THE INFLUENCE

OF F L O W C O N D I T I O N S

ON T H E R E M O V A L

OF H E A V Y M E T A L S IN T H E P R I M A R Y S E D I M E N T A T I O N
PROCESS

A. C. R O S S I N * , R. M. S T E R R I T T ,

and J. N. L E S T E R * *

Public Health Engineering Laboratory, Imperial College, London, SW7, UK

(Received October 27, 1981; Revised January 18, 1982)

Abstract A pilot scale primary sedimentation pilot plant, treating raw sewage, was used to assess the

efficiency of removal ofCd, Cr, Cu, Ni, Pb, and Zn. Heavy metal removals were determined during conditions
designed to simulate normal dry weather flow, three times dry weather flow and diurnal variations in flow.
During these experiments, the flow of sewage to the works where the pilot plant was sited also varied. It
was found that short term variations in heavy metal concentrations in the raw sewage were related to the
flow, although percentage removals appeared to be relatively unaffected by heavy metal concentrations.
Removals during normal dry weather flow conditions were generally in the range of 25 to 50 %, with Cu and
Pb removals highest and Ni removal lowest. Lower removal efficiencies were observed when the flow to the
pilot plant was increased three-fold, and the poorest removals were observed under variable flow conditions.

1. Introduction

Waste water treatment processes have assumed a more important role in the hydrological
cycle with the increasing tendency towards water re-use. In particular their capacity for
the removal of heavy metals is important in maintaining standards for heavy metal
concentrations in water to be abstracted for drinking water (European Economic
Community, 1975), potable supplies (World Health Organisation, 1970; 1971) and
irrigation water (Federal Water Control Administration, 1968).
Lester et al. (1979) and Stoveland et al. (1979) have found removal efficiencies for Cd,
Cr, Cu, Pb, and Zn in the primary sedimentation process of 70~o or greater, although
the mean removal of Ni was only 23 ~o. Similar percentage removals were observed by
Oliver and Cosgrove (1974) who also found removals of Fe, Mn, and Hg of 36 to 49 ~o,
32 to 33 ~o, and 60 ~o respectively. Although relatively efficient removals of most heavy
metals of greater than 50~o have frequently been found, in some cases poor removals
of Cd, Cr, Cu, and Zn have occurred (Brown et al., 1973; Davis and Jacknow, 1975;
Roberts et al., 1977), indicating that the efficiency of the process is variable. Ranges of
heavy metal removal efficiencies reported in the literature are shown in Table I.
Considerable variations in influent heavy metal concentrations and loadings to
primary sedimentation may occur. Roberts et al. (1977) found that concentrations of
heavy metals in a raw sewage were typically 3 to 5 times higher during the day than during
the night, corresponding to a day time to night time load of between 5 : 1 and 8 : 1.
* Present address: Faculdade de Saude Publica, Universidade de S~o Pauto, Avenida Dr. Arnaldo 715,
CP 8099 S~o Paulo - SP, Brazil.
** To whom all correspondence should be addressed.

Water, Air, and Soil Pollution 19 (1983) 105-121. 0049-6979/83/0192-0105502.55.

Copyright 1983 by D. Reidel Publishing Co., Dordrecht, Holland, and Boston, U.S.A.

106

A . C. R O S S I N

ET AL.

!
.o

8~

dL
<
te~

i
d

j~

i.~. tr3

O t"~
~ ~

,~

~=>-~

REMOVAL OF HEAVY METALS IN PRIMARY SEDIMENTATION

107

Although the poor removals observed by Roberts et al. (1977) may have been due to large
variations in loading, Oliver and Cosgrove (1974) found relatively constant removals
when 8 to 10 fold variations in concentration occurred. In contrast, Stoveland et al.
(1979) found that the removal of Ni exhibited considerable variations (0 to 40 ~o) despite
the fact that loading was the least variable of all the metals studied.
Heavy metal removal during primary sedimentation is a physical process, dependent
on the formation of settleable particulates, while removal in secondary biological
treatment is probably a more complex process, dependent on a variety of factors (Brown
and Lester, 1979). Since the metals which are removed in primary sedimentation may
exist initially in insoluble forms or forms which have the capacity for association with
solids, the speciation of metals in the raw sewage may influence their removals. Jan and
Young (1978) found that the dominant species of soluble Cr in raw sewage were trivalent
forms and that about 60 To of the Cr was in a particulate state. Bailey et aL (1970) showed
that trivalent Cr was largely removed in sedimentation, leaving the hexavalent species
in solution. Chert et al. (1974) found variations in the solid phase speciation of heavy
metals in primary effluent, with different paticle size distributions for different metals,
suggesting that the optimum removal of some metals may be dependent on the efficient
sedimentation of smaller particles.
2. Material and Methods

2.1.

PRIMARY

SEDIMENTATION

PILOT PLANT

The circular sedimentation tank has been described in detail by Rossin et al. (1981). Raw
sewage from the Hogsmill Valley Water Pollution Control Works (Thames Water
Authority, UK), at which the pilot plant was located, was fed to the tank by a constant
head loading system. This system included a moveable 30 V-notch weir designed for
a maximum flow of 1.11 1 s- i. Movement of the weir was regulated by a cam in which
had been milled a peripheral groove designed to simulate the daily flow variation under
normal dry weather flow conditions at the Hogsmill Valley Works. The cam was operated
by an electric motor controlled by sequential timers, with which it was possible by
stop-start operation to rotate the cam at the appropriate rate.
The sedimentation tank was cylindrical at the top with a diameter of 1 m and a height
of 1.10 m and conical (60 ) at the bottom. The total height of the tank was 1.90 m. An
internal drum of diameter 0.30 m was mounted in the center of the tank into which the
sewage was fed. The total capacity of the tank was 0.915 m 3 with retention times of 2.27 h
at 0.111 1 s- ~ and 0.76 h at 0.333 1 s- i. The surface loadings were 0.56 and 1.68 m h - 1
at flows of 0.111 and 0.333 1 s -~, respectively. The operation of the plant has been
described previously (Rossin et al., 1981).
The operation of the pilot plant was conducted so that experiments could be
undertaken under three different flow conditions corresponding to normal dry weather
flow (1 DWF), three times normal dry weather flow (3 DWF) and variable flow. The
flow, surface load and retention time for each experimental condition are summarized
in Table II.

108

A. C.

ROSSIN ET AL.

TABLE II
Values for flow, surface load and retention time for the pilot plant when
operated under various conditions
Conditions

1 DWF
3 DWF
Variable flow

Flow

Surface load

Retention time

1 s -1

m h -1

(h)

0.0111
0.333
0.075-0.168

0.56
1.69
0.38-0.85

2.27
0.76
-

2.2. SAMPLING
Samples for solids and heavy metal determinations were collected from raw and settled
sewage by two peristaltic pumps, each with three heads, which operated under the control
of two sequential timers. The samples were collected in borosilicate tall form beakers
(150 ml) positioned in a static tray. A moveable bridge mechanism operated by timers
was used to guide the end of the sampling tubes to the next set of beakers for sequential
collection of samples. The volume of samples remaining in the tubes after each sampling
was the same for all the sampling points. All sampling tubes were made of silicone rubber,
and the entire system was enclosed to avoid contamination. Samples for metal analysis
were preserved with 10 ml of 15 ~o v/v 'Aristar' nitric acid previously added to the beaker
to produce an average concentration of 1~o v/v in nitric acid. Preservation of samples
on which solids determinations were to be made was achieved by using 2 ml mercuric
chloride solution (2 g 1-1) to produce an average concentration of 40 mg 1- l in the
sample. When collecting the samples, the total volumes (generally between 140 and
150 ml) were measured and by deducting the volume of preservative used the dilution
factors could be calculated.

2.3.

ANALYTICAL METHODS

Chemical oxygen demand and solids determinations were performed according to the
methods recommended by the Government of Great Britain (1972). Heavy metals were
determined using the tameless atomic absorption spectrophotometric methods
described by Sterritt and Lester (1980a). Samples of sludge from the tank were
homogenized using an Ultra-Turrax (Scientific Instrument Co., London) with a titanium
shaft and rotor (Stoveland et al., 1978) and preserved with 1~o (v/v) HNO3 after tenfold
dilution.

REMOVAL OF HEAVY METALS IN PRIMARY SEDIMENTATION

109

3. Results

3.1. THE

INFLUENCE

OF INFLUENT

HEAVY METAL CONCENTRATIONS

ON THEIR

B E H A V I O R IN P R I M A R Y S E D I M E N T A T I O N

A total of twelve experiments to study heavy metal removal in the primary sedimentation
pilot plant were undertaken during a period of 4 mo. During this time wide variations
in the concentrations of heavy metals in the raw sewage occurred. Moreover, the daily
flows to the Hogsmill Works also varied, mainly due to weather conditions. Although
the adjustable weir and offset cam assembly permitted the simulation of normal, heavy
and variable flow to the pilot scale sedimentation tanks, it was not possible to simulate
the changes in the nature of the sewage which occur as the result of storm conditions
and other factors which affect the flow. Therefore, the total flow of sewage to the Hogsmill
Works was recorded during each experiment, and the concentrations of heavy metals
were determined every 3 h. These parameters are shown in Figure 1 for a typical instance
of normal flow, and Figure 2 for elevated flow conditions.
During the normal variations in flow the data in Figure 1 indicate that for Cd, Cu, and
Zn, in particular, the concentrations increased with decreasing flow, possibly because
at higher flows the metal concentrations were subject to some dilution. The highest
concentration of Pb appeared in a shorter time after the daily peak flow, possibly
reflecting the transport of larger quantities of Pb from scouring and road run-off. At the
onset of storm conditions (Figure 2) the peak Pb concentration in raw sewage was similar
to that which occurred during normal flow. However, the concentration of Pb decreased
steadily thereafter, indicating that the Pb may have entered the works in a transient peak
arising from run-off and scouring. The large initial peaks of Cd and Ni may also have
been caused by the same phenomenon. The influent concentration of Cu also exhibited
a marked increase towards the end of the storm period. This may have been a result of
the return to the flow of the sewage which had been previously retained in the storm tanks.
As a result of these factors, the mean concentrations of heavy metals, suspended solids
and COD in the influent raw sewage the settled sewage for each three day experiment
varied widely. These mean concentrations are shown in Table III. The ranges of heavy
metal concentrations during the entire experimental period were: Cd 0.37 to 2.07 lag 1- 2,
Cr 67.8 to 36.3 lag 1- 2, Cu 57 to 267 lag 1- l, Ni 6.3 to 22 lag 1- 2, Pb 29 to 117 lag 1- l, and
Zn 105 to 314 lag 1-1. From a comparison of the heavy metal concentrations in Table III
with the removal efficiencies presented in Tables IV and V, it appeared that heavy metal
removal was not influenced by the influent concentration. Moreover, the mean heavy
metal concentrations in the raw sewage over each 3 day period were apparently
unaffected by the flow to the works. These observations indicate that the variations in
influent heavy metal concentrations and heavy metal removal may have been due to a
variety of complex factors.

110

A.C. ROSSIN ET AL.

1000
75O
T ~n

# 5oo
o,
u_

25O

CADMIUM

CHROMIUM
10

100
o~

o
~

50

COPPER

60
LEAD

.-......i.-"

~20
z
0

NICKEL
10

200
100
0

__1
9

12

15

18

21

I_

24

12

Time of the day, h

Fig. 1.

Variations in the flow of raw sewage to the Hogsmill Valley Water Pollution Control Works and
mean concentrations of heavy metals during typical 'normal flow' conditions.

111

REMOVAL OF HEAVY METALS IN PRIMARY S E D I M E N T A T I O N

1000

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~-'-'--4~,.~....q~-,-,--.i-4~o

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250

CADMIUM

CHROMIUM
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/'k,.,~,---4~..,__.

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COPPER

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LEAD

o
u

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ZINC
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100
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~"t"~'~*-~~"~qL,,.
I

12

15

18

21

24

3
6
9
12
Time of the doy~ h

Fig. 2. Variations in the flow of raw sewage to the Hogsmill Valley Water Pollution Control Works and
mean concentrations of heavy metals during 'storm flow' conditions.

112

A . C . ROSSIN ET AL.

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z
<

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o

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z

z
o

V V

A
o

r~

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REMOVAL OF HEAVY METALS IN PRIMARY SEDIMENTATION

113

TABLE IV

Percentage removals of heavy metals and suspended solids in primary sedimentation calculated from samples
of raw and settled sewage taken every 3 h for 27 h
~o Removal

Flow

Pilot plant
1 DWF

Works

Cd

Cr

Cu

Pb

Ni

Zn

SS

< 1 DWF
< 1DWF
1DWF
1DWF

29
31
45
35

25
15
32
33
26

36
56
50
54
49

16
48
10
63
34

15
120
28
27
12

36
55
32
26
37

37
48
48
50
46

< 1 DWF
1 DWF
1 DWF
> 1 DWF

17
17
8
52
23

23
17
22
34
24

24
7
57
57
36

47
56
50
65
54

20
30
18
39
27

22
28
12
44
27

64
66
47
59
59

< 1
1
1
~> 1

3
5
26
30
16

3
12
24

18
19
33
40
27

24
4
34
35
24

7
5
14
3
7

23
7
26
30
19

44
22
30
51
39

Mean
3 DWF

Mean
Variable flow

DWF
DWF
DWF
DWF

Mean

3.2.

THE

INFLUENCE

OF

11
12

FLOW

CONDITIONS

ON

HEAVY

METAL

REMOVAL

EFFICIENCIES

Heavy metal removal efficiencies were determined during conditions designed to

simulate normal dry weather flow (1 DWF), elevated flow (3 DWF) and variable flow.
Experiments were replicated four times for each flow condition. Metal removal
efficiencies were calculated according to the equation

~o Removal = ( I c - Ec) x 100

(1)

where
I c = heavy metal concentration in raw sewage (gg 1-1).
E~ = heavy metal concentration in settled sewage (lag 1-1).
Percentage heavy metal removals were calculated from Equation (1) for samples of raw
and settled sewage taken every 3 h for 27 h, and from composite samples of raw and
settled sewage corresponding to a period of two days. Mass balances were calculated
from the equation:
~o Mass Balance =

lOOIJ~
ScSv + EcEv

where
Iv = influent volume (1);

(2)

114

A. C. ROSSIN ET AL.

,.o

(D

V V

REMOVAL OF HEAVY METALS IN PRIMARY SEDIMENTATION

115

S c = heavy metal concentration in primary sludge (gg 1-1);

S~ = volume of primary sludge (1);
E~ = effluent volullle (1).
Heavy metal suspended solids and COD removal efficiencies calculated using
Equation (1) for samples taken every 3 h and for composite samples are shown in
Tables IV and V, respectively. Removal efficiencies for variable flow conditions are not
shown in Table V, becuase of difficulties in matching discrete sample volumes to the
variations in flow.
A general trend in the relative efficiencies of heavy metal removal was obtained by
calculating the mean removals for all twelve experiments. The removal efficiencies
calculated from the three hourly samples shown in Table IV were Cu and Pb, 37~o, Zn
28~o, Cd 24~, Cr 21~o, and Ni 19~o. Copper and Pb also had the highest recorded
removals in individual experiments of 57~o and 65 ~o respectively, while the lowest Ni
removal was only 3 ~oAlthough there were considerable variations in heavy metal removal efficiency during
each of the three flow conditions studied, the mean values shown in Table IV exhibited
some positive trends. The removals of Cd, Cr, Cu, and Zn were highest during normal
dry weather flow conditions, lower when the flow was increased threefold and poorest
during variable flow conditions. Nickel removals did not follow the same trend, although
the poorest removals occurred during variable flow. The variations in hydraulic loading
did not influence the removal of suspended solids, although there was some correlation
between removal and influent suspended solids concentrations. The removal of Pb,
which did not behave in the same way as the other elements, also appeared to be related
to the suspended solids removal, indicating that Pb may have been in a predominantly
insoluble form.
Heavy metals removals based on composite samples, shown in Table V, are not
concordant with those presented in Table IV. Although the removal efflciencies
calculated from the two types of sample were broadly similar under normal flow
conditions, at elevated flow the removal efficiencies in Table V were higher, and did not
indicate any influence of flow on removal. The suspended solids removals determined
from composite samples at elevated flows were substantially higher than at normal flows,
and the removal of Pb may have been influenced by this factor, with improved Pb removal
at increasing suspended soils removals.
The mass balances of heavy metals through primary sedimentation are also shown in
Table V. Mass balances for Pb were the poorest observed, while those for Cr and Ni
were generally the closest to 100~o. The mass balances for Pb indicate that the
concentrations determined in the raw sewage were generally lower than the actual
concentrations entering the pilot plant, suggesting that much of the Pb in the raw sewage
entered the pilot plant in peaks of short duration, while the influent concentrations of
Cr and Ni were probably less variable. The data in Figures 1 and 2 also indicate that
fluctuations in the influent Pb concentration were more marked than in the case of Cr
and Ni. Relatively poor mass balances were occasionally observed for Cd, Cu, and Zn,

116

A C ROSSIN ET AL,

suggesting that these metals may sometimes be present in raw sewage in the form of
transient spikes.
Due to the possible occurrence of transient fluctuations in heavy metal concentrations
in raw sewage some errors would be involved in the determination of removal efficiencies
if peak concentrations were not detected.
The results shown in Table IV indicate that with the exception of Ni and Pb, an
increase in the flow rate of raw sewage, or the occurrence of variable flow would result
in lower heavy metal removal efficiencies.
3.3.

THE

INFLUENCE

OF SLUDGE

SOLIDS ON METAL REMOVAL

In order to further investigate the significance of particulate forms of heavy metals in

primary sedimentation the association of heavy metals with sludge solids was
determined. Since it was not possible to take representative samples of primary sludge
during the three day experiments due to zonal sedimentation and adhesion of solids to
the side of the tank, analyses were undertaken on the entire contents of the tank after
the termination of each experiment. Thus, it was pos sible to recover all of the sludge solids
from the tank. Although the primary sludge was diluted as a result of this method of
sampling the concentrations of metals contributed by the settled sewage in the tank were
very small compared to the concentrations in the sludge.
The concentrations of heavy metals and total, volatile, and non-volatile suspended
solids are shown in Table VI. Correlations of metal concentrations with the
concentrations of the solids fractions are also shown in Table VI. Volatile solids were
the most predominant solids fraction in the primary sludge, comprising between 79~o
T A B L E VI

Correlations of h e a v y metals concentrations in primary sludge with volatile and non-volatile solids
Flow
Pilot plant
1 DWF

3 DWF

Concentration (rag 1-1)

Works
1
1
< 1
< 1

SS

DWF
DWF
DWF
DWF

3175
2609
3 113
2932

r SS
r VSS
r NVSS

1 DWF
< 1 DWF
> 1 DWF
1 DWF

9714
8926
10355
11 355

r SS
r VSS
r NVSS

r = correlation coefficient

VSS

NVSS

2729
2271
2689
2422

446
338
424
510

Cd

Cr

Cu

Ni

Pb

Zn

0.011
0.008
0.020

0.136
0.098
0.130
0.311

2.11
1.18
2.13
1.96

0.182
0.065
0.089
0.093

0.962
0.943
0.938
1.24

2.39
1.53
2.09
2.37

0.96
-

0.60
-

0.03
0.35
0.75

0.11
0.15
0.86

0.96
0.35
0.76

0.73
0.73
0.37

0.08
0.80
0.78

0.83
0.67
0.92

7914
7895
8180
9944

1800
1067
2175
1411

0.009
0.041
0.015
0.027

0.37
0.41
0.98
0.40

5.46
3.94
6.24
2.00

0.08
0.20
0.12
0.12

2.89
1.36
4.28
2.67

5.26
5.01
8.09
2.74

0.88
-

0.30
-

0.28
0.13
0.87

0.06
0.26
0.66

0.73
0.80
0.73

0.49
0.16
0.71

0.38
0.38
0.59

0.32
0.68
0.71

REMOVAL OF HEAVY METALS IN PRIMARY S E D I M E N T A T I O N

117

and 88 ~o of the total. However, despite a relatively constant composition of sludge solids,
Cd, Cr, and Pb concentrations in the sludge did not correlate well with the total solids
concentrations. In contrast, Cu, Ni, and Zn were fairly well correlated with total solids
in the experiments under normal flow conditions, but poor correlations were observed
for all metals during increased flow.
Under normal flow conditions close correlations between Cd, Cr, Cu, Pb, and Zn and
the non-volatile solids fraction were observed, possibly indicating that the particulate
forms of these metals were predominantly inorganic in nature. In contrast, the Ni
concentrations in primary sludge correlated more closely with the volatile solids
concentration, suggesting the presence of organic forms of the metal. Under conditions
corresponding to three times the normal dry weather flow Cd, Cr, Cu, Pb, and Zn
concentrations again correlated most closely with the non-volatile solids fraction; in
addition Ni also appeared to be associated with the inorganic fraction, unlike its behavior
in the normal dry weather flow experiments. Since the flows to the works during the four
experiments at each of the two experimental flow rates were similar, the marked change
in the association of Ni with the solids fractions may have been a result of the change
in flow rate and may have been a result of the loss of buoyant particles when the flow
rate exceeded the nominal 'design' value.
4. Discussion

Although the removal of heavy metals in sewage treatment processes has long been
recognized, this appears to be only a beneficial side-effect to the main objective of sewage
treatment, and the factors controlling the fairly wide variations in removal efficiency are
not fully understood.
The efficiency of sewage treatment processes in removing heavy metals depends on
two main factors: namely their existence as settleable particulate forms in the sewage
and the conversion of soluble and non-settleable forms within the process. Thus, the
purely physical processes involved would be expected to remove very little soluble metal,
and the efficiency of removal would be related to the ratio of soluble to particulate forms
of each metal in the influent. Oliver and Cosgrove (1974) found that the apparent removal
efficiencies of dissolved metals in primary sedimentation were all less than 1~o for Cu,
Pb, Ni, and Zn.
The heavy metal removal efficiencies in the primary sedimentation pilot plant varied
considerably not only in terms of the effects of hydraulic loading on the process, but also
on different sampling occasions at the same hydraulic loading. These variations may have
been due to the manner of heavy metal input to the process. It appeared that metal input
was not a continuous process, since a comparison of the influent heavy metal
concentrations with the flows to the Hogsmill Works, which were determined every 3 h,
indicated that concentrations ofCd, Cu, Pb, and Zn could increase by a factor of 2 to 3,
and then return to their initial concentrations in periods as short as 12 h. During
experiments at a full scale sewage treatment works, when samples were collected hourly,
Oliver and Cosgrove (1974) found that similar variations in influent heavy metal

118

A. C. R O S S I N E T AL.

concentrations sometimes involving up to 10-fold changes, could occur during periods

of 6 h. This suggests that the method used to calculate heavy metal removals would be
subject to some error due to the limitations imposed by the method of sampling. The
extent of these errors in each case is indicated by the mass balance, which show that in
six out of eight occasions, the mass balances for Pb were less than 70 ~o, demonstrating
that the sampling regime failed to obtain representative estimates of the Pb
concentrations, possibly because this metal entered the works in the form of slugs lasting
for a short period of time (Oliver and Cosgrove, 1974). Similar errors in constructing
mass balances were encountered by Lewin and Rowell (1973). Balances for Cd, Cu, and
Pb calculated to be 69~0,124~o and 137~, respectively, were attributed to limitations
in the sampling technique and the need to make observations over a protracted period
of time. Balances calculated from the data of Lester et aL (1979) and Stoveland et aL
(1979) for four 24 h periods at a full-scale treatment works indicated that Ni and Cr
behaved in a similar fashion to Pb in this study, having mass balances of 46 ~o and 67 yo,
respectively. However, little evidence was obtained to suggest that variations in
concentration influenced heavy metal removal.
The variations in heavy metal concentrations in the raw sewage during the primary
sedimentation studies reported here were fairly large, ranging from three-fold variations
in the concentration of Zn, to six-fold variations in the concentrations of Cd. However,
despite these variations, the variations in percentage removals of heavy metals were much
less and, moreover, those variations in removal which did occur did not appear to be
related to the heavy metal concentrations.
The heavy metal removal efficiencies observed in this study are difficult to compare
quantitatively with those found by other workers since they vary considerably according
to the plant operating parameters. Such variations were exemplified in this study by Pb,
whose removals ranged from 4~o to 65~o under different flow conditions. Generally,
however, typical removals ofCd, Cr, Cu, Pb, and Zn during dry weather flow conditions
were in the range 30 to 50 ~o, while Ni removals were slightly lower, which is in agreement
with previous studies on full scale plants (Table I).
The fairly wide variations in heavy metal removal suggest that the operating
parameters for primary sedimentation can significantly influence heavy metal removals.
The removals of Cd, Cr, Cu, and Zn were adversely affected by increasing the flow by
a factor of three and by operating the plant under variable flow conditions. However,
the suspended solids removals were not affected by increasing the flow, although the
poorest removals of suspended solids occurred during variable flow conditions. Tebbutt
and Christoulas (1975) and White and Allos (1976) found that the suspended solids
removal in primary sedimentation was influenced to a greater extent by influent
suspended solids concentration than by overflow rate. Thus, despite the fact that only
heavy metals in particulate forms are removed in primary sedimentation (0liver and
Cosgrove, 1974), the removal of heavy metals, with the exception of Pb, did not appear
to be related to the removal of suspended solids. This suggests that the distribution of
particulate forms of heavy metals was dissimilar to the distribution of the total suspended
solids. In primary effluent (settled sewage) Chen et al. (1974) found that 65 to 75~o of

REMOVAL OF HEAVY METALS IN PRIMARY S E D I M E N T A T I O N

119

all particulates were greater than 8 gm in diameter; this fraction also contained more than
50~o of the Cd, Cr, Cu, and Zn, but more than 50~o of the Ni and Pb was associated
with smaller particulates. Some evidence of a dissimilarity in size distributions was
obtained from correlations of heavy metal concentrations in the primary sludge with the
volatile and non-volatile solids fractions. These indicated that Cd, Cr, Cu, Pb, and Zn
were probably largely associated with inorganic particulates, whereas the majority of
primary sludge solids appeared to be organic. In contrast, the Ni in primary sludge
appeared to be associated mainly with the organic fraction, except when the flow to the
pilot plant was increased by a factor of three. This may indicate that the particulate
organo-Ni associations in primary sludge were only poorly settled at higher flows of raw
sewage. The reduced removals of heavy metals at higher flow rates may suggest that
particulate forms of heavy metals belong to a class of particles whose settleability is
sensitive to flow rate. If this is so, optimization of metal removal may involve operation
of the primary sedimentation process with relatively low, constant flow rates.
Relatively little attention has been paid to the optimization of sewage treatment
processes for heavy metal removals, despite the fact that a potentially large quantity of
heavy metals may be discharged to receiving waters in sewage effluents. An indication
of this quantity may be obtained from calculations based on U.K. data concerning the
total annual quantity of sewage sludge produced (Government of Great Britain, 1977),
mean concentrations of heavy metals in sewage sludges surveyed in 1964 (Berrow and
Webber, 1972) and 1979 (Sterritt and Lester, 1980b), the volume of raw sewage produced
per day (Ministry of Housing and Local Government, 1970) and mean concentrations
of heavy metals in raw sewage obtained from the data of Lester et al. (1979), Stoveland
et al. (1979) and Lewin and Rowell (1973) for the same U.K. sewage works. Although
the concentrations of heavy metals in raw sewage vary considerably, these data are
typical of the concentrations shown in Table I. A daily flow of sewage of 14 x 106 m 3
containing the heavy metal concentrations shown in Table VII would result in a total
metal load (for these six elements) of over 12 000 t yr- i. If an overall removal efficiency
of 75 ~o were achieved (Oliver and Cosgrove, 1974), approximately 3100 t yr-1 of heavy
metals could be discharged in sewage effluents. Calculations based on typical concentrations of heavy metals in sewage sludges, also shown in Table VII, suggest that
approximately 7800 t yr ~of heavy metals are removed in sewage treatment. If this were
to represent 75 ~o of the total heavy metal load, then approximately 2600 t yr ~ (25 ~o)
would be present in final effluents. Apart from Zn which is the most abundant metal,
a significant proportioia of the total discharge is due to Pb, a metal of considerable
importance not only because of its toxicity but also because of its ubiquity in raw sewage,
arising from urban and road run-off and a variety of industrial processes (MacKenzie
and Purves, 1975). Since such large quantities of heavy metals could be mobilized in the
aquatic environment, slight but consistent improvements in removal efficiency could
potentially have significant effects on the total quantity of heavy metals discharged. Thus,
any control methods employed in order to reduce heavy metal concentrations in sewage
effluents would appear desirable.

120

A. C. R O S S I N ET AL.

TABLE VII
Expected annual quantities of heavy metals discharged in sewage effluents in the
U.K. derived from calculations based on typical heavy metal concentrations in
sewage and sludge and total quantities produced
Metal

Typical conc.
in raw sewage
(mg 1-1) a

Total in
sewage
(t yr-l) b

Typical conc.
in sludges
(mg kg-l)

Total in
sludges
(t yr-l) d

Cd
Cr
Cu
Pb
Ni
Zn

0.0065
0.060
0.295
0.395
0.040
1.65

3
307
1507
2018
204
8431

25
843
845
1185
400
3015

31
1045
1048
1469
496
3739

Total in sewage
(t yr -1)

12500

Total in sludge
(t yr -I)

7828

Total in effluent
(t yr- ~)e

3125

2609

a Mean values from Lester et al. (1979), Stoveland et al. (1979) and Lewin and
Rowell (1973).
b Daily flow of sewage 14 x 106 m 3 (Ministry of Housing and Local Government,
1970).
Mean values of concentration means given by Berrow and Webber (1972) and
Sterritt and Lester (1980b).
d Annual quantity of sludge produced 1.24 x 106 t (Government of Great Britain,
1977).
e Assuming 75% overall removal efficiency for these metals (Oliver and Cosgrove,
1974).

Acknowledgments
T h e a u t h o r s a c k n o w l e d g e the c o - o p e r a t i o n e x t e n d e d to t h e m by the M a n a g e r o f the
H o g s m i l l Valley W a t e r P o l l u t i o n C o n t r o l W o r k s , M r E. E v e s , a n d his staff. O n e o f us
( A C R ) is grateful to the P a n - A m e r i c a n H e a l t h O r g a n i s a t i o n a n d the W o r l d H e a l t h
O r g a n i s a t i o n for the a w a r d o f a p o s t g r a d u a t e scholarship, a n d to C o m p a n h i a

de

T e c n o l o g i a de S a n e a m e n t o A m b i e n t a l a n d F a c u l d a d e de S a n d e Publica, U n i v e r s i d a d e
de S~o P a u l o (Brazil) for their financial s u p p o r t .

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REMOVALOF HEAVYMETALSIN PRIMARY SEDIMENTATION

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