2 0 1 2 - 8 9

2012. 12

1 3

2 19

3 61

4 79

5 83

.

()

:

()

:

()

:

()

()

()

()

()

()

()

- i -

1

1

1.

8

Geosmin , Microcystin 6 Geosmin 50~194 ppt (2012.8.14 ), 2012.8.15 38~97

ppt, 2012.8.13 6,558 /mL(2012.8.13), Geosmin

292 ppt

Region/countryNatural

lakes

Reservoirs, rivers

and irrigation

systems

Estuaries, agoons

and closed areas

Marine coastal

waters

Africa

Central

North

South

+ ++

+

++

+

++ +

Central America

Caribbean

Guatemala/Nicaragua

Mexico

+

+

+

+

++

+

North America

Canada

USA

++

++

+

++

+

++ +

South America

Argentina/Chile

Brazil

Columbia/Ecuador/Peru

Venezuela/Suriname

+

+

+

+

++

++

++

+

+

++

+

++

+

+

+

Asia

China

India/Pakistan

Indochina

Indonesia/Philippines

Japan

++

+

+

++

++

+

++

+

+

+

+

+

++ +

- ii -

Region/countryNatural

lakes

Reservoirs, rivers

and irrigation

systems

Estuaries, agoons

and closed areas

Marine coastal

waters

Oceania

Australia/New Zealand ++ ++ ++ +

Europe (EU countries)

Belgium

Denmark

France

F. Germany, Fed. Rep.

Greece

Ireland

Italy

Netherlands

Portugal

Spain

UK

++

++

++

++

++

+

++

++

+

+

++

++

++

++

++

+

+

+

+

++

+

+

+

++

+

+

++

Europe (other countries)

Austria

Former Czechoslovakia

Filand

Former German Dem. Rep.

Hungary

Norway

Poland

Romania

Sweden

Switzerland

Former USSR

Former Yugoslavia

++

++

+

+

++

++

++

++

+

+

++

+

+

+

++

+

+

++

+

+

+

+

+

+

++

+

+

+ Identified problems, ++ Serious problems, Source Earthwatch, 1992

- Microcystins: ,

- Geosmin 2-MIB:

2.

- iii -

-

-

-

- Algae Mat

,

- , ,

-

- , . Humic

Fulvic THM

- pH ,

- AOC

-

- iv -

-

2

- ,

-

-

- Clay , Clay

-

- , , ,

*

* Telemetry ( Remote sensing)

-

-

-

* DAF

* ,

* ( O&M)

* ( )

* ( )

*

*

- (2-MIB, Geosmin)

- ()

-

- +

-

-

-

- v -

3

, ,

.

2 -a 15mg/m3

500cells/ml

4

( )

1

(, ) ()

- vi -

2 -a 25mg/m3

5,000cells/ml

4

( )

2 (-a, , , )

(, )

()

2 -a 100mg/m3

106cells/ml

4

( )

2 (-a, , , )

,

(, )

()

2 -a 15mg/m3

500cells/ml

4

( )

()

- vii -

2

1

.

Clay (diatomite) (Phoslock) (algicide) : , 1 DAF .

microcystin PCR, ELISA, HPLC

:

- 2010 GOCI

- (KIOST)

(GOCI)

- Lyngbya majscula Landsat 7 ETM+

Microcytin ImmunoAssay Kit- RIA

- ELISA

- ELISA

- viii -

2 ( )

,

,

()

(TiO2) ( , 1999;

, 2000)

, ,

(, 1988)

TOC, UV-254, ( , 1999)

, , (ABS) ( , 2002)

,

(AQfloc) ( , 2001)

( , 2005)

(2-MIB,

Geosmin)

,

Pilot plant ( , 1996)

, / Filter absorber ( , 2004)

,

( , 1996)

TiO2/UV pH Geosmin ( , 1999)

pH , ( , 2003)

( , 2006)

(

)

,

(TiO2) ( , 2002)

,

,

(LD50) ( , 1999)

-LR ( , 2005)

( , 2003)

- ix -

- , : : DAF (Dissolved Air

Flotation)

-

(Interception Impaction) ( (Head loss))

- (Membrane)

ANABAENA MICROCYSTIS Fouling , DAF

-

Hydroxyl radical Geosmin MIB -

Geosmin 2-MIB Hepatotoxins (Microcystins) , +

-

- x -

Geosmin 2MIB ,

- Microstrainer

,

-

3 (Geosmin, 2-MIB)

Geosmin, 2-MIB(2-Methylisoborneol), -Cyclocitral, 3-Methyl-1-Butanol, TCA2,3,6-Trichloroanisole), IPMP (2-Isopropyl-3-Methoxy

Prazine), IBMP (2-Isobutyl-3-Methyoxy Pyrazine), Sesquiterpenes

(2001) - Geosmin 2-MIB

- /

- Geosmin 2-MIB

- 2-MIB Geosmin

4 ()

Microcystin-LR 1-2 ppm

- xi -

Microcystin-LR (DOC: Lake yhnjrvi = 13.1 ppm, Lake Greifensee = 3.6 ppm) (Onstad et al., 2007)

[ 3] Microcystin-RR 1.1, 6

[ 2-5] Microcystin ( , 2003)

Unit process

Concentration of Dissolved Microcystin

(g m-RR eq./L)

Aug. 26 Sep. 11 Sept. 18 Sept. 25

Raw water 0.014 0.01 0.025 0.028

Pre-chlorination 0.03 - - >0.031

Pre-ozonation ND 0.025 0.02 0.005

Coagulation/Sedimentation ND 0.02 0.01 0.011

Filtration ND 0.02 0.01 0.011

Post-chlorination ND ND ND ND

5

1.

(algaecide) Dissolved Air Flotation (DAF)

- xii -

2. pH

3.

4.

, , , , , , /DAF

: (PAC)

6

- xiii -

3

1

- , , 100-500 Da

EDCs

- (RO) (NF) EDCs PPCPs

- GAC EDCs

- kinetic ,

, , carbon , NOM

(Biological and chemical conversion)- ,

(AOPs) EDCs PPCPs

- (supercritical fluid extraction), ,

EDCs

E1 E2

(pH 7, O3 = 1 mg/L, E1 & E2 = 2 mg/L) ( , 2006)

- xiv -

(ng/L, n=20) (Snyder, 2009)

(3.5 mg/L dose)

(Snyder, 2009)

UV (40 mJ/cm2)

(Snyder, 2009)

(2.5 mg/L dose)

(Snyder, 2009)

- xv -

2

- NF 1990

- 2

- , 1

4 Geosmin 2-MIB

(Dixon , 2011)

- xvi -

-

(2-MIB,

Geosmin)

C. Robert Reiss, James S.

Tayler, Christophe Robert

Surface water treatment using nanofiltration - pilot

testing results and design considerations1999

Anand J. Mody

Feasibility of using nanofiltration as a polishing

process for removal of cyanobacterial exudates from

treated surface water

2004

Mike B. Dixon,

Chorlotte Falconet,

Lionel Ho,

Christopher W. K. Chow,

Brian K. ONeill,

Gayle Newcombe

Removal of cyanobacterial metabolites by nanofiltration

from two treated waters2011

(Microcystin)

M. R. Simpson,

B. W. MacLeod

An integrated approach to algal by-products including

bench scale evaluation of nanofiltration for microcystin

removal

2002

D. P. Smith,

V. Falls,

A. D. Levine,

B. W. Mac Leod,

M. Simpson,

T. L. Champlin

Nanofiltration to augment conventional treatment for

removal of algal toxins, taste and odor compounds,

and natural organic matter

2002

Margarida Ribau Teixeira,

Maria Joao RosaMicrocystins removal by nanofiltration membrane 2005

A. J. Gijsbertsen-Abrahamse,

W. Schmidt,

I. Chorus,

S. G. J. Heijman

Removal of cyanotoxins by ultrafiltration and

nanofiltration2006

Margarida Ribau Teixeira,

Maria Joao Rosa

Neurotoxin and hepatotoxic cyanotoxins removal by

nanofiltration2006

M. B. Dixon, C. Falconet,

L. Ho, C. W. K. Chow,

B. K. ONeill,

G. Newcombe

Nanofiltration for the removal of algal metabolites and

the effects of fouling2010

- xvii -

-

20kHz .

/ (cavity)

,

. .

- 5000K, 1000atm

- 500 m/s

(micro-jet) .

- xviii -

[ 3-2]

(: , : , : )

- xix -

4

-

-

-

-

- RFP

- R&D

- xx -

1 3

1 3

2 12

3 13

2 19

1 19

2 ( ) 30

3 (Geosmin, 2-MIB) 43

4 () 46

5 49

6 56

3 61

1 61

2 67

4 79

5 83

- xxi -

Perceived eutrophication problem in different continents and countries 4

12

15

31 DAF+PAC 35

Geosmin, 2-MIB , OH 46

Microcystin-LR , OH 47

Microcystin ( , 2003) 49

57

- xxii -

[ 1-1] 3

[ 1-2] Anabaena 5

[ 1-3] Microcystis 5

[ 1-4] 7

[ 1-5] Microcystins 7

[ 1-6] 10

[ 1-7] 11

[ 1-8] . 15

[ 2-1] 24

[ 2-2] 25

[ 2-3] 25

[ 2-4] 26

[ 2-5] 31

[ 2-6] Typical DAF system 33

[ 2-7] 33

[ 2-8] (Halosource) 33

[ 2-9] Mechanism 36

[ 2-10] Diffusion, Interception, Sedimentation 37

[ 2-11] Mechanism 38

[ 2-12] Spectrum 39

[ 2-13] Glycine Valine (-NH2) functional group , 39

Organic Chloramine

[ 2-14] Macro, Meso, Micro Pores 41

[ 2-15] Geosmin 2-MIB 41

[ 2-16] Fraction of odour compound remaining as a function of time 41

[ 2-17] Geosmin ( , 2004) 45

- xxiii -

[ 2-18] Microcystin-LR 47

[ 2-19] Microcystin-LR 48

[ 2-20] 50

[ 2-21] 50

[ 3-1] 75

[ 3-2] 76

1

1

2

3

1

3

1

1

1.

8

. Geosmin , Microcystin

. 20%

. 2012.8.6 Geosmin 590 ppt

. 2012.8.9 Anabaena, Microcystis

(Microcystin-LR ) . 2012.8.17

-a 14.3~34.2 mg/m3, 1,180~4,470 /mL (2012.8.8 )

. -a 15 mg/m3, 500 /mL

. 6 50~194 ppt (2012.8.14 ) ,

2012.8.15 38~97 ppt . 2012.8.13 6,558

/mL(2012.8.13), 292 ppt .

[ 1-1]

4

Perceived eutrophication problem in different continents and countries

Region/countryNatural

lakes

Reservoirs, rivers

and irrigation

systems

Estuaries, agoons

and closed areas

Marine coastal

waters

Africa

Central

North

South

+ ++

+

++

+

++ +

Central America

Caribbean

Guatemala/Nicaragua

Mexico

+

+

+

+

++

+

North America

Canada

USA

++

++

+

++

+

++ +

South America

Argentina/Chile

Brazil

Columbia/Ecuador/Peru

Venezuela/Suriname

+

+

+

+

++

++

++

+

+

++

+

++

+

+

+

Asia

China

India/Pakistan

Indochina

Indonesia/Philippines

Japan

++

+

+

++

++

+

++

+

+

+

+

+

++ +

Oceania

Australia/New Zealand ++ ++ ++ +

Europe (EU countries)

Belgium

Denmark

France

F. Germany, Fed. Rep.

Greece

Ireland

Italy

Netherlands

Portugal

Spain

UK

++

++

++

++

++

+

++

++

+

+

++

++

++

++

++

+

+

+

+

++

+

+

+

++

+

+

++

1

5

Perceived eutrophication problem in different continents and countries()

Region/countryNatural

lakes

Reservoirs, rivers

and irrigation

systems

Estuaries, agoons

and closed areas

Marine coastal

waters

Europe (other countries)

Austria

Former Czechoslovakia

Filand

Former German Dem. Rep.

Hungary

Norway

Poland

Romania

Sweden

Switzerland

Former USSR

Former Yugoslavia

++

++

+

+

++

++

++

++

+

+

++

+

+

+

++

+

+

++

+

+

+

+

+

+

++

+

+

+ Identified problems, ++ Serious problems, Source Earthwatch, 1992

Anabaeda Filamentous Cyanobacteria . Mosquito fern

.

, Microcystins . Geosmin

2-MIB .

[ 1-2] Anabaena [ 1-3] Microcystis

6

Mycrocystis Cyanobacteria,

Neurotoxins hepatotoxins . Mycrocystis

1996 (Caruaru) 50 .

. .

Microcystin-LR WHO guideline 1 g/L. Microcystins

, 0.5mg Cl2/L 30 pH < 8

100% 1). Microcystins , //

59~97% .2) Microcystin 1931 Ohio

River . Harare(Zimbabwe)

. 1996 55 ( )

. Cynobacteria

. Mycrocystin WHO Guideline

. Tolerable Daily Intake (TDI) level (WHO) 0.04 g/kg/d

. WHO MICROCYSTIN-LR 1 g/L (ppb).

5~10 mg/kg body .

MICROCYSTIN 1 g/L~100 mg/L 3). 20

g of Microcystin-LR per gram of supplement .

Anabaena (Baker and

Humpage, 1994; Codd, 2000). Anabaena anatoxin-a, anatoxin-a(s), (paralytic

shellfish poisoning, PSP) (Rapala and Sivonen, 1998). Anabaena

heterocyst()

. ,

(Kim and Lee, 1996; Lee et al., 1998; Kim et al., 1999).

, ,

3 . 5ppt

. (Earthy Taste)

1) Destruction of cyanobacterial peptide hepatotoxins by chlorine and chloramine, Water Research, Volume 28, Issue 6, June

1994, Pages 1297-1303

2) Endotoxins associated with cyanobacteria and their removal during drinking water treatment, Water Research, Volume 36,

Issue 10, May 2002, Pages 2627-2635

3) http://ntp.niehs.nih.gov/ntp/htdocs/chem_background/exsumpdf/microcystin.pdf

1

7

. Cyanobacteria (blue-green algae) Actinobacteria ( Streptomyces) (Algae)

. Geopsmin , (Algae)

.

[ 1-4] [ 1-5] Microcystins

2.

.

- - - - Algae Mat

,

- , ,

- - , . Humic

Fulvic THM

- pH , - AOC

8

.

EOM (Extracellular Organic Matter)

7~60% (Fogg. 1996)

EOM EOM

pH floc

.

. , ,

. pH Alum

.

, flotation

.

.

2~3

5~6 .

, 10

~20 .

1

9

(Konno, 1993)

2~3 5~6

10~20

,

Geosmin 2-MIB .

, ,

.

.

.

((Fe) (Mn) )

. (Fe)(Mn)

.

(Fe)(Mn) , .

, (Fe)(Mn) .

, (slime) , .

, ,

10

, ,

, .

, ,

.

[ 1-6, 1-7] AWWA Malcolm & Pirnie

. ,

. ,

, .

Br- (BrO3-)

, .

. .

.

.

. ,

.

[ 1-6] 4)

4) AwwaRF Project #3111 "Strategies for Controlling and Mitigating Algal Growth within Water Treatment Plants". (Malcolm

Pirnie, Inc.)

1

11

[ 1-6]

. .

. ,

, .

[ 1-7] 5)

- 2-MIB, geosmin, microcystin

.

- , ,

.

5) AwwaRF Project #3111 "Strategies for Controlling and Mitigating Algal Growth within Water Treatment Plants". (Malcolm

Pirnie, Inc.)

12

2

, ,

.

.

- ,

-

-

- Clay , Clay

-

- , , ,

*

* Telemetry ( Remote sensing)

-

-

-

* DAF

* ,

* ( O&M)

* ( )

* ( )

*

*

- (2-MIB, Geosmin)

- ()

-

-

-

-

-

1

13

3

1.

.

, , , , ,

, LG, Water Journal,

.

2.

- , m m . ,

. 2002

12 ()

,

, , 3

, , 5, 5

. 2050

.

- 16 2030 , ,

.

- 46 A1, A2, A3 3

. A1

12 . A2 , , ( :

+ + + +) 23

. A3 , ,

14

3 . , .

,

20m 1 .

3.

1996 2011 , , ,

, ,

. ,

.

, ,

.

-

.

- WHO

microcystin 1 microcystin-LR/L Microcystis

5,000 cells/ml 10 500 cells/ml

(Chorus and Bartram, 1990; Falconer et al., 1994).

21 ()

, [ 1-8] .

1

15

[ 1-8] .

- .

2 -a 15mg/m3

500cells/ml

4

( )

1

(, ) ()

16

()

2 -a 25mg/m3

5,000cells/ml

4

( )

2 (-a, , , )

(, )

()

2 -a 100mg/m3

106cells/ml

4

( )

2 (-a, , , )

,

(, )

()

2 -a 15mg/m3

500cells/ml

4

( )

()

2

1

2

3

2

19

2

1

1.

, ,

, ,

clay, , , ,

- Clay Clay ,

Clay clay clay

clay

clay clay

(, 2001)

- (diatomite) 2008 75% harmful algal blooms (HABs)

EOM

(Chun-De Wu, 2011)

20

- Clay

(, 1997)

- pH

(, 2000)

- (Phoslock) De Ploeg

(Miquel

Lrling, 2011)- (algicide)

,

2

2

21

Tohoku Microcystis aeruginosa L-lysine malonic acid (Kaya et al. 2002)

Oxford /

(Newman & Barret, 1993)

- , ,

1

-

- () 2

DAF

- ()

,

.

.

.

- DAF , , .

() ()

, 50~100 .

22

, ,

,

,

.

- , (310) , micro-agitation

,

,

.

(PAC)

.

- 5~10 , , ,

,

, .

2.

.

MicrocystisAnabaenaAphanizomenonOscillatoria

,

,

,

synedraAsterionellaCyclotellaMelosira

Melosilra

,

ClosteriumCacuiculatePediastriumScenedesmusBortyococcus

2

23

Eugleoids

TrachelomonasEuglena

Euglena

PeridiniumGymnodinium

,

Uroglena

-

Anabaena Aphanizomenon Heterocyst

seed

Polyphosphate body (Okino, 1973)

pH m

(Lampert, 1981)

.

, , , 4

24

718 1608 cell/ml 81 3943 cell/ml 2

-a 17.5 mg/m3 39.8 mg/m3 2

(anabaena)

, ,

- , ,

microcystin PCR, ELISA, HPLC

.

- Lugol's solution

,

. ( 3)

4

,

.

[ 2-1]

), ) a .

2

25

[ 2-2]

- ()

(, class)

[ 2-3]

26

[ 2-4]

6

- () (AOA fluorometer) 4 phytoplankton

a

AOA a

a - (1)

2008 2010 GOCI

GOCI GOCI 2011 2012

GOCI 555, 745, 865nm

660, 680nm

2

27

Index of floating Green Algae for GOCI (IGAG) NDVI, EVI

2011 2012

- (2)

(KIOST) (GOCI)

- (3) 2007 1997 Lyngbya majscula

,

Landsat 7 ETM+ GPS point boat based - (4)

Baltic Sea

Hyperspectral bloom high revisit

times

ALI, Landsat MODIS MERIS 6 7 band 640nm

28

phycocyanin

- (1) GIST

/

- (2)

algae bloom

Water Research in-vivo fluoroscopy(IVF) calibration , , chlorophyll-a

phycocyanin

Chlorophyll-a IVF

Chlorophy11-a,

- 1998 , , ,

.

- -a , , , microcystin

2

29

(Park et

al., 2007).

- -a

.

.

.

- , ,

.

- , ,

. ( )

.

- Microcystins .

,

.

- ,

sensor .

- ,

.

Microcytin ImmunoAssay Kit

- RIA RIA (tritium) microcystin-LR ,

30

microcystins microcystin-

.

microcystin microcystin

.

- ELISA plate Horseradish peroxidase(HRP) microcystin

.

- ELISA microcystin-LR poly L-lysine plate

, HRP .

3 Microcystin immunoassay kit Millipore() , Satoshi Nagata Monoclonal

Wako() kit

.

(), () microcystin microcystin

sensor .

-a sensing

,

.

2 ( )

, , /, , , , ,

. , ,

. (Algae)

. 4 ~ 100 um .

/, , .

Geosmin, 2-MIB, Microcystins, Protein (Amino Acids) .

2

31

/, , , /

.

[ 2-5]

- , .

,

, ()

(TiO2) ( , 1999;

, 2000)

, ,

(, 1988)

TOC, UV-254, ( , 1999)

, , (ABS) ( , 2002)

,

(AQfloc) ( , 2001)

( , 2005)

(2-MIB,

Geosmin)

,

Pilot plant ( , 1996)

, / Filter absorber ( , 2004)

32

()

(2-MIB,

Geosmin)

,

( , 1996)

TiO2/UV pH Geosmin ( , 1999)

pH ,

( , 2003)

( , 2006)

(

)

,

(TiO2) ( , 2002)

,

,

(LD50) ( , 1999)

-LR ( , 2005)

( , 2003)

, ,

.

,

. ,

, , .

DAF (Dissolved Air Flotation) ,

. [ 2-6] DAF . DAF

, .

. [ 2-7]

. [ 2-8]

.

,

. ,

.

2

33

[ 2-6] Typical DAF system

[ 2-7]

[ 2-8] (Halosource)

a) Algae non-treated b) Algae Chitosan treated

c) Algae non-treated + sand filtered d) Algae Chitosan treated + sand filtered

(DAF : Dissolved Air Flotation)

. 1970

2012 1,100,00ton/day

Croton .

34

1.

DAF system .

. ,

Floc . DAF

. Water Research Centre bench scale pilot plant

DAF system , .

2.

.

,

. DAF

. DAF 1987 2007

. DAF 90~99% ,

2

35

60~90% . NOM

. 1 DAF

(PAC) Anabaena, Microcystin, 2-MIB, Geosmin

. PAC

2-MIB, Geosmin 92%, 98% .

Without PAC With PACa

Anabaena 96% 94%

Microcystin 96% 95%

2-MIB 2% 92%

Geosmin 5% 98%

DAF+PAC

. 1 : Chingford South Plant

DAF 1970 Chingford South Plant 2005

41,700 ton/day DAF , a 14~23 g/L

49~90 g/L .

. 2 : Winnipeg

Winnipeg DAF 400,000 ton/day CH2M Hill

2010 . DAF

, 666,000 cells/mL

DOC . DAF++GAC+UV ,

.

. 3 : Haworth

Haworth 2009 760,000ton/day DAF

, TOC . 300~30,000 cells/mL

, pH 7~9

DAF .

36

3.

DAF system 30 (2-4) ,

(conventional gravity settling system) , ,

, , .

.

, NOM TOC

, THMFP . DAF

,

.

4.

.

, [ 2-9] , Diffusion, Interception, Impaction()

. ANABAENA 4~50 m , MICROCYSTIS 50 m

. [ 2-10] Interception Impaction

() . .

(Head loss) , . 24 ~ 36

8 hr .

.

[ 2-9] Mechanism

2

37

[ 2-10] Diffusion, Interception, Sedimentation

.

, Synedra, Meiosira. Achnanthes,

Asterionella. Fragilaria , Synedra

.

. (, ), (

, , )

. 15~25cm

.

,

. , .

20cm

4~10 . ,

( 0.99mm 1.734) 2~2.5cm

, 3,

38

( 25cm ) 70%

. ,

, ,

.

Roughing filter

Roughing filer Synedra

. Synedra s.p.

, Roughing filter

.

(Membrane)

.

Membrane

. 0.01 m ,

99% , .

,

.

ANABAENA MICROCYSTIS [

2-11. 2-12].

. AOM (Algal-derived Organic Matter),

Fouling , .

, DAF

.

[ 2-11] Mechanism

2

39

[ 2-12] Spectrum

Alage AOM(Algal-drived Organic Matter)

. Geosmin 2-MIB, Neurotoxins Hepatotoxins

, Protein . AOM

, , . AOM

Dissolved Organic Nitrogen (DON)

. DON(Dissolved Organic Nitrogen)

Organic Chloramines . DPD

.

[ 2-13] Glycine Valine (-NH2) functional group ,

Organic Chloramine

40

Chloroform DBP ,

Mutagen . DON Fouling

.

Hydroxyl radical Geosmin MIB .

pH 8 H2O2 AOP (Advanced Oxidation Process)

. OZONE + BAC

. EDCs (Endocrine

Disruptor Chemical) PPCPs (Pharmaceuticals and Personal Care Products) .

Algae , AOC(Assimilable

Organic Carbon) . AOM

.

. THMFP 10% , HAAs .

Microcystins . O3

OH .

.

.

. [ 2-14] PAC() GAC() .

BAC (Biological Activated Carbon) .

Geosmin 2-MIB . Hepatotoxins (Microcystins)

(PAC 50 mg/L ), + .6)

80% Hepatotoxins .7) Hepatotoxins

. ,

. [ 2-15, 16] Geosmin

, 2-MIB .

6) The effect of water treatment processes on the removal of hepatotoxins fromMicrocystis andOscillatoria cyanobacteria: A

laboratory study, Water Research Volume 23, Issue 8, August 1989, Pages 979-984

7) Adsorption of microcystin-LR by activatedcarbon and removal in full scale water treatment, Water Research Volume 30,

Issue 6, June 1996, Pages 1411-1422

2

41

[ 2-14] Macro, Meso, Micro Pores

[ 2-15] Geosmin 2-MIB

[ 2-16] Fraction of odour compound remaining as a function of time

42

.

Geosmin 2MIB ,

. Melosira, Synedra . Microcystis

, .

,

.

,

.

. ,

, .

.

,

, .

. , 0.1 /L

.

5. Microstrainer

. Microstrainer

Microstainer ,

. 1945

,

. Microstainer 3m, 3m

35 . 5 3 ,

. 1

1

2

43

. ,

. , Fragilaria, Asterionella 95% , Synedre 80%

, ( ) .

, ,

,

. .

.

.

, .

.

,

. Microstainer

Microcystis ,

.

3 (Geosmin, 2-MIB)

2

.

,

.

.

90%

.

44

1960 ,

, 30

.

1986

, 1988

. .

.

.

Geosmin, 2-MIB(2-Methylisoborneol),

-Cyclocitral, 3-Methyl-1-Butanol, TCA2,3,6-Trichloroanisole), IPMP (2-Isopropyl-3-Methoxy

Prazine), IBMP (2-Isobutyl-3-Methyoxy Pyrazine), Sesquiterpenes .

Geosmin 2-MIB actinomycetes cyanobacteria

,

. ng/L

( 4 - 20 ng/L) ,

.

(2001) Geosmin 2-MIB

Pilot Scale . /

/ , ,

/ .

Geosmin 2-MIB

2 ppm 40% .

10 ppm 40-55% .

(, 2001) 2-MIB Geosmin

. pH

.

.

2

45

( , 2004) ([ 1]), Geosmin

51-60%, 2-MIB 34-57% . , 3 Geosmin GAC

O3+GAC 100% , 25000Bed volume GAC

10ng/L, O3+GAC 5ng/L . Geosmin GAC

GAC .

[ 2-17] Geosmin ( , 2004)

Geosmin 2-MIB

. Peter and von Gunten (2007) Geosmin

2-MIB OH ([ 1]).

Geosmin 2-MIB 0.10, 0.35 M-1s-1

2 ppm

(99% ) 103 M-1s-1 .

Peter and von Gunten (2007) Geosmin 2-MIB

Rct .

1-2 ppm 59-86% .

[ 2-3] OH , Geosmin

2-MIB OH . Geosmin 2-MIB

OH

/ .

46

(2001) /

Geosmin, 2-MIB .

Geosmin, 2-MIB , OH

(Peter and von Gunten, 2007)

Compound kO3 (M-1s-1) kOH (M-1s-1)

Geosmin 0.10 7.80109

2-Methylisoborneol (2-MIB) 0.35 5.09109

Geosmin, 2-MIB ,

OH Rct

.

/ ( // )

.

4 ()

,

.

Microcystis Anabaena , Microcystis

. Microcystin 7 1,000

, LR, LA, YR, RR 70

( , 1999). Microcystins

, Microcystin-LR .

Onstad et al. (2007) Microcystin-LR OH

(). 4.1105 M-1s-1

Microcystin-LR

.

2

47

Microcystin-LR , OH

(Onstad et al., 2007)

Compound kO3 (M-1s-1) kOH (M-1s-1)

Microcystin-LR 4.1105

1.11010

(Onstad et al., 2007) Microcystin-LR 1-2 ppm

. [ 2-18]

(13.1 ppm) Lake yhnjrvi 2 ppm Microcystin-LR , 3.6 ppm Lake Greifensee

0.5 ppm .

OH Scavenger t-BuOH

Microcystin-LR

Microcystin-LR .

[ 2-18] Microcystin-LR

(DOC: Lake yhnjrvi = 13.1 ppm, Lake Greifensee = 3.6 ppm) (Onstad et al., 2007)

Microcystin-LR [ 2]

.

48

[ 2-19] Microcystin-LR

, cell lysis

. Lam et al.(1995) Microcystin-LR

Microcystin-LR

.

.

Microcystin-LR Daly et al. (2007)

cell lysis Microcystin-LR

. , Maatouk et al.

(2002) Saint-Caprais reservoir (France)

98% .

, ( , 2003)

[ 3] Microcystin-RR 1.1, 6

. /

Microcystin

.

2

49

Microcystin ( , 2003)

Unit process

Concentration of Dissolved Microcystin

(g m-RR eq./L)

Aug. 26 Sep. 11 Sept. 18 Sept. 25

Raw water 0.014 0.01 0.025 0.028

Pre-chlorination 0.03 - - >0.031

Pre-ozonation ND 0.025 0.02 0.005

Coagulation/Sedimentation ND 0.02 0.01 0.011

Filtration ND 0.02 0.01 0.011

Post-chlorination ND ND ND ND

Geosmin, 2-MIB / OH .

/

.

OH

.

5

, , .

,

. . 2-MIB,

geosmin, microcystin

.

,

,

.

50

[ 2-20]

1.

DAF

.

.

[ 2-21]

2

51

- Hu 2003 , cyanobacteria

2-MIB geosmin .

, .

(algaecide)

. Esparza-Soto 2004 99% .

,

.

2~3 .

Dissolved Air Flotation (DAF)

Dissolved air flotation (DAF)

. Fuerst DAF

. DAF 90%

, .

DAF

. DAF

. DAF

70~100% .

DAF

, 2-MIB, geosmin, microcystin

. DAF

Marvin . Marvin DAF

3 . Suthaker

+ DAF

.

52

2. pH

. 1.01-1.18g/, ,

. .

Shehata PAC alum ferric

chloride .

2-MIB, geosmin, microcystin

Jar-test

. Sengco montmorillonite

2-MIB, geosmin, microcystin

, .

Clasen DOC

. DOC

, DOC .

,

.

pH

pH ,

pH .

pH , pH

NaOH . Yahi NaOH pH

, pH

.

Plummer

2

53

, ,

. DOC

.

3.

,

. 1g/cm3

.

.

.

.

.

. ,

, .

4.

- AWWA

.

. Mouchet Bonnelye

,

85% 99% ,

90% .

,

54

.

- Shehata Alum

. Rastogi Knappe 3 ppm 80%

, 0.5 ~ 1 ppm 20% .

.

.

- (ClO2) 91% . Gregory

92% ~ 100% 15

. , EPA 1

ppm .

- Plummer Edzwald

. Steffensen trihalomethane(THM)

haloacetic acid(HAA) 27% ~29%

.

.

- Rusin MIB geosmin

. Burch

, geosmin

2 ppm .

-

. Hao

43.8% 50% .

Ahn Microcystis aeruginosa , 3

66% 0.3% . Lee

2

55

8

,

.

- /DAF . Benoufella

/DAF FeCl3 23%, Al2(SO4)3 8% .

FeCl3 99.6%, Al2(SO4)3 99.7%

. /DAF

.

- (PAC) . Hilal Hankins

PAC 10 ~ 50 ppm 93% ~ 98% ,

, , ,

.

PAC PAC .

- UV UV 2-MIB

geosmin . Bin Alam UV 150 mW-s/cm

37, 75 mW-s/cm . UV37

mW-s/cm 90% , 75, 150 mW-s/cm 100%

.

- ,

. ,

.

.

.

56

- (GAC) (Column)

.

2-MIB geosmin .

.

6

Cynobacteria .

Intracellular Cynotoxin AOM Extracellular Cyanotoxins

. Intracellular Cynotoxin ,

. Preoxidation

AOM , Preoxidation

. /

AOM ,

. ,

.

AOM . DAF

. .

AOM Extracellular Cyanotoxins

MF UF .

. RO NF Cyanotoxins .

Microcystins Anatoxins . Cylindrosspermopsin

. Microcystins, Anatoxins, Cylindrosspermopsin

. Cyanotoxins .

Cyanotoxins . pH 8

Microcystins, Cylindrosspermopsin . Anatoxin-a . UV

Microcystins, Cylindrosspermopsin

2

57

. Microcystins, Cylindrosspermopsin, Anatoxin

. . Microcystins , Cylin-

drosspermopsin, Anatoxin .

8)

AOM .

AOM (Algal-drived Organic Matter) .

DON (Dissolved Organic Nitrogen) . Tight

. 0.1 ~ 1.0 mg/L,

0.1 ~ 0.4 mg/L . AOM ,

Organic Chloramines .

. .

MICROCYSTINS , ()

. , MICROCYSTINS , ,

ClO2 . /, DAF

. MICROCYSTINS

8) Cyanobacteria and Cyanotoxins: Information for Drinking Water Systems , EPA-810F11001 July, 2012

58

, . ()

. .

AOM/DON BAC .

, .

3

1

2

3

61

3

1

1.

3 2 ,

(/ )

( )

, , , , , , ,

.

10

.

.

(, MF/UF)

.

.

. 30

.

62

.

2.

. , ,

.

.

, , EDCs

( , 2009)

10

(P) .

, ,

. ,

, .

(2010) EDCs PPCPs

iopromide, atenolol, TCPP, TECP, musk ketone, naproxen, DEET,

carbamazepine, caffeine, and benzophenone .

3

63

, 6 (2007) 20

.

EDCs

( , 2007)

.

,

.

multiple barrier process .

.

, , 100-500 Da

EDCs . , ,

95 % .

(RO) (NF) EDCs PPCPs

. ,

. (2008)

pH 6.5 NF ,

64

BPA 95 % . ibuprofen

salicylic acids .

(MF), (UF), loose NF/RO

. ,

, .

(2007) (NF) EDCs, PhACs, PPCPs

. 200~300g/mol

NF 90% . , pKa

logKow NF

, .

logKow

( , 2007)

.

GAC EDCs

. kinetic ,

, , carbon , NOM

.

Le Noir (2009)

EDCs . EDCs

.

3

65

(Movingbed reactor) macroporous adsorption medium

EDCs .

macroporous poly(vinyl alcohol) cryogel MIP(Molecularly inprinted polymer) .

, Kim (2009) (iron-tetrasulfophthalocyanine (FeTsPc)

-immobilized Amberlite) H2O2 BPA, cefaclor, diclofenac, ibuprofen

.

(Wen , 2009) zeolite UV photolysis

estrogen .

. (Biological and chemical conversion)

, ,

EDCs .

, (AOPs)

EDCs PPCPs .

(oxidation power) , .

, EDCs .

Atrazine, Meprobamate, Tri(2-chloroethyl)phosphate (TCEP)

60 % , TCEP 5 % .

, UV , ,

EDC BPA

. Olmez-Hanci (Photochemistry and Photobiology Science, 2009)

BPA pH

. , UV (H2O2/UV-C) Dimethyl phthalate(DMP)

.

(supercritical fluid extraction), , EDCs

.

(2006) EE2,

E1, E2 progesterone .

66

EE2 P 4 mg/L , EE2 P (30 )

90%, 3 99% . OH scavenger

TBA , TBA 8 EE2 P

97% . EE2 P kinetic study

EE2(kO31.2104 M-1s-1), P(kO31.0102 M-1s-1 ) ,

.

E1 E2

(pH 7, O3 = 1 mg/L, E1 & E2 = 2 mg/L) ( , 2006)

(ng/L, n=20) (Snyder, 2009)

(3.5 mg/L dose)

(Snyder, 2009)

3

67

UV (40 mJ/cm2)

(Snyder, 2009)

(2.5 mg/L dose)

(Snyder, 2009)

Snyder (Ozone: Science and Engineering, 2008)

, UV , EDCs PPCPs

. 70 %

.

2

1.

.

2 .

, 1

.

.

68

2. (Geosmin, 2-MIB)

Geosmin 2-MIB (i.e. Cyanobacteria or Blue-green algae) 2

. 160-180 dalton ng/L

.

NF 1990 . C. R. Reiss

et al. 200 dalton, 300 dalton NF Geosmin

2-MIB , 300 dalton NF 40~65%

200 dalton NF 1 ng/L .

Geosmin 2-MIB

(Dixon et al.). NTR7450

40% , NF90 DK Geosmin 80% , 2-MIB

100% . Alt et al. 7

NF tight Geosmin 2-MIB 85%

.

3

69

4 Geosmin 2-MIB (Dixon , 2011)

3. (Microcystin)

(cyanotoxins) . (Microcystin)

7 .

,

. 1,000 NF

.

Gijsbertsen-Abrahamse et al. Microcystin-RR, LR, YR,

LA, Anatoxin-a NF .

Trisep TS80-4040 90%

. Anatoxin-a 165 dalton

200 dalton , 10 g/L

WHO 1 g/L .

70

(A. J. Gijsbertsen-Abrahamse , 2006)

.

(2-MIB,

Geosmin)

C. Robert Reiss, James S.

Tayler, Christophe Robert

Surface water treatment using nanofiltration - pilot

testing results and design considerations1999

Anand J. Mody

Feasibility of using nanofiltration as a polishing

process for removal of cyanobacterial exudates from

treated surface water

2004

Mike B. Dixon,

Chorlotte Falconet,

Lionel Ho,

Christopher W. K. Chow,

Brian K. ONeill,

Gayle Newcombe

Removal of cyanobacterial metabolites by nanofiltration

from two treated waters2011

(Microcystin)

M. R. Simpson,

B. W. MacLeod

An integrated approach to algal by-products including

bench scale evaluation of nanofiltration for microcystin

removal

2002

D. P. Smith,

V. Falls,

A. D. Levine,

B. W. Mac Leod,

M. Simpson,

T. L. Champlin

Nanofiltration to augment conventional treatment for

removal of algal toxins, taste and odor compounds,

and natural organic matter

2002

Margarida Ribau Teixeira,

Maria Joao RosaMicrocystins removal by nanofiltration membrane 2005

3

71

(Microcystin)

M. B. Dixon, C. Falconet,

L. Ho, C. W. K. Chow,

B. K. ONeill,

G. Newcombe

Nanofiltration for the removal of algal metabolites

and the effects of fouling2010

4. NF

NF ,

. , NF Lab-scale .

NF ,

lab-scale pilot scale .

5.

.

,

. ,

.

.

, .

(cavitation) ,

. .

72

20kHz .

/

(cavity) ,

.

.

,

(microstreaming) (micro-jet)

. , .

- 5000K, 1000atm

- 500

m/s (micro-jet)

.

, .

.

3

73

.

, .

,

.

,

.

.

()

Simon (1974)Anabaera

cylindricaNot reported; 1000 W/cm

3100 mL 2 75% protein released

Tang et al.

(2003)

Spirulina

plantensis1.7 MHz; 0.6 W/cm

3Not reported 9 Inhibition of growth

Hao et al.

(2004)

Spirulina

plantensis

1.7 MHz; 0.07 W/cm3

20 kHz; 0.014 W/cm3 800 mL 5

~50% reduction

33.33% reduction

Mahvi and

Dehghani

(2005)

Cyanobacteria 42 kHz; 0.07 W/cm3

1000 mL 2.5 100% reduction

Zhang et al.

(2006)

Microcystis

aeruginosa

20 kHz; 0.08 W/cm3

1320 kHz; 0.08 W/cm3 1000 mL 10

14.29% reduction

55% reduction

Joyce et al.

(2010)

Microcystis

aeruginosa

40 kHz; 0.021 W/cm3

864 kHz; 0.049 W/cm3 200 mL 30

Declumping effect

21.3% reduction

Pawalee et al.

(2011)

Natural

blooming algae200 kHz; 0.015 W/cm

3200 mL 0.5 94.9% reduction

Wu (2011) Microcystis

aeruginosa

40 kHz; 0.0466 W/cm3

864 kHz; 0.0929 W/cm3 400 mL 30

4.31% reduction

61.11% reduction

74

, ,

.

.

.

(specific heat ratio)

.

.

. /

/ Geosmin, 2-MIB

.

, Geosmin, 2-MIB

OH

.

.

/ (P) OH

(1) .

k1, k2 P , OH . OH

Rc (=[OH]/[O3]) , (1) (2) . P

( ) Rc,

([O3]dt) . Rc

3

75

.

-d[P]/dt = k1[O3][P] + k2[OH][P] (1) ln([P]/[P]0) = -(k1 + k2Rc)[O3]dt (2)

Rct Geosmin, 2-MIB (Onstad et al., 2007; Peter and von Gunten, 2007).

Full Scale /

. Rc

Rc .

Rct Full Scale ,

.

[ 3-1]

.

. .

(The European Commission, EC) Water Treatment by

Molecularly Imprinted Materials (WATERMIM) 2009-2012

,

.

76

.

[ 3-2]

. () , ()

, ()

OH .

[ 3-2]

(: , : , : )

4

4

79

4

1.

.

. ,

,

- .

2.

.

2 .

,

2 .

.

, 2 .

3. ,

. 2008

, .

.

.

5

5

83

5

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5

85

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