Desalination

ELSEVIER

145 (2002) 333-337

Humic substances removal from drinking water

by membrane filtration
Zoltan Domanya, Ildiko Galambosb, Gyula Vataib*, Erika Bekassy-Molnarb
A.D. Fermin -Yeast-Factory, Senta, Yugoslavia
Scent Istvan UniversiQ, Faculty of Food Science, Department of Food Engineering,
1118 Budapest, MLnesi tit 44., Hungary
Tel. +36 (1) 372-6232; e-mail: gvatai@omega.kee.hu
Received

1 February 2002; accepted 25 March 2002

Abstract
In this study the removal of humic substances from model-solution and well-water using four different ultrafiltration
membranes has been investigated. The permeates were analysed by UV254nmabsorbance, TOC and DOC measurements.
Based on our experiments it can be established that the examined membranes are suitable for the humic acid removal.
The removal efficiency of all investigated membranes was relatively high (~90%) in case of model-solutions.
The
rejection of the membranes in case of natural well-water was lower (=60-70%) due to different composition of the
humics.
Keywords: Humic substances;

Drinking water; Ultrafiltration;

1. Introduction
The drinking water treatment has an increasing
attention because of the strict regulations of the
drinking water quality and the contamination of
the drinking water sources. The problem of humic
substances in water has been focused on the basis
of the new research results in the water quality
measurements. It is proved, that some carcinogenic
*Corresponding author.
Presented at the International
7-12, 2002.

Congress on Membranes

Membrane

screening

substances are the by-products of the reactions

between the water clarifying antiseptics and the
dissolved organic substances, and this secondary
products have negative effect on the health of
people in a long-term period [ 11.
The picture created about humic substances
is still mysterious and full of inconsistencies,
because this name defines a group of very heterogeneous structured organic macromolecules
[2].
The humic substances are coloured from yellowish
and Membrane

Processes

JLIIJ

001 l-9164/02/$-

See front matter 0 2002 Elsevier Science B.V. All rights reserved

PII:SOOll-9164(02)00432-O

(ICOM),

Toulouse, France,

334

Z. Domany et al. /Desalination

to dark brown, faintly acidic macromolecular conglomerations. Their structure can not be classified
without destructive processes, that is the reason
why it is very difficult to determine the exact
physical and chemical characteristics.
Some
humic substance fractions are soluble in water,
but there are fractions, which are present as
colloidal
solutions.
They can be classified
according to their solubility and molecular weight:
a.) fulvic acids: with average molecular weight
12000 Da, the average length of the macromolecules is 60 nm, the average diameter is
2 nm. These substances are generally soluble
in water.
b) humic acids: their average molecular weight
is 2000-5000 Da, in their chemical structure
dominate the phenol-groups, the long carboncyclic fatty acids, etc. These macromolecules
are more hydrophobic in comparison with the
fulvic acids.
humics: they build that fraction of humic substances, which do not dissolve neither in bases
nor in acids. They can be fractionated with
methyl-isobuthyl-keton.
It is determined, that
the humics consist of bitumen, coupled with
fatty acids and humic acids. The composition
of the humic substances are defined always
the place of the huminification (the organic
composition of the soil) [3-4].

c>

On the basis of literature data [3] and the average

molecular weight of the substances the ultrafiltration membranes with or without additives

145 (2002) 333-337

(powdered activated carbon - PAC, flocculent)

are suitable for humic substance removal.
2. Materials and methods
In our experimental investigations the feed
solutions were as follows:
l
deionized water,
l
humic acid model-solution: commercial humic
acid product of the Sigma-Aldrich GmbH.,
Germany, was dissolved in deionized water,
for membrane screening purposes
l
well-water from Senta, Yugoslavia .
DDS 20 Minilab laboratory apparatus in crossflow mode was used for membrane screening.
Four different ultrafiltrations membranes were
tested with nominal molecular weight cut-off
(NMWCO) of 5 kDa, 6 kDa, 15 kDa and 100 kDa,
respectively. The characteristics of investigated
membranes are shown in Table 1.

3. Results and discussion

First we have tested the 4 different membranes
by measuring the flux of the deonized water,
model-solution and well-water. Experiments were
carried out at constant temperature: t = 25*1C,
the recycle flow-rate (Q,) was varied between
260400 L/m*h .
The diagram in Fig. 1 shows, that the 4 membranes (with the smallest MWCO value) had the
lowest fluxes with all investigated feed solutions.

Table 1
The characteristics of investigated membranes
Membrane
Typeandcode

Producer

Material

NMWCO
kDa

Pure water flux*

L/m2h

BFM-70 lOO-Ml
SP 015 A-M2
SP 006 A-M3
BFM-3705-M4

Berghof
Mavibran
Mavibran
Berghof

Polyether-sulfon (PES)
Polyether-sulfon (PES)
Polyether-sulfon (PES)
Poly-aril-ether-ketone(PAES)

100
15
6
5

222.2
213.6
191.5
76.1

*at 25C and 4 bar

Z. Domany et al. /Desalination

335

145 (2002) 333-337

250

200

50

deiomzed water
0
0

4
AP

(bar)

Fig. I. Comparison of the membrane fluxes with different

feed solutions (Ap = 4 bar, QR= 260 L/h).

Fig. 2. Influence of the transmembrane pressure on permeate

flux with model-solution at constant temperature (t = 25C)
and recirculation flowrate (Q, = 260 L/h).

The next diagram in Fig. 2 shows the influence

of the transmembrane pressure on permeate flux
of the model-solution. (The recirculation flow-rate
was constant: 260 L/h.)
The concentration of organic substances in the
feed, permeate and retentate were determined by
measuring the absorbance on UV254nm.Also the
dissolved organic carbon (DOC, [mg/L]) and the
total organic carbon (TOC, [mg/L]) were analysed.
The comparison of the humic acid concentration
in the permeate using different measurement
techniques is shown in Fig. 3.

From the diagram it is obvious that the permeate

concentrations are almost one order of magnitude
lower than the feed concentrations in case of all
membranes measured with different measurement
techniques (UV absorbance, TOC, DOC), with
means that the humics and organics rejection of
the membranes is high.
The humic acid rejection of the membranes
on the basis of TOC, DOC and absorbance measurements were calculated. The comparison of rejections
calculated on the basis of different concentration
measurements is shown in Fig. 4.

/q-------

...-.-.

_._._.._..__,__

oz

ml

Fig. 3. Humic acid concentrations in the permeate measured

with UV absorbance, DOC and TOC.

Fig. 4. Humic acid rejection of different membranes.

336

Z. Domany et al. /Desalination

From the diagram it can be concluded that the

DOC rejection of the membranes was approximately
70% which influenced the lower TOC rejection.
The rejection measured by UV absorbance was
satisfactorily high (~90%) with all membranes.
The following diagram in Fig. 5 represents the
variation of the TOC, DOC and the humic substances concentration in the permeate with the
membrane pore size NMWCO. The concentrations are already constant with membranes around
20 kDa which means that in this region there are
no influence of membrane pore size (NMWCO)
on permeate concentration (UV abs., DOC, TOC).
In Fig. 6 the humic acid concentrations estimated
on the basis of UV254nmabsorbance measurements
in different feed-waters: model-solution and wellwater from Senta (district of Vojvodina, Yugoslavia), and the UF permeates of above feed
waters are compered. From this comparison it is
obvious, that the humic acid concentrations (UV2._,
abs. measurement) in well-water and well-water
permeate are higher than in the model-solutions.
The humic substances rejections calculated
from this results are ~90% in model sulutions and
between 62-69% in case of well-water. These
results correspond to Schafer, Fane and Waites
measurements
[5]. This phenomenon could be
explained with different composition or molecular
weight distribution of different sources, which has
been established by Lin and Huang, as well [3].

145 (2002) 333-337

fDOC

10

NMWCO (kOa)

Fig. 5. TOC, DOC and Abs concentration depending on

the NMWCO (Q, = 400 L/h, Ap = 4 bar).

Fig. 6. Concentration from absorbance (Q, = 260 L/h).

by using membranes with lower pore size; i.e. UF

membranes with lower NMWCO or nanofiltration
membranes (NF).

4. Conclusions

Acknowledgements

Based on our experiments it can be established

that the examined membranes are suitable for the
removal of humic substances. The removal efficiency (rejection) of all investigated membranes is
high enough (85-90%) in case of model-solutions.
The rejection of the membranes in case of natural
well-water was lower (62-69%), as well as the
permeate concentrations were still high (=4 mg/L).
The removal efficiency should be improved by
adding some additives (flocculant, adsorbant) or

This study was financial supported by the OTKA

Foundation (T26140).
References
[l]
[2]

Ci (%lcis, Water clarification - and operation, Egri

Nyomda Kft., 1998 (in Hungarian).
C.-F. Lin, Y.-J. Huang and 0. J. Hao, Ultrafiltration
processes for removing humic substances: effect of
molecular weight fractions and PAC treatment, Wat.
Res., 33 (1999) 1252-1264.

Z. Domany et al. /Desalination

[3] K. Scott, Handbook of Industrial Membranes. Elsevier
Advanced Technology, Oxford, UK, 1995.
[4] M. Alborzfar, G. Jonsson and C. Grgn, Removal of
natural organic matter from two types of humic ground

145 (2002) 333-337

[5]

337

waters by nanofiltration, Wat. Res., 32 (1998) 29832994.

AI. Schafer, A.Ci Fane andT.D. Waite, Fouling effects
on rejection in the membrane filtration of natural
waters, Desalination, 13 1 (2000) 215-224.