Wat. Res. Vol. 35, No. 15, pp.

3738–3742, 2001
# 2001 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(01)00047-1 0043-1354/01/$ - see front matter

RESEARCH NOTE
USE OF SOME NATURAL AND WASTE MATERIALS FOR
WASTE WATER TREATMENT
SHAMIM AHSAN1*, SATOSHI KANECO1, KIYOHISA OHTA1,
TAKAYUKI MIZUNO1 and KEIKO KANI2
1
Department of Chemistry for Materials, Faculty of Engineering, Mie University, Tsu,
Mie 514-8507, Japan and 2 International Center for Environmental Technology Transfer, Japan

(First received 24 July 2000; accepted in revised form 15 January 2001)

Abstract}A fundamental study was conducted to assess removal and filtration capacity of waste
and natural indigenous materials as treatment mediums e.g., shell, limestone, waste paper mixed
with refuse concrete, refuse cement, also processed nitrolite, charcoal-bio and charcoal. Under room
temperature condition removal of phosphoric, nitric and ammonium-ions, filtration of suspended
substance (SS) together with removal of COD in waste water was investigated. Influence of particle
size effect for all treatment mediums except for waste paper was pursued. Significant improvement of
waste water quality with respect to SS, phosphoric ions and decrease in COD is possible by treating
with these filtration mediums. With specific reference to some treatment mediums NO3–N and NH4–N
showed reasonable improvement in quality, although generally removal effect was not very significant.
Efficacy of treatment was dependent on the particle size of treatment mediums in general, however,
nitrolite for NH4–N, charcoal-A for SS and COD, refuse cement mixed with waste paper for PO4
ion removal showed insignificant variability on the particle size effect. Results of this fundamental
study demonstrate effectiveness and feasibility for applied application of these proposed waste
and naturally available treatment ingredients at lower cost. # 2001 Elsevier Science Ltd. All rights
reserved

Key words}waste treatment, removal, filtration, indigenous materials

INTRODUCTION In order to achieve efficient cost effective technol-

Suspended substances, nutrients and organic load as
COD contribute major pollutants in the rivers, lakes
and ponds. Removal of these contaminants in waste
water is one of the fundamental goal in waste
treatment. A range of technologies are available
to treat various types of wastes to adequate levels.
However, conventional waste treatment technologies
as adopted in the industrialized nations are expensive
to build, operate and also maintenance. Therefore,
intensive research efforts are continuing to develop
less costly treatment technologies appropriate
in rural, semi-urban, isolated communities and a
variety of industrial simulations. Moreover during
recent years stringent regulation of nutrients
discharge into waterways is receiving wider
consensus. To comply with stringent regulations
and restore safe environment, it has become im-
perative to find some less costly-adaptable treatment
technology.
*Author to whom all correspondence should be addressed.
Tel.: +81-59-231-9427; fax: +81-59-231-9442/9471/
9427; e-mail: omee99@hotmail.com
ogy, natural materials e.g., sands, red mud (residues
from bauxite refining), soils, gravel, biomass char,
activated carbons and water hyacinth etc., are
generally been applied in waste water treatment
facilities to remove pollutants. A recent review
reported one such successful attributes designated
as ‘Simanto–gawa system’ in Japan (Matsumoto,
1997, 1999), which used plastic filter, nitrolite,
organic matters with high carbon–organic ratio,
charcoal-bio, charcoal, processed limestone as treat-
ment mediums. Nevertheless, promotion of inte-
grated small scale treatment using cheaper
treatment medium is still warranted.
In a previous study (Ohta et al., 1998), it has
been found that the rocks as andesite, granite,
marble, refuse concrete and refuse cement is
very effective as treatment mediums for simple
waste treatment process. In the present study,
the effect and behavior of the various refuse
and naturally available materials (Shells, limestone,
nitrolite, charcoal-bio, charcoal and waste
paper-mixed refuse cement and concrete) was in-
vestigated for more efficient waste water treatment
technologies.

3738
 Waste water treatment by natural and waste materials 3739

MATERIALS AND METHODS one of the detrimental criteria in waste water

treatment. In this study filtration of SS with the
Instrumentations


aforementioned mediums were conducted and treat-
For the determinations of SS, PO3
+
4 , NO3 , NH4 UV-
ment efficiencies are presented in Table 1. The
Double Beam Spectrometer (UVIDEC 610. 650, Japan
Spectroscopic company Limited) was used with a resonance reproducibility (R.S.D.) of this method was better
line of 660, 880, 540 and 630 nm, respectively. Sample mass than 15% for 3 repeated measurements. Filtration of
of the chemicals and samples was determined by using a SS with single medium varied within 42–100%, and
semimicro analytical balance H20 (Mettler) providing a with mixed mediums 55–91%. As in Fig. 1 with
resolution of  0.01 mg. Samples were grounded by an iron
mortar and sieved to different particle sizes with stainless smaller particle diameter mediums filtration of SS
sieves (NIPPON RIKAGAKU KIKAI). Ultrapure water increased in general, while in Fig. 2 filtration was
was prepared using ADVENTEC ultrapure water system lower with smaller and larger particle size mediums
CW-102. of refuse cement and refuse concrete, respectively,
mixed with waste papers. The reason of this
Samples, reagents and standards phenomenon is not clear. Presumably it may be due
Waste samples collected from waste water treatment to the presence of dirt which arose from refuse
plant of Mie university, constitute a mixture of domestic cement. Consequently, best filtration of SS 99–100%
and chemical wastes from the university campus. Reagents was observed with charcoal, independent of particle
and standards were prepared to desired concentration
periodically, as and when required. Chemicals for the size effect, as shown in Fig. 1.


analysis of PO3
+
4 , NO3 , NH4 and COD and standards
3

+
for PO4 , NO3 , NH4 were obtained from Nacalai Tesque
Inc, Kyoto, Japan. All reagents and chemicals used were of Phosphoric ions removal
analytical grade or spectroscopic purity. To remove phosphate from contaminated waste
water both biological and physico–chemical pro-
Medium preparations and analytical procedures cesses have been extensively studied. In European
Treatment mediums were picked up from in and around Union using different biological or physico–chemical
university campus except for shell(oyster) from the sea side. processes allowed to cope with discharge content
Processed nitrolite (a partially processed mineral zeolite),
charcoal (made from coconut) and charcoal-bio (charcoal
of 1–2 mg l
1 (Copper et al., 1994). Nevertheless, in
embedded with microorganisms) were supplied from Toyo
Denko, Japan. Used newspapers were cut to an averages
sizes of 1–2 mm before use. After grinding all mediums were
made to different particle sizes using 25.6, 35.5, 42, and
50 mesh-stainless sieve and then washed with pure distilled
water until visible dirts are removed and dried at room
temperature. An accurately weighed dried 5.0 g of shell,
nitrolite, limestone, charcoal and charcoal-bio were poured
and packed into 50 ml size burette. Alternatively, for mixed
mediums 2.5 g of dried refuse concrete and cement powders
together with 1.0 g (1–2 mm size) of waste paper were
transferred and packed into the burette. Continuous
filtration of 100 ml of waste samples was performed with
different mediums under room temperature at a flow rate of
0.33 ml min
1.

RESULTS AND DISCUSSION

Suspended substances (SS)

Suspended substances play an important (and
often underestimated) role in characterizing the
treatability and hence the degree of contaminant
removal in waste water. Therefore, removal of SS is
Fig. 1. SS removal in the waste water treatment with shell,
nitrolite, limestone, charcoal and charcoal-bio at different
particle sizes: (*), Shell, (4), Nitrolite, (*), Limestone,
(&), Charcoal, (m), Charcoal-bio.

Table 1. Summary of treatment efficiency of different mediumsa

Mediums SS COD PO4 NO3 NH4

Refuse cement and waste paper 62–91% No removal 79–80% 14–23% 0–13%
Refuse concrete and waste paper 55–78% 8–14% 33–54% 11–17% No removal
Shells 42–88% 42–65% 20–32% 17–37% 6–16%
Limestone 76–87% 42–58% 13–27% 12–25% 7–12%
Nitrolite 72–91% 30–61% 36–66% 7–22% 65–75%
Charcoal-bio 54–95% 61–71% 18–32% 29–38% 31–62%
Charcoal 99–100% 85–88% 11–17% 15–19% 11–32%
a
n ¼ 3.
3740 Shamim Ahsan et al.
Fig. 2. SS removal in the waste water treatment with waste
paper-mixed refuse cement and refuse cement at different
particle sizes: (*), Refuse cement mixed with waste paper,
(*), Refuse concrete mixed with waste paper.
Fig. 3. PO4 ion removal in the waste water treatment with
shell, nitrolite, limestone, charcoal and charcoal-bio at
different particle sizes: (*), Shell, (4), Nitrolite, (*),
Limestone, (&), Charcoal, (m), Charcoal-bio.
some regions, more stringent measures (0.8–
0.5 mg P l
1) are applied to control eutrophication
(Galarneau and Gehr, 1997; Matsché, 1997). As
shown in Fig. 3 that with single medium best removal
was obtained with nitrolite i.e., in the range of
36–66%. Contrarily, Fig. 4 illustrates that, most
significant adsorption of PO4 ion was observed with
mixed medium of refuse cement and waste paper,
regardless of any particle size effect. Alternatively,
Figs 3 and 4 show that with other single and mixed
mediums generally removal was better with smaller
particle size grains.
Nitric and ammonium ions removal
In various treatment methods for nitrate removal,
ion exchange have been found to be very efficient
(Dahab and Lee, 1988). Chemical and biological
Fig. 4. PO4 ion removal in the waste water treatment with
waste paper-mixed refuse cement and conerete at different
particle sizes: (*), Refuse cement mixed with waste paper,
(*), Refuse concrete mixed with waste paper.
Fig. 5. NH4 ion removal in the waste water treatment with
shell, nitrolite, limestone, charcoal and charcoal-bio at
different particle sizes: (*), Shell, (4), Nitrolite, (*),
Limestone, (&), Charcoal, (m), Charcoal-bio.
treatment of NH4–N removal is widely used. In
the case of high concentration of NH+ 4 –N
(>3000 mg l
1) in the waste, air stripping process is
the most common method. However, these treatment
process is relatively expensive. Therefore, waste and
natural indigenous materials were applied to nitric
and ammonium ions removal. Results are presented
in Table 1. Removal of NO3 ion with both single and
mixed medium were generally low, supposedly, due
to lesser physical adsorption affinity of NO3 ion with
partially charged ions. However, shell (37%) and
charcoal-bio (38%) demonstrated slightly better
removal than other mediums.
As presented in Table 1, maximum NH4 ion
removal (75%) was obtained with nitrolite. Reason-
ably good and moderate removal were achieved with
charcoal-bio and charcoal, respectively, and other
treatment mediums demonstrated poor removal.
Earlier study (Ohta et al., 1998) reported 58% NH4
 Waste water treatment by natural and waste materials 3741

ion removal was obtained with only refuse concrete,

contrarily, in this investigation with refuse concrete
mixed in waste paper no removal was recorded.
Illustration in Fig. 5 shows that with smaller particle
diameter size generally removal was better than
larger size. However, maximum removal of NH4
ion with processed nitrolite (75%) and charcoal-bio
(62%) was obtained with 0.3 and 0.4 mm particle size
powders, respectively.

Decrease in COD
Various treatment technologies are been utilized
for organic load removal in waste water expressed as
COD or BOD. Nevertheless, yet there is need to
ascertain alternative effective low cost treatment
methods. Therefore, in this study potentials of Fig. 6. Decrease in COD in the waste water treatment with
waste and naturally available indigenous materials shell, nitrolite, limestone, charcoal and charcoal-bio at
different particle sizes: (*), Shell, (4), Nitrolite, (*),
for COD removal was investigated. COD curve Limestone, (&), Charcoal, (m), Charcoal-bio.
of Charcoal in Fig. 6 show that it has little effect
of particle size, while with charcoal-bio there is
3742 Shamim Ahsan et al.
depression of curve with larger size particle. Table 1
shows limestone served to remove 42–58% represent-
ing an oval shaped curve in Fig. 6, while with nitrolite
and shell best removal was recorded with 0.4 mm
diameter particle size powder. Most notable removal
was observed with charcoal in the range of 85–88%,
which is due to high organic matter adsorption
capability of charcoal. In the earlier study (Ohta
et al., 1998) with refuse cement and refuse concrete
as independent treatment mediums COD removal
of 24–30% and 36–53%, respectively. On the
contrary, in this study refuse cement and refuse
concrete mixed with waste paper have shown no
removal and 8–14% removal, respectively, as noted
in Table 1. This phenomenon presumably may have
been contributed by the presence of organic matters
in the waste papers or its less biomass retention
capacity.
Possible treatment mechanism
Rocks and refuse materials generally occur as
silicate, aluminate, and calcium substrates in different
forms. Therefore, using these naturally available
materials the possible basic fundamental mechanisms
for treatment are: filtration/settling, adsorption(phy-
sical) and ion exchange. Suspended substances were
mostly removed by mechanical straining, filtration


and settling, while the PO3
+
4 , NO3 and NH4 were
basically removed by ion exchange or by physical
adsorption (Grimshaw and Harland, 1975). NH+ 4 J. Int. Water Environ. Manag. 8, 84–92.
ions were removed by cation exchange, while other
anions removals likely were attributed by physical
adsorption with partially charged ions. Furthermore,
the weak chelating bond between metal elements and
PO3
4 could occur in the treatment process. Exact
mechanism of holding organic matter by charcoal
materials are not clearly known. However, presum-
ably efficient removal of COD by charcoal and
charcoal-bio have been attributed due to effective
adsorption of organic matters in the large surface
area of charcoal. Removal of organic matter by other
treatment mediums is the possible result of higher
affinity of carbon for silicate or aluminate substrates.
The following hypothetical figures presented are
based on the theoretical elucidation of ion exchange,
dipole interaction and filtration which represents the
possible ion exchange and some physical adsorption
phenomenons presumably have taken place in the
treatment of waste water (Grimshaw and Harland,
1975; Ohta et al., 1998):
CONCLUSIONS
Results of this fundamental study opened a new
dimension on the utilization of waste and naturally
occurring indigenous materials for the treatment of
waste water. This also adds manifest on the use of
cheap treatment mediums for a small scale waste
treatment facilitates. Though in this investigation
processed nitrolite, charcoal and charcoal-bio
showed slightly better removal efficiency for some
specific parameters than waste and indigenous
materials, nevertheless, the most viable point in
utilizing these refuse and indigenous treatment
ingredients are: refuse concretes are abundant and
easily available as waste materials. Moreover, utiliza-
tion of these materials will definitely reduce environ-
mental burdens as well as cost of treatment, so is the
utilization of other naturally available indigenous
rocks. Therefore, results obtained in the laboratory
study proposes for field application of mixed
mediums of refuse materials and rocks in a small
scale treatment system, thus, allow an avenues to
reduce treatment cost.
Acknowledgements}This research work was supported by
the Ministry of Education, Science and Culture of Japan
and the Foundation of International Center for Environ-
mental Technology Transfer, Japan.
REFERENCES
Copper P., Day M. and Thomas V. (1994) Process option
for phosphorus and nitrogen removal from waste water.
Dahab M. F. and Lee Y. W. (1988) Nitrate removal from
water supplies using biological denitrification. J. Water
Pollut. Control. Fed. 60, 1670–1678.
Galarneau E. and Gehr R. (1997) Phosphorus removal form
waste water: experimental and theoretical support for
alternative mechanisms. Water Res. 31, 328–338.
Grimshaw R. W. and Harland C. E. (1975) Ion-exchange:
Introduction to Theory and Practice. The Chemical
Society, London, pp. 1–137.
Matsché N. (1997) Phosphate removal from waste water-the
situation in Austria. In La De´phosphatation des Eaux
Use´es. CEDEBOC, Liége, pp. 145–154.
Matsumoto S. (1997) The conception and execution of
improved river water quality using newly developed
purification method: The Simanto-gawa system. UNEP-
IETC Newsletter, August, 3–6.
Matsumoto S. (1999) Fundamentals and Practices of Soil
Bioremediation. Soil Sci. Plant Nutr. 45(1), 237–251.
Ohta K., Ahsan S., Kaneco S., Suzuki T., Mizuno T. and
Kani K. (1998) Treatment of waste water with rocks
(andesite, granite, marble), refuse concrete and refuse
cement. Proceedings of Fourth Asian Symposium on
Academic Activity for Waste Management and Re-
sources. pp. 162–168.