- Original Paper 351~358. 2012

Corresponding author E-mail: menuturk@hanmail.net Tel: 051-669-4635 Fax: 051-669-4669

Microcystis sp. Cell

Decomposition of Microcystis sp. Cell and Formation of Chlorination Disinfection By-Products

Hee-Jong SonHoon-Sik YeomJong-Mun JungJin-Taek Choi

Water Quality Institute, Water Authority, Busan

(2012 1 11 , 2012 5 29 )

Abstract : Formation of disinfection by-products (DBPs) including trihalomethans (THM), haloacetic acid (HAA) and haloacetonitriles (HAN) from chlorination of extracellular organic matter (EOM) and cells + intracellular organic matter (IOM) of Microcystis sp., a blue-green algae, during decomposed period was investigated. Microcystis sp. cells + IOM and EOM of Microcystis sp. exhibited a high potential for DBP formation. HAAFP (formation potential) was higher than THMFP during decomposed period. In the variations of HAAFP species during decomposed period, the ratio of di-HAAFP species was gradually decreased and the ratio of tri-HAAFP species was gradually increased in the case of EOM during decomposed period, while the opposite result was in the case of cells + IOM during decomposed period. In the variations of HANFP species during decomposed period, the ratio of di-HANFP species was much higher than the ratio of tri-HAAFP species.Key Words : Blue-Green Algae, Microcystis sp., Algogenic Organic Matter (AOM), Chlorination, Disinfection By-Products (DBPs).

: Microcystis sp. AOM disinfection by-products (DBPs) . EOM cell + IOM DBPs , EOM cell + IOM , DBPs HAAFP . , DBP , HAA EOM di-HAA tri-HAA . cell + IOM EOM . , HAN EOM cell + IOM di-HAN . : , Microcystis sp., , ,

1.

, , .1~4) ,

.5,6) (Algogenic Organic Matter, AOM)7)

(Disinfection By-Products, DBPs) .8~10) , AOM

-- ,11) DBPs .12)

AOM (algal cell) (Intracellular

Organic Matter, IOM) (metabolic substances) Ex-tracellular Organic Matter (EOM) .13) IOM

(algal biomolecules) (carbohydrate), (lipid) (protein) , .14,15) , N-acetylglucosamine, N-acetylmuramic acid ,13) fatty acid, polysaccharide .16~18)

, .19)

, EOM (exponential growth phase) glycolic acid amino acid , polysaccharide .13)

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(growth phase) AOM DBPs ,13,20) DBPs EOM 72~90% DBPs , ,

EOM .13)

, EOM Microcystis sp. AOM

Microcystis sp. 20 EOM trihalome-thanes (THMs), haloacetic acids (HAAs) haloacetonitrile (HANs) .

2.

2.1.

2011 10 4 M .

(Millipore) . 300 m3/ pilot-plant 0.45 m (Millipore) 300 mL BOD (2 mL) (chl-a : 225 11 mg/m3) .

. pH 7.0 , DOC UV-254 SUVA 1.97 mg/L, 0.0340 cm-1 1.7279 L/mgm.

2.2.

300 mL BOD 20 60 . , (Scope A1, ZEISS, Germany) 400 .

2.3. AOM

AOM DOC (Sievers 5310C, Sievers, USA) UV-254 (UV-2401PC, Shi-madzu, Japan) , DOC UV-254 SUVA (specific UV absorbance) . , AOM HPSEC (High Performance Size Exclusion Chromatography) , 30 cm, 0.8 cm Zobax GF- 450 (9.4 250 mm, 4 m) UV detector (SPD-6A, Shi-madzu, Japan) HPLC (LC600, Shimadzu, Japan) .

2.4.

10,000 mg/L (Junsei chemical, Japan) 10 mg/L 20 , 10% NaOH (1 + 10) H3PO4 pH 7.0 0.2 20 24

. THMs, HAAs HANs . THMs headspace autosampler GC/ECD (6890N, Agilent, USA) , HAAs US EPA Method 552.3 21) GC/ ECD (6890N, Agilent, USA) , HANs US EPA Method 551.1 22) GC/ECD (6890N, Agilent, USA) .

3.

3.1. AOM

AOM (EOM) DOC, UV-254 SUVA Fig. 1 . Fig. 1 DOC, UV-254 SUVA UV-254 21 0.06803 cm-1 36, 45 60 0.06638, 0.05496 0.04704 cm-1 UV-254 . , DOC 36 3.92 mg/L , SUVA 10 2.04 m-1L/mg .

UV-254 DOC UV-254 DOC . UV-254

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(a) 0 day (b) 10 day after (c) 21 day after

Fig. 2. Photographs of changed Microcystis sp. cells according to increasing storage time.

Fig. 1. Variations of EOM (DOC, UV-254 & SUVA) concentration according to increasing storage time.

AOM (EOM)

(mineralization) UV-254 DOC . Nguyen 23) Henderson 7) AOM 60%~70% .

SUVA / , SUVA 3 . Fig. 1 SUVA 10 2.04 m-1L/mg

AOM , Fang 18) EOM SUVA 1.38 m-1L/mg , Her 24) AOM (Natural Organic Matter, NOM) , SUVA

. , (logarithmic phase) SUVA Henderson 7) .

Microcystis sp. Fig. 2 . Fig. 2(a) 0 Microcystis sp.

IOM . Fig. 2(b) 10 Microcystis sp. IOM , Fig. 2(c) 21 Microcystis sp. IOM

. AOM

Fig. 3 . Fig. 3 (0 day) BAC 50~150 kDa ,

Fig. 3. Variations of molecular weight size distributions of EOM according to increasing storage time.

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10 36 50~200 kDa 50~400 kDa . (0) EOM Fig. 1 BAC (0) DOC UV-254 .

, 10 Microcystis sp.(Fig. 2 (b)) IOM 50 kDa~ 150 kDa AOM AOM 300 kDa , Fig. 1 AOM . Pivokonsky 25) Microcystis aeruginosa EOM IOM EOM IOM , EOM

EOM .

3.2. DBP

EOM AOM (cell + IOM) Fig. 4 . Fig. 4 THMFP, HAAFP HANFP EOM , cell + IOM . EOM (DOC UV- 254) Fig. 2 IOM .

, EOM AOM (cell + IOM) THMFP HAAFP , AOM

NOM

26) THM (THMFP) HAA (HAAFP) , THMFP HAAFP Huang 13) HAAFP .

, EOM HAAFP HANFP 36 , THMFP . EOM Fig. 1 DOC UV-254

Fig. 4. Variations of DBPFP for Microcystis sp. cell + IOM and EOM according to increasing storage time.

Fig. 5. Distribution of HAAFP species for Microcystis sp. cell+ IOM and EOM according to increasing storage time.

, (precur-sor) THMFP DBPs .

EOM AOM (cell + IOM) HAA Fig. 5 . Fig. 5 EOM HAA dichloroacetic acid (DCAA) di-HAA , tri-chloroacetic acid (TCAA) tri-HAA

. AOM (cell +

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34 5 2012 5

Fig. 7. Proposed pathway for the formation of organic chloramines and N-DBPs from chlorination and chloramination of algogenic organic matter (AOM)18).

Fig. 6. Distribution of HANFP species for Microcystis sp. cell + IOM and EOM according to increasing storage time.

IOM) EOM . EOM AOM (cell + IOM) , Huang 13) (death phase)

EOM tri-HAA (lysis) tri-HAA IOM 49% 60 58% tri-HAA , Fig. 2(c) IOM 21 tri-HAA .

EOM AOM (cell + IOM) HAN Fig. 6 . Fig. 6 EOM cell + IOM HANFP 80~90% dichloroacetonitrile (DCAN) di-HAN , 60 . Microcystis aeruginosa Fang (cell + IOM) HAN , TCAN DCAN .27) AOM

Fig. 7 mono-chloramine (RNHCl) di-

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Table 1. Comparisons of DBP formation potential for various organic matter sources

Source SUVA THMFP/DOC HAAFP/DOC HANFP/DOC Reference

NDRWa) - HPIb) 1.26~2.24 16.3~37.3 28.8~32.1 - 26)

NDRWa) - HAc) 2.92~3.52 38.9~55.9 13.8~28.8 - 26)

NDRWa) - FAd) 2.44~3.45 28.1~56.5 9.6~22.5 - 26)

Ce) - HAc) (without Br-) - 40.1 77.7 4.7 31)

Ce) - HAc) (with Br-) - 85.8 50.2 0.2 31)

EOM 1.24~2.04 26.8~30.4 32.4~47.6 1.3~3.1 this studya) NDRW: Nakdong River water, b) HPI: hydrophilic NOM, c) HA: humic acid, d) FA: fulvic acid, e) C: commercial

chloramine (RNCl2) chloramine , halo-aldehyde DCAN .28,29) Halo-aldehyde dihaloacetaldehyde trihaloacetaldehyde , .30) , DCAN (intermediate) dihaloacetamide DCAA dihaloacetic acid

.30) DBP 31)

HAN aspartic acid, histidine, asparagine, tryptophan tyrosine HAN , HAN DCAN .

EOM DOC DBP (DBPFP/DOC, specific DBPFP) Fig. 8 . HAAFP/ DOC (specific HAAFP) 10

, 32.4~45.9 g/mg. ,

Fig. 8. Variations of specific DBPFP for Microcystis sp. EOM according to increasing storage time.

THMFP/DOC (specific THMFP) HANFP/DOC (specific HANFP) 60 , 24.3~ 30.0 g/mg 1.1~3.1 g/mg . DOC specific HAAFP, sp-ecific THMFP specific HANFP .

EOM (DOC) DBPFP Fig. 9 . EOM THMFP EOM (DOC) 0.96 , HANFP EOM 0.93, HAAFP EOM 0.80 .

DOC DBP (DBPFP/DOC) Table 1 . EOM hydrophilic-NOM (NDRW-HPI) SUVA humic acid (NDRW-HA) fulvic acid (NDRW-FA) SUVA . HAAFP/DOC NOM(NDRW-HPI, NDRW-HA NDRW-FA) .

Fig. 9. Relationships between EOM (DOC) concentration and DBPFP concentration.

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4.

Microcystis sp. AOM .

1) Microcystis sp. EOM 20 DOC , UV-254 , EOM 50~150 kDa 50~300 kDa AOM .

2) EOM cell + IOM DBPs , EOM cell + IOM . , DBPs HAAFP , THMFP HANFP .

3) EOM cell + IOM DBP , HAA EOM di-HAA tri- HAA cell + IOM . , HAN EOM cell + IOM di-HAN .

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