ELSEVIER

Desalination 171 (2004) 133-138

DESALINATION
www.elsevier.com/locate/desal
Softening of Hamma drinking water by nanofiltration and by
lime in the presence of heavy metals
S. G h i z e l l a o u i a*, S . T a h a b, G . D o r a n g e b, A . C h i b a n i a, J. Gabon b
Ddpartement de chimie, Universitd de Mentouri de Constantine, Route de Ain El Bey, 25000 Constantine, Algdrie
Tel~fax: +213 (31) 61 43 44 ; emaih gsamira@yahoo.com
bLaboratoire de ehimie des eaax et de I'environnement, Ecole Nationale Supdrieure de Chimie de Rennes,
Avenue du G~ndral Leclerc, 35700 Rennes, France
Received 30 July 2002; accepted 7 May 2004
Abstract
The paper presents results of a study investigating softening by nanofiltration of the Hamma underground water
resource. The Hamma wells supply the City of Constantine with hard drinking water containing calcium bicarbonate.
The main parameters investigated were pressure, cross-flow velocity and water temperature. Nanofiltration was found
to be a very efficient process for partial reduction of the temporary hardness, within the pressure limits considered, the
calcium and bicarbonates retentions reaching 34% and 30%, respectively. Experiments were also conducted to modify
the furring capacity of the water by doping the Hamma water with metal cations. Addition of Zn 2 and Cu 2+ induced
some inhibition, but no effect was observed in the cases of Fe 2+ and Mn 2+.
Keywords: Underground water; Furring; Calcium carbonate; Softening; Nanofiltration; Metal ion impurities
I . I n t r o d u c t i o n
Constantine (the capital of East Algeria) is
supplied wi t h dri nki ng wat er f r om underground
water resources ( Hamma and Boumerzoug), and
wi t h surface wat er from the Hammam Grouz
dam. Chemi cal anal ysi s of the Hamma water
revealed that this wat er source had a scaling
potential correspondi ng to a hardness of 60
French degrees (600 ppm as CaCO3). The scale
*Corresponding author.
deposits consist essent i al l y of cal ci um carbonate.
Undesirable effects i nduced by the scale deposits
include cl oggi ng o f wat er taps and deterioration
of installed equi pment (e.g., furring of pipes and
of water heaters).
To overcome these problems, experiments on
partial softening were undert aken usi ng a com-
mercial nanofi l t rat i on (NF) membrane (Nano-
max 50). The parameters investigated i ncl uded
the effects of pressure, cross-fl ow rate and
temperature on the performance of the membrane.
0011-9164/04/$- See front matter 2004 Elsevier B.V. All rights reserved
doi: 10.1016/i.desal.2004.05.001
134 s. Ghizellaoui et al. / Desalination 171 (2004) 133-138
It may be noted that drinking water can be
contaminated by undesirable or even toxic ele-
ments, which may cause health problems. The
presence of metallic impurities such as Fe 2+, Zn 2+,
Cu 2+ and Mn 2+ is a function of the carbonate
properties of the water as well as of the nature of
the piping material.
Dromgoole and Walter [1], Meyer [2] and
Pemot et al. [3,4] studied the influence of foreign
ions on the precipitation of cal ci um carbonate and
on possible modification of the water furring
capacity by metal cation impurities. The present
work was also concerned with t he behavior and
fate of metal cations such as Cu 2+, Fe 2+, Zn 2+ and
Mn 2+ during chemical softening of Hamma water.
2. Physi cochemi cal characteri sti cs of Hamma
water
The analysis given in Table 1 shows that
Hamma waters have a l ow organic matter content
Table 1
Hamma water analysis
Parameter Value
Temperature, C 31-33
pH 6.95-7.94
EC, mS/cm 0.9-1.30
TOC, mg/L 3.84-7.5
CO2 mg/L 16.21-37.05
HCOf, mg/L 320-432
Cl-, mg/L 128-150
SO~-, mg/L 120-212
PO~-, mg/L 0.006-0.02
NO;, mg/L 3.90-7
NO2-, mg/L
NH4 +, m~/L
TH, mg/L CaCO3 475-600
Ca 2+, mg/ L 124-131
Mg2+,mg/L 30.48-43.2
Na +, mg/L 84-115
K +, mg/L 2.22-13
(TOC: 3.84-7.5 mg/L), a rather high salt content
(EC 0. 9-1. 30 mS/ cm) and an appreciable hard-
ness (TH 475-600 mg/ L CaCO3).
X-ray analysis showed that the scale deposits
consisted of mixtures of calcite and aragonite
crystals.
3. Experi ment al
3.1. Membr ane syst em
The pilot syst em used was a commercial 12L
Millipore Proscale module. It was equipped with
a Nanomax 50 composi t e spiral pol yami de mem-
brane. The membrane MWCO was 350 Dalton
and the filter surface area was 0.37 m 2. All the
experiments were carded out at a constant feed
composition by recycling bot h the retentate and
the permeate to the feed tank.
3.2. Procedure
A 4-L vol ume of Hamma raw water was used
in every NF test. Samples of the retentate and the
permeate were taken for analysis after 30 and
60 mi n of filtration.
Following each experiment the membrane was
washed with a hydrochloric acid solution at a pH
of 2 and then rinsed with distilled water until a
conductivity of about 1 /zS/cm of the flushing
water was reached.
3.3. Anal yt i cal det ermi nat i ons
Determination of the anions (CI-, SO 2-) was
carried out by chromatographic analysis (Waters
501) at a flow rate of 1.3 mL/ mi n using a conduc-
timetric detector (Waters 431) and an anion
col umn (Shodex 1-524A). One liter ofel uant con-
tained 0.207 g ofpara-hydroxybenzoi c acid, 5 ml
of methanol and sufficient ethanolamine to adjust
the solution pH to 8.
The bicarbonates were analyzed with a
Dohrmann-Xertex DC80 apparatus. The concen-
S. Ghizellaoui et al. / Desalination 171 (2004) 133-138 135
t r at i on o f t he cat i ons ( Ca 2+, Mg 2+, Na and K )
was de t e r mi ne d b y a t omi c a bs or pt i on us i ng a
Var i an 1275 appar at us wi t h an a i r - a c e t yl e ne
fl ame.
4. Nanof i l t r at i on res ul t s
4.1. Effect o f pressure on retention
Runs wer e car r i ed out at ope r a t i ng pr es s ur es
o f 0. 5, 1 and 2 bar. Th e s e pr e s s ur e s are sui t abl e
f or a c hi e vi ng par t i al s of t eni ng, l eavi ng s uf f i ci ent
mi ner al s i n t he dr i nki ng wat er . Wa t e r t emper at ur e
was ma i nt a i ne d at 20 C t h r o u g h o u t t he run.
Table: 2 s umma r i z e s mi n i mu m a nd ma x i mu m
val ues o f all c he mi c a l s peci es a na l yz e d i n t he
feed, r et ent at e and p e r me a t e r e s pe c t i ve l y af t er
60 mi n o f fi l t rat i on. Fi gs. 1 a nd 2 s h o w t he ef f ect
o f pr es s ur e on r et ent i on o f t he cat i ons Ca 2+, Mg 2+,
Na , and K + a nd o f t he a ni ons HCO3, C1- and
SOl - . The r et ent i on o f bot h cat i ons and ani ons is
seen t o i ncr ease wi t h t he a ppl i e d pr es s ur e. As
ant i ci pat ed, t he r et ent i on o f di va l e nt cat i ons ( Ca 2+
and Mg 2+) is hi ghe r t han t hat o f mo n o v a l e n t
cat i ons (]b/a + and K+).
The r et ent i on o f Ca 2+ i ons wa s f o u n d t o be
l ower t han t hat o f Mg z+. Thi s ma y be e xpl a i ne d
by t he s mal l er i oni c r adi us o f Mg z+ t he val ue o f
Table 2
Feed and permeate water compositions
Feed Permeate Retention
water (%)
Conductivity, 1010-1032 725-813 18-26
#S/cm at 20C
CI-, mg/1 129-130 121-126 0.75-2
SO~-, mg/l[ 131-132 7.9-9.2 93-94
HCO3, mgfl 408-466 298-365 10-30
Ca 2+, rag/1 120-125 78-89 24- - 34
Mg 2+, rag/1 36-37 21.5-27 23--40
Na +, rag/1 74-77 59-66 11-17
K +, mg/l 4.40-4.60 3.25-3.58 12-24
pH 7.30-7.58 7.72-8.19 - -
5.0
4.0 1
Ca 2+ + Na 2+.
-- Mg2' * K + ~ t _ ~
I . - - - /
.-,2
3.0
O
2 . 0
1.0
0 i
0.4 018 1.2
P (bar)
Fig. 1. Percent retention of cations.
1.6 2.0
100
80
60
O
40
A
20
0 *
' ' ' ' ' l
0.4 0.8
,it_ A
CI"
--~,,- HCO]
+ SO~"
0, .
1'.2 1'.6
P (bar)
Fig. 2. Percent retention of anions.
O
wh i c h r anges f r o m 0. 74 A t o 1.04 A . The
hi gher s ol vat i on e ne r gy o f Mg 2+ i ons act s t o
a u g me n t t hei r r et ent i on.
I n t he cas e o f ani ons , r e t e nt i on o f t he sul f at e
i on was ve r y hi gh, b u t t ot al e l i mi na t i on ( 100%)
was not obt a i ne d be c a us e o f t he r el at i vel y hi gh
sul f at e c onc e nt r a t i on i n t he wat er . Bi car bonat e
i ons wer e bet t er r e t a i ne d t han chl or i de i ons.
4.2. Effect o f pressure on permeat e f l ux
Fi g. 3 s hows t he ef f ect o f pr es s ur e on pe r me -
ate fl ux. Th e us ua l l i near r e l a t i ons hi p i s obs e r ve d
[ 5 ] .
136 S. Ghizellaoui et al. /Desalination 171 (2004) 133-138
4.3. Effect o f temperature on retention
Data on the influence of temperature on
temporary hardness was obtained by carrying out
experiments at a temperature of 25C and a
pressure of 1 bar. Stable retentions were observed
for anions, but a slight increase was noticed in the
retention of the cations (Ca 2+, Na + and K+).
4. 4. Influence o f the circulation cross-flow rate
on the retention
Data on the effect of the circulation cross-flow
rate on permeate flux and ion retention was
obtained by carrying out experiments at two flow
rates (180 and 250 L/h) at a fixed transmembrane
pressure of 1 bar. The effect of cross-flow velo-
city on permeate flux was insignificant, but the
retention of the divalent ions C a 2+, Mg 2+, SO42-
and also of HCO 3 slightly increased with
increasing cross-flow velocity. The augmented
retention is due to the reduction in the concen-
tration polarization level induced by the increase
in mass transfer coefficient with increasing cross-
flow velocity.
5. Li me s of t e ni ng i n t he pres ence of heavy
met al cat i ons
5.1. Apparatus
Fig. 4 shows a sketch of the I L glass reaction
vessel used to study softening effects caused by
the presence of trace concentrations of Cu, Fe,
Zn, Mn. The syringe (S) is provided with a filter
element and enables withdrawal of a known
volume of water.
Contact with air is prevented by lowering the
piston R1 to the water level in the reactor. The pH
of the water is measured by the electrode R2. The
reaction vessels were maintained under agitation
in a thermoregulated bath held at 25C.
5.2. Procedure
A Hamma water sample held in the reaction
vessel was doped with a solution of the tested
cation. The Cu z+ ion was provided by a solution
prepared from CuSO4"5H20, the Fe E+ ion by a
solution prepared from FeSO4.7H20, the Zn 2+ ion
by a solution prepared from ZnSO4.7H20 and the
Mn 2+ by a solution prepared from MnC12"4H20.
1.8
15
~-" 12
g9
6
3
00j
P
/
/
/ /
/ /
/ / / / ' /
, /
0.5 1.3 1.5 2.0 2.5
P (bar)
Fig. 3. Influence of pressure on permeate flux.
L
Fig. 4. Used reactors.
m
Z
w
i
I J
S. Ghizellaoui et aL / Desalination 171 (2004) 133-138
Table 3
Percent reduction in temporary hardness by lime addition in the presence of Cu 2 ions
137
Hamma Water doped with Water doped with Water doped with
raw water 0.5 mg/L Cu 1 mg/L Cu 3 mg/L Cu
HCO~, % 15.87 18 32.53 13.82
Ca 2+, % 28.19 27.08 27.64 21.70
Mg 2+, % 9.53 1.08 3.41 1.78
Cu 2, % - - 89.38 94.58 81.10
pH 7.66 7.65 7.64 7.80
LSI 0.511 0.495 0.464 0.673
Table 4
Percent reduction in temporary hardness by lime addition in the presence of Fe 2 ions
Hamma Water doped with Water doped with Water doped with
raw water 0.2 mg/L Fe 1 mg/L Fe 2 mg/L Fe
HCO~, % 25.19 24.39 44.02 41.43
Ca 2, % 22.35 26.6 22.26 22.82
Mg 2+, % 1 2.19 1.00 2.00
Fe 2+, % - - 99.7 99.8 99.8
pH 7.72 7.77 7.75 7.73
LSI 0.530 0.543 0.408 0.369
Table 5
Percent reduction in temporary hardness by lime addition in the presence of Zn 2+ ions
Hamma Water doped with Water doped with Water doped with
raw water 0.5 mg/L Zn 1 mg/L Zn 5 mg/L Zn
HCO3, % 24.16 28.84 31.95 18.15
Ca z, % 25.48 25.24 26.17 12.97
Mg 2, % 0.94 0.37 0 0
Zn 2+, % 40.98 94.16 95.35 81.75
pH 7.75 7.73 7.74 7.75
LSI 0.554 0.511 0.493 0.617
Experiments were carried out at various ion
concentrations in the range of 0.5 to 5 mg/L. The
tested water sample was held in the thermostatic
bath for 21days. At the start of an experiment, the
water was analyzed to determine the concen-
tration of the added cation and of the other
chemical species (Ca 2+, Mg 2+, CI-, SO42-, NO3,
Na +, K+). The analysis were repeated after 24 h in
order to check for any possible change in the
water composition due to the presence of the
doped cation. At this stage, 0.040 g/L lime was
added to the water in order to achieve partial
softening resulting from precipitation of some of
the temporary hardness.
138 S. Ghizellaoui et al. / Desalination 171 (2004) 133-138
Table 6
Percent reduction in temporary hardness by lime addition in the presence of Mn 2+ ions
Hamma Water doped with Water doped with Water doped with
raw water 0.5 mg/L Mn 1 mg/L Mn 2 mg/L Mn
HCO], % 24.11 28.39 35.29 41.82
Ca 2, % 49.92 53.33 52.19 49.92
Mg 2+, % 1.14 2.64 1.47 0.37
M n 2+, % - - 99.8 99.18 91.01
pH 7.74 7.76 7.74 7.71
LSI 0.506 0.472 0.419 0.369
5.3. Results
Tables 3- 6 show the hardness reduct i on
occurring in the presence of various heavy metal
cations, calculated f r om t he change in wat er
composition 24 h aft er lime dosage. It may be
noted that no further change in wat er composi t i on
was noted after anot her 24-h period.
The presence of Cu 2+ (Table 3) was found to
inhibit the precipitation of CaCO a onl y at the
highest concentration. Whereas 28.2% of the Ca 2
was precipitated by t he lime in the Cu-free raw
water, onl y 21.7% of t he Ca 2+ precipitated in the
presence of 3mg/L Cu 2. The inhibition of Mg 2
precipitation was significant at all Cu 2+ dosages.
Onl y 1-3% of t he Mg was r emoved in the pres-
ence of Cu 2, compared to 9. 5% in t he absence of
Cu 2+ '
Iron (Table 4) totally,+ precipitated before lime
introduction whi l e Ca z~ precipitated after lime
introduction. Except for the run carried out with
0.2 mg/ L Fe 2+, whi ch showed a 27% Ca 2+
reduction, no effect of Fe 2+ concentration coul d
be noted. At all Fe 2+ dosages, t he reduction in
Ca 2+ hardness (22-23%) and in Mg 2+ hardness
(1-2%) was similar. The pH also had similar
values in all cases (7.7-7.8).
As in the case of Cu 2+, dosage of Zn 2+
(Table 5) inhibited Ca 2+ precipitation onl y in the
run conduct ed with a hi gh Zn 2+ dosage. The
precipitation level of Ca 2+ was 25- 26% with no
Zn 2 and with Zn 2+ of up to 1 mg/ L but was
reduced by almost a half, to 13% in the presence
of 5 mg/L Zn.
In t he Mn 2+ experi ment s (Table 6), preci-
pitation of the Ca 2+ was ver y high, around 50%
with and without the presence o f Mn 2+. The added
Mn 2+ was almost compl et el y precipitated.
6. Conc l us i ons
This st udy confi rms that NF is an interesting
possibility for eliminating t emporary hardness
from drinking water. Data are present ed showing
the effect of various paramet ers on the flux and
ion retention of Hamma water.
The paper also presents data characterizing the
inhibitory effect i nduced by the presence of Cu 2+,
Fe 2+, Zn 2+ and Mn 2 ions in t emporary hardness
reduct i on by lime addition. Relatively high
inhibition effects wer e exert ed by Zn 2+ and Cu 2+
while Fe 2 and Mn 2 did not exhibit an inhibitory
influence.
Ref erences
[ 1 ] E. Dromgoole and L. Walter, Chem. Geol., 81 (1990)
311-336.
[2] H.J. Meyer, Crystal Growth, 66 (1984) 639--646.
[3] B. Pemot, M. Euvrard and P.H. Leroy, 12th Days
Information Water (Poitiers), 1996, 35-1 to 11.
[4] B. Pemot, M. Euvrard, F. Remy and P. Simon,
J. Water SRT-Aqua, 48(1) (1999) 16-23.
[5] J. Schaep, B. Van tier Bmggen and S. Uytterhoeven,
Desalination, 119 (1998) 295-302.