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1 s2.0 S0045653503005915 Main PDF
1 s2.0 S0045653503005915 Main PDF
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Abstract
The occurrence and the fate of heavy metals (Cd, Pb, Mn, Cu, Zn, Fe and Ni) during the wastewater treatment
process were investigated in the wastewater treatment plant (WTP) of the city of Thessaloniki, northern Greece, operating in the activated sludge mode. For this purpose, wastewater and sludge samples were collected from six dierent
points of the plant, namely, the inuent (raw wastewater, RW), the euent of the primary sedimentation tank (primary
sedimentation euent, PSE), the euent of the secondary sedimentation tank (secondary sedimentation euent, SSE),
sludge from the primary sedimentation tank (primary sludge, PS), activated sludge from the recirculation stream
(activated sludge, AS), and the digested/dewatered sludge (nal sludge, FS).
The distribution of metals between the aqueous and the solid phase of wastewater was investigated. Good exponential correlation was found between the metal partition coecient, log Kp , and the suspended solids concentration.
The mass balance of heavy metals in the primary, secondary and the whole treatment process showed good closures for
all metal species. The relative distribution of individual heavy metals in the treated euent and the sludge streams
indicated that Mn and Cu are primarily (>70%) accumulated in the sludge, while 4763% of Cd, Cr, Pb, Fe, Ni and Zn
remain in the treated euent.
2003 Elsevier Ltd. All rights reserved.
Keywords: Heavy metals; Wastewater; Wastewater treatment plants; Sewage sludge
1. Introduction
Since the early 1970s there has been growing concern
over the diverse eects of heavy metals on humans and
aquatic ecosystems. Many heavy metals and their compounds have been found that are toxic, while some
are also subjected to biomagnication (Viessman and
Hammer, 1993; Gardea-Torresday et al., 1996). Environmental impact by heavy metals was earlier mostly
connected to industrial sources. In recent years, metal
0045-6535/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0045-6535(03)00591-5
1202
2. Methodology
2.1. Sampling
The WTP of the city of Thessaloniki serves about 1
million residents by treating daily 120 000150 000 tonnes of municipal wastewaters. About 510% of the total
ow is contributed by small enterprises. The plant also
receives the greatest part of the local urban runo
mainly composed of atmospheric deposition, and tracrelated emissions deposited on the road surface. The
treatment process includes screening, grit removal, primary sedimentation without use of chemical coagulants,
conventional activated sludge treatment, and euent
disinfection with Cl2 . The sludge treatment consists of
covered prethickeners, open postthickeners, anaerobic
digesters and dewatering system with belt lter presses
(Manoli and Samara, 1999). The treated wastewater is
discharged in Thermaikos Gulf, while the sewage sludge
is deposited in a municipal landll (Katsoyiannis and
Samara, 2002). The owchart of the plant is shown in
Fig. 1.
Wastewater sampling was conducted in two one-week
campaigns during November and December 2001. In
each campaign, wastewater samples were collected over
ve consecutive days, excluding Saturday and Sunday.
Given that the residence time of wastewater in the WTP
was about 24 h, this sampling rate allowed sucient
matching of inuent and euent samples that is a prerequisite for mass balance calculations. 24-h composite
samples of wastewater, ow proportioned, were collected
from the inuent (raw wastewater, RW) and the euents
of the primary and secondary sedimentation tanks (PSE
and SSE, respectively). Grab samples of sludge were
collected from the PST (PS), the recirculation stream of
activated sludge (AS) concurrently with wastewater
samples. Grab samples of the nal digested/dewatered
sludge (FS) were collected 21 days later, which is the retention time in the anaerobic digesters.
Fig. 1. Flow chart of the Wastewater Treatment Plant of Thessaloniki (QRW : 150 000 m3 /d, QPS : 4500 m3 /d, QAS : 150 000 m3 /d, QAS2 :
3000 m3 /d).
1203
COD, SS) in wasterwater and sludge samples were determined by employing standard methods (APHA,
1989).
Table 1
Mean SD of heavy metal concentrations in wastewaters (lg/l)
Metal
RW
Mean
Cu
Cr
Ni
Pb
Mn
Fe
Cd
Zn
BOD5 (mg/l)
COD (mg/l)
DOC (mg/l)
SS (mg/l)
N 9.
79
40
770
39
67
480
3.3
470
520
1100
72
690
PSE
SSE
SD
Mean
SD
Mean
SD
35
12
200
9.4
12
87
1.1
140
58
25
600
31
26
450
2.3
380
37
12
270
12
4.3
78
0.94
50
33
20
430
27
19
380
1.5
270
5.8
3.5
97
3.6
2.4
47
0.74
53
120
270
35
160
270
630
71
340
57
100
28
129
10
54
19
12
3.9
17
11
9.3
1204
Fig. 2. Distribution of heavy metals in the dissolved ( ) and the particulate (j) phase of wastewater (RW: raw wastewater, PSE:
primary sedimentation euent, SSE: secondary sedimentation euent).
of Zn, Pb and Cr, while biological processes and secondary sedimentation aected mostly the distribution
of Cu, Cd and Ni. In our study, wastewater treatment
appeared to aect only slightly the phase distribution of
examined metals. On the contrary, the phase distribution appears to be metal-specic suggesting that metals
are present in dierent chemical forms with dierent
water solubility at the pH of wastewater (79). Studies
on the chemical fractionation of heavy metals in sewage
sludge have indicated that the water-soluble, exchangeable and carbonate-bound fractions are major carriers
of Ni and Zn, organic matter and sulphides are important carriers of Cr and Cu, iron/manganese oxides and
hydroxides are carriers of Pb, Zn and Ni, while a great
amount of sludge Fe and Pb is associated with the
crystallic phase of sludge particles (Angelidis and Gibbs,
1989; Scancar et al., 2000). In their review, Brown and
Lester (1979) indicated that the solubilities of heavy
metals in sewage followed the order: Pb < Cu < Cd,
whereas Jenkins et al. (1981) found the order to be
Cu < Pb < Cd < Zn. In the present study, Ni was found
primarily in the dissolved phase (8093%) as expected
due to the high mobility of this metal (Sorme and
Lagerkvist, 2002). Manganese also was found strongly
associated with the dissolved phase (6585%). On the
contrary, Cu, Cr, Pb, Cd and Zn were mostly associated
with the particulate phase (7595%), particularly Pb
(>95%). Iron exhibited moderate association with particles (5875%).
1205
Fig. 3. Partition coecients of heavy metals in wastewater (log Kp ) in relation to the concentration of suspended solids (SS).
heavy metals in the sludge samples was 100% for all the
examined species. Zn appeared to be the most abundant
metal and again Cd exhibited the lowest abundance. All
metals were found at comparable concentrations in PS
and AS. On the contrary, concentrations in FS were
about 1020 times higher with most pronounced enrichment shown for Pb. This is due to the weight loss of
fresh sludge during anaerobic digestion, whereby biodegradable organic and inorganic matter is decomposed
to end products including CO2 , CH4 , N2 , H2 S and other
gases (Tchobanoglous and Burton, 1991; Langenbach
et al., 1994). Chipasa (2003) found Cd, Cu, Pb and Zn
contents in digested sludge 5099% higher than corresponding contents in undigested sludge.
Table 3 presents the limits established by various
countries for heavy metals in sewage sludges intended
1206
Table 2
Mean SD of heavy metal concentrations in sludge (lg/g d.w.)
PS
Metal
Cu
Cr
Ni
Pb
Mn
Fe
Cd
Zn
TOC (% w/w)
SS (% w/w)
AS
FS
Mean
SD
Mean
SD
Mean
SD
100
17
37
28
83
240
1.0
350
21
6.1
12
7.9
28
64
0.39
3.1
91
32
31
16
73
360
1.0
440
17
13
16
3.1
17
63
0.37
59
1200
370
300
330
1100
3300
10
4500
220
100
76
84
180
260
4.3
450
25
2.3
1.3
0.44
2.6
0.10
40
22
17
0.72
2.7
0.49
N 9.
Table 3
Maximum permissible concentrations of heavy metals in the sewage sludge for agricultural land application (lg/g d.w.)
Country
Cd
Greece/EU
2040
Austria
Belgium
Denmark
Germany
France
Luxembourg
Holland
Spain
Italy
Slovenia
USA
3
5
0.4
10
20
1.5
1
10
10
5
85
Cr
Cu
Pb
Ni
Zn
Reference
10001750
7501200
300400
25004000
250
200
500
500
800
1000
100
100
100
30
200
200
50
1200
1500
900
1000
100
250
1000
120
900
800
150
2500
3000
400
50
400
600
500
3000
75
50
600
600
4300
100
300
500
500
840
30
120
200
80
420
200
1100
2500
2000
7500
1207
Table 4
Concentrations of heavy metals in sewage sludges from various WTPs (lg/g)
Cd
4
2.1
55.7
2.78
1.81
Cr
128
1228
841
60.5
100.1
552
1.82
34
9.2
3.19
439
322
Cu
147
370
755
436
315.5
1403
258
934
287
167
326
239
Fe
Pb
Ni
Zn
46 000
155
72
930
128
35.9
34
19
260
622
43.5
1878
1500
12 064
2049
54.2
412
326
118
69
75
223
126.8
11.9
967
41
221
58 328
22 445
5098
16 794
36.5
317
Mn
308
3165
679.9
1739
1574
933
254
1636
2451
150
364
Reference
Voutsa et al. (1996)
Lazzari et al. (2000)
Bodzek et al. (1997)
Scancar et al. (2000)
Baralikiewicz and Siepak
(2001)
Perez et al. (2001)
Cornu et al. (2001)
Zorpas et al. (2000)
Bragato et al. (1998)
Madoni et al. (1999)
Planquart et al. (1999)
Alonso et al. (2002)
Abdel-Shafy et al. (1996)
Table 5
Correlation coecients for heavy metals and organic carbon content (N 27)
Sludge
Cu
Ni
Cr
Pb
Mn
Fe
Cd
Zn
TOC
Wastewater
Cu
Ni
0.92
0.88
0.96
0.99
0.97
0.94
0.97
0.90
0.97
0.93
0.93
0.93
0.83
0.92
0.86
Cr
Pb
Mn
Fe
Cd
Zn
DOC
)0.46
0.90
0.89
0.93
0.75
0.93
0.83
)0.44
0.98
0.95
0.88
0.96
0.89
0.98
0.92
0.98
0.91
0.84
0.99
0.90
)0.53
)0.46
0.84
0.78
)0.66
0.90
1208
Fig. 4. Mass balance of heavy metals in the Thessaloniki WTP (g/d). Primary treatment: HMIN g=d HMRW g=m3 QRW m3 =d,
HMOUT g=d HMPSE g=m3 QRW QPS m3 =d HMPS g=g QPS m3 =d SSPS g=m3 . Secondary treatment: HMIN g=d
HMPSE g=m3 QRW QPS m3 =d HMAS g=g QAS1 m3 =d SSAS g=m3 , HMOUT g=d HMSSE g=m3 QRW
QPS m3 =d HMAS g=g QAS m3 =d SSAS g=m3 . Total treatment: HMIN g=dHMRW g=m3 QRW m3 =d, HMOUT g=d
HMSSE g=m3 QRW QPS m3 =d HMPS g=g QPS m3 =d SSPS g=m3 HMAS g=g QAS2 m3 =d SSAS g=m3 .
PRIMARY TREATMENT
IN
OUT
SECONDARY TREATMENT
IN
OUT
TOTAL TREATMENT
IN
OUT
Fig. 5. Release of heavy metals from the WTP via the sludge and the treated euent streams.
4. Conclusions
Heavy metals were determined at dierent stages of
an activated sludge WTP that receives mainly domestic
1209
1210
Sun, G., Shi, W., 1998. Sunower stalks as adsorbents for the
removal of metal ions from wastewater. Ind. Eng. Chem.
Res. 37, 13241328.
Tchobanoglous, G., Burton, F.L., 1991. Wastewater Engineering; Treatment, Disposal and Reuse. McGraw-Hill, New
York.
US EPA, 1986. Report to Congress on the Discharge of
Hazardous Wastes to Publicly Owned Treatment Works
(The Domestic Sewage Survey) (EPA/530-SW-86-004).
Oce for Water Regulation and Standards, Washington,
DC.