,2010

.
:.
.

,.

,,.

.,

.,

iii
 .

. . ,

. ,

,.

,,

..

iv


,
,
.
,
.
,
. ,
,
, .
,,
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,
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.

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v
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.

vi
 Abstract

The continuously increased human activity of the last few decades, because of the

intense urbanization and industrialization, has resulted in the production of a

seriousamountofwastes.Amongtheseissewagesludge,whichisthesemisolid

residue produced by municipal and industrial waste treatment plants. Although

sludge is considered as a waste product which must be disposed, it is actually an

underestimatedresource.Specifically,sludgecontainsvaluablenutrientsandhigh

thermal value making sludge appropriate for a wide range of uses. Nevertheless,

the existence of pathogens and xenobiotics in sludge has attracted the interest of

scientific community. Among various methods that have been used for sludge

treatment, as well as the removal of xenobiotics from environmental systems,

biologicalmethodsareadvantageous.

Theaimofthepresentworkwastoassessthesewagesludgetreatmentbya

biologicalprocess,whichisclosedvesselcomposting.Thisstudyinvolvedalsothe

developmentofamathematicalmodelcapableofdescribingthecompostingprocess.

The efficiency of bioremediation of xenobiotics content during sludge composting

was also studied. Finally, the xenobiotics removal was investigated through

biodegradation using sludge indigenous microbial populations in other aerobic

environments.

Asuitableexperimentalconfigurationwasdesignedandconstructedinorder

to study the composting process. The composting system was designed for

complete control and regulation of the process. Based on the results of the

compostingexperiments,itcanbeconcludedthatcompostingisanefficientmethod

allowing for treating and stabilization of sewage sludge, provided that critical

physicochemical parameters are adjusted. Results revealed also that composting

processisnotinhibitedbythepresenceofhighinitialconcentrationofxenobiotics.

On the contrary, composting results in removal of xenobiotics. With reference to

vii
surfactants (LAS.NP and NPEO), the removal percentages were particularly high,

while the relevant percentages for phthalate ester and polycyclic aromatics

hydrocarbons were also significant. It seems, then, that the variable microbial

population of the composting mixture contributes to the elimination of xenobiotic

compoundsandresultsinasafeandstablefinalproduct.

The experiments which were conducted in aerobic mixed liquid cultures

showed also high xenobiotic removal percentages. Probably, the microbial

consortiumcouldplayasignificantpartinbiodegradationofxenobioticcompounds.

The present study contributes to the development of a reliable method of

sewage sludge treatment. The composting process, totally complies with the

desirablesustainablegrowthforoursocietybythetreatmentofsludgeproducedin

waste water treatment plants and by the elimination of the xenobiotic compounds

thatlimititsvalorisation.

viii


1: 1

1.1 1
1.2 3
1.2.1 3
1.2.2 5
1.2.3 9
1.3 11
1.3.1(2)(di(2ethylhexyl)phthalateester,
DEHP) 14
1.3.1.1(2) 14
1.3.1.2(2) 16
1.3.1.3(2) 18
1.4 (Polycyclic Aromatic
Hydrocarbons,PAHs) 20
1.4.1 23
1.4.2 25
1.4.3 30
1.5 (SurfaceActiveAgents,surfactants) 31
1.5.1(LinearAlkylbenzene
Sulphonates,LAS) 33
1.5.1.1
33
1.5.1.2
35
1.5.1.3 38
1.5.2(AlkylPhenolEthoxylates,APEs) 40
1.5.2.1 41
1.5.2.2 43
1.5.2.3 46
1.6 47
1.7 48
2: 57

2.1 57
2.1.1 59
2.2 61
2.2.1 61
2.2.2 62
2.2.3 63
2.2.4 65
2.2.5 65
2.3 67
2.3.1 67

ix
 2.3.2 69
2.3.3 70
2.3.4pH 71
2.3.5C/N 72
2.3.6 74
2.4 74
2.4.1 75
2.4.1.1(WindrowSystem) 75
2.4.1.2(AeratedStaticPile) 77
2.4.2 78
2.4.2.1(Verticalin
VesselCompostingReactors) 79
2.4.2.2(Horizontal
inVesselCompostingReactors) 80
2.4.2.3(RotatingDrum
Reactors) 81
2.5 82
2.5.1 82
2.5.2 83
2.5.3 84
2.5.4 86
2.5.5 87
2.5.6 88
2.6 91
3:
95

3.1 96
3.1.1 96

3.1.1.1 96
3.1.1.2
98
3.1.1.3 99
D 99
D (2
) 101
D 102
3.1.2 104
3.1.2.1 104
3.1.2.2
104
3.1.2.3 105
D 105
D , (2
),
105
3.2 106

x
 3.2.1 106
3.2.2
107
3.2.3 107
3.2.3.1 107
3.2.3.2 108
3.2.3.3(2) 109
3.2.3.4 109
3.3 ,
110
3.4 pH 110
3.5 (FreeAirSpace,FAS) 110
3.6 111
3.7 111
3.8 112
3.9 (NH3N)Kjeldlah(TKN) 112
3.10 113
3.11 114
4:

117

4.1 117
4.2 118
4.3 121

4.3.1 121
4.3.2 122
4.3.3 125
4.3.4 126
4.3.4.1 126
4.3.4.2
131
4.3.5 132
4.4
133
4.4.1 133
4.4.2 133
4.4.3 135
4.4.4 136
4.4.4.1 136
4.4.4.2

141
4.4.4.3
141
4.4.5 143
4.5 (2) ,

xi

143
4.5.1 143
4.5.2 144
4.5.3 145
4.5.4 147
4.5.4.1 147
4.5.4.2

149
4.5.4.3
150
4.5.5 155
4.6 155
4.6.1 155
4.6.2 156
4.6.3 158
4.6.4 160
4.6.4.1 160
4.6.4.2
164
4.6.5 166
4.7
167
4.7.1 167
4.7.2 168
4.7.3 169
4.7.4 170
4.7.4.1 172
4.7.4.2PAHs

172
4.7.5 176
4.8 177
5:
179

5.1 179
5.2 180
5.3 182
5.3.1 182
5.3.2 186
5.3.3 187
5.4 AQUASIM2.0 190
5.5 192
5.6 194
5.7 199
5.8 201

xii
6:
203

6.1 203
6.1.1 204
6.1.1.1
204
6.1.1.2
207
D
SO42 207
D
208
6.1.2 210
6.1.2.1
210
6.1.2.2

212
6.1.2.3
213
6.1.3 218
6.2 219
6.2.1 219
6.2.1.1
219
6.2.1.2
221
6.2.1.3

222
6.2.2 223
6.2.2.1
223
6.2.2.2
226
6.2.2.3

227
6.2.3 229
6.3 (2) 229
6.3.1 230
6.3.1.1
(2) 230
6.3.1.2
(2) 231
6.3.2 231
6.3.2.1

xiii
 (2) 231
6.3.2.2
(2) 232
6.3.3 232
6.4 233
6.4.1 233
6.4.1.1
233
6.4.2 235
6.4.2.1
235
6.4.3 238
6.5 239
7: 241

7.1 242
7.2 246
247

251

257

259

xiv





1

1.1

.

.
, , ,
,
.

,
.
,
,
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,
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-1-
 1

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.
,

.

,
.
,.

,
. ,
91/271/EC ,
,,

,
,
.
,,
,
. , ,
,,
.

. ,

100.000
,30%.,
, 70.000,
/.,
,

-2-


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.

,
.
,
,
.


.
.

.

.

,

.

1.2

1.2.1

,
,
, ,
,
. 91/271/EC 21 1991,
,
.
, ,

.

-3-
 1

(...),
.
Hoffmann [Hoffmann et al., 2008],
... 15
, 2005
8.3g().
151.1.

,1.3%
. 212 ... [...., 2009]

91/271/EC.

1.1: 15

2005[ETCRWM].

,[,2005]:
,
,

.

:
.

-4-


:
.

:.

:
.

1.2.2

, ,
.
1.1.,
(, , , )
(, , , , , ),
,
.
[Jensen&Jepsen,2005].
1.1:
[Europeancommission,DGenvironment,2001].

1 2 C D

3
(DS) [kgm ] 12 9 7 10 30

(VS) [%DS] 65 67 77 72 50
pH 6 7 7 6,5 7
C [%VS] 51,5 52,5 53 51 49
H [%VS] 7 6 6,7 7,4 7,7

[%VS] 35,5 33 33 33 35
N [%VS] 4,5 7,5 6,3 7,1 6,2
C/N 11,4 7,0 8,7 7,2 7,9
P [%DS] 2 2 2 2 2

Cl [%DS] 0,8 0,8 0,8 0,8 0,8

K [%DS] 0,3 0,3 0,3 0,3 0,3
Al [%DS] 0,2 0,2 0,2 0,2 0,2
Ca [%DS] 10 10 10 10 10

Fe [%DS] 2 2 2 2 2
Mg [%DS] 0,6 0,6 0,6 0,6 0,6

[%DS] 18 8 10 14 10
[%DS] 24 36 34 30 18
[kWht1DS] 4.200 4.100 4.800 4.600 3.000

A:,
B1:(>0,20kgBOD5kg1MLSS),

-5-
 1

B2:(<0,20kgBOD5kg1MLSS),
C:(),
D:

,
.


[Fytili & Zabaniotou, 2008].
,
( . 2003/2003
13 2003).
(. 1565/1985, 1, 2, 164//26.09.1985 .
2732/1999, 6, 154//30.07.1999)
,
[,
2007].

.,

(N, S, Mg .),


. , ,

.

, 1.2,
.

.

,,,
.
() ,
.

-6-


,
.
4 % 60 %.

.
, 40 %
, .
,
.

, , ,
, (.. , , , ) [,
2005,Singh&Agrawal,2008].

1.2:[,2005].

[%]

6070

4050

<40

<40

5085

4060

3060

4585

,
,.
: ,
.

.
, ,
.,,
,

-7-
 1

[Singh&Agrawal,2008].

, . ,

,
.
,,
, ,
,
[, 2005, Singh &
Agrawal,2008].

,,
,.
, ,
.86/278/C121986,

,
.,
.
86/278/EC (
1.3)[,2005].
. , ...
.

,
.
/
, ,
,
, .
,

-8-


1.3:(mgkg1 ..)
[,2005].

PCDD,PCDF PCB AOX LAS DEHP NPE PAHs

0,8 500 2.600 100 50 6
86/278

50100 0,21 500 6

1.300 50 10 3

0,8 1,55

100

0,4 100 3

PCDD:PolychlorynatedDibenzopDioxins
PCDF:PolychlorynatedDibenzopFurans
PCB:PolychlorynatedBiphenyls
AOX:HalogenatedOrganicCompounds
LAS:LinearAlkylbenzeneSulphonates
DEHP:Di(2ethylhexyl)phthalate
NPE:NonylPhenolEthoxylates

1.2.3

...

(,).
,
,
.

: ()
, ()
,()
[&,2009].
,(CaO)
,

.
,.

-9-
 1

.
, (anaerobic digestion)
,(aerobicdigestion)
,
[&,2009].

1.2:[&,
2009].

. 1.2
.
CO2,H2O,NO3
. ,
( )

- 10 -


, ,
. ,
,pH,
, . ,
,,
( Cr6, pH)
.
,
.

.
,,

, .
,
, ,
60 %.
.

,
, ,
.
,,

.
.

1.3

(plasticizers)
150%
.
,
.
,
[ECPI,2009].

- 11 -
 1

300
(PhthalicAcidEsters,PAEs),
(phthalates), .
(HOCO[CH2]xCOOH)
(x=4), (x=7) (x=8).

.

900.000tn
PVC. PVC

, .
PVC ,
, (
,:,
),,.
,
.
,
, , , ( , ..), ,
... 6.000
[ECPI,2009].

1.4 ,

[Staples et al., 1997, ECPI, 2009].


.1.4
Staples[Staplesetal.,1997].

,[Bauer&Herrmann,1997].,
, ,
, ,
,[Dargnatetal.,2009].

- 12 -


1.4: ,
.

di(2ethylhexyl)phthalate DEHP ..:390.5 ,

(2) logKOW:7.94 ,
: , ,
0.34mgL1 ,
di(nbutyl)phthalate DBP ..:278.4 ,
logKOW:4.45 ,
:
11.2mgL1 ()
dimethylphthalate DMP ..:194.2
,
logKOW:1.61
,
:

4200mgL1
diethylphthalate DEP ..:222.2
,
logKOW:2.38
,
:

1100mgL1

, (,
, , )
PAEs [Staples et al., 1997, Aparicio et al., 2009, Dargnat et al.,
2009]. 0.3 77 ngm3
, 0.3 98 gL1 , 0.2 8.4 mgkg1 ..
28154mgkg1..[Dargnatetal.,2009].
(MarneAval)[Dargnatetal.,2009]
. 1.3

. (2) (di(2ethylhexyl)
phthalate, DEHP)
78.1%.

,
,
.
[Voss et al., 2005]. (2)
(DEHP) ,
, .

,.

- 13 -
 1

1.3:

[Dargnat et al., 2009].

1.3.1(2)(di(2ethylhexyl)phthalate,DEHP)

(2)(di(2ethylhexyl)phthalate,DEHP)
2.

(1.4).

1.4:(2).

4
, 95%
PVC [DEHP Information Center].
1.4.

1.3.1.1(2)

DEHP
[Aparicio et al., 2009, Dargnat et

- 14 -


al., 2009].
(logKow)
[Marttinenetal.,2003].

[Stapples et al., 1997],
...Marttinen[Marttinenet
al., 2003] (2)
.. Espoo .
29 %
, DEHP (163 g.g1 ..)
.
.. Aparicio [Aparicio et al., 2009]
DEHP , ,
,.
1.5.

1.5: DEHP , ,

4 ..
[Aparicioetal.,2009].

[mg kg ..]
. 1 [mg kg ..]
. 1 (RSD)[%]
12103 53 53
3492 65 32

13345 159 70

24124 75 41

,
12 345 mg.kg1 ...

DEHP[Gavalaetal.,2003],
.

DEHP

86/278/EC (100 mg.kg1 ..).
(2)

- 15 -
 1

1.3.1.2(2)

,
.
PAs,,
[Stapples et al., 1997].


[Gavalaetal.,2003,Chang
et al., 2004, Zeng et al., 2004, Nakamiya et al., 2005, Fang et al., 2007]. 1.5

1.5:
[Stapplesetal.,1997].

2002, Zeng [Zeng et al., 2002]

(2) Pseudomonas
Fluorescens FS1,

- 16 -


, ( 1.6). (2
)()
(MEHP). MEHP
,CO2H2O.

1.6: (2)
PseudomonasFluorescens FS1 [Zeng et al.,2002].

, [Zeng et al., 2004]

, DEHP,
.Chang
[Chang et al., 2004],
(Springomonas sp. Corune bacterium sp.).
(2) ,
, PAEs.

DEHP , (NP)
(PAHs).

Banat[Banat
et al., 1999],
DEHP . ,
(2)22%,31%44%20,5262
C, .
1.

- 17 -
 1

DEHP
[Banat et al., 1999],
, ,
(2)
. 1.6
DEHP.

,
(2) ,
.

,
.
,
,.
1.6,

Marttinen [2004], ,
DEHP.

,
,
DEHP.

1.3.1.3(2)

.,
2000,DEHP33
( 2000/60/CE), ,
.
(2)
R60:R61:
[, 2006]. ,
2,
[USEPA,2000].

- 18 -


1.6: (2)
.

- 19 -
 1

(in vitro)
. DEHP
,
, , [Tickneretal., 2001, Latini et
al.,2006].,DEHP
.(2)

[Latini,2005].

,
. Yin [Yin et al., 2003]
,
() [Sung et al., 2003,
ForgetLeray,2005].

DEHP
.
DEHPDBP
[AlatristeMondragon et al., 2003,
Gavalaetal.,2003].

1.4 (Polycyclic Aromatic

Hydrocarbons,PAHs)

(Polycyclic Aromatic Hydrocarbons,

PAHs)
.
(fused) (
) .
(500900
C) .
(USEPA) 16
, 7
.

, ,

- 20 -


,
. ,
, (, , , ..)
,
( , ,
,..)

[Haritash&Kaushik,2009].

,
(logKow),

[Johnson et al., 2005]. 1.7

[Haritash &
Kaushik,2009].,
,
.,.

,
, ,
, , [Halsall et al., 1997, Juhasz & Naidu, 2000,
Pakou et al., 2007, Li et al., 2010, Sojinu et al., 2010].

.
,
[Blanchard et al., 2004]. ,
[]50
[Halsalletal.,1997].
PAHs
.

Li
[Lietal.,2010]15
(15)3951842
gkg1.

- 21 -
 1

, , 15 404 883
gkg1.
1.7:

.

- 22 -


2003Tsapakis[Tsapakisetal.,2003],
.
24
(24) 2.22 mgL1 1056 mgL1
.
PAHs 870 gkg1 [Baumard et al., 1999].
, ,
gL1
[Juhasz&Naidu,2000].

,
.
.

1.4.1

.
,..PAHs,
, ,
.,
,
[Blanchardetal.,2004].,
,,
.

Blanchard[Blanchardetal.,2004]

. 26

8.,
.

1.8
,
. ,
,
.

- 23 -
 1

.
25.000 gL1. 40 %
, 21 % 15.5 % ,
.
, 98 %
, .
26.7 kgyr1 0.53
kgyr1.

.

1.8: 16*

(mgkg 1..)

[Blanchardetal.,2004].

PAHs
napthalane
0.73 3.42 1.7

anthacene
0.36 0.39 0.36 0.47

phenantherene
2.40 3.32 3.12 4.86

fluoranthene
3.63 4.94 4.32 5.96

pyrene
5.37 7.19 6.13 8.64

benzo[a]pyrene
1.16 0.93 0.83 1.09
[]
benzo[b]fluoranthene
1.85 1.75 1.54 2.09
[]

*
16PAHs 21.7 28.2 22.3 30.9

*
16 16
[USEPA,
2001].

[Perez et al., 2001]

- 24 -


.
1.916PAHs5mgkg1...
1.9:(gkg1 ..)
[Perezetal.,
2001].

PAHs
/ /

napthalane
198 93

anthacene
234 61

phenantherene
2030 357

fluoranthene
629 56

pyrene
702 187

benzo[a]pyrene
35 32
[]

benzo[b]fluoranthene
52 45
[]

*
16PAHs 5520 1460

*
16 16
[USEPA
2001].

1.4.2

,
.
.
,
,
[Haritash&Kaushik,2009,Yuanetal.,2001].

PAHs /
(mineralization)
,CO2,,CH4

- 25 -
 1

.
pH, , ,
,
, , .. [Haritash &
Kaushik,2009].

PAHs ,
. ( 1.7)
.
[Harayamaetal.,1992].
.
2 3
,
PAHs[Haritash&Kaushik,2009].

, ,
.
PAHs
[Zhangetal.,2009,Wuetal.,2009].

1.7:
[Haritash&Kaushik,2009].

- 26 -


Romero [Romero et al., 1998],

Pseudomonas Aeruginosa ,
.

30 . , Rehmann
[Rehmann et al., 1998], Mycobacterium spp.
.
.
, 60 %
(0.5mgmL1)820C.

, 2 3

. PAHs ,
,
. , [] (benzo[a]pyrene, B[a]P)
Wu
[Wuetal.,2009]Ochrobactrum
50mgB[a]PL1,20%20.
3.8%Rentz[Rentzetal.,
2008], Sphingomonas Yanoikuyae.

[Kanalyetal.,2000].,
[Leietal.,2007]
PAHs,
85%.

. , , Kumar
[Kumar et al., 2009]
.
,
88%65
%21.

PAHs
,

- 27 -
 1

(1.10).[Huaetal.,2008]

.
9 PAHs
70.91 mgkg1 .. 16 PAHs 95.05 mgkg1. ..,
.. (6 mgkg1. ..)
. 50
79 %. 50 %
. ,


.
,.

Cai [Cai et al., 2007]

,
.
,
64 %,
,
.

(>68%),PAHs
100 %, Hafidi [Hafidi et al., 2008]
.
Hua[Huaetal.,2008],16PAHs
, 0.5 mgkg1. ..
.

4 ,
.

, ,
PAHs
. ,

.

- 28 -


1.10:
.

- 29 -
 1

,

[Plaza et al., 2009]. ,


.,,

, PAHs.


, ,
[Oleszczuk et al.,
2007,Hafidietal.,2008,Huaetal.,2008,Plazaetal.,2009].

1.4.3

,

.(USEPA)
16 PAHs , 7
([a], [a], [b], [k]
, , [a,h] [1,2,3cd])
. ,
[a]
.

,
,
, .

,
DNA, ,
[Flowersetal.,2002].

,
,
, .

- 30 -


,
[Smithetal.,2006].

,
. ,
PAHs,

[Awataetal.,1998].

1.5(S
SurfaceA
ActiveA
Agen
nts,ssurfactants)

,
.
.

,
. ,
.

(Critical
Micelle Concentration, CMC) [Cirelli et al., 2008]. 1.8
. , ( )
, ( )
,.

,.,
.
, ,
, , ,
,,...

,

.
1940 1970,
,

- 31 -
 1

50%.,
( )
. 1960, PT (Propylene
Tetramer Benzen).
.

.

[Cirellietal.,2008].

1.8: . ()
()
[Wikipedia.org].

18
(2003),13.
40 %
[Hauthal, 2004]. ,

.,
, .
,
.
[Mungay&Kumar,2008].

,
(Linear Alkylbenzene Sulphonates, LAS). LAS
40 % .
,

- 32 -


(Alkyl Phenol Ethoxylates, APEs).

.

1.5.1 (Linear Alkylbenzene Sulphonates,

LAS)

. 1964

.LAS
,
(para) (
1.9).
HERA(Human&EnvironmentalRiskAssessmentoningredientsofEuropean
household cleaning products) [HERA, 2009], 1.11
.

1.9: , LAS [HERA,

2009].

1.5.1.1

(...). , LAS
,
,
[Jensen, 1999]. LAS
,

- 33 -
 1

[Pratsetal.,1993].

1.11:
[HERA,2009].

(C11.6) 342.2gmol1
1.6kgL1
(Pa25C) 317E13Pa

250gL1

logKow 3.32

0.65gL1
(CMC)
637oC
277oC

, LAS
95 99.9 % [Brunner et al., 1988, Schrder et al., 1999,
Mungray & Kumar, 2009]. 1.12
LAS,
.

1.12:

[mgL1] [mgL1] [%]

3.48.9 0.0190.07 9899.6 Matthijsetal.,1999

115 0.039 99.1 Venhuis&Mehvar,2004

5.71 0.39 >97 Morenoetal.,1994

5.57 0.67 88 Mungray&Kumar,2009

.. 4.6 0.068 98.5 DiCorciaetal.,1994

321 0.0080.27 99 HERA,2009

- 34 -


, ... ( 1.13).
Berna [1989]
1020%LAS.
3035%
[Bernaetal.,1989].

1.13:

LAS
[mgkg1..]

290011900 McEvoy&Giger,1986

160011800 deHenauetal.,1986

13309930 Matthjis&deHenau,1987

182432 Matthjis&deHenau,1987

500 Bernaetal.,1989

1210017800 Pratsetal.,1997

930018800 Holt&Bernstein,1992

, LAS
.

,[Jensen,
1999]. 1.13 LAS

.

1.5.1.2

(LAS)
. ,

- 35 -
 1

.
LAS ,

.

LAS.
[Mungray &
Kumar,2009].

LAS
[Federle&Schwab1989,Schberl,1989,Jimnezetal.,1991,Federle&
Itrich, 1997, Len et al., 2004]. LAS ( 1.10)
,
.
(sulpho phenyl carboxylates,
SPCs)
LAS.
.CO2,
.

,
.

[van Ginkel, 1996]. , LAS,
,
,
,
.,

LAS[Schberl,1989,Sigoillot&Nguyen,1990,Jimnezet
al.,1991,Yadavetal.,2001].

LAS

. ,,
()

- 36 -


LAS[Terzietal.,1992,Yadanetal.,2001,Eichhornetal.,2002,Marcominietal.,
2002].
,LAS.Jimnez
[Jimnez et al., 1991]

,
CO2. , 1996 van Ginkel,

1.10:
, LAS. Mungray Kumar [Mungray
&Kumar,2009].

, , LAS
.

(commensalism)(synergism)
LAS.

- 37 -
 1

Prats,19931999[Prats
et al., 1993, Prats et al., 1999]
LAS
. , Moeller
[Moelleretal.,2003],LAS
99 % 25
. , ,

LAS
55C(1.14.).

, ,
, ,
LAS .

.

1.5.1.3

: )
)
, , ,
[Jensen,1999].

LAS
. ,
. ,
,
[Pratsetal.,2003].

.
,
,
,
.

- 38 -


1.14:
.

2004, Venhuis Mehrvar [Venhuis & Mehrvar, 2004]

0.02 1.0 mg LASL1
.,

- 39 -
 1

,
, .
, LAS 40 60 mgkg1 ..

.
van de Plassche [van de Plassche et al., 1999],

0.25mgL1.

LAS . ..
2600mgkg1..[EU,1999].

1.5.2(AlkylPhenolEthoxylates,APEs)

.
,.,
(dispersing agentes)
, ,
,.

[Thieleetal.,1997].

APEs 1997 500.000 tn,

80 % (Nonylphenol Ethoxylates,
NPEs) 20 % (Octylphenol Ethoxylates, OPEs)
[Renner, 1997]. , 1984 ,

[Scott&Jones,2000].

.
(octylphenol,

- 40 -


OP) (nonylphenol, NP), ,

.

APEs ( 1.15)
.

. APEs
5, [Ahel &
Giger, 1993 (a)]. ,
OPEs (12.6 24.5 mgL1) NPEs (5.43
7.65 mgL1),
.
(logKow) APEs 3.90 4.48
[Ahel&Giger,1993
(b),Yingetal.,2002].

1.15:

[Ahel&Giger,1993(a),(b)].

logKOW

[gmol1] [mgL1]
n=1:264 3.02 4.17
Nonylphenolethoxylate, n=2:308 3.38 4.21
NPEO

n=3:352 5.88 4.20
n=4:396 7.65 4.30

Nonylphenol,NP
E 220 5.43 4.48

1.5.2.1

.
. ,
()
,
. ,

- 41 -
 1

,[Yingetal.,2002].

APEs
.

...,
.

APEs
.NP,NPEO1NPEO2

[GomezRico et al., 2008]. 1.16

. NP
0.675mgkg1..601mgkg1..,NPEO
2.1mgkg1..135mgkg1...
NP
NPEO. ,
95%NP5%NPEO1+NPEO2,NP,

NP[Warhurst,1995].

1.16:
.

NP NPEO
[mg.kg1..] [mg.kg1..]

Petrovic&Barcelo,2000 172601 21135

234 2.1
25.5 21
DeVoogtetal.,1997 6.8 40.16

Vikelsoeetal.,2002 0.675 23.72
Brunneretal.,1988 190 490
1500 165

NPEONP
.

- 42 -


86/278/..,50
mgkg1..,.

1.5.2.2

,
.
APEs[Thieleetal.,1997].

, .

, [Ying et al., 2002].
APEs1.11.

1.11:APEs (
Renner[1997]).

- 43 -
 1

APEs .
, Nasu et al., 2001

86%99%,66%
99 % . ...,
93 99 % [Naylor, 1995]. ,
,APEs
,.

, APEs
[,2005].
[Scott&Jones,
2000]. Hesselse et al., 2001,
NP
.

NPEO
, ,
, [Corti et al., 1995, Maki et al., 1996, Mann &
Boddy,2000,Staplesetal.,2001,Soaresetal.,2003].vanGinkel[1996],

.,Vallini
[Vallinietal.,1997]NP
, Candida aquaetextoris sp..
NP,
. ,
NPEO NP
.

NPEO
.
[Jones&Westmoreland,1998,Moeller&Reeh,2003(b),Das&Xia,2008]
NPEO(1.17).

Jones & Westmoreland [1998]

(wool scour),
NPEO. 14
NPEO91%.,

- 44 -


NPEO1, NPEO2, NPEC1,
NPEC2 NP.
,
.
1.17:
.

- 45 -
 1

, NPEO1, NPEO2 NP,

Moeller&Reeh[2003].
NP
(65 oC).
NP
,
.NP
.

,
,
.

1.5.2.3

APEs

,
APs.
APEs 1938 Dodds & Lawson
. 1991, Soto
[Soto et al., 1991] NP
.

NPEO NP
.,
NP 17 ,
( 1.12). 17

. , ,
[Lee&Lee,1996].
, NP
.

NP[Whiteetal.,1994,Lawsetal.,
2000]. NP
,,
. , Colerangle & Roy [1996]

- 46 -


0.01 mgd1. , Jobling
[Jobling et al., 1998]
20gL1NP.

1.12:17
[Warshurst, 1995].

1.6

, ,

. ,

. ,
(
, , ),
( (2) )
(, , ,
[],[]).
,

,.

,
,
,
.

- 47 -
 1

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Bacillus, .. B. subtilis, B. stearothermophilus, B. circulans, B. licheniformis,
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.
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.

Bacillus B.stearothermophilus Strom,1985(a)&(b),Fujio&
Kume,1991
VanHeerdenetal.,2002

B.subtilis Strom,1985(a)
VazMoreiraetal.,2008
B.lichenformis VazMoreiraetal.,2008
VanHeerdenetal.,2002

Thermus T.thermophilus Fujio&Kume,1991,Beffaetal.,
1996
Thermomonospora T.mesouviformis Stegeretal.,2007

T.alba Stegeretal.,2007
Thermoactinomyces T.vulgaris Strom,1985(b)
T.kribbensis Stegeretal.,2007
Micromonospora M.endolithia Stegeretal.,2007
Streptomyces S.hebeiensis Strom,1985(b)
Stegeretal.,2007
Aspergillus A.fumigatus Strom,1985(b),Mriaetal.,2008
A.candidus Ryckeboeretal.,2003

A.terreus Mriaetal.,2008
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Thermomyces T.lanuginosus Mriaetal.,2008
VanHeerdenetal.,2002

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Nocardia ( 2.1) [Tuomela et al., 2000].

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2008].

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A.terreusTrichodermahamatum
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Wry [Wry et al., 2008],

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.

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, pH,
[Strom,1985(a)].

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Haug [1993],
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- 83 -
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[Sanz et al., 2006, Hafidi et al., 2008, Das &
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2000].

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- 85 -
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- 87 -
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- 88 -


, . ,

, ( 2.8) ( 2.9),
(COMPOST HELLAS) ( 2.10),

(CRETA
FARM).1998

.

2.8:

,,,
.,
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.
,
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2.9:
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,
,
, 1415 , , ... URL:
http://library.tee.gr/digital/m2116.pdf.
., 2003, ,
, :
, ,
.
., ., ., . ., 2002,
:,
http://www.epem.gr/pdfs/2002_8.pdf.
.,2007,
, ,
, ,
,.

(Internetwebpages)

Cornel University, Department of Crop and Soil Sciences (CUCSS), 2007.

URL:http://css.cals.cornell.edu/
OfficialwebsiteofCOMPOSTHELLAS..,URL:http://www.compost.gr
OfficialwebsiteofWasteMINZ.URL:http://www.wasteminz.org.nz
, , URL:
http://kallithea.hua.gr/compost.net/

- 94 -





3

.,

.


.,
,

.,

, .

- 95 -
 3

3.1

().

.
,
,[Letellier&Budzinski,1999].

,

.

.

3.1.1

(Microwave Assisted Extraction, MAE)
20.
Ganzler 1986 [Ganzler et al., 1986]

,
, ,
,[Barnabasetal.,1995,Dean&Xiong,
2000,Bartolometal.,2005,Herbertetal.,2006,FidalgoUsedetal.,2007,PortetKoltaloetal.,
2008].

[Villaretal.,2004,Fountoulakisetal.,2005,Pakouetal.,2007].

3.1.1.1

( 0.3 300 GHz)

.
,

- 96 -


2.45 GHz.

.

,
.
:
.

.

.

.

[Neas&Collins,1988].

.
. ,
.

(3.1).
, ,
[Camel,2000].

3.1::()()
.

- 97 -
 3

(Pressurised Microwave Assisted Extraction),
(AtmosphericMicrowave
Assisted Extraction) [Camel, 2000, Dean & Xiong, 2000].
,

[Camel,2000].

.
( ),
, , ,
[Letellier&Budzinski,1999].

,
,
. , (United
States Environmental Protection Agency, US EPA)
,
,,,,..(USEPA,Method3546).
( 3.1)

.

3.1.1.2

MARS 5
CEM (North Carolina, USA).
14 (PFA, Teflonlined extraction
vessels)100mL.,,
,
(300, 600 1200 W).
(,
)
.

- 98 -


,
/ ,
.
MilliQ
(Millipore).

3.1:
.

Barnabasetal.,1995

LopezAvilaetal.,1995

VzquezBlancoetal.,2000


PieiroIglesiasetal.,2000

Shen&Lee,2003

Croceetal.,2003


Villaretal.,2004


,
Bartolometal.,2005
,

Herbertetal.,2006

3.1.1.3

(LinearAlkylbenzeneSulfonates,LAS)
3.2. ,
(0.03 0.3 g )
40 oC. ,
(MARS5CEM)20mL
.

- 99 -
 3

LAS3.2
100 oC.
(15)
100 oC.
600W.

. ,
40 oC
1 mL.
/:1/10.05SDS1%.

.

(0.7m)

40oC

HLBVacRc60mg 20mL
1.5mLCH3OH 100oC

2min
100oC15min
1.5mLH2O
0.1SDS2%HCHO
1mL

CH3OH/H2O:1/1
0.05SDS1%HCHO

HPLC

3.2:
(LAS).

- 100 -


D (2)

(Polycyclic Aromatic Hydrocarbons,
PAHs) (2) (di(2ethylhexyl) phthalate, DEHP)
3.3.,(0.030.3g
)
(MARS5CEM)20mL/:1/1.
,
.
100 oC2
15 .

. ,

.

(0.7m)

20mL/:1/1

100oC
2min
100oC15min

1mL

HPLC

3.3:
(PAHs) (2)
(DEHP).

- 101 -
 3

(NP)(NPEO)

.
()
( /: 1/1
/: 3/7)
. 3.4
NPNPEO.

3.4: NP NPEO
: (1) / : 1/1, 100 oC, 600W, (2)
/:1/1,100oC,600W,,(3)/:1/1,100oC,1200W,
(4)/:1/1,1mLH2O,100 oC,1200W,(5)/:1/1,120 oC,1200W,(6)
/:1/1,1mLH2O,120oC,1200W,(7)/:3/7,100oC,600W,
(8) / : 3/7, 120 oC, 1200W, (9) / : 3/7, 1 mL
H2O,120oC,1200W.

,600
W1200W100 oC
NP NPEO. ,
120 oC 1200 W
.,

. , 1 mL
.
NPNPEO(100120
o C).

- 102 -


/:3/7,
. ,

,
NP[Fountoulakisetal.,2005].

/ 1 mL
120 oC 1200 W.
NP NPEO
3.5.

(0.7m)

40oC

20mL/:1/1
1mLH2O
120oC
2min

120oC 15min

1mL

HPLC

3.5:
(NP)(NPEO).

, (40 oC)
(MARS5CEM)1
mL 20 mL /.

- 103 -
 3

.
0.22m
NPNPEO.

3.1.2

3.1.2.1

(SolidPhaseExtraction,SPE)
.
,
.
. 3.6
.

3.6::() ,()

,(),
(),
[LeBlanc&Majors,2001].

CCCN.pH

3.1.2.2

HLB VAC Rc 60 mg Extraction Cartridges, Water Oasis.

- 104 -


,
(HydrophilicLipophilic Balance, HLB)
, .
Varian(VacElut20,16x100MM),
(PALL, Vacuum / Pressure Pump, No.DOAP181
BN),
.

,
.

MilliQ(Millipore).

3.1.2.3

.,
0.7 m ( 3.2)
.
3.1.1.3.
HLB
(Oasis Waters). LAS HLB 1.5 mL
1.5 mL 0.1 M SDS2 %
.,LAS
.

D , (2)
,

.,
.

- 105 -
 3

LAS
3 mL
.

3.2

3.2.1

.
.
,
.

, .

.

,
.
,
.
,
.
.

,
.

(High Pressure Liquid Chromatography, HPLC)

.,
( ),
(.. )
[Pecsoketal.,1980].

- 106 -


3.2.2

(HPLC
Varian 9010). ,
. ,
: ) XTerra RP18
(250x4.6mm,5m)(20x3.9mm)
Waters,)
CCHypersil1305BDSC8(250x4.6mm)(CC8/4
HYP 120 5 BDS C8) MachereyNagel.
UV (Star 9050, Varian)
(ProStar363,Varian).

SigmaAldrich
97%.

, MilliQ
(Millipore).

3.2.3

: ()

,(),(),()
()
.
.

3.2.3.1

OLASCC
Hypersil 130 5 BDS C8 analytical column (250x4.6 mm) CC
8/4 HYP 120 5 BDS C8 ( MachereyNagel).
Prostar 363 Fluorescence detector
Varian.29%(A)71%
/: 75/25 11 g NaClO4 (B).

- 107 -
 3

1.5 mLmin1
,ex:222nmem:290nm.

,
, ,
Standardsmethodsfortheexaminationofwaterandwastewater[1995].3.2
, (L.O.D.)
LAS
(R.S.D.) (n=6)
LAS. LAS (C10,
C11, C12, C13 10, 11, 12 13 , )
.

3.2: , , ,
.

L.O.D. L.O.Q.
R2
[%] R.S.D.[%] [gg1..] [gg1..]
C10 0.9996 102.3 3.1 1.04 2.808
C11 0.9998 92.3 7.0 4.02 10.854
LAS

C12 0.9998 97.7 5.1 2.68 7.236

C13 0.9998 96.5 22.5 4.38 11.830

NPEO 0.9990 62.0 3.62 1.82 7.72

NP 0.9990 91.0 4.69 2.86 4.90

DEHP 0.9993 96.8 12.93 6.72 18.14

phenanthrene 1.0 80.27 4.16 0.27 0.73

fluoranthene 1.0 76.45 2.99 0.21 0.57
pyrene 1.0 76.15 2.95 0.17 0.46
PAHs

benzo[b]
0.999 82.03 8.53 0.57 1.54
fluoranthene
benzo[a]
1.0 80.38 5.98 0.38 1.03
pyrene

3.2.3.2

XTerra RP 18 analytical column
(250x4.6 mm) (20x3.9 mm)

- 108 -


Waters.60%()40%()
0.7 mLmin1. PAHs
,ex:250nm
em:370nm(022min)ex:234nmem:420nm
(2258min).

PAHs,
, ,
, Standards methods for the examination of
waterandwastewater[1995].PAHs
0.01 gL1
0.50 gL1.
0.999 (R2 > 0.999).
3.2.

3.2.3.3(2)

PAHs.
83%()17%()
1.5mLmin1.DEHP224
nm UV.
,
(3.2).

3.2.3.4

PAHs .
. , : 50 % (A)
50 % () 3 66 %
(A)34%(),320min2030
min.2.1mLmin1:ex:222nm
em:305nm.,
(3.2).

- 109 -
 3

3.3 ,

(TotalSolids,TS),(Volatile
Solids, VS)
,Standardmethodsfortheexamination
ofwaterandwastewater(2540D2540E).(TS)
103105 oC.,
103105 oC,
, . ,
. ,
, .
(VolatileSolids,VS)
550 oC. ,
, 550 oC.
.

(TotalSuspendedSolids,
TSS) (Volatile Suspended Solids, VSS),
.
TSS VSS , ,
,.

3.4pH

pH ,
pH (Hanna Instruments, pH 211,
MicroprocessorpHmeter).

pH
, 3 g
30mL 5.
pH
[Bachetal.,1985].

3.5(FreeAirSpace,FAS)

(FreeAirSpace,FAS),

- 110 -


.(FAS)

[Haug,1993].

3.6

(Total Organic Carbon, TOC),

(InorganicCarbon,IC),
(Analytika Jenna
Multi N/C 2000)
().
(DissolvedOrganicCarbon,DOC),
0.22 m Millipore.
.

3.7

(ChemicalOxygenDemand,COD)

.
,,
.

(
2 g ClL1) (K2Cr2O7)
141143C(H+).,
( )
(AgSO4). , AgSO4 ,
( )
(
).()
,,(
, HgSO4), .
(Cr227)
:

C n H a Ob + cCr2 O27 + 8cH +

nCO2 + [( a + 8c ) / 2] H 2 O + 2Cr 3+
(3.1)

- 111 -
 3

2 1 1
c= n+ n b
: 3 6 3

(Dissolved
Chemical Oxygen Demand, DCOD)
600 nm ( Hach DR/2010),
Standardmethodsfortheexaminationofwaterandwastewater
[1995](5220D).Cr3+.

, (Total
Chemical Oxygen Demand, TCOD)
, Standard methods for the examination of
waterandwastewater[1995](5220B).
Cr6+.

3.8

,
Josefsson [Josefsson, 1983].
L (H3BO3) (H2SO4)
20 , ( )
520 nm.

520 nm,
D.

3.9(3)Kjeldahl
(TKN)

(NH3N),
Standardmethodsfortheexaminationofwaterandwastewater
[1995] ( 4500).
(Na2B4O7)0.1pH
9.56.
, 70 80 %
. ,
(H3BO3)(
methyl blue methyl red).
, .

- 112 -


,
0.02.

Kjeldahl (Total Kjeldahl Nitrogen, TKN)

[Standard methods for the
examination of water and wastewater, 4500]
,
3.Kjeldahl
50ml.:
(H2SO4),(K2SO4)(HgSO4)
(340 oC),
(NH4HSO4),
.
pH
(Na2S2O35H2O),
.
,
,.

3.10

(TotalPhosphorus,TP)
Standard methods for the examination of water and
wastewater ( 4500). : )
(PO43, HPO42, H2PO4), )
[(PO3)6,(P3O10)5,(P2O7)4]).

.
100 oC.

.
,
(persulfatedigestionmethod)
, .

(ascorbicacidmethod).
880 nm,
(KH2PO4).

- 113 -
 3

3.11
Bach P.D., Shoda M. and Kubota H., 1985, Composting reaction rate of sewage sludge in an
autothermalpackedbedreactor,Journaloffermentationandtechnology,63,271278.
Barnabas I.J., Dean J.R., Fowlis I.A. and Owen S.P., 1995, Extraction of polycyclic aromatic
hydrocarbons from highly contaminated soils using microwave energy, Analyst, 120, 1897
1904.
Bartolom L., Cortazar E., Raposo J.C., Usobiaga A., Zuloaga O., Etxebarria N. and
Fernndez L.A., 2005, Simultaneous microwaveassisted extraction of polycyclic aromatic
hydrocarbons, polychlorinated biphenyls, phthalate esters and nonylphenols in sediments,
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BlangerJ.M.R.andParJ.R.J.,2006,Applicationsofmicrowaveassistedprocesses(MAPTM)to
environmentalanalysis,Analyticalandbioanalyticalchemistry,386,10491058.
Camel V., 2000, Microwaveassisted solvent extraction of environmental samples, Trends in
analyticalchemistry,19,229248.
Croce V., Patrolecco L., Polesello S. and Valsecchi S., 2003, Extraction of Nonylphenol and
Nonylphenol Ethoxylates from river sediments: Comparison of different extraction techniques,
Chromatographia,58,145149.
Dean J.R. and Xiong G., 2000, Extraction of organic pollutants from environmental matrices:
selectionofextractiontechnique,Trendsinanalyticalchemistry,19,553564.
FidalgoUsed N., BlancoGonzlez E. and SanzMedel A., 2007, Sample handling strategies
for the determination of persistent trace organic contaminants from biota samples, Analytica
chimicaacta,590,116.
FountoulakisM.,DrilliaP.,PakouC.,KampiotiA.,StamatelatouK.andLyberatosG.,2005,
Analysis of nonylphenol and nonylphenol ethoxylates in sewage sludge by high performance
liquid chromatography following microwaveassisted extraction, Journal of chromatography
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Ganzler K., Salg A. and Valk K., 1986, Microwave extraction A novel sample preparation
methodforchromatography,Journalofchromatography,371,299306.
Haug R.T., 1993, The practical handbook of compost engineering, Boca Raton, Lewis
publishers.
Herbert P., Morais S., Paga P., Alves A. and Santos L., 2006, Analysis of PCBs in soils and
sediments by microwaveassisted extraction, headspaceSPME and high resolution gas
chromatography with iontrap tandem mass spectrometry, International journal of
environmentalanalyticalchemistry,86,391400.
JosefssonB.,1983,Rapidspectrophotometricdeterminationoftotalcarbohydrates.In:Methodsof
seawater analysis, K. Grasshoff, M. Ehrhardt K. Kremling (eds), Verlag Chemie GmbH,
340342.
LeBlanc G. and Majors R.E., 2001, A review of EPA sample preparation techniques for organic
compoundanalysisofliquidandsolidsamples,LCGC,19,11201130.
Letellier M. and Budzinski H., 1999, Microwave assisted extraction of organic compounds,
Analusis,27,259271.
LopezAvila V., Young R., Benedicto J., Ho P. and Kim R., 1995, Extraction of organic
pollutantsfromsolidsamplesusingmicrowaveenergy,Analyticalchemistry,67,20962102.

- 114 -


Neas E.D. and Collins M., 1988, Introduction to microwave sample preparation, American
chemicalsociety:WashingtonD.C.,Chapter2,732.
PakouC.,FountoulakisM.,DrilliaP.,KampiotiA.,StamatelatouK.andLyberatosG.,2007,
Occurrence and fate of polycyclic aromatic hydrocarbons in sewage treatment plants using
microwaveassisted extraction followed by liquid chromatography coupled with fluorescence
detector,Freseniusenvironmentalbulletin,16,16.
Pecsok R.L., Shields L.D., Cairns T. and McWilliam I.G., 1980,
, 2 , : . , : ..
.
PieiroIglesias M., LpezMaha P., VzquezBlanco E., MuniateguiLorenzo S., Prada
Rodrguez D. and FernndezFernndez E., 2000, Microwave assisted extraction of
polycyclicaromatic hydrocarbonsfromatmospheric particulate samples, Freseniusjournalof
analyticalchemistry,367,2934.
PortetKoltalo F., Oukebdane K., Dionnet F. and Desbne P.L., 2008, Optimisation of the
extraction of polycyclic aromatic hydrocarbons and their nitrated derivatives from diesel
particulate matter using microwaveassisted extraction, Analytical and bioanalytical
chemistry,390,389398.
ShenG.andLeeH.K.,2003,Determinationoftriazinesinsoilbymicrowaveassistedextraction
followedbysolidphasemicroextractionandgaschromatographymassspectrometry,Journalof
chromatographyA,985,167174.
Standardmethodsfortheexaminationofwaterandwastewater,1995,19thedition,APHA
AWWAWEP,editedbyEatonA.D.,ClesceriL.S.andGreenbergA.E.,WashingtonDC,
USA.
USEPAMethod3546,February2007,Microwaveextraction,EPA,WashingtonD.C..
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304.

- 115 -
 3

- 116 -


4.1

,
.
.,
,,
.,
, ,

- 117 -

4

,
.

,
, ,
.
,,

.

.

, .

(Linear Alkylbenzene Sulphonates, LAS), (Nonyl
Phenol Ethoxylates, NPEO)
(NonylPhenol),(2)(di(2ethylhexyl)phthalate,DEHP)
, , ,
[][].

4.2

,
.
(
4.1). , 30 cm,
40cm,28L.

.

.,

.

- 118 -


()

()
4.1:
.()()
.

- 119 -

4

. ,
(..
).

4.1 ,
,
,
.4.2
,
.

4.2:
.

.
.,
,
. ,

,
, ,

- 120 -


.
(DL2eDataLogger).

, ( 4.1()),
,
.
.
.,

,
.
(LMSxi Type G3.18)
.

.
Labview 7.0
(NationalInstruments).

4.3

4.3.1

,
.
,
.
,

,[Haug,1993].

. ,

. ,

- 121 -

4

,.

4.3.2

2.5/1,,.
4.1.

, (/:
2.5/1)
.
.

. , ,
(2 4 oC)
.

,.

.,
.
.

4.2.

4.1:(12)
(,kg..).

o1 3.0 2.75 2.75

o2 1.7 3.4 3.4

,
(4.1).,

- 122 -


(17 %) .

.

.
,
83.6 %.
, .
, ,
(),.

4.2:
.

(TS) [gL1] 55.80 46.60

[gL1] 53.60 39.1

(TSS)
(VS) [gL1] 34.40 31.00
[gL1] 33.30 24.70
(VSS)

[gL1] 0.875 1.10

(dCOD)

[gL1] 30.90 35.50

(TCOD)

[gCaCO3L1] 1.75 5.06

pH 6.32 6.83

NH3 [mgNL1] 560 163

Norg(Kjeldah) [gL1] 3.36 5.02

[mgg1..] 158 200

[mgg1..] 376 350

[gL1] 0.82 1.50

- 123 -

4

4.1 ( )

. , ,
( 1),

( 2), .

.

.
10 g,
.

4.3.

4.3: ( 1 2)
*.

1 2

(TS) [%mg..mg1..] 33.00.8 39.91.1

(VS) [%mg..mg1..] 58.72.9 49.12.8

[%] 67.0 60.0

F.A.S. [%] 36 60

pH 9.6 9.5

C/N 23.9 27.3

LAS [mgkg1..] 12110.7 16216.8

LAS [mgkg1..] 2130188 1880224

*
..:,..:,..:

,,pH,(F.A.S.)
C/N.

- 124 -


3.

,,
. ,

, 40 oC
.

4.3.3

,
,
60.

.

,
( 1)

( 2). 8.5 kg
.

30 rpm 2
4 ,
.

,
.
500 mLmin1,
,1100mLmin1.

.
60oC,
,10
%.

( ) (
) ,

- 125 -

4

.
5 . ,

,,
,pH,.

4.3.4

4.3.4.1

4.3
12.
, ( 1 2)

.
()
.
1 2.
2,
(60 %) FAS (60 %),

1.

, 47 oC
10 . ,
,
.
( 4 )
(10 %) .

,
.
2

- 126 -


40oC,,

46 oC.
15
.
, , 21 ,
.

.

4.3:

12.

1,
( 4.3). ,

8 39 oC.

,
[Haug, 1993, Liang et al., 2003, Trmier et al., 2009].
,

.

(4.4)
. , 2

- 127 -

4

5,
,
.

4.4:

12.

( 4.5 4.6), 2
1.
Bernal[Bernaletal.,1998],
. ,


.

1CO2

.
.,
2
1 . CO2 5
,

. CO2, O2
5
.,

- 128 -


2
.

10 % ( )
.

4.5:
12.

4.6:
12.

(4.7),1
2,100%
.,

- 129 -

4

, ,
.

,
. , ,

,
. ,
,
()
.

4.7: ,
,
12,.

1 2 4.4.
, 67 % 59.3 %
1,60%50.3%2.
pH .
,

[Kutzner, 2000]. [Bertoldi et al., 1983,

Sundberg et al., 2004, Khan et al., 2009],

- 130 -


pH,311,pH
,5.58.,

4.4:(12)

*.

1 2

(TS) [%mg..mg1..] 33.00.8 39.91.1

(VS) [%mg..mg1..] 58.72.9 49.12.8

[%] 67.0 60.0

pH 9.6 9.5

(TS) [%mg..mg1..] 40.70.6 49.71.2

(VS) [%mg..mg1..] 50.21.3 36.010.7

[%] 59.3 50.3

pH 8.2 8.5

*
..:,..:,..:

4.3.4.2

,
(Linear Alkylbenzene Sulphonates, LAS) .
LAS (C10, C11, C12 C13)
, 4.5.
30
LAS.
2,
, 1.
LAS .

- 131 -

4

Sanz ,
LAS40C[Sanzetal.,2006].

4.5:LAS1
2.

1 2

LAS [mgkg1..] 12110.7 16216.8

LAS [mgkg1..] 33.42.8 24.82.9

[%] 15.51 21.96

LAS [%] 77.4 84.7

4.3.5

,
,
,
.


60%60%.

. ,
pH
.

.
(6 )
.,
LAS
.

- 132 -


4.4

4.4.1.

,
.
,
(Linear Alkylbenzene Sulphonates, LAS),
. ,
,

LAS.

4.4.2

,
2.5/1, ,
2.

.
4.6.
4.6:(34)
(,kg..).

LAS
/

o3 3.4 3.2 1.9

o4 3.4 3.2 1.9

(/: 2.5/1)
(12)
...

- 133 -

4

.(
10%)
(F.A.S.)
.

()
33mL6
pH .
.

.
,
( 4), LAS.

LAS 1000 mgkg1 ...
,.

( )
.

.

.,,
(3),
, LAS,
(4),.


.

.
10 g,
.

4.7.

- 134 -


4.7: ( 3 4)
*.

3 4

(TS) [%mg..mg1..] 45.50.1 44.11.5

(VS) [%mg..mg1..] 57.73.1 66.53.0

[%] 54.5 55.9

F.A.S. [%] 60 65

pH 7.4 7.3

C/N 26.6 26.6

LAS [mgkg1..] 555.1101 1490.7117

LAS [mgkg1..] 119222171 310432436

*
..:,..:,..:

,
, pH, (FAS) C/N.

3.

LAS.,

, 40 oC
.

4.4.3

,
,
30.

.

- 135 -

4

( 3)
LAS
( 4).
8.5kg.

30 rpm 2
12 ,
.

,
.
415 mLmin1,
,855mLmin1.

.
65oC,
. ,
5 %
7 %. ,
65 oC

.

,
, .
,
.
5.,

,,
,pH,.

4.4.4

4.4.4.1

- 136 -


.
,
.

4.8
(34).

.,
63 64 oC.
,
2,
.,
34,50 oC4
.[USEPA]
55 oC

[USEPA,1993].4
1036oC.

4.8:
34.

34
(4.9).
4,LAS
, 3.

- 137 -

4

4.9:

34.

( 4.10)
34.
.

,
(4.11)34,
10.CO2
5.
Miller [1996], ,
.
, ,

[Miller,1996].

10
2 %. .

,pH
[, 2007].
(4.8),

- 138 -


4.10:

34.

4.11:
34.

,

3 4,

- 139 -

4

.
.

5 % ( )
.

3 4 4.8.

. , 3
54.5%47.2%455.9%43.5%.

4.8:(34)

*.

3 4

(TS) [%mg..mg1..] 45.50.1 44.11.5

(VS) [%mg..mg1..] 57.73.1 66.53.0

[%] 54.5 55.9

pH 7.4 7.3

(TS) [%mg..mg1..] 52.80.4 56.52.5

(VS) [%mg..mg1..] 44.80.4 48.94.4

[%] 47.2 43.5

pH 8.6 8.9

*
..:,..:,..:

pH.
( 3 4) ,
.,

.22.35%
3,426.5%.

- 140 -


4.4.4.2

34.(3)

LAS.,

,
. 4.84.10

3 4. LAS 4
3
.
LAS
.

4.4.4.3

(Linear
Alkylbenzene Sulphonates, LAS) ,
LAS(C10,C11,C12C13)
.
4.124.13LAS
3 4, .
LAS .
,
. , LAS
5.20
LAS
3468.23%80.13%,.

LAS
40
77.3 % 83.9 % 3 4,

- 141 -

4

. ,
,
. ,
, ,
LAS
.

4.12: LAS

3.
.

4.13: LAS

4.
.

- 142 -


LAS
Prats et al., 1999 Moeller & Reeh, 2003(),
.
Prats
,
. Moeller & Reeh, 2003(),

.
,
LAS55oC.

4.4.5

55%60%,,
.

. ,
LAS
.
. LAS
,
.

LAS. ,

, , LAS
.,LAS,
,
.

4.5 (2) ,

4.5.1

- 143 -

4

,
, . ,
,(2)(di(2ethyl
hexyl) phthalate, DEHP) ,
(Nonyl Phenol Ethoxylates, NPE).

(logKow),
[Marttinenetal.,2003].,

86/278/E.C..

,

[AlatristeMondragon et al., 2003, Gavala et al., 2003].

DEHPNPEO
.

4.5.2

,
2.5/1, ,
3.
3,
LAS.

.
4.9.

(/: 2.5/1)
(1,2,34)
...

.

- 144 -


( 10 %)

(FAS).

4.9:(56)
(,kg..).

DEHP NPEO

o5 3.4 3.1 2.0

o6 3.4 3.1 2.0

()
28mL6
pH.,
(6),
DEHPNPEO.,
, 40 mL
. , ,
5
.
.

( 4.10).
DEHP
NPEO .

3.1
3.2.

4.5.3

,
,

- 145 -

4

30.

( 5)

( 6). 8.5 kg
.

4.10: ( 5 6)

*.

5 6

(TS) [%mg..mg1..] 49.81.5 47.40.1

(VS) [%mg..mg1..] 60.83.7 58.22.8

[%] 50.2 52.5

F.A.S. [%] 65 55

pH 8.6 8.7

C/N 26.3 26.3

LAS [mgkg1..] 51990.5 37849.5

DEHP [mgkg1..] 55.12.65 22715.2

NPEO [mgkg1..] 22.13.87 19733.5

NP [mgkg1..] 3.730.78 0.440.16

*
..:,..:,..:

4.4.3 .
5 . ,
,
, , pH,
.

- 146 -


4.5.4

4.5.4.1

(56)
4.14.
, 3 4,
.

4.14:
56.

6263 oC,50 oC3.
3
533 oC.,

40 oC10.
.


.

,
(4.154.16)
.

- 147 -

4

,
(6).

4.15:

56.

4.16:
56.

CO2 4
.,
, 10
.

- 148 -


,
,
[Ryckeboeretal.,2003]..

4.11

.
.,
550.2%40.3%
4 52.5 % 49.7 %. pH
.
,
.

4.11:(56)

*.

3 4

(TS) [%mg..mg1..] 49.81.5 47.40.1

(VS) [%mg..mg1..] 60.83.7 58.22.8

[%] 50.2 52.5

pH 8.6 8.7

(TS) [%mg..mg1..] 59.70.8 50.41.1

(VS) [%mg..mg1..] 51.00.2 46.20.9

[%] 40.3 49.7

pH 9.2 9.1

*
..:,..:,..:

4.5.4.2

- 149 -

4

56.
(5)
DEHP NPEO.
,

,
. 4.14 4.15
.
NPEODEHP693
, ,
.,
2003 [AlatristeMondragon et al., 2003, Gavala et al., 2003]
DEHP
,
.

4.5.4.3

5 6
DEHP,
(NPEO),
NPEO, (nonylphenol, NP).
, LAS
(DEHP,NPEONP).

4.17
DEHP 5 6.

.
6 ,
. DEHP
,
( 5 6). 5 DEHP
. 55 mg DEHPkg1
.., 1.64 mg DEHPkg1 .. 20 .
97%.
6.

- 150 -


, 20
60 %. ,
40,
67%.,DEHP
.

4.17:DEHP
56.
.

, .

DEHP ( ).
Amir
[Amiretal.,2005],DEHP
. ,


DEHP.Moeller
&Reeh,2003(a),DEHP91%25,

4.18.

- 151 -

4

.
,
.

4.18:

56.

,
, () ( 4.19).

.

4.19:

56.

- 152 -


[Jones & Westmoreland, 1998].
5,,
69%(4.12).,
6,
.

4.12:(mgkg1..)

56,.

LAS DEHP NPEO NP

51990.5 55.12.65 22.13.87 3.730.78

57.812.4 55.12.65 0.520.1 0.090.02

[%] 88.88 97.02 74.12 68.90

37849.5 22715.2 19733.5 0.440.16

34.75.6 74.336.3 9.782.37 4.841.71

[%] 90.81 67.23 95.04 90.96

(,
DEHP)
5 6, LAS.
. 4.20,

6. , LAS 17
,
5.
DEHP(6),
LAS
34,
(, DEHP) ,

- 153 -

4

. 17 ,
,
LAS
5.

4.20: LAS
.
.

,
,
LAS. o DEHP ,
6,
[Staplesetal.,1997,Yingetal.,2002].

4.12
,
.

[EU, 1999]. ,
,
,
.

- 154 -


4.5.5

DEHP,
. ,

LAS.,

( ). ,
,

67%.,
.
,

4.6
.

4.6.1.

,
,

.
.

,
,

. , , ..
,
. ,

,

.

- 155 -

4

4.6.2

4.13.

,.
,
.

4.13: ( 7 10)

(,kg..).

o7 3.7 6.5 2.7

o8 3.7 6.5 2.7

HRT10d

o9 3.7 6.3 2.9

o10 3.7 6.3 2.9

HRT15d

,
2.5/1.
, ,

,
. 4.14
.

15
10.

,

- 156 -


(phenanthrene), (fluoranthene) (pyrene),

, (2) (DEHP)
0.5mgL1PAHs5mgL1DEHP.

4.14:/:2.5/1,
HRT10d15d.

/
:2.5/1 (HRT10d) (HRT15d)

[gL1] 31.3 26.0 25.1

(TSS)
[gL1] 20.4 15.7 15.1
(VSS)
[gL1] 1.96 0.4 0.4

(dCOD)

[gL1] 33.15

(TCOD)

[gCaCO3L1] 2.86

pH 6.68 7.2 7.2

NH3 [mgNL1] 269

Norg(Kjeldah) [gL1] 1.05

[mgL1] 63.6

, ,
. ,
,
(4.15).

,
,,
pH, (FAS) C/N. ,
.

- 157 -

4

4.15: ( 7 10)
*.

7 8 9 10
(TS) 59.91.7 59.60.7 59.50.1 60.22.4
[%mg..mg1..]

(VS) 34.64.2 35.13.9 25.70.6 26.80.7

[%mg..mg1..]
[%] 40.1 40.46 40.5 39.8
F.A.S.[%] 57 50 57 55

pH 8.0 8.2 7.8 8.0

C/N 27.4 25.9 27.1 24.8

LAS 173.624.2 220.67.5 203.420.3 187.73.5

[mgkg ..]
1

NPEO 2.290.24 1.900.76 3.040.02 2.390.22

[mgkg1..]

NP 0.660.24 0.850.36 3.60.28 4.80.8

[mgkg1..]

DEHP 9.861.78 7.881.64 11.63.67 6.852.78

[mgkg ..]
1

1.020.21 0.990.06 0.970.07 0.900.03

[mgkg1..]

0.470.19 0.480.04 0.440.03 0.380.05

[mgkg1..]

0.360.09 0.360.02 0.410.05 0.420.03

[mgkg1..]

*
..:,..:,..:

4.6.3

3055.

(79)
(810).

- 158 -


,
3 PAHs . ,

,
.

(4.21)PAH
.
,
(PolyUrethaneFoam,PUF).

4.4.3 .
5 . ,
,
, , pH,
.

4.21:

5PAHs.

- 159 -

4

4.6.4

4.6.4.1

,
,
4.224.23.(7
8)
,
10 . ( 9 10)

,
15.

(78),
50 55 oC 1.5
50 oC4.

[USEPA,1993].
35oC20.

4.22: ,

(7)
HRT10(8).

( 7 8)
. ,

- 160 -


7, ,
8.
8
HRT 10 d
(4.14).

( 9 10),

15 .
HRT15d
.,
9 .

.

4.23: ,
(9)
HRT15(10).

,
1215 ,
( 4.24 4.25).
( 7 8)
20
.3
.

- 161 -

4

( 9 10)
,
. ,

.

4.24:

,(7)

HRT10(8).

4.25:

,(9)

HRT10(10).

- 162 -


,
,
. ,

.,
,
.

4.16
.

.pH
8.

4.16:(710)
*.

7 8 9 10

(TS) 59.91.7 59.60.7 59.50.1 60.22.4

[%mg..mg1..]

(VS) 34.64.2 35.13.9 25.70.6 26.80.7

[%mg..mg1..]
[%] 40.1 40.46 40.5 39.8

pH 8.0 8.2 7.8 8.0

(TS) 62.22.0 61.80.3 62.40.2 62.01.3

[%mg..mg1..]

(VS) 31.00.6 32.11.8 24.20.6 24.31.7

[%mg..mg1..]
[%] 37.8 38.2 37.6 38.0

pH 7.9 8.1 7.4 7.5

..:,..:,..:

- 163 -

4

4.6.4.2

(710),
( 4.17 4.18). ,
DEHP,


,.

4.17:
(mgkg1..)710,
.

LAS DEHP NPEO NP

173.624.2 9.91.8 2.30.2 0.70.2

9.41.1 6.10.5 0.50.2 0.40.01

[%]19 94.5 38.4 78.3 42.9

55 97.0 40.0 98.2 12.1

220.67.5 7.91.6 1.90.7 0.90.3

4.00.5 6.00.1 0.30.01 0.30.1

[%]19 98.2 24.1 84.2 66.7

55 98.9 29.4 92.1 63.5

203.420.3 11.63.7 3.040.02 3.60.28

2.70.6 3.50.7 .. 0.11

[%]23 98.7 68.8 ~100 96.9

10

187.73.5 6.852.78 2.390.22 4.80.8

.. 3.60.8 0.1 0.3

[%]23 ~100 47.4 95.8 93.8

- 164 -


, LAS
( C10, C11, C12
C13)
94.5%19.
LAS
.

, ,
.78%
19 7
.98%
55 . (
)

,().
,
,.

(DEHP) .
19 7 8,
38.4 % 24.1 %, .
.,
(8
10) . , DEHP

. DEHP
( 9 10)
.

,
( 4.18).

(PUF)
3 PAHs.
PAHs.,
, ( 7 8)
(910).

- 165 -

4

4.18:
(mgkg1 .. ) 7 10,
.

1.020.21 0.470.19 0.360.09

0.420.09 0.370.05 0.310.01

[%]19 58.8 21.3 13.4

55 84.3 23.0 33.3

0.990.06 0.480.04 0.360.02

0.310.03 0.320.08 0.270.04

[%]19 68.7 33.3 25.0

55 82.8 41.7 30.6

0.970.07 0.440.03 0.410.05

0.320.05 0.240.03 0.130.01

[%]23 67.0 45.5 68.3

10

0.900.03 0.380.05 0.420.03

0.320.03 0.220.03 0.100.01

[%]23 64.4 42.1 76.2

,
4.17 4.18,
.

4.6.5

,
. ,

- 166 -


DEHP,
,

, .
LAS
, .

.,
.

PAHs.

4.7

4.7.1

,
.
. ,
2 3
, PAHs
,,
[Wuetal.,2009].

. PAHs
. , Hafidi
[Hafidi et al., 2008] 16 PAHs 0.48
mgkg1. .. 68 % 90
. (87.5 %) 16 PAHs
Oleszczuketal.,2006.

5PAHs.

- 167 -

4

5PAHs.

4.7.2

11 12 4.19 .
( / : 2.5/1), 5
(Polycyclic Aromatic Hydrocarbons,
PAHs):,,,[]
[].
PAHs,
12,
5PAHs.

.
5 PAHs,

(TSS = 0.85 gL1 VSS = 0.85 gL1).
,
1 L
.

4.19: ( 11 12)
(,kg..).

o11 4.4 6.0 3.2 5PAHS

5 PAHS
o12 4.4 6.0 3.2

,

.

- 168 -


,(4.20)
.

4.20: ( 11 12)
*.

11 12

(TS) [%mg..mg1..] 58.11.1 57.11.4

(VS) [%mg..mg1..] 23.41.3 24.72.6

[%] 41.9 42.9

F.A.S. [%] 45 46

pH 7.7 7.5

C/N 28.4 28.4

LAS [mgkg1..] 618.454.1 598.563.7

NPEO [mgkg1..] 6.90.6 6.70.8

NP [mgkg1..] 1.570.02 1.730.15

DEHP [mgkg1..] 20.051.3 10.542.4

[mgkg1..] 3.830.45 3.690.08

[mgkg1..] 3.950.45 3.940.12

[mgkg1..] 3.880.45 3.810.13

[] [mgkg1..] 1.490.16 1.500.03

[] [mgkg1..] 1.500.16 1.570.03

*
..:,..:,..:

4.7.3

,,
.
,,
30.

. , :
12 2 ,

- 169 -

4

415mLmin1855mLmin1,

65 oC
3 %
65oC.

.
5 ,
,
,
,pH,.

4.7.4

4.7.4.1

,

.
4.26,
( 11 12), ,
( 4.8 4.14)
50oC.

4.26:
1112.

- 170 -


,
(
4.27()).,
( 4.27()).

(40 60 %)
[Haug1993,Liangetal.,2003,Trmieretal.,2009].
,

.

()

()

4.27:()(),

1112.

11 12 4.21.

- 171 -

4

.
, .
pH .
(1112),
.

4.21: ( 11 12)
*.

11 12

(TS) [%mg..mg1..] 58.11.1 57.11.4

(VS) [%mg..mg1..] 23.41.3 24.72.6

[%] 41.9 42.9

pH 7.7 7.5

(TS) [%mg..mg1..] 58.30.5 58.21.25

(VS) [%mg..mg1..] 21.60.2 21.41.7

[%] 41.7 41.8

pH 8.13 8.168.9

*
..:,..:,..:

4.7.4.2 PAHs

5
PAHs1112(4.28),

4 5 PAHs .
PAHs (PUF)
, .
, PAHs

- 172 -


12
PAHs,
.,

PAHs.

() ()

() ()

()

4.28: : () , () , ()

,()[]()[]

1112.

- 173 -

4

0.02%,

, . 4.22
PAHs,
.
[], PAHs
. , 5 PAHs
80%.
26
.

4.22: 5 PAHs (mgkg .. )

1

1112,.

[] [] 5PAHs

11

3.830.45 3.950.45 3.880.45 1.490.16 1.500.16 14.65

0.240.04 0.330.07 0.170.04 0.630.04 1.220.11 2.59

[%] 93.5 91.6 95.6 57.7 18.7 82

12

3.690.08 3.940.12 3.810.13 1.500.03 1.570.03 14.51

0.230.04 0.40.04 0.230.01 0.650.02 1.350.06 2.86

[%] 93.7 89.8 93.9 56.7 14 80.3

,
PAHs
. , PAHs
,
.,

[Plazaetal.,
2009]. ,

- 174 -


. ,
,
,
PAHs.

,
,
[Hafidietal.,2008,Huaetal.,2008,Plazaetal.,2009].

1112
,LAS,NPEO,NPDEHP.

4.23.
LAS, DEHP
( 3, 5)
.
,
.

4.23: LAS, NPEO, NP DEHP (mgkg1 .. )

11 12,

LAS DEHP NPEO NP

11

618.454.1 20.051.3 6.90.6 1.570.02

5.11.17 .. 0.050.003 1.030.002

[%] 99.17 ~100 99.27 34.39

12

598.563.7 10.542.4 6.70.8 1.730.15

34.75.6 .. 0.10.03 1.870.5

[%] 94.20 ~100 98.50 10

- 175 -

4

4.7.5

.PAHs,
5PAHs80%
( 11 12)
26 .
PAHs
.,
PAHs ,

PAHs . ,
()

.

- 176 -


4.8
AmirS., Hafidi M.,MerlinaG.,HamdiH.,JouraiphyA., GharousM.andRevelJ.C.,2005,
Fateofphthalicacidestersduringcompostingofbothlagooningandactivatedsludges,Process
biochemistry,40,21832190.
AlatristeModragonF.,IranpourR.andAhringB.K.,Toxicityofde(2ethylhexyl)phthalateon
theanaerobicdigestionofwastewatersludge,Waterresearch,37,12601269.
Bernal M.P., Paredes C., Monedero M.A.S. and Cegarra J., 1998, Maturity and stability
parametersofcompostspreparedwithawiderangeoforganicwastes,Bioresourcetechnology,
63,9199.
Bertoldi M., Vallini G. and Pera A., 1983, The biology of composting: A review, Waste
managementandresearch,1,157176.
EuropeanUnion,1999,WorkingdocumentontherevisionofDirective91/271/EC.
GavalaH.N.,AlatristeMondragonF.,IranpourR.andAhringB.K.,2003,Biodegradationof
phthalate esters during the mesophilic anaerobic digestion of sludge, Chemosphere, 52, 673
682.
Hafidi M., Amir S., Jouraiphy A., Winterton P., El Gharous M., Merlina G. and Revel J.C.,
2008, Fate of polycyclic aromatic hydrocarbons during composting of activated sewage sludge
withgreenwaste,Bioresourcetechnology,99,88198823.
Haug R.T., 1993, The practical handbook of compost engineering, Boca Raton, Lewis
publishers.
Hua L., Wu W., Liu Y., Chen Y. and McBride M.B., 2008, Effect of polycyclic aromatic
hydrocarbonsremovalinsewagesludge,Water,airandsoilpollution,193,259267.
Jones F.W. and Westmoreland D.J., 1998, Degradation of nonylphenol ethoxylates during the
composting of sludges from wool scour effluents, Environmental science & technology, 32,
26232627.
Khan E., Khaodhir S. and Ruangrote D., 2009, Effect of moisture content and initial pH in
composting process on heavy metal removal characteristics of grass clipping compost used for
stormwaterfiltration,Bioresourcetechnology,100,44544461.
Kutzner H.J., 2000, Microbiology of composting, In: Klein J. and Winter J. eds.,
Biotechnology: A multivolume comprehensive treatice, Environmental processes III,
2ndcompletelyrevisededition,Volume11c,35100.
Liang C., Das K.C. and McClendon R.W., 2003, The influence of temperature and moisture
contentsregimesontheaerobicmicrobialactivityofabiosolidscompostingblend,Bioresource
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MillerF.C.,1996,Compostingofmunicipalsolidwasteanditscomponents,In:PalmisanoA.C.
andBarlazM.A.eds.,Microbiologyofsolidwaste,CRCPress,115154.
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MSWandsewagesludgeduringcomposting,Compostscienceandutilization,11,370378.
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aromatichydrocarbons(PAHs)duringsludgecomposting,Water,airandsoilpollution,175,
1532.
PlazaC.,XingB.,FernandezJ.M.,SenesiN.andPoloA.,2009,Bindingofpolycyclicaromatic
hydrocarbonsbyhumicacidsformedduringcomposting,Environmentalpollution,157,257

- 177 -

4

263.
Prats D., Rodriguez M., Muela M.A., Liamas J.M., de Ferre J. and Berna J.L., 1999,
Eliminationofxenobioticsduringcomposting,Tensidesurfactantsdetergents,36,294298.
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94,127137.
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anaerobically digested sludge from a wastewater treatment plant, Waste management, 26,
12371245.
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phthalateesters:aliteraturereview,Chemosphere,35,667749.
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alkylphenolethoxylatesareview,Environmentinternational,28,215226.
.,2007,
, ,
, ,
,.

- 178 -





5

5.1

,
.

.

.

,
.

- 179 -
 5

,
, . ,

.

4.

AQUASIM2.0,
.

. AQUASIM 2.0

.

5.2

(mathematical tool)
. ,
,
, ,
, ,
[Petric &
Selimbai,2008].

,
.

.
,.


[Higgins&Walker,2001].

,
, 1976,
[Mason,2006].

- 180 -


.

.

Haug [1993] ,
,
.
,
.

Das Keener [Das & Keener, 1997]

.

,
. VanderGheynst [VanderGheynst et al., 1997],

,

.
,
.

Stombaugh Nokes [Stombaugh & Nokes, 1996],

,
.

. , Hamelers [1993],
,

.
.

.

, Seki [2000]
(deterministic model) .
,
.

, ,

- 181 -
 5

.,
.
Nakasaki[Nakasakietal.,
1987]HigginsWalker[2001].

1[Haug,1993,
Das & Keener, 1997, Higgins & Walker, 2001] Monod [Hamelers, 1993,
Stombaugh & Nokes, 1996, Seki, 2000,]
.,
,
.
Monod, , ,
.

Hamelers [1993]

,1,
.[Kaiser,1996]
(, , )
( , ,
).Monod.

,
,
(comprehensive),,
, . ,
[210].

,
, ,
.

5.3

5.3.1

5.1.
,

- 182 -


,.

,,
.

HigginsWalker[Higgins&
Walker, 2001],
.
.
:

5.1:
.

,.

i. , ,
.

ii. ,
(),.
1
,V.

iii.
( M X S ), ( M X I ), ( M Wl ),

( M Wg ) ( M N 2 , M O2 , M CO2 ), kg

mol

- 183 -
 5

iv. ,
( TS )

( Tg ). ,

v. :

rX

 + Om O2 CO
m
CO2 +Wlm H 2O (l ) (5.1)
2 2

: im : (mol

/mol) rX :.

()
()
rev
H 2O (l ) H 2O ( g ) (5.2)

: rev :.

vi. ,
Monod. ,
rX , 1

Monod ( 5.3). Higgins Walker [2001]

,,1
.,,
,
.

pO2
rX = k X M X S IT (5.3)
K S ,O2 + pO2

: k X : (d1), pO2 :

(bar), K S ,O2 :

(bar) IT :
. K S ,O2 IT ,

,HigginsWalker[2001],:

- 184 -


K S ,O2 = 0.79 + 0.040 X Wl 0.044(TS 273) (5.4)

: X Wl :(

) TS :(K).

(TS Tmax ) (TS Tmin ) 2

IT = (5.5)
(Topt Tmin ) [(Topt T min ) (TS Topt ) (Topt Tmax ) (Topt + Tmin 2TS )]

: TS : ( ) (K),

Tmax :
(K), Tmin :
(K) Topt :

(K).
vii.
.
, rev ,:

rev = kev
(p sat pWg )
(5.6)
R Tg

: kev : (d1) psat :

(saturated vapour pressure) (bar)

, Tg (K).(5.6)

kev , .
Tg

1 1
5290
298 Tg
psat = 0.0313 e
(5.7)

viii. .
, (orifice) [Batstone et al.,
2001],:

Fout = k p pi Patm (5.8)
i = H 2O , N 2 ,O2 ,CO2

: k p : (m3d1bar1), Patm :

(1.013 bar) pi :

- 185 -
 5

i.
ix.
.
x.
,
.
xi.
.

5.3.2

i
( ),
,
.
m
dM i
= M i ,in M i + ij rj (5.9)
dt j =1

 M
:Mi:i(kgkmol),t:(d), M i ,in i

i
, , (kgd1 kmold1), rj : j

(kgd1kmold1)i
ij.

( M X S , kg),

( M X I ,kg),( M Wl ,kmol),( M Wg ,

kmol), ( M N 2 , M O2 , M CO2 , kmol).

5.9:

dM X S
= rX (5.10)
dt

dM X I
= 0 (5.11)
dt

dM Wl
= Wl rX rev V (5.12)
dt

dM Wg
= M Wg ,in Fout M Wg (V ) + rev V (5.13)
dt

- 186 -


dM N2
= M N2 ,in Fout M N 2 (V ) (5.14)
dt

dM O2
= M O2 ,in Fout M O2 (V ) O rX (5.15)
dt 2

dM CO2
= M CO2 ,in Fout M CO2 (V ) + CO rX (5.16)
dt 2

: rX : (kgd1), rev :

(kmolm3d1), V: (m3), : (
) , vi: i
(molkg1) Fout :

(m3d1).

RTg
pi = M i (5.17)
V

: R: (0.08314 Lbarmol1K1) Tg

(K). ( 5.17)
(V),
5.13,5.155.16V.

5.3.3

. ( 5.1).
n ,
,:

d n n  n

dt i =1
M i H i =
i =1
M i , in H i , in
i =1
M i H i + Q (5.18)

: H i ,in H i :i

, , Q :
.
5.18
5.9,5.19:

- 187 -
 5

n n m
dH i
Mi = M i ,in ( H i ,in H i ) H j rj + Q (5.19)

i =1 dt i =1 j =1

H j j.

,,
. , , ,
5.20 ,
():

dT
C p ,S = H X rX H 2O rev V UASA (TS Tg ) (5.20)
dt

(M )
2
: C p , S : ( C p , S = i C P ,i ), HX:
i =1

,
H O : , UASA :
2

,
,
:

dTg
= rev V C p ,Wg (TS Tg ) + UASA (TS Tg ) + M i ,in C p ,iTamb M i C p ,iTg UAves (Tg Tamb ) (5.21)
. .
C p,g
dt

(M )
n
: C p , g : ( C p , g = i C P ,i )
i =1

Tamb : UAves :
.

5.1

.

5.1:
.

C p ,i i kJkmol1K1

Fin m3d1

Fout m3d1

- 188 -


Hi,in i
kJkg1

Hi i
kJkg1

IT

kj j d1

kp m3d1bar1

K S ,O2
bar

M i ,in i kmold1kgd1

M i i kmold1kgd1

Mi i kmolkg

Patm bar

pi i

psat bar

Q
kJd1

R Lbarmol1K1

rj j kmold1kgd1

t d

T K

T amb K

Tmax/ min/ opt //

K

Tmean K

Tspan
K

UASA
Jd1K1

UAves
Jd1K1

- 189 -
 5

V m3

XW

H X
kJkg1

im
kmolkmol1
i

Wi
kmolkg1
i

H O 2
kJkmol1

CO2

ev
g

i (O2,CO2,N2,2)

j (in)(out)

N2

O2

Wl

Wg

Xi

Xs

5.4AQUASIM2.0

AQUASIM 2.0 [Reichert, 1998].
, Swiss Federal

- 190 -


Institute for Environmental Science and Technology (EAWAG), CH8600 Dubendorf,

Switzerland, Peter Reichert. AQUASIM 1.0
[Reichert, 1994(a)], 19911994,
EAWAG,
[Reichert, 1994(b), Reichert, 1995],
[www.eawag.ch].

AQUASIM
.
(simulation) (parameter estimation).

.

,
.
,
.

.

.

AQUASIM,

, ,
:

2
n y y ( p )
x 2 ( p ) = meas , (5.22)

=1 meas ,
ymeas,:,meas,:,y(p):
, p=(p1,,pm):
n: .
5.21pi
,:pmin,ipipmax,i,pmin,i pmax,i
pi.

5.22
:)simplex[elder &Mead,

- 191 -
 5

1965])secant[Ralston&Jennrich,1978].simplex

x2,.,
secant
,.

5.5

CSTR
(intensiveproperties),
.
, ,
,
. 5.20
.

24 ( ). ,

.
Tspan
Tamb = Tmean + cos(2 t ) (5.23)
2

: Tmean : Tspan :

[Higgins & Walker, 2001]

,
.

.,
.

C X HY O . ,
,:

CX HY O + Om2 O2 CO
m
2
CO2 +WW
m
H 2O (5.24)

- 192 -


: im : (mol /mol

).
5.13,5.165.17,
5.24.

18 O2
Om = (5.25)
2
1 + 4 O2 + 8 CO2

18 CO2
CO
m
= (5.26)
2
1 + 4 O2 + 8 CO2

1 + 32 O2 44 CO2
Hm O = (5.27)
2
1 + 4 O2 + 8 CO2

O2 CO2 ,

,5.255.27.

, O2 CO2 ,

.:

, k X

, Tmean

, Tspan

, UAVES ,

UASA

,.

.

,
,
UAVES UASA ,

,
.

- 193 -
 5

, .
(secantmethod)[Ralston
&Jenrich,1978].

5.6
5.6

4
,
. ,

3 5,
.AQUASIM2.0.

(5.2).
.

5.2:
.

cP ,biom 1.8 (Jg1K1) Haug,1993

cP ,CO2 37.1 (Jmol1K1) Perry&Chilton,1973

C P ,O2 29.4 (Jmol1K1) Perry&Chilton,1973

C P ,N 2 29.1 (Jmol1K1) Perry&Chilton,1973

CP,Wl 75.3 (Jmol1K1) Haug,1993

CP,Wg 33.6 (Jmol1K1) Haug,1993

12720 kJkg1 Higgins&Walker,2001

H O
2
40680 (Jmol1) Perry&Chilton,1973

Tmax 71.6 (oC) Higgins&Walker,2001

Tmin 5 (oC) Higgins&Walker,2001

Topt 58.6 (oC) Higgins&Walker,2001

3 5 ( 4)

- 194 -


5.3 . ,

, kX,
,
.
.,
,kX
.
5.3:
35.

3 5

Ow
2
(103molg1) 35.420.2123 35.530.4473

CO
w
2
(103molg1) 27.860.2305 27.020.5039

k X (d1) 0.42740.0037 0.44240.0066

Tmean (K) 305.60.0361 302.90.1190

Tspan (K) 3.1320.1997 6.49860.6061

UAves (Jd1K1) 1.18300.0083 1.37030.0298

UASA (Jd1K1) 2.5890.0417 4.01550.2560

CO2 O2 .

. ,
kX,
. ,
, O2 , CO2 ,
m m

Hm O 5.25,5.265.27,,
2

5.5. , C X HY O
5.24.3,
C0.788 H 2.8575O ,

5 C0.7581H 2.9535O .

.,
,

- 195 -
 5

( 3 5)
,
.

, , 2 oC,
.,
3,5
.,
,,53.

, UAves , .

.
UASA ,

,
5.2 5.3.

, ,

1.

25 25

20 20
(%)
(%)

(%)
(%)

15 15

10 10

5 5

0 0
0 4 8 12 16 20 0 4 8 12 16 20

(d) (d)
(d)
(d)

() ()

5.2:()()
,
:()3()5.

- 196 -


25

(%)
(%)


20

15

10

0
0 4 8 12 16 20

(d)
(d)
()

25

(%)
(%)

20

15

10

0
0 4 8 12 16 20

(d)(d)

()

5.3:()()

,:()3()5.

.

(5.4).

- 197 -
 5

70

Ts

Tg
60

( C)
(oC)

o
50

40

30

20
0
0 4 8 12 16 20
(d)
(d)

()

70
Ts

Tg

60
(oC)( C)

50

40

30

20
0
0 4 8 12 16 20
(d)
(d)
()

5.4: ()
()
,:()3()5.

,
. ,
,
.,
,.

- 198 -


( 5.5). ,
.
,
.

10

(kg)
(kg)

0
0 10 20 30 40

(d)
(d)

()

10

(kg)
(kg)

0
0 10 20 30 40

(d)
(d)

()

5.5:,

, : () 3 ()
5.

5.7
.7

- 199 -
 5

.
AQUASIM 2.0,
.

,
. ,

.

- 200 -


5.8
Das K. and Keener H.M., 1997, Numerical model for the dynamic simulation of a large scale
compostingsystem,TransactionsoftheASAE,40,11791189.
HamelersH.V.M.,1993,Atheoreticalmodelofcompostingkinetics,Scienceandengineering
ofcomposting,3658.
HaugR.T.,1993,Thepracticalhandbookofcompostingengineering,LewisPublishers,USA.
Higgins C.W. and Walker L.P., 2001, Validation of a new model for aerobic organic solids
decomposition:simulationswithsubstratespecifickinetics,Processbiochemistry,36,875884.
Kaiser J., 1996, Modelling composting as a microbial ecosystem: a simulation approach,
Ecologicalmodelling,91,2537.
Mason, I.G., 2006. Mathematical modelling of the composting process: A review, Waste
management,26,321.
Nakasaki K., Kato J., Akiyama T. and Kubota, H., 1987, A new composting model and
assessment of optimum operation for effective drying of composting material, Journal of
fermentationtechnology,65,441447.
NelderJ.andMeadR.,1965,Asimplexmethodforfunctionminimization,Computerjournal,
7,308313.
Perry R.H. and Chilton C.H., 1973, Chemical engineers handbook, McGrawHill, fifth
edition.
Petric I. and Selimbai V., Development and validation of mathematical model for aerobic
compostingprocess,Chemicalengineeringjournal,139,304317.
Ralston M. and Jenrich R., 1978, DUD a derivative free algorithm for nonlinear least
squares,Technometrics,20,714.
Reichert P., 1994(a), Concepts underlying a computer program for the identification and
simulation of aquatic systems, Schriftenreihe der EAWAG 7, Swiss Federal Institute for
EnvironmentalScienceandTechnology(EAWAG),CH8600Dbendorf,Switzerland.
Reichert P., 1994(b), AQUASIM A tool for simulation and data analysis of aquatic systems,
Watersciencetechnology,30,2130.
ReichertP.,1995,Designtechniquesofacomputerprogramfortheidentificationofprocessesand
thesimulationofwaterqualityinaquaticsystems,Environmentalsoftware,10,199210.
ReichertP.,1998,AQUASIM2.0UserManual,Technicalreport,SwissFederalInstitutefor
EnvironmentalScienceandTechnology(EAWAG),CH8600Dbendorf,Switzerland.
Seki,H.,2000,StochasticmodelingofcompostingprocesseswithbatchoperationbyFokkerPlanck
equation,TransactionsoftheASAE,43,169179.
Stombaugh D.P. and Nokes S.E., 1996, Development of biologically based aerobic composting
simulationmodel,TransactionsoftheASAE,39,239250.
VanderGheynst J.S., Walker L.P. and Parlange, J.V., 1997, Energy transport in a highsolids
aerobicdegradationprocess:mathematicalmodelingandanalysis,Biotechnologyprogress,13,
238248.

(Internetwebpages)

Eawag, Swiss Federal Institute of Aquatic Science and Technology, URL:

http://www.eawag.ch.

- 201 -
 5

- 202 -





6

6.1

(Linear Alkylbenzene Sulphonates, LAS)

.
,
(para)
.

()
LAS [Terzi et al., 1992, Yadav et al., 2001, Eichhorn et al., 2002,
Marcomini et al., 2002].
, LAS.
,LAS
,
.

- 203 -
 6

[Schberl,1989].
CO2,.

,
.

[vanGinkel,1996].

LAS
. ,
LAS, ,
,
LAS.

6.1.1

6.1.1.1

(
).
,LAS.

.
4.36gTSSL1,3.00gVSSL13.33gTSSL1,2.21gVSSL1,.

6.1. ( )
,
.

400 mL 600 mL
1, 6.1.
,LAS

- 204 -


10mgL1.50mL
50 mL 1
10 mg LASL1.
800 mgL1, pH
7.5.
LAS.

6.1:
LAS.

6.1:1
.

(NH4)2SO4 0.235gL1

MgSO47H2O 0.200gL1
CaCl22H2O 0.026gL1
K2HPO4 5.000gL1
KH2PO4 3.000gL1
NaHCO3 0.700gL1
0.1mLL1

- 205 -
 6

6.2:

.

CuSO45H2O 0.786gL1

FeSO47H2O 5.000gL1

NaMoO42H2O 12.609gL1

NiCl26H2O 4.050gL1

ZnSO47H2O 4.398gL1

CoCl26H2O 2.453gL1

KI 0.750gL1
H3BO3 3.000gL1
MnCl24H2O 5.000gL1
EDTA 5.000gL1

LAS
,
. (
) , , 200 mL
1000mL.
1LAS
50mgL1. ,
, , .

.
121 oC 20 . LAS

.
0.22mMillipore
LAS.

LAS

. 100 mL

500 mL. 1

- 206 -


LAS ( 50 mg LASL1)
.LAS,
.

LAS(50mgLASL1 200mgLASL1).
,
LAS,
.

6.1.1.2

,
.
,
LAS
.,
LAS

.

W SO42

()LAS
.,
.
,(1)
SO42, . 2 ( 6.3)
1(6.1)
SO42
LAS.

, 100 mL
10 .
( 100mL)
2. 3
. ,

- 207 -
 6

500 mL
2 500 mL. LAS
50 mg
LASL1.
.

LASSO42.

6.3: 2
.

NH4Cl 0.059gL1

MgCl2H2O 0.169gL1

CaCl22H2O 0.026gL1

K2HPO4 0.250gL1

KH2PO4 0.150gL1
NaHCO3 0.700gL1
0.1mLL1

LAS

LAS.
LAS ,
.

301
(Organisation
for Economic Cooperation and Development, OECD),
[OECD, 1992]. ,
,
,
.
25,

- 208 -


LAS
.

, .
.,,
.

1 L ( 6.2). ,
LAS
(12),(34)
. 3
(biomasscontrol)LAS,4
(abiotic control)
.12,
LAS
(TSS),
,30mgL120mgL1,
. 3
301 OECD
(6.4).

6.2:
LAS.

- 209 -
 6

6.4: 3
LAS.

Na2HPO42H2O 334.00mgL1

NH4Cl 5.00mgL1

CaCl22H2O 36.00mgL1

MgSO47H2O 22.50mgL1

FeCl36H2O 0.25mgL1

K2HPO4 218.00mgL1

KH2PO4 85.00mgL1

( 3)
1 2, ,
LAS.,(4)
LAS 1 2,
, . ,
1 % v/v
.

25 oC.
,
4.55Lh1.

30 mL 0.0125 , .

0.05 .

LAS,,,
pH.

6.1.2

6.1.2.1

- 210 -


LAS.
16.500.58mgLASL10.200.02mgLASL17.
, , LAS
,10mgLASL1.

LAS
.

LAS,
LAS.,(
),
LAS.
,
().6.3,LAS
()
. , LAS
.

6.3:LAS (),
().

, . ,

1,
LAS.

- 211 -
 6

LAS,
.,
LAS(50mgLASL1
250mgLASL1).

6.1.2.2

LAS, () ,
.
LAS,
. 6.4
LAS.

44.50 1.58 mg LASL1 12 5.71
0.40mgLASL1.5mg
SO42L1. 6.4,
5.85mgSO42L1,
.

LAS.
LAS.

6.4:LAS

LAS.
- 212 -


6.1.2.3

LAS,

.LAS
( 1 2)
(34).3
(biomass control) LAS,
4 (abiotic control)
.

6.5 ,
mgTOCL1(TotalOrganicCarbon,TOC),1,2
3.
25.

()

()
6.5:,mg TOCL1,:()
LAS(12)()
(3).

- 213 -
 6

LAS1,
2 4 6.6.
1 2 . LAS
12(6.6())
, . ,
4
,
.

()

()

6.6:LAS :()
LAS(12)()
(4).

- 214 -


,6.7
(DissolvedOrganicCarbon,DOC),

1, 2 4. ,
LAS
( 6.6)
, mg DOC L1. DOC

, DOC
LAS.

()

()

- 215 -
 6

()

6.7:
(DOC):()LAS
1, () LAS 2 ()
(4).

,
LAS.
( 10 mgL1)
,
DOC. ,LAS

, LAS
4(6.7()).
LAS
. DOC
4 ( )
,

. DOC
.

,LAS
,

- 216 -


12.,
LAS.

, LAS

( 6.8). ,
( LAS ), (
)
. 6.8,
,
.

()

()
6.8:

LAS:()1()2.

- 217 -
 6

,
.,LAS100%.
LAS,
.

Marcomini[Marcominietal.,2002]
LAS
. LAS

LAS,
. LAS ,

20 .
.
,
,
LAS(6.8).

6.1.3

,

,
LAS. LAS
LAS
.
,
,
LAS . ,

LAS . ,
,
LAS
.
,.

,
,

- 218 -


LAS
(HRT).

6.2

.
[Thieleetal.,1997].
,
, .

(NPEO1 NPEO2) () [Ying et al., 2002,
GomezRicoetal.,2008].

NPEO
,,,
[Staplesetal.,2001,Soaresetal.,2003].
van Ginkel [1996],
.

,
.

.
,
.

6.2.1

6.2.1.1

- 219 -
 6

,
.

(4.40 g TSSL1 2.94 g VSSL1)

(4.00 g TSSL1 , 2.21 g VSSL1).
,
5mgL1.,
,
(stock solution) 10 g L1.
1000 mgL1,
pH7.45.
,
.

,

. 100 mL

500 mL. 1
(20mgL1,),
,
.
,
. ,

,
.

,
. ,
.
100 mL
,400mL1.
1,
, 10

- 220 -


mgL1..
,
,5%
.

6.2.1.2

, ,

.
,
.

,
. 6.5
. , Pseudomonas P & F,

121oC1.5atm30,
(Laminar Flow Hood).
Petri
510.

,
. ,


. , 5 g /L ,
0.22m.0.5mL

(12)
.,
.

- 221 -
 6

6.5: YEP Pseudomonas P & F

.

YEP 3.00gL1

5.00gL1

18.00gL1

PseudomonasP&F 15.00gL1

5.00gL1

MgCl2 0.70gL1

K2SO4 5.00gL1

K2HPO4 0.75gL1

MgSO4 0.75gL1

5mlL1

15.00gL1

30 oC 24 . 24
.

.3
.

6.2.1.3

, ,
.
.

(6.6).

. , 4
100mL1.5mL5
g NPL1 . ,

- 222 -


50 mL
.
25 oC.
.
.
6.6: YEP Pseudomonas P & F
.

YEP 0.2gL1

2.0gL1

NH4NO3 0.2gL1

PseudomonasP&F 15.000gL1

5.000gL1

MgCl26H2O 1.494gL1

K2SO4 5.000gL1

K2HPO4 0.750gL1

MgSO47H2O 1.535gL1
10mlL1

. pH
600nm
.

6.2.2

6.2.2.1

. 4.79 0.66 mg L1
0.270.01mgL110,
4.970.54mgL1
0.270.03mgL1.,
94.36 % 89.13 %, .

- 223 -
 6

,
.

[Renner, 1997],
,,

. ,

,.
,
. ,

.

,

.

1,
(20mgL1).

,

.
6.9,
. , 7 13
,
.

() ()
6.9: () ()
.
.

- 224 -


,
, 5 %
,.

, 6.10
.
,
. 6
97.6%,
.

6.10:,
.

(6.11).
9.67 mg L1 6
0.83 mg L1,
91%.

,
,5
% .
.

- 225 -
 6

6.11:
.

6.2.2.2

,

.

.

,
. 24 ,
YEP,

.


125 mg NPL1.

.

- 226 -


,
,
.
3 , .
,
,
.

6.2.2.3

,
.
YEP(1,23)PseudomonasP&F(45).

pH
6.12.
pH
.

() ()
6.12:pH :
() 1, 2, 3 YEP () 4 5
PseudomonasP&F.

600 nm ( 6.13). ,
, .

- 227 -
 6

.

30.

() ()
6.13:
:()1,2,3YEP()4
5PseudomonasP&F.

,
(6.14),
13
YEP.90.5%193.8%2.
5Pseudomonas
52.2%.
20,
.

, .
2 4,
.

1, 3 5

.
.

1, 2 5
.

- 228 -


() ()
6.14:
:()1,2,3YEP()4
5PseudomonasP&F.

6.2.3

,
,.

, .
5

.

.

6.3(2)

(2) (di(2ethylhexyl) phthalate, DEHP)

,
.

[Gavala et al., 2003, Zeng et al., 2004, Fang et al., 2007]. ,
,DEHP,
[Changet al.,2004,Zeng et al., 2004].,Chang
[Changetal.,2004], DEHP
, (NP)

- 229 -
 6

(PAHs).

DEHP.

.

6.3.1

6.3.1.1 (2
)

DEHP

( 6.2.1.1).
,DEHP.

(5.23gTSSL13.24
g VSSL1) (3.87 g TSSL1 ,
2.32 g VSSL1). ,
5 mg L1. ,
DEHP ,
(stock solution) DEHP 10 g L1.
1500mgL1,
pH7.5.
,
DEHP.

.

,
DEHP.
100 mL

500 mL. 1 DEHP
( 20 mgL1), ,
.

- 230 -


DEHP ,
,5%
.

6.3.1.2 (2
)

,
.

6.2.1.2.

6.3.2

6.3.2.1 (2
)

.
4.93 0.82 mg DEHPL1 2.18 0.02 mg DEHPL1 7
.,DEHP55.78%.

,DEHP.

,
DEHP
.

1,
DEHP 20mgL1.
(6.15).

6.15,
DEHP.17.231.70
mg DEHPL1 88 % 14 . ,

DEHP. ,

- 231 -
 6

DEHP.

6.15: DEHP

,
5%.

DEHP.

6.3.2.2 (2
)

DEHP
,
DEHP.

.

6
. YEP
Pseudomonas.

6.3.3

DEHP
.

- 232 -


DEHP
DEHP.

.

6.4

(Polycyclic Aromatic Hydrocarbons,

PAHs)(fused)
().
,

(logKow),

[Johnsonetal.,2005].

, 2 3

. PAHs ,
,
[Wu et al., 2009].

[Kanalyetal.,2000].

. ,
, , , ,
[] []. ,
PAHs
.

6.4.1

6.4.1.1

- 233 -
 6

.


.

,
6.16.
500 mL ,
.
,
PAHs .

. , PAHs
,,,
().

6.16:
5 PAHs (, , ,
[],[].

150mL350mL
1(6.1).PAHs
2 mgL1. ,
,
(stock solutions)
6.7.
. 1
,

- 234 -


6.7: (stock solutions) 5 PAHs

10.0gL1

10.0gL1

1.0gL1

[] 0.5gL1

[] 0.5gL1

PAHs.
(TSS)
(VSS)1247mgTSSL1660mg
VSSL1,,pH7.2.
,5PAHs
.

. , 100 mL

500 mL. 1
PAHs(2mgL1),
,.
20%
.
PAHs.

6.4.2

6.4.2.1

.
,5PAHs.

- 235 -
 6

, 6.17, 30
77.3 %, 64.6 %,
21.7%,[]17.7 %[] 21.8%.
,
3.9 % [] 16.4 %
.
PAHs.

6.17: 5 PAHs ,
.

2 3

, PAHs ,
,

- 236 -


[Haritash&Kaushik,2009].

(20 %)
5PAHs
.,

.
(TSS) (VSS)
745 mg TSSL1 395 mg VSSL1, ,
pH7.1.

,
6.18.
5PAHs.

,
,
(97%)(19%).,

.
, 90 % 14 %
.

PAHs, , []
[], ,
10 %.
, 18 .

,
.
42 56 %, 38 % 35 %,
.,
.

.

,,[][].

- 237 -
 6

6.18: 5 PAHs ,
.

6.4.3

,

,
.,,
[] []
. , 5 PAHs

.

- 238 -


6.5
ChangB.V.,YangC.M.,ChengC.H.andYuanS.Y.,2004,Biodegradationofphthalateestersby
twobacteriastrains,Chemosphere,55,533538.
EichhornP.,RodriguesS.V.,BaumannW.andKnepperT.P.,2002,Incompletedegradationof
linear alkylbenzene sulfonate surfactants in Brazilian surface waters and pursuit of their polar
metabolitesindrinkingwaters,Thescienceofthetotalenvironment,284,123134.
Fang H.H.P., Liang D. and Zhang T.,2007, Aerobic degradation of diethyl phthalate by
Sphingomonassp.,Bioresourcetechnology,98,717720.
GavalaH.N.,AlatristeMondragonF.,IranpourR.andAhringB.K.,2003,Biodegradationof
phthalate esters during the mesophilic anaerobic digestion of sludge, Chemosphere, 52, 673
682.
GomezRicoM.F.,FontR.,VeraJ.,FuentesD.,DisanteK.andCortinaJ.,2008,Degradation
oforganicpollutantsinMediterraneanforestsoilsatendedwithsewagesludge,Chemosphere,
71,21292138.
Haritash A.K. and Kaushik C.P., 2009, Biodegradation aspects of polycyclic aromatic
hydrocarbons(PAHs):Areview,Journalofhazardousmaterials,169,115.
JohnsonA.R.,WickL.Y.andHarmsH.,2005,PrinciplesofmicrobialPAHdegradationinsoil,
Environmentalpollution,133,7184.
Kanaly R.A, Bartha R., Watanabe K. and Harayama S., 2000, Rapid mineralization of
benzo[a]pyrenebyamicrobialconsortiumgrowingondieselfuel,Appliedandenvironmental
microbiology,66,42054211.
Marcomini A., Giacometti A. nad Pojana G., 2002, Aerobic biotransformation of linear
alkylbenzenesulphonatesunderlaboratoryconditions,Annalidichimica,92,2740.
Organisation for Economic Cooperation and Development (OECD), 1992, OECD guideline
fortestingofchemicals,Readybiodegradability,301BCO2evolutiontest,Paris,France.
Renner R., 1997, European bans on surfactant trigger transatlantic debate, Environmental
scienceandtechnology,31,316320.
SchberlP.,1989,BasicprinciplesofLASbiodegradation,Tensidesurfactantsdetergents,26,
8694.
Soares A., Guieysse B., Delgado O. and Mattiasson B., 2003, Aerobic biodegradation of
nonylphenolbycoldadaptedbacteria,Biotechnologyletters,25,731738.
StaplesC.A.,NaylorC.G.,WilliamsJ.B.andGlendhillW.E.,2001,Ultimatebiodegradationof
alkylphenol ethoxylate surfactants and their biodegradation intermediates, Environmental
toxicologyandchemistry,20,24502455.
Terzi S., Hrak D. and Ahel M., 1992, Primary biodegradation kinetics of linear alkylbenzene
sulphonatesinestuarinewaters,Waterresearch,5,585591.
Thiele B., Gnther K. and Schwuger J., 1997, Alkylphenol ethoxylates: Trace analysis and
environmentalbehaviour,Chemicalreviews,97,32473272.
Van Ginkel C.D., 1996, Complete degradation of xenobiotics surfactants by consortia of aerobic
microorganisms,Biodegradation,7,151164.
Wu Y., He T., Zhong M., Zhang Y., Li E., Huang T. and Hu Z., 2009, Isolation of marine
benzo[a]pyrenedegrading Ochrobactrum sp. BAP5 and proteins characterization, Journal of
environmentalsciences,21,14461451.

- 239 -
 6

YadavJ.S.,LawrenceD.L.,NuckB.A.,FederleT.W.andReddyC.A.,2001,Biotransformation
oflinearalkylbenzenesulfonate(LAS)byPhanerochaetechrysosporium:oxidationofalkylside
chain,Biodegradation,12,443453.
Ying G.G., Williams B. and Kookana R., 2002, Environmental fate of alkylphenols and
alkylphenolethoxylatesareview,Environmentinternational,28,215226.
ZengF.,CuiK.,LiX.,FuJ.andShengG.,2004,Biodegradationkineticsofphthalateestersby
PseudomonasfluorescencesFS1,Processbiochemistry,39,11251129.

- 240 -





7

,.,

.,

,
,(2),
(, , ,
[] []),
. ,
.,
,

- 241 -
 7

,.

.,,,
.

7.1

,
,:

D
60%
60%.

D pH,,
.

D
,
.

(LAS) ,
:

D
55%60%,,
.

D
.

D LAS
.
.

D LAS
.

- 242 -


LAS.

D LAS,
,
.

(2)(DEHP)
() (),
,:

D DEHP,
.

D DEHP,
LAS.

D
().

D
,
.

D
.

,
,
.,
,
(HRT) 10 15 .
:

D
.

D DEHP,
.

D LAS
.

D
.

- 243 -
 7

D
.

,
(PAHs)
.
:

D

.

D 5 PAHs
80%
.

D PAHs
.

D ,
PAHs.

D ()

.

.
AQUASIM 2.0
.
:

D
,
.

D
.

,

,:

- 244 -


D
,
LAS.

D LAS
.

D
,LAS
.

D LAS
().

D LAS
.

D
,
,.

D .

D 5
.

D
.

D , [] []
.

D 5 PAHs
.

DEHP

- 245 -
 7

7.2

,

. ,

,
,
.

,

. ,

. ,
PAHs.

- 246 -


1: 1

1.1
[Europeancommission,DGenvironment,2001]. 5

1.2 [,2005]. 7

1.3 (mgkg1 ..)

[,2005]. 9

1.4 ,
. 13

1.5 DEHP,,
4..
[Aparicioetal.,2009]. 15

1.6 (2)
. 19

1.7
. 22

1.8 16
(mgkg1 ..)
[Blanchardetal.,2004]. 24

1.9 (gkg1..)

[Perezetal.,2001]. 25

1.10
. 29

1.11
[HERA,2009]. 34

1.12
. 34

1.13
. 35

1.14
39

1.15
[Ahel&Giger,1993(a),(b)]. 41

1.16
. 42

1.17
. 45

- 247 -


2: 57

2.1
. 64

2.2 .....[Brinton,
2000]. 85

3: 95

3.1
. 99

3.2 , , ,

. 108

4: 117


4.1 ( 1 2)
(,kg..). 122

4.2
. 123

4.3 ( 1 2)
. 124

4.4 ( 1 2)
. 131

4.5 LAS1
2. 132

4.6 ( 3 4)
(,kg..). 133

4.7 ( 3 4)
. 135

4.8 ( 3 4)
. 140

4.9 ( 5 6)
(,kg..). 145

4.10 ( 5 6)
. 146

4.11 ( 5 6)
. 149

4.12 (mgkg1 .. )
56,
. 153

4.13 ( 7 10)
(,kg..). 156

- 248 -


4.14 /:2.5/1,
HRT10d15d. 157

4.15 ( 7 10)
. 158

4.16 (710)
. 163

4.17
(mgkg1..)7
10,. 164

4.18 (mgkg1
.. ) 7 10,
. 166

4.19 ( 11 12)
(,kg..). 168

4.20 ( 11 12)
. 169

4.21 ( 11 12)
. 172

4.22 5 PAHs (mgkg1 .. )

11 12,
. 174

4.23 LAS, NPEO, NP DEHP (mgkg1 .. )

1112,
. 175

5:
179

5.1
. 188

5.2
. 194

5.3
35. 195

6:
203

6.1 1

. 205

6.2

. 206

6.3 2
. 208

6.4 3

- 249 -


LAS. 210
6.5 YEP Pseudomonas P & F
. 222

6.6 YEP Pseudomonas P & F

. 223

6.7 (stocksolutions)5PAHs
. 232

- 250 -


1: 1

1.1 15
2005[ETCRWM]. 4

1.2 [ &
,2009]. 10

1.3
[Dargnatetal.,2009]. 14

1.4 (2). 14

1.5
[Stapplesetal.,1997]. 16

1.6 (2)
PseudomonasFluorescensFS1[Zengetal.,2002]. 17

1.7
[Haritash&Kaushik,2009]. 26

1.8 .()
()
[Wikipedia.org]. 32

1.9 , LAS
[HERA,2009]. 33

1.10
, LAS. Mungray
Kumar[Mungray&Kumar,2009]. 37

1.11 APEs (
Renner[1997]). 43

1.12 17
[Warshurst,1995]. 47

2: 57

2.1 . 58

2.2 ( Balmer
[2004]). 68

2.3 . 76

2.4 ()Rudgers
()Beltsville[,2003] 77

2.5 Magherafelt

. 79

2.6
Rolleston

- 251 -


,[www.wasteminz.org.nz]. 80
2.7 ()
()

, ,
,... 81

2.8
. 89

2.9
. 90

2.10 [www.compost.gr]. 90

3:
95

953.1 : () ()
. 97

3.2
(LAS). 100

3.3
(PAHs) (2)
(DEHP). 101

3.4 NP NPEO
: (1) / :
1/1, 100 oC, 600W, (2) / : 1/1, 100 oC, 600W,
, (3) / : 1/1, 100 oC, 1200W, (4) / : 1/1, 1
mL H2O, 100 oC, 1200W, (5) / : 1/1, 120 oC, 1200W, (6)
/ : 1/1, 1 mL H2O, 120 oC, 1200W, (7)
/ : 3/7, 100 oC, 600W, (8)
/ : 3/7, 120 oC, 1200W, (9)
/:3/7,1mLH2O,120oC,1200W. 102

3.5
(NP)(NPEO). 103

3.6 : ()
, () , () ,

() ,
[LeBlanc&Majors,2001]. 104

4:

117

4.1
.()()
. 119

4.2
. 120

- 252 -


4.3
12. 127

4.4
12. 128

4.5
12. 129

4.6
12. 129

4.7 ,
,
12,. 130

4.8
34. 137

4.9
34. 138

4.10
34. 138

4.11
34. 138

4.12 LAS
3.
. 142

4.13 LAS
4.
. 142

4.14
56. 147

4.15
56. 148

4.16
56. 148

4.17 DEHP
5
6.
. 151

4.18
56.
. 152

4.19
56.
. 152

4.20 LAS
.
. 154

- 253 -


4.21
5 PAHs
. 159

4.22 ,
( 7)
HRT10(8). 160
4.23 ,
( 9)
HRT15(10). 161
4.24
,(
7)HRT10(8). 162
4.25
,(
9)HRT10(10). 162
4.26
1112. 170
4.27 ()(),
1112. 171
4.28 : () , ()
, () , () [] ()
[]
1112. 173

5:
179

5.1
.
,
. 183
5.2 ()
()
,:()3()
5. 196
5.3 ()
()
, : ()
3()5. 197
5.4 ()
()
,:()3()
5. 198
5.5 ,
,:()
3()5. 199

- 254 -


6:
203

6.1
LAS. 205

6.2
LAS. 209
6.3 LAS
(),(). 211
6.4 LAS

LAS. 212
6.5 , mg TOCL1,
: () LAS ( 1
2)()(3). 213
6.6 LAS : ()
LAS ( 1 2) ()
(4). 214

6.7
(DOC) : ()
LAS1,()LAS
2()
(4). 216
6.8
LAS:()1()2. 217
6.9
.

. 224
6.10 ,
. 225
6.11
. 226
6.12 pH
: () 1, 2, 3
YEP () 4 5
PseudomonasP&F. 227
6.13
: () 1, 2, 3
YEP () 4 5
PseudomonasP&F. 228
6.14
: () 1, 2, 3
YEP()45
PseudomonasP&F. 229
6.15 DEHP

- 255 -


. 230
6.16
5 PAHs (,
,,[],[]. 231
6.17 5 PAHs
,. 236
6.18 5 PAHs
,. 238

- 256 -


AOX HaloganatedOrganicCompounds,

APEs AlkylPhenolEthoxylates,

COD ChemicalOxygenDemand,

DBP Di(nbutyl)phthalate,(n)

DCOD DissolvedChemicalOxygenDemand,

DEHP Di(2ethylhexyl)phthalate,(2)

DEP Diethylphthalate,

DMP Dimethylphthalate,

DOC DissolvedOrganicCarbon,

FAS FreeAirSpace,

HLB HydrophilicLipophilicBalance,

HPLC HighPressureLiquidChromatography,

IC InorganicCarbon,

LAS LinearAlkylbenzeneSulphonates,

LOD LimitofDetection,

LOQ LimitofQuantification,

MAE Microwave Assisted Extraction,

MEHP Monoethylhexylphthalate,()

NP NonylPhenol,

NPE NonylPhenolEthoxylates,

OP OctylPhenol,

OPE OctylPhenolEthoxylates,

PAEs PhthalicAcidEsters,

PAHs PolycyclicAromaticHydrocarbons,

PCB PolychlorinatedBiphenyls,

PCDD PolychlorinatedDibenzopDioxins,

PCDF PolychlorinatedDibenzopFurans,

qPCR quantitative Polymerase Chain Reaction,

RSD RelativeStandardDeviation,

- 257 -


SPE SolidPhaseExtraction,

TCOD Total ChemicalOxygenDemand,

TOC TotalOrganicCarbon,

TP TotalPhosphorus,

TS TotalSolids,

TSS TotalSuspendedSolids,

USEPA United States Environmental Protection Agency,

VS VolatileSolids,

VSS VolatileSuspendedSolids,

- 258 -


.
.

:071978
: :

:149,,26500,

:2610525373

:6937332987

Fax:2610526406

email:pakou@chemeng.upatras.gr

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: 2005 :

2002 2005:

2002:

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: 1996:

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2003: ()

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(CertificatoSuperiore,Palso)

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2007 2010:

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:

2008 2009:

2003 2005:

260
: 1. Fountoulakis,M.,Drillia,P.,Pakou,C.,Kampioti,A.,Stamatelatou,K.,

Lyberatos, G., 2005, Analysis of nonylphenol and nonylphenol

ethoxylates in sewage sludge by high performance liquid

chromatographyfollowingmicrowaveassistedextraction,Journalof

ChromatographyA1089(12),p.4551.

2. Constantina Pakou, Michalis Fountoulakis, Panagiota Drillia,

Adamantia Kampioti, Katerina Stamatelatou and Gerasimos

Lyberatos, 2007, Occurrence and Fate of Polycyclic Aromatic

HydrocarbonsinSewageTreatmentPlantsusingMicrowaveAssisted

Extraction followed by Liquid Chromatography coupled with

Fluorescence Detector. Fresenius Environmental Bulletin 16 (2), p.

127132.

3. Constantina Pakou, Katerina Stamatelatou, Michael Kornaros and

Gerasimos Lyberatos, 2007, On the complete aerobic microbial

mineralization of linear alkylbenzene sulfonate. Desalination 215, p.

198208.

4. Constantina Pakou, Michael Kornaros, Katerina Stamatelatou and

GerasimosLyberatos,2009,OnthefateofLAS,NPEOsandDEHPin

municipal sewage sludge during composting, Bioresource

Technology,100,p.16341642.

5. C.E.Marazioti, G.Flessia,, P. Vlachos, E. Koutrouli, I. Ntaikou, G.

Antonopoulou, C. Pakou, . Kalfas, M. Kornaros and G. Lyberatos,

2010, The Environmental State of the Mesologgi lagoon in Greece,

FreseniusEnvironmentalBulletin19(6).

6. Pakou C., Stamatelatou K., Kornaros M. and Lyberatos G., On the

removal of xenobiotics during the composting of different sludge

types, accepted for publication in Water Science and Technology

(2009).

261


: 1. Pakou C., Kornaros M., Stamatelatou K. and Lyberatos G., Fate of Linear

Alkylbenzene Sulfonate (LAS) during Composting, Proc. WasteEng 2005,

Albi,France(2005).

2. Pakou C., Kornaros M., Stamatelatou K. and Lyberatos G., Fate of NPEO,

DEHP and PAHs during Composting of Raw and Anaerobically Digested

Sludge,15thAnnualmeeting,SETACEurope,Lille,France(2005).

3. Kornaros M., Pakou C., Stamatelatou K. and Lyberatos G. Modelling of

linearalkylbenzenesulfonates(LAS)biodegradationkineticsduringsewage

sludge composting, 15th Annual meeting, SETAC Europe, Lille, France

(2005).

4.ChristensenN.,MosbkH.,GarciaH.,LyberatosG.,StamatelatouK.,Drillia

P.,FountoulakisM.,PakouC.,KampiotiA.,PatureauD.,CariaG.,Schmidt

J.E.ComparativeAnalysisofTraceAmountsofToxicOrganicComounds

in Sewage Sludge, 15th Annual meeting, SETAC Europe, Lille, France

(2005).

5.BatstoneD.J.,TrablyE.,ChristensenN.,PatureauD.,StamatelatouK.,Pakou

C., Kornaros M., Lyberatos G. and Schmidt J.E. Assessing Microbial

Potential for Degradation of Complex Organic Compounds, 15th Annual

meeting,SETACEurope,Lille,France,(2005).

6. Pakou C., Fountoulakis M., Drillia P., Kampioti A., Stamatelatou K. and

Lyberatos G., Microwaveassisted Extraction HPLC FD for the

Assessment of the Occurrence and the fate of Polycyclic Aromatic

HydrocarbonsinSewageSludge,Proc.WasteEng2005,Albi,France(2005).

7.M.,.,.,K.,.,

I..,

,5

,2005,.

8. Michalis Fountoulakis, Panagiota Drillia, Constantina Pakou, Adamantia

Kampioti, Katerina Stamatelatou and Gerasimos Lyberatos, Fate of

nonylphenolandnonylphenolethoxylatesinsewagetreatmentplants,9th

Conference on environmental science and technology 2005, September

2005,Rhodesisland,Greece.

262
 9. Gerasimos Lyberatos, Katerina Stamatelatou, Michael Fountoulakis,

Constantina Pakou, and Michael Kornaros, On the Fate of Xenobiotic

Compounds during Alternative Methods of Municipal Sludge Treatment,

AIChE2006AnnualMeeting,November1217,2006,SanFrancisco,USA.

10. . , . *, . , . , .

,.,J.E.Schmidt,N.Christensen,I.Angelidaki,D.J.

Batstone,E.Trably,L.Metzger,N.Ameall,J.Watson,K.Garca,S.Ayuso,A.

Bala and D. Patureau

, 2

,,342006.

11. arazioti C.E, Flessia G., Vlachos P., Koutrouli E., Ntaikou I.,

AntonopoulouG.,C.Pakou,C.Kalfas,M.KornarosandG.Lyberatos.On

the Environmental State of the Mesologgi lagoon in Greece, poster at the

8th International Conference Sacharov Readings 2008: Environmental

ProblemsoftheXXIthCentury,2223May2008,Minsk,RepublicofBelarus.

12.PakouC.,StamatelatouK.,KornarosM.andLyberatosG.,Ontheremoval

of xenobiotics during the composting of different sludge types,

InternationalconferenceXENOWAC2009,Paphos,Cyprus(2009).

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