungarian parametric value, but it was the same range as in water supplies using chlorine for disinfection. The concentration of trihalomethanes, haloacetic acids, haloacetonitriles and adsorbable organic halides in finished water was found to correlate with residual free chlorine (r > 0.5) and raw water temperature (r > 0.48). At high bromide concentration (cBr- > 0.2 mg/L) of the raw water the proportion of brominated by-products (trihalomethanes and haloacetic acids) increased up to 50%. Chlorate concentration was particularly high at drinking water treatment plants using hypochlorite (0.66–2.0 mg/L). By-products are mostly generated at breakpoint chlorination, but their additional formation within the water distribution system is also significant, especially where the concentration of free chlorine is high and the residence time is long. Elimination (potentially biodegradation) of haloacetic acids and haloacetonitriles was observed at several sampling sites. The efficiency of the granulated activated carbon filters in removing adsorbable organic halides, trihalomethanes and haloacetic acids amounted generally under 25%.

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