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ISSN: 2322-4657
DOI 10.12983/1-2014-03-01
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ii
PREFACE
As the global population grows and many developing countries modernize, the importance of
water supply and wastewater treatment becomes a much greater factor in the welfare of nations.
Clearly, in todays world the competition for water resources coupled with the unfortunate
commingling of wastewater discharges with freshwater supplies creates additional pressure on
treatment systems. Recently, researchers focus on wastewater treatment by difference methods
with minimal cost and maximum efficiency.
This volume of the Wastewater Engineering: Advanced Wastewater Treatment Systems is a
selection of topics related to physical-chemical and biological processes with an emphasis on
their industrial applications. It gives an overview of various aspects in wastewater treatments
methods including topics such as biological, bioremediation, electrochemical, membrane and
physical-chemical applications. Experts in the area of environmental sciences from diverse
institutions worldwide have contributed to this book, which should prove to be useful to
students, teachers, and researchers in the disciplines of wastewater engineering, chemical
engineering, environmental engineering, and biotechnology. We gratefully acknowledge the
cooperation and support of all the contributing authors.
Amin Mojiri
cehamidi@usm.my
amin.mojiri@gmail.com
iii
TABLE OF CONTENTS
1:
INTRODUCTION
OF
PRELIMINARY
AND
SECONDARY
TREATMENTS ...................................................................................................................... 1
1.1 Introduction of preliminary and Secondary Treatments; Z. Amirossadat .............. 2
CHAPTER 2: WASTEWATER BY TREATMENT BY PHYSICAL-CHEMICAL
TECHNOLOGIES ............................................................................................................... 05
2.1 Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent
Prepared From Waste Material; N. Azmi, J.K. Bashir, S. Sethupathi, C.A. Ng ......... 06
2.2 Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from
Psyllium Husk; I. Dahlana and S.M.O. Tayeh ............................................................. 15
2.3 COD and BOD Removal from Textile Wastewater Using Naturally Prepared
Adsorbents and Their Activation forms Using Sulphuric Acid; Patel and Vashi ........ 31
2.4 Fenton oxidation for the Treatment of Liquid Waste with High COD and
Anionic/Non-ionic Surfactants; M. Collivignarelli, S. Sorlini, A. Abb, M. Sordi ..... 41
2.5 Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
W.L. Peng, G. Xinxin, M.J.K. Bashir .......................................................................... 48
CHAPTER 3: WASTEWATER TREATMENT BY BIOLOGICAL METHODS ........ 62
3.1 Wastewater Treatment by Biological Methods; A. Dadrasnia, N. Shahsavari and
C.U. Emenike ............................................................................................................... 63
3.2 Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic
Inclining-Baffled (MAIB) Bioreactor; H.M. Zwaina and I. Dahlan ............................ 71
3.3 Augmentation of Biological Nitrogen Removal via Optimization of Support Media
Size and Aeration Strategy in Moving Bed Sequencing Batch Reactor; J.Wei Lim, M.J.K.
Bashir, S.L. Ng, S. Sethupathi, L.P. Wong. ................................................................. 87
iv
5:
WASTEWATER
TREATMENT
BY
BIOREMEDIATION
7:
WASTEWATER
TREATMENT
BY
PHYTOREMEDIATION
vi
1. INTRODUCTION
Recently, the amounts of wastewater are sharply
increasing and the kinds of pollutants are also varied
as the world wide industry is being developed
incessantly. With respect to both the quantity and
composition, the textile processing wastewater is
recorded as the most polluted source among all
industrial sectors (Chang et al., 2009). At wastewater
treatment plants, wastewater is treated before it is
allowed to be returned to the environment, lakes, or
streams.
Discharge criteria required the installation of
facilities that performed what is now called primary
treatment of wastewater. This involved using screens
and sedimentation tanks to remove most of the
materials in the wastewater that float or settle. As
subsequent discharge criteria were tightened,
secondary treatment became necessary. Secondary
treatment is accomplished by bringing together waste,
bacteria and oxygen in trickling filters or the activated
sludge process. Bacteria are used to consume the
organic parts of the wastewater. Facilities and their
designers are now considering and installing tertiary
treatment facilities to comply with the latest
regulatory and permit parameters. These advanced
treatment processes go beyond conventional
secondary treatment and include the removal of
recalcitrant organic compounds, as well as excess
nutrients such as nitrogen and phosphorus (Coppen,
2004). Conventional wastewater treatment consists of
a combination of physical, chemical, and biological
processes and operations to remove solids, organic
matter and, sometimes, nutrients from wastewater.
General terms used to describe different degrees of
treatment, in order of increasing treatment level, are
preliminary, primary, secondary, and tertiary and/or
advanced wastewater treatment. In some countries,
disinfection to remove pathogens sometimes follows
the last treatment step.
2. Primary treatment
The objective of primary treatment is the removal of
settleable organic and inorganic solids by
sedimentation, and the removal of materials that will
float (scum) by skimming. Approximately 25 to 50%
of the incoming biochemical oxygen demand (BOD5),
50 to 70% of the total suspended solids (SS), and 65%
of the oil and grease are removed during primary
treatment. Some
organic
nitrogen,
organic
phosphorus, and heavy metals associated with solids
are also removed during primary sedimentation but
colloidal and dissolved constituents are not affected.
The effluent from primary sedimentation units is
referred to as primary effluent. In many industrialized
countries, primary treatment is the minimum level of
reapplication treatment required for wastewater
irrigation. It may be considered sufficient treatment if
the wastewater is used to irrigate crops that are not
consumed by humans or to irrigate orchards,
vineyards, and some processed food crops. However,
to prevent potential nuisance conditions in storage or
flow-equalizing reservoirs, some form of secondary
treatment is normally required in these countries, even
in the case of non-food crop irrigation. It may be
possible to use at least a portion of primary effluent
for irrigation if off-line storage is provided. Primary
sedimentation tanks or clarifiers may be round or
rectangular basins, typically 3 to 5 m deep, with
hydraulic retention time between 2 and 3 hours.
Settled solids (primary sludge) are normally removed
from the bottom of tanks by sludge rakes that scrape
the sludge to a central well from which it is pumped to
sludge processing units. Scum is swept across the tank
surface by water jets or mechanical means from which
it is also pumped to sludge processing units.
(http://www.fao.org/docrep/t0551e/t0551e05.htm).
Primary treatment involves:
Amirossadat
Advanced Wastewater Treatment
2. Secondary treatment
Secondary wastewater treatment is the second stage of
wastewater treatment that takes place after the
primary treatment process. The process consists of
removing or reducing contaminants or growths that
are left in the wastewater from the primary treatment
process. Usually biological treatment is used to treat
wastewater in this step because it is the most effective
type of treatment on bacteria, or contaminant, growth.
Secondary treatment processes can remove up to 90
percent of the organic matter in wastewater by using
biological treatment processes. The two most common
conventional methods used to achieve secondary
treatment are attached growth processes and
suspended
growth
processes
(http://www.water.siemens.com/en/applications/waste
water_treatment/secondary-treatment).
Secondary treatment typically utilizes biological
treatment processes, in which microorganisms convert
nonsettleable solids to settleable solids. Sedimentation
typically follows, allowing the settleable solids to
settle out. Three options include:
1. Activated Sludge- The most common option
uses microorganisms in the treatment process to break
down organic material with aeration and agitation,
then allows solids to settle out. Bacteria-containing
activated sludge is continually recirculated back to
the aeration basin to increase the rate of organic
decomposition.
2. Trickling Filters- These are beds of coarse
media (often stones or plastic) 3-10 ft. deep.
Wastewater is sprayed into the air (aeration), then
allowed to trickle through the media. Microorganisms
attached to and growing on the media, break down
organic material in the wastewater. Trickling filters
drain at the bottom; the wastewater is collected and
then undergoes sedimentation.
3. Lagoons- These are slow, cheap, and relatively
inefficient, but can be used for various types of
wastewater. They rely on the interaction of sunlight,
algae, microorganisms, and oxygen (sometimes
aerated).
After primary and secondary treatment, municipal
wastewater is usually disinfected using chlorine (or
other disinfecting compounds, or occasionally ozone
REFERENCES
Chang W, Tran H, Park D, Zhang R, Ahn D (2009).
Ammonium nitrogen removal characteristics
of zeolite media in a Biological Aerated Filter
(BAF) for the treatment of textile wastewater.
Journal of Industrial and Engineering
Chemistry, 15: 524-528.
Cppen J (2004) Advanced Wastewater Treatment
Systems. Courses ENG4111 and 4112
Research Project, University of Southern
Queensland, Faculty of Engineering and
Surveyin.
1. INTRODUCTION
As the exponential population and social civilization
growth, together with the developments of industries
and technologies, rapid generation of MSW has
becomes a global environmental problem (Saeed et
al., 2009). There are many options available for MSW
disposal such as sanitary landfill, open dump,
incineration, composting, grinding, hog feeding,
milling, and anaerobic digestion (Aziz et al., 2010).
Sanitary landfill is the most common MSW disposal
method due to such advantages as the simple disposal
procedure, low cost, and landscape-restoring effect on
holes from mineral workings (Bashir et al., 2010).
However, the production of highly contaminated
leachate is a major drawback of this method (Aziz et
al., 2010).
Landfill leachate is defined as any contaminated
liquid effluent percolating through deposited waste
and emitted within a landfill or dump site through
external sources (Taulis, 2005). In a more precise
definition, it is a soluble organic and mineral
compound formed when water infiltrates into the
refuse layers, which extracts a series of contaminants
and instigates a complex interplay between the
hydrological and biogeochemical reactions that acts as
a mass transfer mechanisms for producing of moisture
content sufficiently high to start the liquid flow (Aziz
et al., 2004). As shown in Figure 1, leachate
generation induced by the gravity force, precipitation,
irrigation, surface runoff, rainfall, snowmelt,
recirculation, liquid waste co-disposal, refuse
decomposition, groundwater intrusion and initial
moisture content present within the landfills
(Achankeng, 2004). As the consequences, leachate
may contain high concentration of organic matter
(biodegradable and non-biodegradable), ammonia
nitrogen, heavy metals, chlorinated organic and
Azmi et al.
Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material
Young
<5
Intermediate
5-10
Stabilized
>10
pH
<6-5
6-5-7-5
>7.5
>10 000
4000-10 000
<4000
BOD5/COD
TOC/COD
NH-N
Heavy metal (mg L-1)
0.5-1
<0.3
<400
Low to
medium
80%
VFA
0.1-0.5
0.3-0.5
NA
Low
<0.1
>0.5
>400
Low
5-30%
VFA+ HA+ FA
HA+FA
Biodegradability
Important
Medium
Low
0.1-0.2
NA
NA
Organic compound
Azmi et al.
Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material
Table 2: Common activating agent for different activation method in preparation of AC (Alslaibi et al., 2013)
Fig. 2: A schematic diagram of the experimental apparatus used in activation process (Deng et al., 2009)
10
Azmi et al.
Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material
11
REFERENCES
Achankeng E (2004). Sustainability in municipal solid
waste management in Bamenda and Yaounde,
Cameroon, PhD thesis of Geographical and
Environmental Studies University of Adelaide,
Australia.
Agamuthu P (2001). Solid Waste: Principles and
Management: with Malaysian Case Studies,
Insitute of Biological Sciences, University of
Malaya.
Alvarez-Vazquez H, Jefferson B, Judd SJ
(2004).Membrane bioreactors vs conventional
biological treatment of landfill leachate: a brief
review. Journal of Chemical Technology and
Biotechnology, 79 (10): 10431049.
Alslaibi TM, Abustan I, Ahmad MA, Foul AA (2012).
Production of Activated Carbon from
agriculture
byproduct
via
conventional
microwave heating : a review. J. Chem.
Technol. Biotechnol., 88(7): 1183-1190
Aziz HA, Adlan MN, Zahari MSM, Alias S (2004).
Removal of ammoniacal nitrogen (N-NH3)
from municipal solid waste leachate by using
activated carbon and limestone. Waste Manage.
Res, 22: 371375.
Aziz SQ, Aziz HA, Yusoff MS, Bashir MJK, Umar M
(2010). Leachate characterization in semiaerobic and anaerobic sanitary landfills: A
comparative study. Journal of Environmental
Management, 9: 2608-2614.
Babel S, Kurniawan TA (2003). A research study on
Cr (VI) removal from contaminated wastewater
using natural zeolite. J. Ion Exch., 14: 289292
Bernache G (2003). The environmental impact of
municipal waste management: the case of
Guadalajara metro area, Resour. Conserv.
Recycl, 39: 223237.
6. CONCLUSION
Landfill leachate treatment by adsorption process
using AC has a potential to be practice in sanitary
12
Azmi et al.
Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material
13
14
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from
Psyllium Husk
Irvan Dahlan1*, Somaia M.O. Tayeh2
1
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal,
Pulau Pinang, Malaysia.
2
School of Civil Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau
Pinang, Malaysia.
*Corresponding Author: chirvan@eng.usm.my
Abstract. Color removal from textile effluents has been given much attention in the last few years by the adsorption process
using low cost adsorbents. In this study, four different adsorbents were prepared from psyllium husk (i.e. PH/CFO-Al,
PH/CFO-Ac, QPH and NPH) for removal of direct blue dye (DB71) from synthetic wastewater. From the preliminary study,
PH/CFO-Ac adsorbent gave the highest color removal efficiency. PH/CFO-Ac adsorbent was prepared from psyllium husk and
CoFe2O4 by a facile refluxing route in acidic solution. PH/CFO-Ac adsorbent was selected to be used for further batch studies
to examine the effect of various experimental parameters, i.e. contact time, adsorbent amount, shaking rate, initial dye
concentration, pH and temperature. The best conditions for dye removal using PH/CFO-Ac adsorbent were obtained at pH 9.0,
temperature of 30C, shaking rate of 150 rpm and contact time of 2 hours. The adsorption kinetics was found to follow pseudosecond-order kinetic model. The experimental data fitted well with the Langmuir model with a monolayer adsorption capacity
of 188.7mg/g. It was also found that prepared and spent PH/CFO-Ac adsorbents have a homogenous particle size distribution.
In addition, the surface morphology of the spent PH/CFO-Ac adsorbents had more compact structures with small granular
particles attached on the surface.
Keywords: Colour removal, Synthetic Dye Wastewater, Psyllium Husk
1. INTRODUCTION
Due to the increase in the world population and
development of industrial applications, environmental
pollution problem became very important, especially
wastewater pollution problem. Communities produce
both liquid and solid wastes. The liquid waste, i.e.
wastewater, is essentially the water supply of the
community after it has been used in a variety of
applications. Wastewater handling, disposal &
treatment are serious worldwide problem. Many
industrial and agricultural activities use water in an
excessive way. However, it is now well known that
the fresh water resources are limited and fragile, so
they must be protected. Discharge of sanitary
wastewater, industrial effluent and agricultural fields
runoff can be the main source of freshwater pollution.
This causes many diseases for human, and it is known
that 70-80% of illness in developing countries is
related to water contamination, particularly for
children and women (WHO/UNICEF, 2000).
Textile industries consume large volumes of water
and chemicals for wet processing of textiles. The
chemical reagents used are very diverse in chemical
composition, ranging from inorganic compound to
polymers and organic compound (Correia et al.,
1994). The color is an evident indicator of water
pollution by the dyes. Industrial dye effluents are
visible even at concentrations lower than 1 mg/l.
Moreover, some dyes and their degradation products
are carcinogenic (Ahn et al., 1999). Also, some dyes
15
16
17
rate constant
dye adsorbed
t (min). The
expressed in
18
19
20
Fig. 4: (a) Adorbent selection based on dye concentration, and (b) adsorbent selection based on adsorbent amount.
Fig. 5: Effect of contact time on the adsorption of DB71 from synthetic wastewater
21
Fig. 6: Effect of adsorbent amount on the adsorption of DB71 from synthetic wastewater
Fig. 7: Effect of shaking rate on the adsorption of DB71 from synthetic wastewater
22
Fig. 8: Effect of initial dye concentration on the adsorption of DB71 from synthetic wastewater
3.2.5. Effect of pH
The pH of the solution plays an important role in the
whole adsorption process. To determine the optimum
pH for the adsorption of DB71 using PH/CFO-Ac, the
effect of solution pH was investigated in the range of
310.5 and the results are shown in Figure 9. The
removal efficiency of DB71 at pH less than 7 is
relatively lower than at pH more than 7. It increased
23
Fig. 10: Effect of temperature on the adsorption of DB71 from synthetic wastewater
Fig. 11: The variation of adsorption capacity of DB71 onto PH/CFO-Ac with adsorption time, 1L solution, 1g adsorbent,
200mg/L dye concentrations, pH 9, at 30 C
24
Y= -0.013X + 0.545
R2 = 0.85
Fig.12: Pseudo-first-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C0 = 200mg/L, pH 9)
Y = 0.00509 X + 0.00083
R2 = 0.997
Fig. 13: Pseudo-second-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C0 = 200mg/L, pH 9)
Table 2: Kinetic parameters for adsorption of DB71 onto PH/CFO-Ac
q e,exp
(mg g -1)
196.48
Pseudo-rst-order
Pseudo-second-order
K1 (min-1)
q e,cal
(mg g -1)
R2
K2
(g mg-1 min-1)
q e,cal
(mg g -1)
R2
0.032
3.0
0.85
0.031
196
0.997
25
Table 4: Langmuir and Freundlich isotherm model constants and correlation coefficients for adsorption of DB71 onto
PH/CFO-Ac
Langmuir
isotherm
Freundlich isotherm
b (L/mg)
Q (mg/g)
7.57
188.7
0.00066
0.997
KF
Q (mg/g)
203
177.7
40
R
0.991
26
27
Fig. 16: Particle size distribution of prepared PH/CFO-Ac adsorbent, spent adsorbent with high removal efficiency, and spent
adsorbent with low removal efficiency.
4. CONCLUSIONS
28
Fig. 17: SEM micrographs of (a) raw psyllium husk, (b) prepared PH/CFO-Ac adsorbent and (c) spent PH/CFO-Ac adsorbent
ACKNOWLEDGMENT
The authors wish to acknowledge the financial
support from the Universiti Sains Malaysia (Short
Term Grant A/C. 60310014 and Incentive Grant).
REFERENCES
Ahmad A, Hameed B, Aziz N (2007). Adsorption of
direct dye on palm ash: Kinetic and equilibrium
modeling. Journal of Hazardous Materials, 141:
70-76.
Ahn DH, Chang WS, Yoon TI (1999). Dyestuff
wastewater treatment using chemical oxidation,
physical adsorption and fixed bed biofilm
process. Process Biochemistry, 34: 429-439.
Ai L, Huang H, Chen Z, Wei X, Jiang J (2010).
Activated carbon/CoFe2O4 composites: Facile
29
30
COD and BOD Removal from Textile Wastewater Using Naturally Prepared
Adsorbents and Their Activation Forms Using Sulphuric Acid
Himanshu Patel*, R.T. Vashi
Department of Chemistry, Navyug Science College, Rander Road, Surat 395009, Gujarat, INDIA
*Corresponding Author: hjpatel123@yahoo.co.in
Abstract. Comparative adsorption studies of naturally prepared adsorbents (Neem leaf powder, Gauva leaf powder and
Tamarind seed powder) and their activation forms using sulphuric acid were conducted for removal COD and BOD from
textile wastewater. Process parameters like adsorbent dose, conduct duration, temperature and pH were examined in this study.
The adsorption data were analyzed using Freundlich, Langmuir, Dubinin-Raduskevich, Flory-Huggins, Redlich-Peterson, Sips,
Toth and Khan model to understand adsorption mechanism. Activated Neem leaf powder was most suitable than investigated
adsorbents. The maximum adsorption capacities were found to be 87.58, 85.65 and 81.25 mg/g for NLPs, GLPs and TSPs
respectively for COD and 84.51, 81.45 and 75.54 mg/g for NLPs, GLPs and TSPs respectively for BOD.
Keywords: Textile wastewater, Naturally prepared adsorbents and their activated form, Process Parameters, Adsorption
equilibrium isotherms
1. INTRODUCTION
Increasing public pressure and administrative concern
to arrest further deterioration of the environment may
result in more stringent standards. The objective of
wastewater treatment has expanded considerably from
simple nuisance control to include public health,
environmental,
aesthetic
and
ecological
considerations. The day is not far off when industries
will have to acquire a nonpolluting or zero polluting
status to meet future environmental regulations. The
problem is more severe for the textile industry
because of its dynamic nature. Constantly changing
process lines result in diverse and complex wastes that
are ever changing in constitution and color (Venkata
Mohan et al., 1999). The textile industry is very
chemical-intensive;
wastewater
from
textileprocessing contains huge residues from different
textile dyeing and finishing operations. Of particular
concern are dyestuffs, which are often major sources
of heavy metals, salt, adsorbable organic halogens and
color in dyehouse effluent, sizing agents, which have
high BOD and COD levels; and anionic/non-ionic
surfactants, most of which are still of poorly
biodegradable nature (Alaton et al., 2006).
There are many methods for the removal of
contaminations from wastewater, such as membrane
process, ion exchange, biological degradation and
adsorption using various kinds of adsorbent.
Adsorption process is proven to be an effective
process for the removal of various pollutants from its
aqueous solutions because adsorption process can
remove pollutant in wide range of concentrations
(Budyanto et al., 2008). The adsorption process has
not been used extensively in wastewater treatment, but
demands for a better quality of treated wastewater
effluent, including toxicity reduction, have led to an
intensive examination and use of the process of
31
Temperature (K)
pH
300
180
5.0
300
Effect of temperature
5.0
180
Effect of pH
5.0
180
3, 5, 7, 9 and 11
32
G0 = - RT/ In KFH
Where R is universal gas constant 8.314 J/K/mol,
T is absolute temperature (K) and KFH is equilibrium
constant from Flory-Huggins isotherm equation
(Israel et al., 2010).
33
Fig. 1: Effect of adsorbent dose for percentage COD and BOD removal using NLPs
34
Fig. 2: Effect of adsorbent dose for percentage COD and BOD removal using GLPs
Fig. 3: Effect of adsorbent dose for percentage COD and BOD removal using TSPs
35
Table 2: Effect of contact duration for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent
a-NLP
NLP
a-GLP
GLP
a-TSP
TSP
% Removal
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
30
30.3
26.1
20.1
15.2
19.6
14.6
11.2
9.2
9.5
5.2
13.4
10.1
60
39.9
31.2
30.2
20.5
32.3
28.6
20.2
15.4
14.5
10.2
20.9
18.8
90
50.4
39.0
41.2
28.5
44.3
34.5
30.2
20.4
19.5
16.5
30.5
24.7
180
60.1
55.7
55.2
45.5
58.5
48.1
45.5
40.1
39.5
30.2
53.1
38.0
210
63.6
57.4
57.2
46.2
63.4
49.7
47.4
42.1
41.5
32.1
56.2
40.1
240
63.6
57.4
57.2
46.2
63.4
49.7
47.4
42.1
41.5
32.1
56.2
40.1
3.5. Effect of pH
The effect of pH (3 to 11) is represented in Table 4
using NLPs, GLPs and TSPs (dose: 5.0 g/L) for
removal of COD, BOD and color from textile
wastewater at constant contact duration of 180 min,
temperature of 300 K and agitator speed of 400 rpm.
The percentage removal was increasing, as pH of
system increases. The highest percentage removal of
COD was found to be 64.8, 55.5, 57.4, 47.5, 50.2 and
56.5 by a-NLP, NLP, a-GLP, GLP, a-TSP and TSP
respectively at pH 11. The highest percentage removal
of BOD was found to be 60.0, 54.2, 48.7, 40.2, 41.2
and 44.7 by a-NLP, NLP, a-GLP, GLP, a-TSP and
TSP respectively at pH 11. Though, the factor pH is
an important parameter in adsorption studies, but due
to presence of various elements in dyeing mill
wastewater such as starches, dextrin, gums, glucose,
waxes, pectin, alcohol, fatty acids, acetic acid, soap,
detergents, sodium hydroxide, carbonates, sulfides,
sulfites, chlorides, dyes, pigments, carboxymethyl
cellulose, gelatin, peroxides, silicones, flourcarbons,
resins; the moderate removal of COD, BOD and color
was found with change of factor, pH (ONeill et al.,
1999).
36
Table 3: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent
% Removal
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
a-NLP
NLP
a-GLP
GLP
a-TSP
TSP
298
39.1
34.7
20.1
20.2
30.3
29.0
20.0
18.2
15.2
7.8
24.3
18.7
303
48.6
41.4
32.2
32.2
39.1
35.0
28.5
25.5
20.2
12.5
37.9
25.9
308
56.0
48.0
45.5
35.6
54.6
45.4
44.2
34.4
26.5
25.5
44.9
38.6
Temperature (K)
313
318
62.2
70.1
52.6
60.1
50.5
61.2
42.5
51.2
62.2
68.3
52.1
61.6
52.1
57.2
41.1
54.2
37.3
44.5
35.8
43.6
52.2
56.5
45.9
51.6
328
75.6
63.0
65.6
55.5
72.3
67.6
61.2
60.0
47.5
47.7
62.5
58.1
328
76.0
63.2
65.6
55.5
73.0
68.0
61.2
60.0
47.5
47.7
63.0
58.1
Table 4: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent
a-NLP
NLP
a-GLP
GLP
a-TSP
TSP
% Removal
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
3
14.8
9.7
10.0
5.2
7.5
3.2
5.5
1.2
4.5
3.5
8.0
5.7
5
23.6
17.6
15.5
10.5
14.8
10.2
10.2
5.5
12.5
15.2
24.2
21.7
pH
7
39.0
32.1
27.4
20.5
26.5
20.2
15.5
11.1
24.5
20.5
34.8
31.7
9
56.5
50.1
45.5
41.4
42.1
34.7
30.2
25.5
41.5
31.5
50.4
40.0
11
64.8
60.0
55.5
54.2
57.4
48.7
47.5
40.2
50.2
41.4
56.5
44.7
37
Table 5: Freundlich and Langmuir parameters for COD and BOD removal using naturally prepared adsorbents
Freundlich Parameters
Langmuir Parameters
Adsorbent
Removal
KF (L/mg)
n
Qmax (mg/g)
KL (L/mg)
COD
79.39
0.1377
87.58
0.049
a-NLP
BOD
41.64
0.2262
84.51
0.037
COD
45.12
0.1379
80.45
0.045
NLP
BOD
40.25
0.1919
79.58
0.012
COD
28.69
0.4065
85.65
0.12
a-GLP
BOD
12.13
0.1447
81.45
0.14
COD
20.45
0.3175
82.41
0.21
GLP
BOD
15.18
0.2809
78.57
0.54
COD
17.4
0.2353
75.14
0.14
a-TSP
BOD
7.45
0.1212
70.45
0.024
COD
23.07
0.1570
81.25
0.17
TSP
BOD
11.71
0.1350
75.54
0.016
Table 6: DubininRadushkevich and Flory-Huggins parameters for COD and BOD removal using naturally prepared
adsorbents
Adsorbent
a-NLP
NLP
a-GLP
GLP
a-TSP
TSP
Particular
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
Dubinin-Radushkevich Parameters
qm (mg/g)
(mmol2/J2)
E (kJ/mol)
18.45
4.613
1.2412
13.27
10.332
0.9574
15.21
15.485
0.8747
8.27
22.258
0.8547
15.27
0.3547
0.8258
12.17
0.3948
0.6847
12.41
0.5158
0.5258
7.55
0.7414
0.6868
8.65
0.3470
0.7265
5.87
0.5081
0.8584
10.65
0.6587
0.7457
8.54
0.8714
0.6585
Flory-Huggins Parameters
nFH
kFH (mg/g)
G0 (kJ/mol)
-0.699
0.0552
-6.9707
-0.657
0.0452
-7.2395
-0.547
0.0212
-6.1091
-0.512
0.0392
-6.7909
-0.431
0.0450
-10.2111
-0.379
0.0402
-11.2551
-0.3954
0.0166
-9.1909
-0.354
0.0305
-10.7929
-0.407
0.0185
-9.4405
-0.317
0.0205
-12.6157
-0.375
0.0252
-10.2332
-0.298
0.0301
-13.8271
38
Table 7: Redlish-Peterson and Sips parameters for COD and BOD removal using naturally prepared adsorbents
Adsorbent
Redlish-Peterson Parameters
KRP
aRP (Lmg)
RP
(1/mg)
2.40
0.234
0.874
3.18
7.489
0.907
1.25
45.12
0.915
1.02
0.245
0.995
1.23
61.67
0.940
0.31
0.032
1.007
0.915
75.45
0.954
0.29
0.025
0.54
0.83
149.8
0.991
0.24
0.004
0.96
0.71
158.5
0.542
0.12
0.0011
0.547
Particular
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
a-NLP
NLP
a-GLP
GLP
a-TSP
TSP
Sips Parameters
qm (mg/g)
Ks (L/mg)
19.7
18.5
14.4
10.8
17.9
15.2
10.5
7.4
12.1
7.2
15.5
10.0
1030.2
9217.4
9845.5
5545.5
8462.5
1251.4
4578.5
1020.2
1656.5
768.5
754.5
625.5
0.734
0.847
0.745
0.824
0.885
0.755
0.705
0.821
0.927
0.835
0.812
0.714
Table 8: Toth and Khan parameters for COD and BOD removal using naturally prepared adsorbents
Adsorbent
a-NLP
NLP
a-GLP
GLP
a-TSP
TSP
Particular
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
COD
BOD
qm (mg/g)
14.25
7.87
11.24
4.58
10.47
5.84
8.66
4.58
5.58
3.85
6.58
4.58
Toth Isotherm
bT (1/mg)
0.025
0.058
0.047
0.052
0.047
0.065
0.043
0.045
0.042
0.028
0.045
0.036
nT
0.854
0.754
0.687
0.847
0.856
0.884
0.785
0.847
0.748
0.789
0.840
0.705
qm (mg/g)
17.34
15.82
14.14
10.25
11.44
10.78
7.45
15.45
8.45
7.45
11.14
10.47
Khan Isotherm
bK (L/mg)
0.245
0.547
0.657
0.847
0.574
0.632
0.478
0.558
0.874
0.658
0.782
0.687
aK
0.057
0.047
0.068
0.084
0.064
0.057
0.068
0.062
0.041
0.038
0.057
0.047
4. CONCLUSION
This study provides characterization of textile
wastewater and, simple and effective adsorption
process for COD and BOD removal using naturally
prepared adsorbents (NLP, GLP and TSP) and their
activation forms using sulfuric acid. It is observed
from the present investigation that the textile
wastewater contains various types of pollutants, which
are not easily removed. Batch adsorptive treatment
was carried out using various parameters like
adsorbent dose, conduct duration, temperature and
pH, in whixch activation of Neem Leaf Powder and
Guava Leaf Powder using sulphuric acid was found
more proficient than investigated regular NLPs and
GLPs. Regular Tamarind Seed Powder (TSP) was
found to be more efficient than activated TSP using
sulphuric acid. The adsorption equilibrium isotherms,
viz. Freundlich, Langmuir, Dubinin-Raduskevich,
Flory-Huggins, Redlich-Peterson, Sips, Toth and
Khan isotherm ware analyzed, in which maximum
adsorption capacities of linear equation Langmuir
isotherm was calculated and found to be 87.58, 85.65
and 81.25 mg/g for NLPs, GLPs and TSPs
respectively for COD and 84.51, 81.45 and 75.54
mg/g for NLPs, GLPs and TSPs respectively for
BOD. Also, Langmuir isotherm best-fits the isotherm
REFERENCES
Alaton IA, Insel G, Eremektar G, Babuna FG, Orhon
D (2006). Effect of textile auxiliaries on the
biodegradation of dyehouse effluent in
activated sludge, Chemosphere, 62: 1549-1557.
APHA (1992). Standard Methods for the examination
of water and wastewater, 18th ed. American
Public Health Association, Washington, DC,
USA.
Budyanto S, Soedjono S, Irawaty W, Indraswati N
(2008). Studies of Adsorption Equilibria and
Kinetics of Amoxicillin from Simulated
Wastewater using Activated Carbon and
Natural Bentonite, Journal of Environmental
Protection Science, 2: 72-80.
Fanchiang J, Tseng D, Guo G, Chen H (2009).
Ozonation of complex industrial park
wastewater: effects on the change of wastewater
39
characteristics,
Journal
of
Chemical
Technology and Biotechnology, 84: 1007-1014.
Foo K Y, Hameed B H (2010). Insights into the
modeling of adsorption isotherm systems,
Chemical Engineering Journal, 156: 2-10.
Gulipalli CS, Prasad B, Wasewar KL (2011). Batch
Study, Equilibrium and Kinetics of Adsorption
of Selenium using Rice Husk Ash (RHA),
Journal
of
Engineering
Science
and
Technology, 6(5): 586-605.
Hameed B H, Mahmoud D K, Ahmad AL (2008).
Equilibrium modeling and kinetic studies on the
adsorption of basic dye by a low-cost
adsorbent: Coconut (Cocos nucifera) bunch
waste, Journal of Hazardous Materials, 158: 6572.
Israel A, Ogali R, Akaranta O, Obot IB (2010).
Removal of Cu(II) from aqueous solution using
coconut (Cocos nucifera L.) coir dust, Der
Pharma Chemica, 2(5): 60-75.
Li W, Zhang L, Peng J, Li N, Zhang S, Guo S (2008).
Tobacco stems as a low cost adsorbent for the
removal of Pb(II) from wastewater: Equilibrium
and kinetic studies, Industrial Crops and
Products, 28: 294-302.
Malkoc E, Nuhoglu Y (2007). Potential of tea factory
waste for chromium(VI) removal from aqueous
solutions: Thermodynamic and kinetic studies,
Separation and Purification Technology 54:
291-298.
Martins AF, Wilde ML, da Silveira C (2006).
Photocatalytic Degradation of Brilliant Red
Dye and Textile Wastewater, Journal of
Environmental Science and Health, Part A, 41:
4, 675-685.
Mohanty K, Das D, Biswas MN (2006). Preparation
and characterization of activated carbons from
Sterculia alata nutshell by chemical activation
with zinc chloride to remove phenol from
wastewater, Adsorption, 12: 119-132.
Ozacar M, Sengil IA (2005). Adsorption of metal
complex dyes from aqueous solutions by pine
sawdust, Bioresource Technology, 96(7): 791795.
40
Fenton Oxidation for the Treatment of Liquid Waste with High COD and
Anionic/Non-ionic Surfactants
M.C. Collivignarelli1, S. Sorlini2*, A. Abb1, M. Sordi1
1
Department of Civil Engineering and Architecture, University of Pavia, via Ferrata 1, 27100, Pavia, Italy
Department of Civil Engineering, Architecture, Land, Environment and Mathematics, University of Brescia, via Branze 43,
25123, Brescia, Italy
*Corresponding Author: Email: sabrina.sorlini@ing.unibs.it
Abstract. In the present work, liquid wastes from different kinds of industrial plants, characterized by high COD (up to
100,000 mg/L) and surfactants (up to 16,000 and 3,800 mg/L for non-ionic and anionic respectively) concentrations were
treated by means of Fenton oxidation. During the experimental research 28 tests at laboratory scale were performed. Each test
was characterized by specific dosage of reagents (Fe2+ e H2O2) and contact time. In particular, Fe2+/H2O2 ratio varied from 0.25
to 0.50, H2O2/COD ratio from 0.72 to 1.5 while the contact time increased from 30 to 120 minutes. The main objective of this
work was to define the dosage of reagents and the reaction contact time able to optimize the process performance in terms of
removal yields of COD and surfactants. The results showed that the optimal treatment conditions could be obtained with a
Fe2+/H2O2 ratio equal to 0.25, a H2O2/COD ratio of 1 and a reaction time of 30 minutes. An average removal yield of 70% for
AS (non-ionic surfactants) and COD and 95% for MBAS (anionic surfactants) respectively was obtained.
Keywords: Surfactants, Fenton Oxidation, High COD
1. INTRODUCTION
Surfactants are a group of compounds used daily in
huge amounts mainly in household applications and as
industrial cleaning agents (Gonzalez et al., 2007;
Hosseinnia et al., 2006). As is known, the surfactants
can be classified in different groups depending on the
electrostatic charge of its hydrophilic groups: anionic
(MBAS), non-ionic (TAS), cationic and amphoteric
surfactants (the last compounds behave as acids or
bases, depending on the solution acidity). The first
two groups are the most common and account for over
80% of the total usage in detergents. Cationic
surfactants are used mainly in fabric conditioners to
give a pleasant soft feel to the product while
amphoteric surfactants are used mainly for their skin
mildness properties (AISE, 2012). The new European
Detergent Regulation (Regulation 648/2004, that
entered in force on 2005) requires that the surfactants
used in household detergents must be biodegradable,
while derogation may be accepted for surfactants in
detergents used in special industrial or institutional
sectors. In Western Europe each year over 2.5 million
tonnes of surfactants are produced (45% anionic, 43%
non-ionic, 8% cationic, 4% amphoteric) (CESIO,
2012).
In the past, some types of surfactants (non-ionic)
resulted to be dangerous for the humans and the
environment also after biological treatment. In fact,
although they were easily removable in well operating
treatment plants with removal yields of about 90-95%,
the last oxidation step was much slower due to the
formation of by-products that are toxic and refractory
to biological treatment (Gonzalez et al., 2007). The
main methods for the treatment of sewage and liquid
41
Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants
Fig. 1: Equipment used for Fenton oxidation tests 1 a - pH measurement 1 b - settling of the mixture 1 c
U.M.
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
-
LW I
17800
24.7
102
8000
307
37.4
17.3
0.2
393
6.7
green/limpid
42
LW II
56680
1033
1490
6000
< 0.5
< 0.5
< 0.5
< 0.1
< 0.5
5.8
white/mushy
LW III
50450
845
13100
8.8
5.5
gray/mushy
LW IV
101900
16000
3870
65
8.6
brown/limpid
F1
F2
F3
F4
F5
F6
F7
F8
F 11
F 12
F 13
F 14
F 15
F 16
F 17
F 18
F 19
F 20
F 21
F 22
F 23
F 24
F 25
F 26
F 27
F 28
I
(mix 1)
I
(mix 2)
II
III
IV
Operative conditions
Contact time [minutes]
(H2O2/COD)0
30
0.36
30
0.36
30
0.72
60
1
60
0.72
60
0.72
60
1.17
60
2
60
0.72
60
1
60
0.72
30
0.72
60
1.5
120
0.72
60
0.72
60
1
60
1.5
30
0.72
60
1
120
1
60
0.72
60
1
60
1.5
30
0.72
60
1
120
1
Fe2+/H2O2
1/2
1/5
1/4
1/2
1/2
1/2
1/2
1/4
1/4
1/4
1/2
1/4
1/4
1/4
1/4
1/4
1/4
1/4
1/2
1/4
1/4
1/4
1/4
1/4
1/2
1/4
43
Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants
44
Fig. 5: Effect of the hydrogen peroxide dosage on TAS and MBAS removal
45
Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants
4. CONCLUSION
The results showed that the optimal treatment
conditions for surfactant removal from liquid wastes
can be obtained with a Fe2+/H2O2 ratio equal to 0.25
and a H2O2/COD ratio of 1 and a reaction duration of
46
http://www.cefic.org/Documents/AboutUs/Industry%20sectors/CESIO/CESIOStatistics-2012.pdf
Dias de Melo E, Mounteer A H, Henrique de Souza
Leo L, Cibele Barros Bahia R, Ferreira
Campos IM (2013). Toxicity identification
evaluation of cosmetics industry wastewater.
Journal of Hazardous Materials, 244245: 329
334.
European Commission (2004). Regulation (EC) No
648/2004 of the European Parliament and of the
Council of 31 March 2004 on detergents.
Official Journal of the European Union.
http://eurlex.europa.eu/LexUriServ/LexUriServ.do?uri=
OJ:L:2004:104:0001:0035:en:PDF
Gonzalez S, Petrovic M, Barcelo D (2007). Removal
of a broad range of surfactants from municipal
wastewater Comparison between membrane
bioreactor and conventional activated sludge
treatment. Chemosphere, 67: 335 343.
Hosseinnia A, Hashtroudi M S, Pazouki M,
Banifatemi M (2006). Removal of surfactants
from wastewater by Rice Husk. Iranian Journal
of Chemical Engineering, 3(3).
Kowalska I, Majewska-Nowak K, KabschKorbutowicz
M
(2006).
Ultrafiltration
treatment of detergent solutions. Desalination
200: 274276.
Kurt U, Apaydin O, Gonullu MT, (2007). Reduction
of COD in wastewater from an organized
tannery industrial region by electro-fenton
process. Journal of Hazardous Materials, 143:
3340.
ACKNOWLEDGEMENT
The authors would like to give a special thanks to the
company ASMortara spa for the financial support to
the experimental research; moreover we want to thank
l'Eng. Chiara Clemente for the assistance in carrying
out the tests.
REFERENCES
Ahammad SZ, Zealand A, Dolfing J, Mota C,
Armstrong DV, Graham DW (2013). Lowenergy treatment of colourant wastes using
sponge biofilters for the personal care product
industry. Bioresource Technology, 129: 634
638
AISE (2012). The new detergents regulation: fact
sheet on aerobic biodegradation of surfactants.
http://www.aise.eu/downloads/05_Fact%20shee
t%20biodegradabilityupdated%2027082012.pdf
APHA, AWWA, WEF (2001). Standard methods for
the examination of water and wastewater, 21st
edition. American Public Health Association,
Washington DC, USA.
CESIO - European Committee of Organic Surfactants
and their Intermediates (2012). CESIO
surfactants statistics for Western Europe.
47
1. INTRODUCTION
Recalcitrant aromatic compounds have been
extensively used in many industrial processes like
textile industry for dying leather, silk wool and paper.
Consequently, these industrial wastewater streams
always contain high concentration of aromatic
compounds which is harmful to human due to their
carcinogenicity and genotoxicity by accumulating in
fat tissue (Berberidou et al., 2007; Gogate and Pandit,
2004a; Gregory, 2009; Ju et al., 2008). Therefore it is
necessary and important to remove aromatic
compounds from wastewater before discharge and
keep the concentration of chemicals in the effluent
stream at a certain minimum level (Gogate and Pandit,
2004a; Zhou et al., 2012). Due to the stringent
environmental laws and regulations against hazardous
pollutants, the technologies for wastewater treatment
have been extensively developed in the last decades
(Pera-Titus et al, 2004). However, aromatic
compounds are resistant to conventional biological
wastewater treatment process due to high toxicity and
carcinogenicity of the pollutants. So, it is necessary to
develop novel and efficient methods degrade
biorefractory aromatic compounds into smaller
molecules, which can be complete minimized by
conventional
biological
or
photochemical
technologies.
Researchers have tested various methods with
advanced oxidation processes (AOPs) for the
degradation of biorefractory aromatic compounds,
such as ozone oxidation, hydrogen peroxide oxidation,
Fenton with UV light or catalysts and cavitation
generated by ultrasonic irradiation (Ai et al., 2010;
Berberidou et al.,2007; Guinea et al., 2009; Meric et
al., 2005; Zhang and Zheng, 2009). Cavitation have
been found to be the most attractive and suitable
system in degradation or decolorization of recalcitrant
48
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
2.1. Cavitation
The diffuse energy of sound is enhanced through
cavitation (Suslick, 1990). The process is principally
based on the phenomenon of acoustic cavitation,
which includes the formation, growth, and implosive
collapse of micro-bubbles in a liquid. When a liquid is
sonicated, positive and negative pressures are exerted
on a liquid by compression and expansion cycles
respectively of ultrasound waves (Suslick, 1989). The
dissolved gas molecules are entrapped by microbubbles that grow and expand upon rarefaction of the
acoustic cycle; when a sufficiently large negative
pressure is applied to the liquid, the average distance
between the molecules would exceed the critical
molecular distance necessary to hold the liquid intact,
and the liquid will break down and voids or cavities
will be created; cavitation bubbles will then be formed
(Mason and Lorimer, 1988). These cavities, voids or
bubbles may grow in size until the maximum of the
negative pressure then extreme temperature release
upon adiabatic collapse (Mason and Lorimer, 1988;
Lin et al., 2008; Wang et al., 2007).
49
OH + H H2O
H + O2 HO2
2OH H2O2
2HO2 H2O2 + O2
IN
(1)
(2)
(3)
(4)
(5)
50
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
Degradation
of
Aromatic
of
Chlorinated
Aromatic
51
Aromatic compounds
Sonochemical conditions
Chlorobenzene (ClBz)
2,4dichlorophenoacetic
acid
Polycyclic
aromatic
hydrocarbons (PAH)
Bisphenol A (BPA)
Ultrasonic power: 50 W
Ultrasonic frequency: 640 kHz
Results
At concentration above 1000 M,
pyrolysis was the dominant mechanisms,
at
concentration
1-5M,
radical
mechanisms played a crucial role.
Reference
Dewulf et al., 2001
an
88.3% decolorization
He et al., 2007
Sponza
and
Oztekin, 2010
Aromatic
intermediates:
2-(4hydroxyphenyl)-2-(3,4dihydroxyphenyl)propane,
commonly
known as 3-hydroxybisphenol A were
detected.
Bisphenol A (0.50mM) was completely
degraded after 10, 3 and 2 h of ultrasonic
irradiation at a frequency of 404 kHz, and
intensities of 3.5, 9.0 and 12.9kW/m2
respectively.
52
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
53
OH + OH H2O2
(6)
C6H5-OH + OH C6H5(OH)2 (7)
However, the degradation of phenol by ultrasound
was comparable low due to the hydrophilic nature of
phenol which made it unavailable for free radical
reaction with OH radicals (Maleki et al., 2005).
Zheng et al. (2005) conducted a study to enhance the
sonochemical degradation of phenol by applying the
hydrogen atom scavenger. The additional of CCl4
traps the hydrogen atoms and prevents their
recombination with OH radicals. This increased
availability of OH radical that ultimately accelerated
the sonochemical degradation of phenol.
To understand the degradation mechanisms of 4ClPh during sonolysis, Hao et al. (2003) have
performed an oxidation experiment between 4-ClPh
and H2O2. The experiment result showed that high
temperature pyrolysis was the dominant degradation
for 4-ClPh. On the other hand, Jiang et al. (2006)
reported that the 4-ClPh degradation mechanism was
strongly dependent on solute concentration. Teo et al.
(2001) used ion selective electrode to measure the
produced Cl ions during 4-ClPh degradation. The
results precisely showed the presence of Cl from the
cleavage of CCl bond of the 4ClPh due to ultrasonic
irradiation. The Cl balance in the system suggested
the formation of chlorinated intermediates.
Kotronarou et al. (1991) expressed the degradation
of p-nitrophenol (PNP) as a first order reaction. This
was because PNP did not diffuse into the imploding
cavities at a low vapor pressure, but collected at the
liquid/gas interface where it was pyrolyzed and/or
attacked by the solvent radicals. The decomposition
mechanism of PNP was based on a combination of
both pyrolysis and radical reaction (Colarusso and
Serpone, 1996). In another study, Tauber et al. (2000)
found that the reaction mechanism was pH dependent.
At acidic pH (4.0) oxidative pyrolytic decomposition
was predominant whereas at alkaline pH (10.0) free
radical mechanism mainly occurred.
The ultrasonic degradation of hydrophobic
organics such as PAHs can occur when they penetrate
to the surrounding of the hot heart of the cavitation
bubble being pyrolyzed, burnt and/or ionized in the
plasma core (Flannigan and Suslick, 2005). According
to Sponza and Oztekin (2011), sonication alone had a
6. COMBINATION OF ULTRASONICATION
AND
OTHER
DEGRADATION
TECHNOLOGIES
Although sonochemical reactions were quite efficient
for degradation of organic compounds, however,
complete mineralization was not achieved sometimes.
This might be due to higher polarity of the organic
compound, low availability of OH radical or lack of
dissipated power. Therefore, to overcome these
disadvantages in the sonochemical process, ultrasound
has been widely used as an auxiliary process with
other treatment techniques mostly biochemical,
electrochemical, ozonation, photolysis, photocatalysis
and Fenton processes.
Studies of the combined process involving
ultrasound and ozone had shown faster degradation
rates for a range of chemical contaminants than either
method applied alone (Mason and Petrier, 2004). As
the mass transfer rate of ozone in the solution was the
limiting parameter, thus the combined operation of
sonolysis and ozonation renders synergistic effected in
degradation and accelerateed the mass transfer of
ozone in the solution due to ultrasonic effects. When a
liquid was sonicated in the presence of ozone (O3), the
thermal decomposition of ozone in the cavitation
bubbles enhanced OH and H2O2 yields. Xu et al.
(2005) studied on synergetic effect of ozonation with
ultrasonic treatment for p-nitrophenol degradation. In
O3/ultrasonic system produced more OH and H2O2
than the sonolysis system alone. This combined
sonolysis/ozonolysis
process
showed
116%
enhancement in removal rate for p-nitrophenol.
Gultekin and Ince (2006) investigated the
degradation of aryl-azo-naphthol dyes with
ultrasound, ozone and combination of the two
processes at optimized condition. The US/O3
combination was the best option for the degradation of
these dyes. The synergetic effect incorporated three
main factors, i) increased mass transfer of ozone, ii)
54
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
55
OF
ULTRASONIC
8. CONCLUSION
Ultrasound technologies have been widely used for
the degradation of aromatic compounds at laboratory
scale and the combination of ultrasound with other
relevant treatments can prove to achieve complete
mineralization and be more economically attractive
than the use of individual techniques due to the
generation of higher quantum of free radicals and high
degree of energy efficiency. It has been observed that
the efficacy of sonochemical reactions in cavitation
process is influenced by many important operating
parameters such as resonance frequency of bubbles,
reaction temperature and energy intensity. An
optimised reactor configuration should be able to
maximize the expected output. Thus, the
configurations of the sono-reactor may significantly
affect the efficacy of ultrasonic system for
sonochemical degradation.
REFERENCES
Adewuyi YG (2001). Sonohemistry: environmental
science and engineering applications. Industrial
& Engineering Chemistry Research, 40: 4681
715.
Adewuyi YG (2005). Sonochemistry in environmental
remediation.1.
Combinative
and
hybrid
sonophotochemical oxidation processes for the
treatment of pollutants. Environmental Science
& Technology, 39: 34093420.
Ai ZH, Li JP, Zhang LZ, Lee SC (2010). Rapid
decolorization of azo dyes in aqueous solution
by an ultrasound-assisted electrocatalytic
oxidation process. Ultrasonics Sonochemistry,
17 (2): 370375.
Ai ZH, Lu LR, Li JP, Zhang LZ, Qiu JR, Wu MH
(2007). Fe@Fe2O3 core-shell nanowires as iron
reagent. 1. Efficient degradation of Rhodamine
56
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
57
58
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
59
60
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
61
62
Institute of Biological Sciences, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
2
Science and Research Branch, Islamic Azad University, Sirjan, Iran
*Corresponding Author: are.dadrasnia@gmail.com
Abstract. Wastewater generation is just inevitable but discharging it into the environment in a sustainable way is the subject of
concern. Hence, treatments adopted have the common goal of conforming to water quality standards to ensure environmental
protection. Different sources that range from industrial productions to domestic use of water has continued to generate
wastewater and various treatment methods are employed, which includes biological methods. For effective treatment,
considerations are paid to wastewater characteristics, requirement of treated wastewater quality, treatment alternatives and
associated sampling techniques with analysis. Most biological treatments often take care of the removal of biochemical oxygen
demand, chemical oxygen demand, suspended solids, ammonia and even other inorganic compounds that includes heavy
metals. This chapter evaluated the use of oxidation, anaerobic, aerobic ponds, and activated sludge process as biological
treatment methods for wastewater. Common to the options is the utilization of microorganisms to degrade pollutants of
interest, but varied on certain conditions that border on design and oxygen utilization and limitation. Biological treatments can
be achieved under reduced cost when compared to physical and chemical methods, yet time consumption appear to be its
drawback.
Keywords: Wastewater, Treatment, Biological Methods
1. INTRODUCTION
Wastewater emanates from many sources which
includes industrial production and domestic use of
water. Hence, wastewater characteristics are highly
dependent on the source, and when it is not properly
treated before discharge, it can significantly pollute
watercourses. Regardless of the treatment option
adopted for any form of wastewater, the end
expectation is to relate to discharge/effluent standards
and quality. With high level of varied forms of
production and changing lifestyle, chemical
composition and loading of most wastewater are of
significant interest world over, excess organic
Chemical pollution from heavy metals, dyes,
solvents and pesticides is one of the major threats to
water quality. Chemicals enter the aquatic
environment through different ways, among which are
via wastewater treatment plants (WWTP) that do not
fulfill their obligations (Oller et al., 2011), and direct
discharge of industrial effluents. Similarly, indirect
chemical pollution of water arises from the use of
plant health products, such as biocides and, fertilizers
in agriculture (Oller et al., 2011). Considering the fact
that water soluble substances can be distributed and
transported more easily in the water cycle, treatment
of wastewater by discharge becomes paramount.
Wastewater treatment refers to the process of
removing pollutants from water, especially those
associated with agricultural, industrial and municipal
activities. This process is designed to achieve the
expectation and/or standard level in the quality of the
wastewater. Current methods used for removing
pollutants present in the wastewater can be divided
63
Dadrasnia et al.
Wastewater Treatment by Biological Methods
64
65
Dadrasnia et al.
Wastewater Treatment by Biological Methods
4.
MODELING
PROCEEDING
THE
BIOLOGICAL
66
67
Dadrasnia et al.
Wastewater Treatment by Biological Methods
-ASP 2
An aeration source is the second vital component
which supplies sufficient oxygen to the tanks and
ensures adequate mixing within the system. The
oxygen supply can be in form of mechanical aeration
or introduction of pure compressed oxygen.
Equipment for the supply of oxygen to this system can
vary in design and operation due to the number and
modifications in shape of aeration tanks used.
-ASP 3
Third in the line of ASP equipment are the secondary
clarifiers. Here, separation of activated sludge solids
from water occurs. This is based on the principle of
flocculation (aggregation of large particles or flocs
due to adherence of floc-forming organisms to
-ASP 4
The RAS generated must be removed from the
clarifiers and reintroduced into the aeration tank(s)
before depletion of the dissolved oxygen present. By
so doing, there is replenishment of the biological
68
-ASP 5
Here, the activated sludge which is characterized of
high microbial load must be removed or discarded
(referred to as waste activated sludge or WAS) from
the treatment process. It is done using pumps and
carried out in parts so as to regulate the food-tomicroorganism ratio (F:M) inside the aeration tank.
5.2. ASP Process Requirements
Acknowledgement
A standard activated sludge process will require the
following for effective operation;
(a) Formation of flocs as it ensures effective
separation of the microbial biomass.
(b) The mean cell residence time (MCRT) should
be increased alongside adequate aeration in order to
enhance settling ability of the microbial biomass.
(c) Oxygen level needs to be properly regulated.
(d) Microorganisms constitute the biological
component of activated sludge system. The microbes
can contain about 70 90% organic matter. In fact,
the wastewater composition and the specific
characteristics of microbes in the biological
community determine the cell makeup.
(e) Most commonly found organisms within the
biological component of activated sludge are bacteria,
fungi, protozoa and rotifiers. In some cases, nematode
worms which are from metazoan can be present.
However, the growth of higher microbes can be
impaired by the constant agitation in the aeration
tanks in addition to recirculation connected with
sludge.
In 1990s when ASP was developed, it was
characterized of fill and draw reactors (batch process).
The continuous flow reactors were developed in order
to tackle the problem of regulating a number of batch
reactors that always have varied influent flow rate.
Interestingly, over the years, sequential batch reactor
(SBR) has replaced the old system and aeration
process is the significant energy consumption
operation of the system, whereas operations on RAS
and clarifiers are insignificant. Yet, the major
expenses can arise from the sludge processing and
disposal.
6. CONCLUSION
Previously, water was regarded as the most abundant
natural resource based on its global distribution, and
as such less caution was taken to on securing its
natural quality. Unfortunately, it has turned out to be
the scarcest resource now and no thanks to some
socio-economic developments that do not take into
69
Dadrasnia et al.
Wastewater Treatment by Biological Methods
70
School of Civil Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal,
Pulau Pinang, Malaysia.
2
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal,
Pulau Pinang, Malaysia.
*Corresponding Author: chirvan@eng.usm.my
Abstract. Industrial wastewater treatment has gained importance due to the insistence of the environmental groups,
environmental regulation and public awareness. Wastewater from pulp and paper industry is among the most harmful
wastewater that needs to be treated since it contains high organic substances. Although the raw materials of this kind of
industry has been replaced by recycled materials in order to reduce wastes, however effluent from this recycled paper mill is
still highly polluted that need to be treated. In this study, the start-up performance of treating recycled paper mill wastewater
using a modified anaerobic inclining-baffled bioreactor (MAIB-R) has been studied. The MAIB-R was started with a hydraulic
retention time (HRT) of 5 days at 37C. The start-up process took 14 days before it reached steady state on day 15. The MAIBR, after successful start-up, can achieve relatively high average COD removal of 92% with pH level of effluent relatively
stable at 6.63. In addition, the biogas production reached 0.77L/d with methane content up to 57% on day 15. The result shows
that during the start-up period, MAIB-R was successfully operated in treating recycled paper mill wastewater.
Keywords: Anaerobic Inclining-Baffled, Biological Treatment, Paper Mill Wastewater
1. INTRODUCTION
1.1. Recycled Paper Mills
Paper and pulp industry together with recycled paper
mill ranked among the largest industries in the world.
There are mills found in more than 100 countries in
every region of the world. The major pulp and paper
producing nations include the United States, China,
Japan, Canada, Germany, Brazil, Sweden, Finland and
72
Range
7.0-7.7
3770-9330
816-2495
1.4-3.8
2051-11161
200-892
603-8495
40-850
Mean S.D.
7.30.22
5539412
1372108
2.360.8
4654276
59550
3993216
48058
Ca
398.78
Cd
0.39
0.02
Co
0.64
Cr
0.51
0.05
Cu
1.10
1.00
Fe
2.39
1.00
Li
0.65
Mg
12.19
Mn
0.85
0.20
Mo
0.92
Ni
0.72
0.20
Pb
1.11
0.50
Sb
1.47
Se
1.63
Ti
0.99
Tl
0.82
V
0.86
Zn
1.39
1.00
*Acceptable conditions for discharge of industrial effluent or mixed effluent of standards B.
73
Unit operations
Screening
Comminution
Flow equalization
Sedimentation
Floatation
Granular-medium filtration
Chemical precipitation
Adsorption
Disinfection
Dechlorination
Other chemical applications
74
(1.1)
1.6. Anaerobic Baffled Reactor
Nowadays, many researchers have focused on
anaerobic reactors for the treatment of wastewater. As
one of the high-rate anaerobic reactors, ABR was
extensively used in treating wastewater (Liu et al.,
75
HRT
(h)
10
Influent COD
(mg/L)
501
COD Removal
(%)
90.7
OLR
(kg/m3d)
1.2
Gas Produced
(LCH4/g COD d)
0.36
48
305.1836.22
745
(Gopala Krishna
Kumar, 2007)
(Feng et al., 2008)
350
86
2.62
0.34
(Bodkhe, 2009)
500
88
0.31
Diluted wastewater
10
500
95
0.13
0.3
(Langenhoff
Stuckey, 2000)
Domestic
wastewater2
Low
strength
wastewater
Low
strength
wastewater
22
71654.4
723
12
550
89
1.69
850
90
6.9
Synthetic
wastewater
Domestic
wastewater1
Municipal
wastewater
Complex
wastewater
Reference
and
and
HRT
(h)
72
Influent COD
(mg/L)
16000
COD Removal
(%)
77.3
OLR
(kg/m3d)
5.33
Whisky distillery
wastewater
96
9500
96.1
2.38
Brewery wastewater
19.23
10720
93
13.38
(Baloch et al.,
2007)
39.5
1000
97
6.0
Reference
(Faisal and Unno,
2001)
(Akunna and Clark,
2000)
76
Recommendations
Low initial loading rates will encourage granule/ floc growth.
Pulses of methane precursors (e.g. acetate) have been successfully used to encourage
methanogenic growth and dampen the effects of increases in loading rate.
Start-up with long retention times reduces solids loss due to low liquid upflow
velocities and promotes higher methanogenic populations in every compartment.
Recycle
Recycle is beneficial with respect to diluting toxicants in feed stream, increasing front
pH and reducing production of foam and SMPs.
Low retention time enables better mass transport due to improved hydraulic mixing
and reduces biomass starvation in latter Compartments.
methane production will originate from scavenging bacteria (Methanosaeta).
Long retention times reduce solids washout caused by high gas production, otherwise
the reactor may be modified (by adding packing) to decrease biomass loss.
Methane production will be mainly due to Methanosarcina, and hydrogen scavenging
methanogens.
A larger front compartment has proved to be effective in treating wastewater with high
solids content.
Temperature
Reducing temperature to 25C from 35C has no effect on easily degradable waste,
further decreases in temperature are detrimental on reactor performance, this may be
due to potential toxicity, nutrient bioavailability and slower kinetic rates.
Reactors started-up and kept at lower temperatures perform consistently well
77
Table 8: Advantage associated with the anaerobic baffled reactor (Barber and Stuckey, 1999)
Advantage
Construction
Biomass
Operation
1. Simple design
2. No moving parts
3. No mechanical mixing
4. Inexpensive to construct
5. High void volume
6. Reduced clogging
7. Reduced sludge bed expansion
8. Low capital and operating costs
1. Low HRT
2. Intermittent operation possible
3. Extremely stable to hydraulic shock loads
4. Protection from toxic materials in influent
5. Long operation times without sludge wasting
6. High stability to organic shocks
78
of
Recycled
Paper
Mill
C
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
6.2-7.8
35-45
1650-2565
3380-4930
0.488-0.52
3530-6163
1630-3025
1900-3138
840-2920
Table 10: Environmental Quality Act 1974 and Regulations. Environmental Quality (Industrial Effluent) Regulations (PU (A)
434), Fifth Schedule
Standard
Parameters
Units
Temperature
pH value
Suspended solids
C
mg/l
40
6.0-9.0
50
40
5.5-9.0
100
Table 11: Acceptable conditions for discharge of industrial effluent containing chemical oxygen demand (COD) for specific
trade or industry sector
Trade/Industry
(a) Pulp and paper industry
(i) pulp mill
(ii) paper mill (recycled)
(iii) pulp and paper mill
Unit
Standard A
Standard B
mg/L
mg/L
mg/L
80
80
80
350
250
300
79
80
Fig. 3: pH profiles for each compartment of MAIB bioreactor during continuous feeding period
Fig. 4: COD concentration and removal efficiencies in the MAIB bioreactor during continuous feeding
81
Table 12: Methanogenesis of RPM wastewater using MAIB bioreactor at different time
Day
2
4
6
11
13
15
Average
Biogas yield
(L/d)
70
69
52
46
58
55
65
64
60
50
53
57
66
62
65
46
59
59
67
65
59
47
57
57
0.65
0.44
0.57
0.67
0.77
0.77
pH Level
82
Fig. 5: pH profiles for each compartment of the MAIB bioreactor at steady state on day 15
3.3.2.
COD Removal
83
REFERENCES
ACKNOWLEDGMENT
The authors wish to acknowledge the financial
support from the Universiti Sains Malaysia (RU-I
Grant A/C. 1001/PJKIMIA/814148).
84
85
86
Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul
Rahman, 31900 Kampar, Perak, Malaysia
2
School of Science, Monash University Sunway Campus, 46150 Petaling Jaya, Selangor, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449
Abstract. As the discharge of wastewater containing nitrogen is in soaring trend, the objectives of this research aim to
optimize the size of support media and aeration strategy in moving bed sequencing batch reactor (MBSBR) for the biological
nitrogen removal enhancement. In accordance with these objectives, MBSBRs packed with polyurethane (PU) foam cubes of
sizes 8 to 125-mL as the support media and operated with continuous aeration (CA) strategy was initially experimented to
determine the optimum size of support media, reflected by the highest total nitrogen (TN) removal. Subsequently, the
operation of MBSBR packed with optimum size of support media was converted to intermittent aeration (IA) strategy and its
performance in terms of TN removal was investigated again. The results of these two steps experiments vindicated that the
MBSBR packed with 8-mL PU foam cube and operated with IA strategy removed the highest TN removal, signifying the
optimum condition. This optimum condition had eventually resulted the MBSBR procured the highest total weight of attachedgrowth biomass that was associated to the maximum amount of internally stored carbon source in which favorable the
simultaneous nitrification and denitrification (SND) process.
Keywords: Nitrogen Removal, Sequencing Batch Reactor, Biological Method
1. INTRODUCTION
The increasingly discharge of nitrogen wastes from
industrial, livestock and agricultural wastewaters
without prior channeling to a proper treatment can
adversely contaminate the quality of receiving waters.
Serious concern related to the adverse impacts of
nitrogen wastes particularly ammonium-nitrogen
(NH4+-N) includes dissolved oxygen (DO) depletion,
toxicity and eutrophication (Gerardi, 2002; Magri et
al., 2013). Therefore, the necessity to remove NH4+-N
in wastewaters before the disposal is utmost crucial to
comply with the stringent discharged limits for
wastewaters containing nitrogen.
Biological nitrogen removal has been widely
recognized to offer a more economical and
environmentally friendly approach in removing NH4+N via nitrification and denitrification processes
(Gerardi, 2002; Jokela et al., 2002; Leta, 2004;
Dempsey et al., 2005; Aslan et al., 2009; Yao et al.,
2013). Over the decades, various operational
parameters had been studied with intention to
optimize the biological nitrogen removal (Deguchi
and Kawashiwaya, 1994; Pochana and Keller, 1999;
Katsogiannis et al., 2003; Daniel et al., 2009; Chu and
Wang, 2011).
(3)
87
Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor
(4)
(5)
1.3. Moving Bed Sequencing Batch Reactor Support Media Size and Aeration Strategy
Sequencing Batch Reactor (SBR) system has been
extensively manipulated for the treatment of domestic,
municipal and industrial wastewaters and also offers
an attractive option in the biological wastewater
treatment systems with the advantages as below
(Irvine and Ketchum, 1989; Wobus et al., 1995;
Louzeiro et al., 2002; Goh, 2007):
(a) Resistant to influent loading fluctuation;
(b) Simplicity and cost effective;
(c) Flexibility in terms of sequence and cycle time;
(d) Ideal quiescent settling condition;
(e) Ability of combining aerobic and anoxic phases in
a single reactor.
Incorporated with an activated sludge system, SBR
is primarily running on the fill and draw principle.
The operation of the SBR is usually achieved by five
sequential periods, namely FILL, REACT, SETTLE,
DRAW and IDLE in a single tank instead of
simultaneously in the separate tanks as typically
observed in the conventional activated sludge system
(Arora et al., 1985). Thus, permits the construction of
smaller treatment plant which is suitable in the area
with limited land availability. Nevertheless, a
conventional SBR system is generally incapable of
executing an effective biological nitrogen removal
(Goh, 2007; Li et al., 2011). As a result, an
improvement of SBR system is deemed essential
when the bio-treatment of wastewater containing
nitrogen is to be addressed.
For years, numerous attempts have been
committed to modify the SBR system in order to
enhance the performance. Among others, the moving
bed sequencing batch reactor (MBSBR) which is
developed by retrofitting support media into the SBR
has attracted much interest among the researchers in
the field of biological wastewater treatment (GarzonZuniga
and
Gonzalez-Martinez,
1996;
Sirianuntapiboon and Yommee, 2006; Goh et al.,
2009; Hosseini Koupaie et al., 2012). In general, three
88
89
Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor
2. METHODOLOGY
To achieve the aforementioned objectives, two major
experiments were carried out with the first experiment
aimed to determine the optimum size of support media
used to pack the MBSBR and the subsequent
experiment targeted to investigate the optimum
aeration strategy; both emphasized on the
enhancement of biological nitrogen removal via SND
process.
2.1. Determination of Optimum Support Media
Size Packed in MBSBR
Five plexiglass reactors were inoculated with the
activated sludge collected from municipal sewage
treatment plant and fed with synthetic wastewater
simulating the municipal wastewater composition
with NH4+-N and COD concentrations of
approximately 48 and 200 mg/L, respectively. The
reactors were operated with a cycle time of 24 h in the
following sequencing periods: instantaneous FILL, 0
h; aerobic REACT, 10 h; anoxic REACT, 2 h;
SETTLE, 1.5 h; DRAW, 1 h and IDLE, 9.5 h.
Adequate amount of ethanol solution was
instantaneously added into the reactor as a carbon
source at the beginning of the anoxic REACT period
Fig. 1: Schematic diagram of the MBSBR: (a) plexiglass reactor; (b) aquarium air pumps; (c) addition of feed solution by the
peristaltic pump; (d) addition of ethanol solution by the peristaltic pump; (e) draw out tubing to remove treated effluent
containing unsettled suspended solids by the peristaltic pump; (f) support media of PU foam cubes; (g) ejector; (h) air
diffusers; (i) aeration tubing; (j) working volume of 12.8 L; (k) residual volume of 3.8 L.
90
Figure 2: SEM image of PU foam cube with 40X magnification and captured at WD of 7 mm using EHT and
signal of 5.00 kV and SE2, respectively.
Instead, an increasing percentage of TN removal was
observed in the order of R1 < R5 < R4 < R3 < R2.
The removal of nitrogen can be plausibly
explained by the assimilation and SND processes
(Valdivia et al., 2007). Several studies have reported
the aeration condition and carbon source as the
parameters affecting the yield of the SND process
(Pochana and Keller, 1999; Third et al., 2003; Walters
et al., 2009; Khor et al., 2011). The percentage of TN
removal was found to be the lowest in R1. The
occurrence of SND process was not favored in R1 due
to the high DO and low COD concentrations in the
mixed liquor (Pochana and Keller, 1999; Chu and
Wang, 2011; Seifi and Fazaelipoor, 2012). Therefore,
the TN removal in R1 was deemed to be caused by
only assimilation process in which the lost TN was
used to build cell mass. In MBSBRs, aerobic
condition was kept on the surface of the acclimated
PU foam cubes whereas, distinctive DO gradient
91
Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor
Fig. 3: Profiles of nitrogen species concentrations during the REACT period for (a) R1, (b) R2, (c) R3, (d) R4 and (e) R5.
(a)
(b)
(c)
(d)
Fig. 4: SEM images of (a) internal surface of acclimated 8-mL PU foam cube, (b) internal surface of acclimated 27-mL PU
foam cube, (c) internal surface of acclimated 64-mL PU foam cube and (d) internal surface of acclimated 125-mL PU foam
cube all with 40X magnification and captured at WD of 7 mm using EHT and signal of 5.00 kV and SE2, respectively. The
internal surface of each size of the PU foam cube is referring to the surface of the cube cross sectional area.
92
Fig. 5: Profiles of nitrogen species concentrations during the REACT period for IA-MBSBR.
REFERENCES
Arora
93
Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor
94
95
96
Department of Environmental Engineering, Faculty of Engineering and Green Technology, Universiti Tunku Abdul Rahman,
31900 Kampar, Perak, Malaysia
3
Department of Civil Engineering, College of Engineering, University of SalahaddinErbil, Iraq
2
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia,14300 Nibong Tebal, Penang, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449
Abstract. In recent years, electrochemical oxidation process has gained increasing interest due to its exceptional technical
features to eliminate a wide range of pollutants exist in various types of wastewaters, e.g., refractory organic matter, nitrogen
species, microorganisms, etc. Serve as a clean, adaptable and powerful tool in removing pollutants, this review paper focuses
on the fundamental mechanisms of electrochemical oxidation process and provides discussions on the possible applications in
wastewater treatment. To top it off, special attention on the most recent developments and challenges are as well highlighted in
this review.
Keywords: Electrochemical, Wastewater, Oxidation Process
pollutants
in
wastewater.
Furthermore,
electrochemical method presents many significant
gains since it does not require any ancillary chemical,
appropriate for large range of pollutants removal and
does not require high pressures and temperatures for
the reaction to commence. However, the efficiency of
the electro-oxidation techniques depends strongly on
the operation conditions and on the nature of the
electrode materials (Wang et al., 2008). Recently, the
strict wastewater discharge limits with health quality
standards obligation set by legislation may be met by
applying electrochemical oxidation. Wastewaters
generated from municipal landfill and a wide diversity
of industries including the food, textile, and tannery
productions have been successfully treated by this
process. Thus, due to its high competence together
with its disinfection capabilities, electro-oxidation is a
suitable technique for water reuse programs. On the
other hand, treatment costs have to be cut down prior
to full-scale application of this technology.
Accordingly, the employment of electrochemical
oxidation together with other technologies and the use
of renewable energy sources to operate this process
are two significant steps required to reduce the overall
operational cost (Anglada et al., 2009).
1. INTRODUCTION
Basically, wastewater treatment aims to improve the
quality of wastewater before discharging to the
receiving water bodies by using reliable technology.
The conventional sequence of wastewater treatment
starts with draining the wastewater in a central,
separated location and subjecting the wastewater to
several treatment processes. Wastewater treatment can
be generally categorized by the character of the
treatment process operation being used such as
biological, chemical or physical methods. Wastewater
treatment via biological technology is the most
economical means of treatment and normally utilizes
for the removal of biodegradable organic pollutants
presented in the wastewater. Nevertheless, the
presence of toxic and refractory substrates in the
wastewater would virtually foil the biological
treatment process as these substrates are potentially
inhibiting the bioactivity of microorganism (Grimm et
al., 1998). Among the various techniques, the use of
electro-chemical oxidation process in the wastewater
treatment has engrossed many researchers attention,
particularly in remediating industrial wastewater. To
date, electrochemical oxidation processes have been
shown to be a valuable option for the elimination of
refractory organic compounds from various types of
wastewaters (Bashir et al., 2013). Electrochemical
oxidation is highly capable and efficient in reducing
the organic compounds from various types of
wastewater as compared with other types of physiochemical technologies which only bring about phase
transfer of the contaminants in question with no
chemical destruction is taking place.
Similarly, Kapalka et al. (2009) stated that the
electrochemical oxidation process is a clean, versatile
and powerful tool for the destruction of organic
2.
ELECTROCHEMICAL
PROCESS
OXIDATION
97
Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters
Fig. 1: The electrochemical reactor in the laboratory experiments. (1) DC power supply, (2) magnetic stirrer, (3) cover, (4)
electrodes, (5) magnetic bar-stirrer, (6) wastewater and (7) electric wire (Source: Bouhezila et al., 2011).
98
Fig. 3: Schemes for direct and indirect electrolytic treatment of pollutants (Chiang et al., 1995).
Electrochemical
conversion.
Organic
substances (R) are partially oxidized as presented in
Eq. 1. Thus, a following treatment is needed to
completely destroy the oxidized substrates.
R RO + e
Anodic reactions:
2Cl Cl2 + 2e
(1)
(3)
2H2O O2 + 4H+ + 4e
(5)
Bulk reactions:
Cl2 +H2O HOCl + H+ + Cl
(6)
HOCl H+ + OCl
(7)
Cathodic reactions:
2H2O + 2e- 2OH + H
OCl + H2O + 2e Cl + 2OH
(2)
(8)
(9)
99
Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters
Table 1: Potential of oxygen evolution of different anodes, V versus normal hydrogen electrode (Chen, 2004)
Anode
Pt
Pt
IrO2
Graphite
PbO2
SnO2
TiO2
Si/BDD
Ti/BDD
Potential (V)
1.3
1.6
1.6
Conditions
0.5 mol L1 H2SO4
0.5 mol L1 H2SO4
0.5 mol L1 H2SO4
1.7
1.9
1.9
2.2
2.3
2.7
anodes are generally preferred. For example, borondoped diamond (BDD) anodes have been confirmed
to yield higher organic oxidation rates and superior
current efficiencies than other commonly used metal
oxides including PbO2 and Ti/SnO2-Sb2O5 (Anglada et
al., 2009).
2.3.2. Cell design
Maintaining high mass transfer rates as the main
reactions that occur in electrochemical process
transpire on electrode surfaces are the most important
issue in cell design. To improve mass transfer,
100
Fig. 4: Categorization of electrochemical reactors in regards to cell configuration, electrode geometry and flow type (Anglada
et al., 2009).
101
Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters
102
103
Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters
Electrode material
Performance
references
Slaughterhouse
Wastewater
aluminum
Awang et al.(2011)
Textile Wastewater
iron electrode
Textile Wastewater
graphite electrodes
Landfill leachate
graphite Carbone
Kariyajjanavar et al.
(2011)
Bashir et al. (2009)
Landfill leachate
Moraes and
Bertazzoli, (2005)
Industrial paint
wastewater
stainless steel
(Krbahti and
Tanyola, 2009)
paper
mill effluents
El-Ashtoukhy et al.
(2009)
paper
mill effluents
-Ti/RuPb(40%)Ox as anode
-Ti/PtPd(10%)Ox as
cathode.
RuO2 coated Ti
Pharmaceutical
Wastewater
Carbon electrode
Deshpande
(2012)
Tannery
Wastewater
-graphite cathodes
-Ti/SnO2/PdO2/RuO2 anode
Naumczyk
and
Kucharska (2011)
and
Un et al.(2008)
et
al.
5. CONCLUSION
ACKNOWLEDGEMENTS
104
105
Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters
106
107
1. INTRODUCTION
The population explosion currently experienced in the
world today especially in the urban centres of the
world poses a considerable threat to the environment
as a result of the generation of huge amounts of
wastewater (Amenaghawon et al., 2013; Akpor and
Muchie, 2010). The increasing population has resulted
in a corresponding increase in industrial and
agricultural activities from which these wastewaters
are produced (Godos et al., 2009; Morill et al., 2009).
The discharge of untreated wastewater generated from
these operations into natural water bodies represents a
huge environmental burden such as the accumulation
of hazardous and toxic chemicals in the receiving
water
bodies
with
potentially
deleterious
consequences on the immediate ecological
environment. This has necessitated the need to
monitor the quality and quantity of wastewater
generated and discharged into natural water bodies
(Amenaghawon et al., 2013; Kshirsagar, 2013). This
has also led to the development of wastewater
treatment strategies that focus on effective removal of
pollutants from water rather than disposal.
Wastewater treatment is presently carried out
mainly through chemical and biological means.
Irrespective of the advantages of chemical treatment
methods which include the mineralisation of
otherwise non-biodegradable substances and the use
of a smaller reactor size, the disadvantages of this
method are still significant (Agarry et al., 2008; Akpor
108
1.2. Biostimulation
The indigenous microbial population present in
wastewater implies that there is possibility for
remediation through natural attenuation. Nevertheless,
the remediation of wastewater through natural means
is still limited by several factors which might inhibit
microbial growth and activity. Some contaminated
wastewater might contain complex synthetic and
recalcitrant pollutants which are not readily amenable
to biodegradation. Also, there might be deficiency of
electron acceptors or donors and low availability of
nutrient sources such as nitrogen and phosphorus
(Nyyssnen et al., 2009; Qin et al., 2013). In
situations like these, it becomes imperative to improve
the conditions of remediation in the form of external
nutrient supplementation to improve bioavailability,
supplying air or adding electron acceptors or donors to
the substrate analogue (Cosgrove et al., 2010; El
Fantroussi and Agathos, 2005). The process of
externally stimulating microbial growth and activity
for the remediation of contaminants is referred to as
biostimulation. Biostimulation enhances the rate of
bioremediation since the addition of rate limiting
nutrients to the remediation medium promotes the
109
110
OPERATION
OF
111
Fig. 1: Conventional activated sludge process configuration with aeration and settling tanks
use of deeper filters can enhance nitrification potential
and can serve as a second stage in a two-stage
biological system design for nitrification (Guyer,
2011). Wastewater that has gone through primary
treatment is trickled or sprayed over the filter set up
using a rotating sprinkler. The filter arrangement
provides support for the growth of microorganisms
and the wastewater flowing downward through the
filter provides nutrients for the microorganisms. It is
important to first take the wastewater through the
primary treatment step to prevent clogging and ensure
an efficient treatment process. As the wastewater
trickles through the filter, the organic pollutants in it
are degraded by the microorganisms growing on the
filter to simple and non toxic compounds like carbon
dioxide and water and in the process more microbial
cells are produced. A secondary clarifier is typically
needed to clarify the effluent from the trickling filter.
For a completely functional trickling filter system,
reduction levels in biochemical oxygen demand in the
range of 80 to 90 percent have been obtained.
The primary justification of trickling filter systems
has been their low start up, operating and maintenance
112
3.
FORMS
AND
BIOREMEDIATION
STRATEGIES
OF
113
Biosparging:
114
bioremediation
strategy
using
an
efficient
acclimatised microbial consortium. After a treatment
period of 225 days, they observed that the process was
highly efficient in remediating the wastewater as seen
in the performance of the bioaugmented reactor
demonstrated by the reduction levels of up to 95 and
97.5% respectively for chemical oxygen demand
(COD) and total hydrocarbon content. They further
reported that the use of the mixed cultures resulted in
a high degradation performance for hydrocarbons
range of n-alkanes (C10C35). Li et al. (2005) treated
wastewater produced from an oil field using Bacillus
sp. immobilised on polyvinyl alcohol (PVA). They
reported over 90% reduction in chemical oxygen
demand for continuous wastewater treatment using
immobilised bacteria cells. They further reported that
the efficiency of COD removal was improved when
the remediation medium was supplemented with a
nitrogen source such as (NH4)2SO4.
The effectiveness of the application of
bioremediation technology to contaminated sites
varies from site to site and it requires information on
the characteristics of the site, the type of contaminant
and the factors that affect the growth of pollutant
degrading microorganisms (Obahiagbon and Aluyor,
2009). Okoh, (2006) reported that a number of factors
such as the composition of crude oil contaminant,
availability of nutrients especially nitrogen and
phosphorus, and the nature of the contaminated
environment could affect the biodegradation of
petroleum hydrocarbons.
5. BIOREMEDIATION OF POLYCYCLIC
AROMATIC HYDROCARBON POLLUTED
WASTEWATER
Polycyclic aromatic hydrocarbons (PAHs) are a group
of compounds that consists of two or more benzene
rings fused together in various configurations (Woo et
al., 2009). These compounds enter the environment
through two major avenues which are natural and
anthropogenic. Natural sources of PAHs include
volcanic eruptions and forest fires (Bamforth and
Singleton, 2005). They also enter the environment
through a host of anthropogenic activities such as
incomplete combustion of gasoline and diesel in
internal combustion engines, combustion of coal and
oil for power generation, wood burning, tobacco
smoking, fumigants, and many other sources (Jia and
Batterman, 2010; Li et al. 2010; Wilson et al. 2003).
They are typically hydrophobic and have low
solubility in water; however they can be mobilised
into the aqueous phase through discharges from
industrial and domestic effluents, leaks of PAHs
containing materials, runoff from paved roads,
parking lots among other sources (Alamo-Nole et al.
115
116
117
118
8. FACTORS OF BIOREMEDIATION
8.3. Temperature
8.2. Oxygen
This is one of the most important requirements for
microbial degradation. Most wastewater treatment
facilities adopt aeration based treatment strategies. In
such cases, the availability of oxygen becomes a
critical factor. Oxygen is generally necessary for the
initial degradation of oil, and subsequent reactions
may also require direct incorporation of oxygen.
Typically, 3 to 4 parts of dissolved oxygen are
necessary to completely oxidize 1 part of oil into
carbon dioxide and water (Giavasis et al., 2006).
Though anaerobic degradation of oil in wastewater
can occur, it is however in very small degrees. For oil
spills on the ocean surface, oxygen is not usually a
factor that limits the rate of biodegradation as there is
plentiful supply of oxygen close to the surface of the
ocean. However, inadequate supply of oxygen limits
the extent of biodegradation. This is the reason why it
takes longer to degrade oil that has sunk below the
surface of the water.
8.1. Nutrients
Microorganisms need nutrients to survive. These
nutrients are the basic building blocks of living things
and enable microorganisms to carry out metabolic
activities needed for the breakdown of contaminants
during bioremediation. All microorganisms need
119
REFERENCES
Adebayo MA, Adebayo AA, Adediji JF, Adebayo TO
(2012). Isotherm, Kinetic, and Thermodynamic
Studies of Lead (II) Biosorption by Streblus
asper. Pacific Journal of Science and
Technology. 13(2): 283-293.
Adekunle AA, Adebambo OA (2007). Petroleum
hydrocarbon utilization by fungi isolated from
Detarium senegalense seeds. Journal of
American Science, 3(1): 69-76.
Adenipekun CO, Fasidi IO (2005). Bioremediation of
oil-polluted soil by Lentinus subnudus, a
Nigerian white-rot fungus. African journal of
biotechnology, 4(8): 796-798.
Agarry SE, Durojaiye AO, Solomon BO (2008).
Microbial degradation of phenols: a review.
International Journal of Environment and
Pollution, 32(1): 12-28.
Ahluwalia SS, Goyal D (2007). Microbial and plant
derived biomass for removal of heavy metals
from wastewater. Bioresource technology, 98:
2243-2257.
Akpor OB, Muchie M (2010). Bioremediation of
polluted wastewater influent: Phosphorus and
nitrogen removal. Scientific Research and
Essays, 5(21): 3222-3230.
Alamo-Nole LA, Perales-Perez O, Roman-Velazquez
FR (2011). Sorption study of toluene and xylene
in aqueous solutions by recycled tires crumb
rubber. Journal of hazardous materials, 185(1):
107-111.
Amenaghawon NA, Aisien FA (2011). Investigation
of the effect of influent substrate concentration
on the dynamic response of an activated sludge
reactor system by dynamic modelling and
simulation. Journal of Nigerian Institution of
Production Engineers, 13: 9-20.
Amenaghawon AN, Asegame PA, Obahiagbon KO
(2013). Potential Application of Urea and NPK
15: 15: 15 Fertilizers as Biostimulants in the
Bioremediation
of
Domestic
Wastewater. American
Journal
of
Environmental Protection, 1(4): 91-95.
Ardern E, Lockett WT (1914). Experiments on the
oxidation of sewage without the aid of
filters. Journal of the Society of Chemical
Industry, 33(10): 523-539.
ATSDR. (2005).
Toxicological
Profile for
Naphthalene, 1-methylnaphthalene, and 2methylnaphthalene; U.S. Department of Health
and Human Services, Agency for Toxic
Substances and Disease Registry: Atlanta, GA,
USA, 1-291.
120
121
International
Biodeterioration
and
Biodegradation Journal, 59: 40-43.
Hedlund BP, Staley JT (2001). Vibrio cyclotrophicus
sp. nov., a polycyclic aromatic hydrocarbon
(PAH)-degrading
marine
bacterium.
International journal of systematic and
evolutionary microbiology, 51(1): 61-66.
Hidayat A, Tachibana S (2012). Bioremediation of
Aliphatic Hydrocarbon in Three Types of Crude
Oil by Fusarium sp. F092 under Stress with
Artificial Sea Water. Journal of Environmental
Science and Technology, 5(1): 64-73.
Ho YS (2005). Effect of pH on lead removal from
water using tree fern as the sorbent. Bioresource
Technology, 96: 12921296.
Janbandhu A, Fulekar MH (2011). Biodegradation of
phenanthrene
using
adapted
microbial
consortium isolated from petrochemical
contaminated environment. Journal of hazardous
materials, 187: 333-340.
Jia C, Batterman S (2010). A Critical Review of
Naphthalene Sources and Exposures Relevant to
Indoor and Outdoor Air. International Journal of
Environmental Research and Public Health, 7:
2903-2939.
Kadirvelu K, Senthilkumar P, Thamaraiselvi K,
Subburam V (2002). Activated carbon prepared
from biomass as adsorbent: elimination of Ni(II)
from aqueous solution. Bioresource Technology
81: 8790.
Kao CM, Huang WY, Chang LJ, Chen TY, Chien
HY, Hou F (2006). Application of monitored
natural attenuation to remediate a petroleumhydrocarbon spill site. Water Science and
Technology, 53: 321328.
Kim SJ, Choi DH, Sim DS, Oh YS (2005). Evaluation
of bioremediation effectiveness on crude oilcontaminated sand. Chemosphere, 59(6): 845852.
Khan K, Naeem M, Arshed MJ, Asif M (2006).
Extraction and characterization of oil degrading
bacteria. Journal of Applied Sciences, 6: 23022306.
Kshirsagar AD (2013). Bioremediation of wastewater
by using microalgae: an experimental study.
International Journal of Life Sciences
Biotechnology and Pharma Research, 2(3): 339346.
Lendvay JM, Lffler FE, Dollhopf M, Aiello MR,
Daniels G, Fathepure BZ, Adriaens P (2003).
Bioreactive barriers: a comparison of
bioaugmentation and biostimulation for
chlorinated solvent remediation. Environmental
Science & Technology, 37(7): 1422-1431.
Li PF, Mao ZY, Rao SJ, Wang XM, Min MZ, Qiu
LW, Liu ZL (2004). Biosorption of uranium by
122
amended
with
biochar. International
Biodeterioration & Biodegradation, 85: 150155.
Rling WF, Milner MG, Jones DM, Lee K, Daniel F,
Swannell RJ, Head IM (2002). Robust
hydrocarbon degradation and dynamics of
bacterial communities during nutrient-enhanced
oil
spill
bioremediation. Applied
and
Environmental Microbiology, 68(11): 55375548.
Samanta SK, Singh OV, Jain RK (2002). Polycyclic
aromatic hydrocarbons: environmental pollution
and bioremediation. Trends in biotechnology,
20(6): 243-248.
San Miguel V, Peinado C, Catalina F, Abrusci C
(2009). Bioremediation of naphthalene in water
by Sphingomonas paucimobilis using new
biodegradable surfactants based on poly (caprolactone). International Biodeterioration &
Biodegradation, 63(2): 217-223.
Schiewer S, Patil SB (2008). Modeling the Effect of
pH on Biosorption of Heavy Metals by Citrus
Peels. Journal of Hazardous Materials. 157:817.
Schmidt LM, Delfino JJ, Preston JF, Laurent GS
(1999). Biodegradation of low aqueous
concentration
pentachlorophenol
(PCP)
contaminated groundwater. Chemosphere, 38:
28972912.
Sharma S (2012). Bioremediation: Features, Strategies
and applications. Asian Journal of Pharmacy
and Life Science, 2(2): 202-213.
Smith AE, Hristova K, Wood I, Mackay DM, Lory E,
Lorenzana D, Scow KM (2005). Comparison of
biostimulation versus bioaugmentation with
bacterial strain PM1 for treatment of
groundwater contaminated with methyl tertiary
butyl ether (MTBE). Environmental health
perspectives, 113(3): 317-322.
Srivastava NK, Majumder CB (2008). Novel
biofiltration methods for the treatment of heavy
metals from industrial wastewater. Journal of
hazardous materials, 151: 1-8.
Subramanian M, Oliver DJ, Shanks JV (2006). TNT
Phytotransformation Pathway Characteristics in
Arabidopsis: Role of Aromatic Hydroxylamines.
Biotechnology Programme, 22: 208 -216.
Thavasi R, Jayalakshmi S, Balasubramanian T, Banat
IM (2006). Biodegradation of crude oil by
nitrogen fixing marine bacteria Azotobacter
chroococcum.
Research
Journal
of
Microbiology 1(5): 401-408.
Ting WTE, Yuan SY, Wu SD, Chang BV (2011).
Biodegradation of phenanthrene and pyrene by
Ganoderma
lucidum. International
123
spatially
varying
redox
conditions.
Biodegradation, 15: 435451.
Woo OT, Chung WK, Wong KH, Chow AT, Wong
PK (2009). Photocatalytic oxidation of
polycyclic
aromatic
hydrocarbons:
Intermediates identification and toxicity
testing. Journal of hazardous materials, 168(2):
1192-1199.
Wilson NK, Chuang JC, Lyu C, Menton R, Morgan
MK (2003). Aggregate exposures of nine
preschool children to persistent organic
pollutants at day care and at home. Journal of
Exposure
Science
and
Environmental
Epidemiology, 13(3): 187-202.
Yerushalmi L, Manuel MF, Guiot SR (1999).
Biodegradation of gasoline and BTEX in a
microaerophilic biobarrier. Biodegradation, 10:
341352.
Yu KSH, Wong AHY, Yau KWY, Wong YS, Tam
NFY (2005). Natural attenuation, biostimulation
and bioaugmentation on biodegradation of
polycyclic aromatic hydrocarbons (PAHs) in
mangrove
sediments. Marine
pollution
bulletin, 51(8): 1071-1077.
Zhuang P, Yang QW, Wang HB, Shu WS (2007).
Phytoextraction of heavy metals by eight plant
species in the field.Water. Air and Soil
Pollution, 184: 235-242.
Zouboulish AI, Loukidou M, Matis KA (2004).
Biosorption of Toxic Metals from Aqueous
Solutions by Bacteria Strains Isolated from
Metal Polluted Soils. Process Biochemistry, 39:
909-916.
124
Supplementation of Novel Solid Carbon Source Prepared from Dried AttachedGrowth Biomass for Bioremediation of Wastewater Containing Nitrogen
Jun-Wei Lim, Mohammed J.K. Bashir*, Choon-Aun Ng, Xinxin Guo
Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul
Rahman, 31900 Kampar, Perak, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449
Abstract. The main objective of this study is to validate the feasibility of using dried attached-growth biomass from the
polyurethane (PU) foam cubes as a solid carbon source for the enhancement of denitrification process in the intermittently
aerated moving bed sequencing batch reactor (IA-MBSBR). The IA-MBSBR packed with PU foam cubes coated with dried
attached-growth biomass could maintain approximately 80% of total nitrogen (TN) removal efficiency for 8 consecutive cycles
of operation. Subsequently, the exhausted stored carbon source within the PU foam cubes could be replenished by merely
drying the fresh attached-growth biomass formed when the cubes were used as a carbon source. Thus, the reuse/recycle of
biomass-coated PU foam cubes is possible, making it a sustainable solid carbon source for the enhancement of denitrification
process in bioremediating wastewater containing nitrogen-cum-low COD/N via IA-MBSBR.
Keywords: Bioremediation, Wastewater, Solid Carbon Source
1. INTRODUCTION
It is undeniable that water is an indispensable element
for survival of all living creatures. Although the
Earth's surface is virtually covered with 70% of water,
its presence is not limitless. Of all the water, 97%
consist of salt water which is unacceptable for the
direct human consumption. To top it off, of the
remaining 3% of potable water, only about 15% is
easily accessible, e.g., rivers, streams, creeks, ponds,
etc., and about 85% is found in ice floes and glaciers,
neither of which are readily accessible (Sills, 2003).
Owing to the tremendous increase of human growth in
recent decades, water scarcity has emerged as one of
the dire issue for communities across the country. In
United States, almost all the region of the country has
experienced water shortages in the last five years
(USEPA, 2008). As per United Nations, every day
approximately 4400 children under the age of five die
because of diseases cause by contaminated water
ingestion and sanitation (Ghaitidak and Yadav, 2013).
In a third worlds population, one in every six persons
has no access to clean water within a kilometer of
reach (Ghaitidak and Yadav, 2013). In parts of Asia
and Africa, it was estimated that the people under a
threshold of water stress, i.e., accessible of renewable
water resources <1700 m3/person/year, would surge to
three billion by 2025 (FAO, 2012; WHO, 2012;
Ghaitidak and Yadav, 2013).
Globally, although the storage of potable water is
getting lesser due to the excessive consumption, the
problem of potable water contamination particularly
the groundwater and surface water with nitrate is
inevitable. The nitrate pollution is mainly caused by
the intensive use of nitrogen-based fertilizers in
agriculture and irrigation with ammonia-rich effluents
discharged by wastewater treatment plants and
125
Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen
126
Fig. 1: Tree diagram presenting category of carbon sources used for denitrification process
127
Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen
128
Fig. 2: Laboratory set-up of IA-MBSBR packed with PU foam cubes, (a) side view and (b) top view of the bioreactor.
129
Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen
Fig. 3: SEM images of (a) fresh PU foam cube, (b) fresh attached-growth biomass formed on the surface of dried biomasscoated PU foam cubes after one cycle in the IA-MBSBR and (c) dried biomass-coated PU foam cubes all with 150X
magnification and captured at WD of 7 mm using EHT and signal of 5.00 kV and SE2, respectively.
Fig. 4: Profiles of nitrogen species concentrations during the REACT period for (a) first cycle of the 8-cycle operational mode,
(b) last cycle of the 8-cycle operational mode, (c) last cycle of the 10-cycle operational mode and (d) last cycle of the 12-cycle
operational mode under 1:1 IA strategy.
130
Fig. 5: TN removal efficiency for different operational modes under 1:1 IA strategy. Error bars indicate standard deviations.
131
Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen
Fig. 6: Profiles of nitrogen species concentrations during the REACT period for the last cycle of the 8-cycle operational mode
under (a) 1:1, (b) 1:2 and (c) 1:3 IA strategies.
Table 1: Concentrations of NH4+-N and NO3--N in the treated effluent and percentages of TN removal in the IA-MBSBR
operated with 8-cycle mode.
Parameter
Effluent NH4+-N concentration
(mg/L)
Effluent NO3--N concentration
(mg/L)
TN removal (%)
1:1
0.0
IA strategy
1:2
0.0
1:3
6.4
10.7
7.1
0.0
71
79
83
132
4. CONCLUSIONS
The dried attached-growth biomass from the PU foam
cubes could be exploited as a novel solid carbon
source to enhance the denitrification process in the
IA-MBSBR. With the packing volume of 8% (v/v) of
prepared dried biomass-coated PU foam cubes, the
TN removal efficiency of approximately 80% could
be achieved up to 8 consecutive cycles of operation
when 1:2 IA strategy during the REACT period was
adopted during the treatment of low COD/N
containing wastewater. Once the stored carbon source
133
Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen
134
135
136
Abstract. Supported liquid membrane (SLM) has been investigated by many researchers recently. The application of SLM in
wastewater treatment, pharmaceutical purposes, metallurgy, biological process and medical science has made it an interesting
topic for researchers globally. Different methods of SLM systems such as simple, facilitated and active transport have been
described and discussed, as well as solute transport mechanism from the aqueous feed phase through the polymeric
microporous support into the aqueous stripping phase. SLM stability, selectivity, recovery and reuse are the other topics which
in this chapter have been discussed and described. For future trend, green supported liquid membrane and the application of
ionic liquids in SLM system have been suggested.
Keywords: Supported Liquid Membrane, Wastewater Treatment
1. INTRODUCTION
1.1. Bulk Liquid Membrane
Liquid membrane (LM) is water insoluble
(immiscible) liquid with the feed and stripping phases.
Once a specific solute of a mixture moves through the
liquid membrane from feed phase towards the
stripping phase, extraction can be achieved.
Liquid membrane systems are being investigated
widely in various fields such as chemistry (organic,
inorganic and analytical), biotechnology, biomedical
technology, wastewater treatment, etc. (Muthuraman
et al., 2009; Talebi et al., 2013). LM can be applied
for different purposes such as selective removal and
recovery of heavy metals, separation of aromatics
from
hydrocarbons,
antibiotics
purification,
purification of aromatics such as benzene, xylene and
toluene, protein extraction using aqueous two-phase
systems, dyes and pigments removal, metallurgical
purifications, etc. (Chang et al., 2011).
The term solvent extraction refers to the
distribution of a solute between two immiscible liquid
phases, which are somehow in contact with each
other. For this process, the International Union of Pure
and Applied Chemistry (IUPAC) recommends the
term liquid-liquid extraction (LLE) (Rydberg et al.,
2004). The mechanism of the contact of two
immiscible liquid phases with each other makes three
different liquid membrane types: Bulk Liquid
Membrane (BLM), Supported Liquid Membrane
(SLM) and Emulsion Liquid Membrane (ELM).
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Supported Liquid Membrane in Wastewater Treatment
2. LIQUID-LIQUID EXTRACTION
Liquid-Liquid Extraction (LLE) is considered as the
principal and first step for liquid membrane
application. Recently, separation techniques such as
solvent extraction or liquid-liquid extraction (LLE),
liquid membrane, etc. have been widely used in the
separation of heavy metals from aqueous solutions
(Cox, 2004; Talebi et al. 2012). The principle of
liquid-liquid extraction (LLE) is based on distribution
of a solute between an aqueous phase and an organic
phase (Thornton, 1992). LLE is a process where a
138
D = [A]org/[A]aq
(1)
where [A]org is the solute concentration in organic
phase and [A]aq is the solute concentration in aqueous
phase at equilibrium stage.
The percentage of extraction (%E) is given by:
%E= [D/(1+D)]*100
(2)
Jf = kf ([Sf] [Sfm1])
(6)
This is the first step of all three LM configurations
(BLM, SLM and ELM). [Sf] is solute concentration at
feed phase and [Sfm1] is solute concentration at the
feed phase-LM interface.
After this step, solute partition takes place due to
thermodynamic
conditions
and
the
solute
concentration changes from [Sfm1] to [Sfm2].
J = D
(3)
where D is diffusion coefficient and d is membrane
thickness. For steady state diffusion across a thin
membrane, only one dimension can be considered. By
applying the mass transfer coefficient k
k = D/d
(4)
Equation (3) can be simplified and integrated to give
Js = ks ([Sms2] [Ss])
(8)
where [Ss] is the solute concentration at the stripping
phase.
139
Teng et al.
Supported Liquid Membrane in Wastewater Treatment
Fig. 4: Solute transport configuration from aqueous feed phase to aqueous stripping phase through BLM
140
Fig. 5: Solute concentration [S] Vs distance (H) profile from the aqueous feed phase through the LM to the aqueous stripping
phase
Fig. 6: Simple transports of Species (S) from Feed phase (F), through LM (M) to Stripping phase (S)
141
Teng et al.
Supported Liquid Membrane in Wastewater Treatment
Di = RT d ln ci + RT d ln i
(9)
where i is chemical potential of the species
(solute) i, R is universal gas constant, T is absolute
temperature and Ci is the concentration of the species
i, i is activity coefficient of the species i.
The solute transport from the feed phase to the
stripping phase can be simplified into the five
sequential steps as follows:
142
J = Ds=c Ss=c/d
(14)
where Ds=c is diffusion coefficient of carrier-solute
complex, Ss=c, is the concentration gradient of the
carrier-substance complex and is equal to the initial
concentration of the transported substance multiple by
the extraction constant:
Ss=c, = Ss Kext
(15)
and Kext (extraction constant) can be written as:
Kext = Kf Ka
(16)
where Kf is partition coefficient between organic
phase and feed phase, and Ka is dissociation constant
(Park et al., 2006).
D = kT/(6 r)
(11)
where D is diffusion coefficient (cm2/s), k is
Boltzmann constant, T is absolute temperature
(Kelvin), is the organic phase viscosity and r is the
pore radius of the solute.
4.1. Permeation in SLM
Permeation is the process in which a solute dissolves
in the organic phase and diffuses towards the stripping
phase. Substance solubility plays the major role in
simple transport permeation and equilibrium level is
the final step of permeation. In other words, the
transported compound is in the same condition either
in feed phase or stripping phase (Cussler et al., 1989).
The advantage of SLM system is that by using
facilitated organic phase, the transport of solute
through the LM and as a consequence solute
permeability and selectivity can be enhanced
drastically. In this method, the reaction between solute
and the selected carrier only takes place at the
membrane or in better words at the interface of feed
phase and membrane (Juang et al., 1998).
If C is the carrier in the LM which is able to form a
complex with the solute S:
S + C S=C
(12)
then the dissociation constant is:
Ka = [S=C]/[S][C]
(13)
From the Ficks first law, the flux is:
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Teng et al.
Supported Liquid Membrane in Wastewater Treatment
Table 1: selected parameters of the commonly used organic solvents in SLM (Rydberg et al., 2004)
Organic Solvent
Dodecane
Heptane
Toluene
Kerosene
Diphenyl methane
Diheyl ether
1-octanol
Density x 10-3
(kg/m3)
0.75
0.68
0.78
0.79
1.00
0.79
0.83
Surface tension x 10 3
(N/m)
24.9
19.6
27.9
25.3
38.4
27.1
Solubility in water x
10-3 (kg/m3)
0.07
6.51
-
144
and
145
Teng et al.
Supported Liquid Membrane in Wastewater Treatment
REFERNCES
Ashraf MW, Mian A (2006). Selective separation and
preconcentration studies of chromium(VI) with
Alamine 336 supported liquid membrane.
Toxicological and Environmental Chemistry,
88: 187-96.
Azzoug S, Arous O, Kerdjoudj H (2014). Metallic
ions extraction and transport in supported liquid
membrane using organo-phosphoric compound
as mobile carriers. Journal of Environmental
Chemical Engineering, 2: 154162
Chang SH, Teng TT, Norli I (2011). Optimization of
Cu(II) Extraction from Aqueous Solutions by
Soybean-Oil-Based Organic Solvent Using
Response Surface Methodology. Water Air Soil
Pollution, 217:567576
Chiarizia R (1991). Stability of supported liquid
membranes containing long-chain aliphatic
amines as carriers. Journal of Membrane
Science, 55: 65-77.
Cot L, Ayral A, Durand J, Guizard C, Hovnanian N,
Julbe A, Larbot A (2000). Inorganic membranes
and solid state sciences. Solid State Sciences, 2:
313-334.
Cox M (2004). Solvent extraction in hydrometallurgy,
In : J. Rydberg, M. Cox, C. Musikas and G.R.
146
147
Teng et al.
Supported Liquid Membrane in Wastewater Treatment
148
Abstract. Liquid membranes (LM) have received much attention over the last decades. In recent years, a remarkable increase
of the applications of emulsion liquid membranes in separation processes is observed. Emulsion liquid membrane (ELM) is
reputed to be a standout amongst the most guaranteeing detachment techniques for extraction of metal contaminants. Emulsion
liquid membrane systems in which two immiscible phases are separated by a third phase which is immiscible with the other
two phases, are divided into two types: (1) facilitated mass transfer, (2) mass transfer without any reaction involved.
Keywords: Emulsion Liquid Membrane, Separation Process
1. INTRODUCTION
Liquid membranes (LM) have received much
attention over the last decades: liquid membrane
applications having different configurations and have
recently
become
of
substantial
practical
consequentiality
in
separation
technology,
macromolecular chemistry and membrane technology.
The benefits of utilizing LM are high selectivity,
utilizing carriers for the transport mechanism, and
concrete molecular recognition. Therefore, the
synthesizing of incipient type of carriers having high
selectivity for categorical applications becomes very
consequential and a number of researchers have been
working in the area (Muthuraman et al., 2009; Chang
et al., 2011; Talebi et al., 2012).
LM in general plays a paramount role in disunion
science. Their efficiency and economic advantages
distinguish them as a solution for some vital
environmental quandaries such as metals recovery,
hazardous species elimination (metals, organic
molecules) from wastewaters or selective applications.
LM can be modified as bulk liquid membranes
(BLM), supported liquid membranes (SLM), emulsion
liquid membranes (ELM), polymer inclusion
membranes (PIM) and activated composite
membranes (ACM).
In this deference, emulsion liquid membranes have
shown great potential, especially in cases where solute
concentrations are relatively low and other techniques
cannot be applied efficiently, since they cumulate the
process of extraction and divesting in a single unit
operation. The extraction chemistry is rudimentally
identical tantamount to that found in solvent
extraction, but the transport is supported by kinetic
rather than equilibrium parameters, that is, it is
governed by a non-equilibrium mass transfer (Len
and Guzmn, 2004; Teng et al., 2013).
Since emulsion liquid membrane (ELM) as an
enhanced solvent extraction method was at first
149
Teng et al.
Role of Emulsion Liquid Membrane (ELM) in Separation Processes
150
151
Teng et al.
Role of Emulsion Liquid Membrane (ELM) in Separation Processes
152
153
Teng et al.
Role of Emulsion Liquid Membrane (ELM) in Separation Processes
6. SUMMARY
6.1. Applications
In recent years, a remarkable increase of the
applications of emulsion liquid membranes in
separation processes is observed. The main
advantages of the ELM system are: (a) high interfacial
area for mass transfer, especially at the inner
membranewater interface, due to the small size of
the aqueous phase droplets; (b) high diffusion rate of
metal ions through the membrane; (c) simultaneous
performance of extraction (at the outer interface) and
stripping (at the inner interface) in the same system,
and (d) capability of treating a variety of elements and
compounds in industrial setting at a greater speed and
with a high degree of effectiveness, with varying
contaminant concentrations and volume requirements.
6.2. Disadvantages
This system has several disadvantages, all having to
do with the formation of the emulsion.
154
155
Teng et al.
Role of Emulsion Liquid Membrane (ELM) in Separation Processes
156
157
Abstract. Liquid membrane separation is a process which is depending on rate process and chemical potential gradient. The
theory of membrane-based solvent extraction suggests that overall mass transfer of solute consists of several steps: diffusion of
the solute through the aqueous layer from the bulk source aqueous solution to the phases interface (nonequilibrium process),
interaction of the solute with extractant and formation of the solute-extractant complex (as a rule, the process is rapid and
reaches equilibrium at the interface), diffusion of the solute-extractant complex through the membrane support itself
(nonequilibrium process), and diffusion of the solute-extractant complex through the organic layer to the bulk organic solution
(nonequilibrium process).
Keywords: Bulk Liquid Membrane, Wastewater Treatment
1. INTRODUCTION
After the novel study in liquid membrane (LM)
extraction method by Li (1968), LM technology was
further investigated by various researchers for the
recovery of metal ions (Gyves and Rodriquez, 1999;
Chang et al., 2011) and organic compounds
(Muthuraman et al., 2009). LM process combines
extraction and stripping into one single stage and thus
involves non-equilibrium mass transfer characteristic
where the separation is not limited by the conditions
of equilibrium. Membrane can be defined as selective
barrier between two phases with mass transfer taking
place from the feed phase to the stripping phase.
There are mainly three types of liquid membrane
(LM) namely bulk liquid membrane (BLM),
supported liquid membrane (SLM) and emulsion
liquid membrane (ELM). BLM consists of three
phases, namely an organic phase that is sandwiched
between an aqueous feed phase and an aqueous
stripping phase. The organic solvent contains a carrier
that is insoluble in both aqueous solutions. The
samples diffuse from the aqueous feed solution
through the organic liquid membrane into the aqueous
receiving solution (Yang et al., 2009).
The BLM term includes several similar LM
systems, developed by different research groups such
as hybrid liquid membrane (HLM) (Majumdar and
Sirkar, 1992; Kislik et al., 1996 a&b; Gega et al.,
2001), hollow-fiber contained liquid membrane
(HFCLM) (Boyadzhiev, 1987; Bovadzhiev and
Lazarova, 1987; Sengupta et al., 1988; Bovadzhiev,
1990; Boyadzhiev and Alexandrova, 1992; Lazarova
and Bovadzhiev, 1992; Lazarova and Bovadzhiev,
1993; Schlosser et al., 1993; Boyadzhiev and
Dimitrov, 1994; Schlosser and Rothova, 1994;
Kawasaki et al., 1996; Qin and Cabral, 1998;
Schlosser et al., 1999; Dai et al., 2000; Cara et al.,
2001; Cichy et al., 2001a; Dimitrov et al., 2002;
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Bulk Liquid Membrane and Its Applications in Wastewater Treatment
Fig. 1: Hollow fiber contactor with cross-flow of phases (Schlosser et al., 2005)
4. KINETICS of TRANSPORT
In a liquid membrane setup, variation of solute
concentration versus time can be directly measured in
both feed solution (feed phase, [Sf]), stripping solution
(stripping phase, [Ss]) and the solute concentration in
the membrane phase is established from the material
balance.
The transport of solute can be expressed by the
following equations.
d[Sf]/dt
= -k1 Sf* = Jf
d[SLM]/dt = k1 SLM* - k1 SLM*
d[Ss]/dt
= k1 Ss* = Js
(1)
(2)
(3)
Sf*
= [Sf]/[Sf,0]
SLM* = [SLM]/[Sf,0]
Ss*
= [Ss]/[Sf,0]
where [Sf,0] is the initial concentration of solute in
the feed phase.
If the differential Equations (1) to (3) are
integrated, the following equations are obtained
(Gyves and Miguel, 1999).
Sf* = exp(-k1t)
SLM* = 2k1/2(k2-k1) [exp(-k1t) exp (-2k2t)]
Ss* = 1- 1/2k2-k1 [2k2 exp(-k1t) k1 exp(2k2t)]
(4)
(5)
(6)
159
SLMmax = (k1/k2)-k2/(k1-k2)
tmax = ln(2k1/k2)/2k1-k2
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
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Teng et al.
Bulk Liquid Membrane and Its Applications in Wastewater Treatment
Solvent (extractant/diluent)
TOA/(MIBK; octanol; n -alkanes)
Amines/n alkanes
(TOA; TOPO; TBP)/hexane
Propionic acid
Butyric acid
TOA/n alkanes
Valeric acid
5-Methyl-2-pyrazinecarboxylic
acid (MPCA)
Succinic acid
Aconitic, oxalic, malic acids
Lactic acid
TOA/xylene
TOA/xylene
n Butanol
TBP/Shellsol 2046
Tertiary amines/(n -alkanes, isodecanol, isotridecanol)
Aliquat 336/Shellsol A
TOPO/kerosene
(TOA; TOPO)/(oleyl alcohol, n -hexane)
Alamine 336/(kerosene, oleyl alcohol)
Alamine 336/2-octanol
(Amines; Aliquat 336)/(n -alkanes; oleyl alcohol)
TOA/xylene
TOMAC/oleyl alcohol
TOMAC/oleyl alcohol
TOMAC/1-decanol
TOPO, TOA, TBP
Tertiary amines/(n -alkanes, isodecanol, isotridecanol)
TBP/(isooctane, SPAN80)
Amines/n alkanes
TOA/xylene
(Amines; TOA; TOPO; TOMAC; TBP)/(kerosene; hexane; toluene; oleyl alcohol)
(Amines; trialkylphosphinoxides)/(kerosene; oleyl alco -hol)
Citric acid
Phenylalanine
L-Isoleucine
Phenylalanine, L-isoleucine
L-Lysine
Tryptophan, dipeptide
Tryptophan
N -(Benzyloxycarbonyl)-L-
161
Reference
Lee et al., 2001
Solichien et al., 1995
Eyal and Bressler, 1993; Wodzki and
Nowaczyk , 2002
Juang and Wu, 1999
Senol, 1999
Solichien et al., 1995
Juang et al., 1993
Wodzki et al., 2000; Wodzki and
Nowaczyk, 2002
Sabolova and Schlosser, 2000, 2001,
Kertesz and , Schlosser, 2005)
Wu and Yang, 2003
Sabolova and Schlosser, 1998; 2000
Sabolova and Schlosser, 1999
Rodriguez et al., 1997; Viegas et al.,
1997; Coelhoso et al., 2000; Gonzalez
et al., 2001
Luque et al., 1995
Schlosser et al., 2001
Schlosser et al., 2001; Sabolova et al.,
1999; Schlosser and Sabolova, 2002
Sabolova et al., 2001; Kubisova et al.,
2002a, 2004
Kubisova et al., 2002b
Prasad et al., 1988
McMurray et al., 2002
Kubisova and Schlosser, 1996
Coelhoso et al., 1997; Coelhoso et al., 2000
Scheler et al., 1999
Hano et al., 1996
Chen and Lee, 1997
Huang et al.,2004
Giorno et al., 1996
Juang et al., 2000
Tong et al., 1998
Tong et al., 1999
Gonzalez et al., 2004
Kondo et al., 2004
Kubisova and Schlosser, 1996; GonzalezMunoz et al., 2004
Demirci et al., 2007
Scholler et al., 1993
Juang et al., 1998
Hano et al., 1993
Siebold et al., 1995
Tik et al., 2001
Juang et al., 2000; Juang and Chen, 2000
Basu and Sirkar, 1991
Juang et al., 1998; Friesen et al., 1991
Yordanov and Boyadzhiev, 2004
Escalante et al., 1998; Escalante and
Irabien, 2001
Ma et al., 2002
Wang et al., 2004
Boyadzhiev and Atanassova, 1991
Hossain, 2000
Coelhoso et al., 2000
Rindfleisch et al., 1997; Lazarova et al.,
Antibiotics: Penicillin G
Cephalosporine
Erythromycin
Tylosin
2002
Kedem and Bromberg, 1993; Isono et
al.,1997
Sahoo et al., 1999
Kawasaki et al. 1996
Boyadzhiev and Kirilova, 2000;
Boyadzhiev et al., 2003
Kelly et al., 2000
Prasad and Sirkar, 1989
Prasad and Sirkar, 1990
Decylalcohol
Aliquat 336/butylacetate
TOA/(kerosene, octanol)
Ionic liquids
Quaternary ammonium salt/isooctane
Cyclodextrine derivatives
Cyanex 923/kerosene
Cyanex 923/kerosene
1-Octanol
Fig. 2: Schemes of pertractors and their operation: (A) simple bulk liquid membrane pertractor (BLM), (B) multimembrane
hybrid system (MHS), (C) multimembrane hybrid system coupled to Donnan dialysis (DD-MHS). f: feed solution, s: stripping
solution, m: liquid membrane, CEM: cation-exchange membrane, ms: mediating solution. Specific subprocesses1: interfacial
extraction or back-extraction, 2: loaded (C2 M) and unloaded (CH) carrier diffusion, 3: ion-exchange sorption or desorption of
cations from/into aqueous solution, 4: cation-exchange dialysis, 5: interfacial cation-exchange between the carrier and CEM
functional groups, 6: Donnan dialysis between f and ms through CEM.
162
Teng et al.
Bulk Liquid Membrane and Its Applications in Wastewater Treatment
cation-exchange dialysis,
163
Fig. 3: Schemes of new pertractors and their operation: (A) double multimembrane hybrid system (d-MHS), (B) double
multimembrane hybrid system supported by Donnan dialysis unit (DD-d-MHS). Detailed description: the same as in Fig. 2.
6. CONCLUSION
REFERENCES
Liquid membrane separation is a process which is
depending on rate process and chemical potential
gradient. This is important to take notice that
equilibrium between phases has not any effect on the
separation process.
The theory of membrane-based solvent extraction
suggests that overall mass transfer of solute consists
of several steps: diffusion of the solute through the
aqueous layer from the bulk source aqueous solution
to the phases interface (nonequilibrium process),
interaction of the solute with extractant and formation
of the solute-extractant complex (as a rule, the process
is rapid and reaches equilibrium at the interface),
diffusion of the solute-extractant complex through the
membrane support itself (nonequilibrium process),
and diffusion of the solute-extractant complex through
the organic layer to the bulk organic solution
(nonequilibrium process). Here, only one of the
components may be equilibrium based in two phases:
(1) if the kinetics of solute-extractant interaction is a
rate-controlling process, which is not true in the
majority of separations published in the literature, and
(2) if the overall mass transfer of the solute from the
bulk source solution to the bulk membrane solution
reaches equilibrium.
164
Teng et al.
Bulk Liquid Membrane and Its Applications in Wastewater Treatment
165
acid
derivatives.
Biotechnology
and
Bioengineering, 56: 162.
Juang RS, Lee SH, Huang RH (1998). Modeling of
amine-facilitated liquid membrane-transport of
binary organic-acids. Separation and Science
Technology, 33: 2379.
Juang RS, Wu RT (1999). Extraction of acetate from
simulated waste solutions in chloromycetin
production. Separation and Purification
Technology, 17: 225.
Juang RS, Chen JD (2000). Mass transfer modeling of
citric and lactic acids in a microporous
membrane extractor. Journal of Membrane
Science, 164: 67.
Juang RS, Chen JD, Huan HC (2000). Dispersion-free
membrane extractioncase-studies of metalion and organic-acid extraction, Journal of
Membrane Science, 165: 59.
Kaul R, Mattiasson B (1991). Extractive
Bioconversions in aqueous Two phase systems.
In Entractive Bioconversions, Mattiasson B and
Holst O, Eds, M. Dekker, New York, USA.
Kawasaki J, Egashira R, Kawai T, Hara H,
Boyadzhiev
L
(1996).
Recovery
of
erythromycin by a liquid membrane. Journal of
Membrane Science, 112: 209-217.
Kedem O, Eyal AM, Bromberg L, Bressler E (1992).
Membrane Extraction in the Fermentation of
Carboxylic Acids, Israel Patent No. 101905,
1992.
Kedem O, Bromberg L (1993). Ion-exchange
membranes in extraction processes. Journal of
Membrane Science, 78: 255-261.
Kelly NA, BReuben BG, Rhoades J, Roller S (2000).
Solvent extrac-tion of bacteriocins from model
solution and fermentation broth. Journal of
Chemical Technology and Biotechnology, 75:
777.
Kertesz R, Schlosser S (2005). Design and simulation
of two phase hol-low fiber contactors for
simultaneous membrane based solvent extraction and stripping of organic acids and
bases. Separation and Purification Technology,
41: 275.
Kislik V, Eyal A (1996a). Hybrid liquid membrane
(HLM) system in separation technologies,
Journal of Membrane Science, 111: 259-272.
Kislik V, Eyal A (1996b). Hybrid liquid membrane
(HLM) and supported liquid membrane (SLM)
based transport of titanium (IV). Journal of
Membrane Science, 111: 273-281.
Kislik V, Eyal A (2000a). Aqueous hybrid liquid
membrane process for metal separation. Part I.
A model for transport kinetics and its
experimental verification. Journal of Membrane
Science, 169: 119-132.
166
Teng et al.
Bulk Liquid Membrane and Its Applications in Wastewater Treatment
167
168
Teng et al.
Bulk Liquid Membrane and Its Applications in Wastewater Treatment
Germany.
Schugerl K (2000). Integrated processing of
biotechnology
products.
Biotechnology
Advances, 18: 581.
Sengupta A, Basu R, Sirkar KK (1988). Separation of
solutes from aqueous solutions by contained
liquid membranes. AIChE Journal, 34: 16981713.
Senol A (1999). Extraction equilibria of formic,
levulinic and acetic-acids using (Alamine
336/diluent)
and
conventional
solvent
systemsmodeling considerations. Journal of
Chemical Engineering of Japan. 32: 717.
Siebold M, Vonfrieling P, Joppien R, Rindfleisch D,
Schugerl K, Roper H (1995). Comparison of the
production of lactic-acid by 3 different
lactobacilli and its recovery by extraction and
electrodialysis, Process Biochemistry, 30: 81.
Solichien MS, Obrien D, Hammond EG, Glatz CE
(1995).
Membrane-based
extractive
fermentation to produce propionic and aceticacidstoxicity
and
mass-transfer
considerations,
Enzyme
and
Microbial
Technology, 17: 23.
Swatloski PR, Holbrey DJ, Rogers DR (2003). Ionic
liquids are not always green: hydrolysis of 1butyl-3-methylimidazolium
hexafluorophosphate. Green Chemistry, 5: 363363.
Talebi A, Teng TT, Abbas FMA, Norli I (2012).
Optimization of nickel removal using liquid
liquid extraction and response surface
methodology.
Desalination
and
Water
Treatment, 47 (1-3): 334-340.
Teramoto M, Matsuyamaa H, Takayaa H (1987a).
Development of spiral type supported liquid
membrane module for separation and
concentration of metal ions. Separation Science
and Technology, 22: 2175-2201.
Teramoto M, Matsuyama H, Ohnishi N (1989).
Development of a spiral-type flowing liquid
membrane module with high stability and its
application to the recovery of chromium and
zinc. Separation Science and Technology, 24:
981-999.
Teramoto M, Matsuyama H, Ohnishi N (1990).
Selective facilitated transport of benzene across
supported and flowing liquid membranes
containing silver nitrate as a carrier. Journal of
Membrane Science and Technology, 50: 269278.
Teramoto M, Matsuyama H, Nakai K, Uesaka T,
Ohnishi N (1994). Facilitated uphill transport of
eicosapenaenoic acid ethyl ester through bulk
and supported liquid membranes containing
silver nitrate as carrier: A new type of uphill
169
170
Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul
Rahman, 31900 Kampar, Perak, Malaysia
2
Department of Petrochemical Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul
Rahman, 31900 Kampar, Perak, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449
Abstract. In this study, a multi component dope solutions with the range of polymer concentration 13 wt.% to 17 wt.% were
prepared using polyethersulfone, 1-methyl-2-pyrrolidinone and water. The PES-UF membranes were prepared based on a
dry/wet phase inversion technique. Membrane performances in terms of pure water permeability, salt water permeation, salt
water rejection and bacteria removal had been evaluated using low operating pressure (100 kPa to 500 kPa). The results
showed that membrane with polymer concentration of 13.60 wt.% had the best performance in terms of flux production and
salt water rejection. High salt water permeation from 1027.4 L/m2.h to 4109.6 L/m2.h and also 99.7% of salt water rejection
were achieved. In addition, a total rejection for E. coli and E. faecalis with flux rate of 320 L/m2.h and 400 L/m2 were obtained,
respectively. SEM image obtained also showed a fine asymmetrical membranes structures.
Keywords: Membrane, Water, Treatment
1. INTRODUCTION
Water is an important essence for every living
creature throughout the world. We hardly separate our
daily life with the water. As water is so important to
us, various water treatment plants had been built up in
order to make sure the water we use is safe and free
from any threats. Water that passes through all the
treatments such as coagulation, flocculation,
sedimentation, filtration, and disinfection had been
guaranteed to be clean enough for us to drink, but
there is doubt about the safety to drink the water.
Since cases of waterborne breakout caused by
pathogens had been detected in many countries all
over the world, it indicates that water treatment plants
had face difficulties in providing water that is
perfectly safe for us (Drinking Water Contamination,
2006). One of the reasons is the water treatment plant
involves complicated and complex system in treating
process (Xia et al., 2004). With many systems
involved, some avoidable technical error will occur
causing severe effect to the users. In addition, the
disinfection product, usually chlorine had been long
time ago proven to cause side effects to the users
(Rook et al., 1974; Monarca et al., 2004). Over the
last decades, the tightening of water quality
regulations and the increased attention given to trace
contaminants in surface water and drinking water has
been urging of alternative treatment technologies in
order to improve conventional water treatment
processes (Hassan et. al., 2013). In order to serve the
purpose, membrane technology has become an
alternative since it can provide clean water and
rejecting all threats during the treatment process.
Moreover, the technology also has easier handling
system than the commercial water treatment plant.
2. MEMBRANE TECHNOLOGY
Generally a membrane is defined as a selective barrier
between two phases; the term selective being
inherent to a membrane or a membrane process
(Mulder, 1996). There are several types of membrane,
such as microfiltration membrane (MF), ultrafiltration
membrane (UF), nanofiltration membrane (NF), and
reverse osmosis (RO). These membranes are listed in
Table 1 below according to their type, pore radius,
material, pressure, and application.
Membrane processes including microfiltration,
ultrafiltration, and nanofiltration experienced rapid
growth in drinking water purification applications in
past two decades (Liu, 2014). The low pressure
membrane processes, which are microfiltration (MF)
and ultrafiltration (UF) play an important role in the
171
Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
Membrane
Material
Process Diving
Force
Applications
Microfiltration
Symmetric
microporous, 0.110 microns
Cellulose nitrate or
acetate,
Polyvinylidene
difluoride (PVDF),
Polyamides,
Polysulfone, etc.
Hydro-static
pressure
difference at
approx.
10-500 kPa
Sterile filtration,
Clarification
Ultrafiltration
Asymmetric
microporous,
1-10 nm
Polysulfone,
Polypropylene,
Nylon 6, PTFE,
PVC, Acrylic
Copolymer
Hydrostatic
pressure
difference at
approx.
0.1-1.0 Mpa
Separation of
macromolecular
solutions
Reverse
Osmosis
Asymmetric skintype,
0.5-1.5 nm
Polymers,
Cellulosic acetate,
Aromatic
Polyamide
Hydrostatic
pressure
difference at
approx.
2-10 Mpa
Separation of salts
and microsolutes
from solutions
Gas Separation
Asymmetric
homogeneous
polymer
Polymers &
copolymers
Hydrostatic
pressure and
concentration
gradients
Separation of gas
mixtures
Nanofiltration
Thin-film
membranes
Cellulosic Acetate
and Aromatic
Polyamide
9.3-15.9 bar
Removal of
hardness and
desalting
Process
172
OF
wt .% of component
x Volume of dope needed
100%
ASYMMETRIC
(1)
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Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
4. Permeation Test
Membrane was prepared by casting solution with the
pre-determined composition. The membranes were
produced by dry/wet phase inversion technique using
casting machine. Firstly, solution was cast on a clean
smooth glass plate and supported with knife gap
setting of 150m. Ambient temperature was around
27C 30C. Time used in membrane casting was 10
174
Flux, Jv
Volume permeationrate, (V )
Membranearea, ( A) time(t )
Pm
Jv
P
(3)
(2)
Components
Casting
Solution 1
Casting
Solution 2
Casting
Solution 3
Casting
Solution 1
Casting
Solution 2
Casting
Solution 3
PES
15
17
19
13.60
15.40
17.70
NMP
85
83
81
77.40
75.30
75.70
Water
9.00
9.30
6.60
175
Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
176
4500
4200
PES 13 wt.%
3900
PES 15wt.%
3600
PES 17wt.%
3300
3000
2700
2400
2100
1800
1500
1200
900
600
300
0
0
P ressure (Bar)
Fig. 3: Fluxes of NaCl (0.01M) vs pressure for fabricated membrane with different polymer concentration
177
Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
120
100
Rejection (%)
80
60
40
PES 13wt.%
PES 15wt.%
20
PES 17wt.%
0
0
3
Pressure (Bar)
Fig.4: Electrolyte rejection vs pressure for fabricated membrane with different polymer concentration
178
179
Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
Fig. 5: SEM cross-sections of novel AULP membranes at different composition; (a) 13 % polymer; (b) 15 % polymer and (c)
17 % polymer
180
Feed
Concentration,
Cf (cfu/ml)
Permeate
Concentration,
Cp (cfu/ml)
Flux
(L/m2.h)
BRI
(%)
BRLI
(log)
7x106
342.47
100
>6
7x108
286.72
100
>6
7x106
616.44
100
>6
7x108
440.31
100
>6
7x106
725.22
100
>6
7x108
513.70
100
>6
6.
CHALLENGES
IN
FABRICATING
SUITABLE
MEMBRANE
FOR
WATER
TREATMENT APPLICATION
There are several parameters must be considered in
order to produce high performance membranes, such
as dope formulation, casting condition, ambient
temperature during membrane casting, shear rate,
membrane thickness and so on. Changes on each
parameter, may affect membrane properties, and
hence changing the membrane performance in
different application. In order to reproduce a high
performance membrane, all the parameters involved
during membrane fabrication must be recorded in
detail.
Another challenge is to produce membranes which
give good fluxes and rejection. These always become
a limitation when it comes to the flux and selectivity
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Challenges in Fabricating Suitable Membrane for Water Treatment Application
ACKNOWLEDGEMENTS
We would like to extend our gratitude to Ministry of
Science, Technology and Innovation (MOSTI) for
the fund with project No. 03-02-11-SF0161.
REFERENCES
Brock TD (1983). Membrane Filtration: A Users
Guide and reference Manual. Springer, New
York.
Cheryan M (1998). Ultrafiltration and microfiltration
handbook. Technomic Publishing, Lancaster,
2nd Edition, Florida.
Choi K Y J, Dempsey BA (2004). In-line coagulation
with low-pressure membrane filtration. Water
Research, 38: 42714281.
Drinking Water Contaminants (2006). Basic
information about E. coli O157:H7 in drinking
water.
http://www.epa.gov/safewater/contaminants/eco
li.html.
Fane AG, Yeo A, Law A, Parameshwaran K,
Wicaksana F, Chen V (2005). Low pressure
membrane processes ~ doing more with less
energy. Desalination, 185: 159-165.
Gupta
V
K,
Ali
I
(2013).
Water
Treatment by Membrane Filtration Techniques.
Environmental Water. 135-154.
Li S G (1993). Preparation of Hollow Fiber
Membranes for Gas Separation. Enschede.
Netherlands. 1-22
Hasan A A, Victor K, Nidal H (2013). Hybrid ion
exchange Pressure driven membrane
processes in water treatment: A review. Vol
116, 253264.
Hendricks D (2005). Water Treatment Unit Processes
Physical and Chemical. Taylor & Francis
Group, Boca Raton, 913-915.
Ismail AF, Hassan AR (2005). Formation and
Characterization of Asymmetric Nanofiltration
Membrane: Effect of Shear Rate and Polymer
Concentration. Journal of Membrane Science,
270: 57 72.
Ismail AF, Lai PY (2004). Development of defect-free
asymmetric polysulfone membranes for gas
separation using response surface methodology.
Separation and Purification Technology, Vol.
40 (2): 191-207.
Ismail AF, Rahman AR (2004). The deduction of fine
structural details of asymmetric nanofiltration
membrane using theoretical models. Journal of
Membrane Science, 231: 25-36.
182
1. INTRODUCTION
Heavy metals are inorganic pollutants commonly
found in wastewaters discharged from industries like
metal-plating, tanneries, batteries, automobile and
fertilizer manufacturing. The pollution of natural
water-bodies especially rivers by the metalcontaminated industrial effluents is becoming one of
the most serious environmental problems. Several
conventional methods had been widely adopted to
scavenge metal ions from aqueous solution including
ion exchange resins, electrodialysis, chemical
precipitation, adsorption and membrane separation.
However, the efficiency of these methods has been
constraint by some unsolved challenges such as
production of secondary sludge, low selectivity and
low metal-recovery efficiency (Lazaridis et al., 2004,
Dermentzis et al., 2009, Ghodbane et al., 2008).
In terms of low energy consumption and high
solute-rejection efficiency, ultrafiltration (UF) is
deemed as a promising membrane separation process
for the treatment of industrial wastewaters. The
average pore diameters of UF membranes fall within
the range of 10 1000 (1 100 nm). The pore
structures at this range of pore diameters allow
permeation of microsolutes with molecular weight
(MW) less than 300 g/mol. Nevertheless, copper
divalent ion (Cu2+) as a transition metal ion with
molar mass of merely 63.55 g is too low to be retained
by a UF membrane. The shortcoming of UF process
183
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
(1.1)
2. APPLICATION OF THERMO-RESPONSIVE
PNIPAM-co-AA POLYMER HYDROGEL AS
NOVEL CHELATING AGENT
Selection of a suitable chelating agent is important for
optimizing the efficiency of metal ions-complexing in
PEUF. Water-soluble polymers are usually chosen as
potential metal chelators due to the presence of
hydrophilic functional groups that act as ligands for
metal chelation such as amide (-CONH), carboxylate
(-COO-) and carbonyl (-C=O). These functional
ligands are Lewis acids or bases that donate electron
pair to fill the unoccupied d-orbital of a metal ion to
form a chelated complex (Flora and Pachauri, 2010,
Hancock and Martell, 1989).
There are numbers of studies reported on the use of
different water-soluble polymers as metal chelating
agents in PEUF processes. Among them,
polyethyleneimine (PEI), poly(vinyl sulfonic acid)
(PVSA) and poly(acrylic acid) (PAA) are the most
common chelators for the evaluation studies of PEUF.
Ca izares et al. (2002) applied water-soluble PEI
(MW = 25,000 g mol-1) and PAA (MW = 250,000 g
mol-1) for recovering Cu2+, Ni2+, Pb2+ and Cd2+ cations.
The affinity of these two types of polymer toward
metal ions are attributed to their metal-chelating
ligands like amines (-NH) groups in PEI and
carboxylic (-COOH) in PAA (Ca izares et al. 2002).
PEI also attracted interest from slamolu et al. (2006)
184
185
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
(a)
(b)
Fig. 1: Thermo-responsiveness of hydrogels: (a) before and (b) after copper complexation
4.1. Effect of pH
pH is a critical parameter for influencing the rate,
efficiency and stability of metal-polymer complex
formation by altering the charges of ligands. Most of
the polymers bearing functional groups like NH
(amine) and -COOH (carboxylic acid) as chelating
ligands are inactive for chelating metal ions at low pH
(< pKa) due to protonation of the functional groups
and electron donors are not available for donating
electrons to metal ion. As pH increases above pKa of
the acidic ligand of polymer, the functional group
(ligand) is deprotonated and increases affinity of the
ligand toward metal ion. Nevertheless, at high pH (
pH 6), the formation of insoluble metal hydroxide
precipitates reduces free metal ions from being
chelated by polymer ligands leading to a decline in
metal-chelating efficiency of the polymer.
In the case of copper, it exists as a hydrated
tetracopper cationic complex, [Cu(H2O)4]2+ at pH 6
in aqueous solution. At pH range of 3 5,
mononuclear complexes of one ligand (LM+) or two
ligands (L2M) are formed. In condition where the
concentration ratio of ligands to copper cations is low
(<10), formation binuclear complexes (two central
copper ions) is induced at pH 4 8. Then at pH 6,
insoluble hydroxide species of copper, Cu(OH)2 is
precipitated. In the presence of high concentration of
carboxylate ligands, Cu(OH)2 tends have hydrophilic
interaction with the polymer ligands through hydrogen
bonds. The formation of binuclear, mononuclear
copper-ligand complexes and Cu(OH)2 species leads
to the increase in adsorption capacity of polymer
hydrogels with increasing solution pH at range of pH
4 7 (Yao et al., 2010, Powell et al., 2007, 2011).
Figure 2 shows the pH effect on copper removal
efficiency in percentage % in the presence of
PNIPAM-co-AA hydrogels. A sharp increase
186
5.
MEMBRANE
FOULING
CONCENTRATION POLARIZATION
LAYER FORMATION)
BY
(GEL
187
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
Fig. 4: Plot of qe of PNIPAM-co-AA as a function of C0 at different temperatures (303, 313 and 323 K).
188
(a)
(b)
Fig. 5: Effect of P-30 hydrogel concentrations on: (a) permeate flux and (b) Cu 2+ rejection (50 ppm Cu2+ in feed; T = 303 K;
pH =5; transmembrane pressure, P = 1.5 bar).
6. CONCLUSION
The authors wish to thank the financial support
granted by Ministry of Higher Education Malaysia
(MOHE) FRGS (203/PJKIMIA/6071252)
189
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
(a)
(b)
(c)
(d)
Fig. 6: AFM images of membrane surface after PEUF processes for different hydrogel concentration: (a) 0.01 g L-1, (b) 0.1 g
L-1, (c) 0.5 g L-1 and (d) 0.7 g L-1.
REFERENCES
190
191
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
192
193
1. INTRODUCTION
The anthropogenic emissions of metallic elements
globally ends up to wastewater and industrialization
caused a lot of environmental problems .Heavy metals
spectacular Zn, Cu, Ni and Cr are most common
contain of industrial wastewater (Sun and Shi, 1998).
For example recently report from China indicate that
anthropogenic emissions of cadmium to atmosphere
from 1990 to 2010 increased from 474 to 2186 ton
(Shao et al., 2013). Most Cd is emitted to the
atmosphere at the first stage and then precipitate on to
water and soil (Yamagata, 1979). Meanwhile
vulnerability of ground water as drinking water
sources, is higher than surface water (Landmeyer,
2012). levels of arsenic in groundwater sources is
higher in comparing with surface-water sources
(Bissen and Frimmel, 2003). On the other hands,
concentrate ions and accumulation of some pollutants
same as 137Cs in aquatic media are higher than
sediment or soils (Ashraf et al., 2013), so it shows
critical statue of decontamination of wastewater (Shao
et al., 2013).
2. PYTOREMEDIATION
Phytoremediation is vast, emerging term which has
been used in recent decades for a group of green
ecofriendly technologies that fundamentally based on
plants (aquatic, semiaquatic and terrestrial) and
related associated enzymes, microorganism and water
consumption, uptake, remove, retain, transform,
degrade or immobilize contamination (organic and/or
inorganic) with different origin, from soil, sediment
and aquatic media or atmosphere (Mueller et al., 1999,
Pivetz, 2001, Ghosh and Singh, 2005; Vishnoi and
Srivastava, 2007; Mulbry et al., 2008; Ridzuan et al.
2010, Dhir 2013). To sum it up, phytoremediation in
aquatic media is directly up take and accumulation of
contaminant from water media and assimilation by
194
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Wastewater Treatment by Phytoremediation Methods
2.5. Phytovolatilization
This kind of phytoremediation involves the utilization
of plants to take up pollutions from contaminated
media, transforming them into volatile form and
finally
transpiring
them
into
the
air.
phytovolatilization normally occurs in plants for up
taking water, organic and inorganic compounds so
some of contamination can pass through the plant
parts to the leaves and at low concentration ,volatilize
into the atmosphere (Mueller et al., 1999) In a
nutshell, the use of plant species for volatilize
contaminants from the leaves which can use for soil
and sediment pollutions (Mueller et al., 1999) air
contaminations (Burken and Schnoor, 1999) and water
195
2.6. Phytodegradation
Phyodegradation or phytotransformation refers to two
kind of plant reactions it is independent on
rhizospheric microorganisms (Vishnoi and Srivastava,
2007) contain phytoreduction which is the reductive
transformation of oxidized organic compounds by
reducing plant enzymes and phytooxidation which is
the oxidative transformation reactions catalyzed by
plant oxidizing enzymes (Nzengung and Jeffers,
2001).Plant
enzymes
contain
five
various
nitroreductaces (Schnoor et al., 1995), dehalogenase
and oxygenase (Vishnoi and Srivastava, 2007)
degrade
organic
compounds.
The
main
phytodegradation process for organic contamination in
plants are, uptake, translocation and metabolism
(Dzantor et al., 2002).Taken up of most of Polycyclic
aromatic hydrocarbons (PAHs)is hard for plants and
less suitable for phytodegradation (Reichenauer and
Germida, 2008). Some of the main organic compound
that successfully degraded by plant species are
hexachloroethane
(HCA),
dichlorodiphenyltrichloroethane (DDT) (Nzengung
and Jeffers, 2001) and carbon tetrachloride (Wang et
al., 2004). Inorganics compounds like as sulfur oxides
and atmospheric nitrogen oxides can be taken up by
plants for degradation. Genetically modified plant
species also had been used for phytodegradation (Doty
et al., 2000).
2.8. Phytomining
Phytomining or bio-ore is a green technology which
could generate revenue from saleable metallic
elements that accumulated in ash of plants biomass
(Ghosh and Singh, 2005). Mining of nickele has been
already a patented technology (Chaney et al., 1998).
Normally phytomining occurs in situ at the
contaminated mine lands or sub-economical ore
(Anderson et al., 1998). Phytoextraction or
bioextraction of metals for commercial gain contain
cropping, harvesting, drying and ashing are main
process of phytomining (Sheoran et al., 2009). Cattails
(Typha latifolia) used for absorbing boron (B) from
the effluent of biggest borax mine of the world and
250mgkg-1 boron absorbed in constructed wetland
system (Trker et al., 2013).
2.9. Phytostabilization
This technology applied for decreasing bioavailability
of contamination from environment and stabilizing of
pollutants
occurs
more
than
removing
them(commonly metallic elements) by plants
(hydraulic control) ? (Padmavathiamma and Li, 2007).
Enhancing appropriate soil modification by plants
,caused to decreasing bioavailability of metallic
elements on the other hands plant cover decreased
leaching and enhance environmental protection
(Houben et al., 2011).Plants can help to stabilize
pollutants with up taking in adsorption system or
accumulate them in root system (Vangronsveld et al.,
2009). Plant selection for phytostabilizing is a critical
issue
and
perennial
species,
well
local
environmentally adapted ,high biomass production
and high resistance to pollution recommended (PilonSmits, 2005). Since there is no natural
hyperaccumulator phytoremediator
for mercury
controlling this toxic metallic element is critical so
Indian mustard (Brassica juncea L.) reported as a
suitable plant species for stabilization of mercury in
soil and wastewater (Shiyab, Chen et al. 2009).
Aquatic plant Hydrilla verticillata reported as
2.7. Rhizodegradation
Rhizodegradation
is
breakdown
organic
compounds(fuels and solvents) to plants nutrients in
rhizospher trough microbial (fungi, yeast , bacteria
and other microorganisms )activity which is very
slower than phytodegradation process and also called
phytostimulation (Hutchinson et al., 2003; Ghosh and
Singh, 2005; Ridzuan et al., 2010).This technology
widely applied in treatment of soils so that in
Germany there are more than 100 years background
for rhizoremediation (Wand et al., 2002). Generally,
plant exudates same as carboxylic , amino acids and
carbohydrates are capable to stimulate entire
rhizosphere
microbial
action
and
enhance
rhizodegradation proceeding (Dzantor, 2007) Some of
196
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Wastewater Treatment by Phytoremediation Methods
2.11. Phycoremediation
Phycoremediation is using macro and micro algae for
bio transforming or removing pollutions from
wastewater furthermore CO2 as air pollution from
waste air (Mulbry et al., 2008; Rawat et al., 2011).
Algae is a suitable plant for decontamination of
metallic elements, xenobiotic, nutrients in various
wastewater and consume of carbon dioxide from
exhausts ( gu , 2003). Micro algae is a capable
plant for treatment of various type of wastewater such
as industrial wastewater ,domestic wastewater and
solid wastes both aerobically and anaerobically
(Safonova et al., 2004). For this technology ,oldest
scientific research carried out in half century ago
(Oswald and Gotaas, 1957). In a pilot study on
chrome sludge, phycoremediation with Desmococcus
olivaceus
could effectively decrease nitrate,
phosphate, ammonia, TDS ,TSS
and chrome
(Sivasubramanian et al., 2010). Fresh water blue green
algae used successfully for treatment of dairy manure
effluent(Mulbry et al., 2008). Sewage water treated by
different algae and Chlorella vulgaris could remove
almost all of contaminations and after treating process
it can be thrown in water bodies 1n 2013.
2.10. Phytofiltration
Phytofiltration or rhyzofiltration is a green technology
for removing contaminations by plants roots in aquatic
media like as ground water, most of wastewaters and
extracted ground water (Pivetz, 2001; Mukhopadhyay
and Maiti, 2010). Terrestrial, aquatic and wetland
plants are suitable material for phytofiltration and
constructed wetlands are the best method for
removing metallic elements from wastewater (Cheng
et al., 2002). Limnocharis flava (L.) reported as
suitable plant species for phytofiltration of low
concentration Cd contaminated water (Abhilash et al.
2009) Wolffia globosa is a suitable nominated for
arsenic metabolism studying via phytofiltration
(Zhang et al. 2009).For effective accumulation of
cadmium and hyperaccumulation of arsenic,
micranthemum umbrosum introduced as suitable
macrophyte (Islam et al., 2013). Indian mustard
(Brassica juncea (L.) Czern) could uptake 95%
mercury from contaminated water via phytofiltration
(Moreno et al., 2008). Aquatic plants, Pteris
creticacvMayii (Moonlight fern) and Pteris.vittata
(Chinese brake fern) as arsenic hyperaccumulator
plants, used via phytofiltration (Alkorta et al., 2004;
Tu et al. 2004; Baldwin and Butcher, 2007). The
mechanism of phytofiltration is similar to
phytoextraction containe 1) chemisorption 2)
complexation 3) ion exchange 4)micro precipitation
5)hydroxide condensation 6) surface adsorption
(Cheng et al., 2002; Gardea-Torresdey et al., 2004).
Plant specification in phytofiltration should be 1)
tolerance to high level of metallic elements 2) facile
handling 3) high root biomass or surface area 4)
reasonable maintenance cost 5) least secondary waste
requirement (Dushenkov, 2003).
2.12. Phytoextraction
Phytoextraction /phytoaccumulation (Khan et al.,
2000) can be considered as suitable green technology
for removing metallic elements from aquatic media
(Wang et al., 2008). This kind of remediation used for
accumulation of Zinc by duckwood (Lemna gibba)
(Khellaf and Zerdaoui, 2009), Cadmium by water
spinach (Ipomea aquatic) (Wang et al., 2008),
Chromium with small pondweed
(Potamogeton
pusillus) in presence of Cu2+ (Monferrn et al., 2012).
recently reported study carried out for accumulation of
Pb by Ceratophyllum demersum and Myriophyllum
spicatum and finally introduced as phytoremediator
and bioindicator of Pb. (El-Khatib et al., 2014) Water
hyacinth (Eichhornia Crassipes) used for removing
heavy metals from coastal water (Agunbiade et al.,
2009), Crude oil from artificial wastewater amended
by urea fertilizer (Ndimele and Ndimele 2013) and
palm oil mill effluent treatment (Christwardana and
Soetrisnanto, 2013). Furthermore, heavy metals from
industrial wastewater have been removed by vetiver
(Chrysopogan zizanioides) (Roongtanakiat, 2009).
3. HEAVY METAL
Generally speaking, heavy metals which nowadays
known as metallic elements (Mbengue et al., 2014),
confined as element with density higher than 4.5- 5
mg mL-1 /kg dm -3 (Sarkar, 2002)but the collective
197
Fig. 1: Relative uptake and biological accumulation potential in plant species (Bradl, 2005)
198
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Wastewater Treatment by Phytoremediation Methods
4. HYPERACCUMULATORH
Hyperaccumulator used as first time in 1948 by Italian
scientist (Fingerman and Nagabhushanam, 2005). The
plant spices which accumulate heavy metals more
than 1% dry weight, named hyperaccumulator
(Zavoda et al., 2001). Most common aquatic
hyperaccumulators
are
Spirodelta
polyrhiza,
Eichhornia crassipes and Elodeu nuttali (Dhir et al.,
2009), meanwhile Marchand reported there is no
aquatic hyperaccumulator plant species(Marchand et
al., 2010). Tow pictures of native natural terrestrial
hyperaccumulator plants(Figure 2 and Figure 3)
collected in China and Malaysia(Xue et al. 2004; van
der Ent et al., 2013) .Effective phytoremediation
highly correlated to suitable plant selection
(Manousaki, Kadukova et al., 2008).High biomass
,deep and/or wide roots, easy harvesting easily
provide renewable energy and resistance to high
concentration of pollutant are common characters of
phytoremediators (Ghosh and Singh, 2005).
Collecting plants from high polluted area is scientist
preferred method for finding metallic elements
hyperaccumulators (Gleba et al., 1999).Through the
all plant species only 400 species (Brooks, 1998) or
500 species (Ma et al., 2001)reported as
hyperaccumulators. Heavy metals hyperaccumulators
belong to approximately 500 tax of angiosperm (less
than 0.2%) (Krmer, 2010). Recently study in China
introduced three aquatic hyperaccumulator species
for heavy metals Najas marina for arsenic (As) and
cadmium (Cd), Vallisneria natans for lead (Pb) and
Ceratophyllum demersum for cobalt (Co), chromium
(Cr) and ferrum (Fe) plant species selection for this
study carried out from native nominated plants from
5. FUTURE STUDIES
Micro propagation is the best way for mass production
of some aquatic machrophyte, since produce a lot of
unique genetically plants in short time for analytical
data collection (Kan et al. 1990),which may use for
phytoremediation of contamination particular metallic
elements, first report in this area reported by (Delmail
et al., 2013), There is no reports on natural Mercury
phytoremediator plants(Shiyab et al., 2009)and high
toxicity of this element for human (Harris et al.
2003)presents a critical circumstance for introducing
suitable candidate for phytoremediation of Mercury.
A genetically studying is trying to make Hg
hyperaccumulator by the
Meagher laboratory
(Fingerman and Nagabhushanam, 2005).Nowadays
researches on different concentration of heavy metals
in sediments, soil and water, in unique case study also
(Falinski et al. 2014), introducing suitable spectacular
plant species for water, soil and sediment
phytoremediation(Nan, et al., 2013) and using
different enhancers like as microbial and Zeolite in
phytoremediation process(Karimzadeh et al., 2012) is
leading researches toward using constructed wetland
(CW) as a complete ecological system for treating
wastewater
spectacular
for
continues
phytoremediation in practical treatment for example
removing metals from road runoff (Borne et al.
2014),electric industry wastewater (Yang et al., 2013)
fresh oilfield produced water (Alley et al., 2013).
199
Metallic
elements
Pb2+
Cd
Talinum Triangular
Cyperus rotundus L.
Pteris vittata L.
Nasturtium officials
diplazium Esculentum
Eichhornia crassipes
(Ash)
pistia stratiotens
Lemna minor
Ceratophyllum demersum
Lemna gibba
Eleacharis acicularis
Salvinia minima (fern)
As
Heavy
metals
Cd
Hg
Pb, Cr
Heavy
metals
Pb2+
Results
Media
Reference
Artificially polluted
water
Sediment
(Snchez-Galvn et al.,
2008)
(Clabeaux et al., 2011)
Hydroponic system
hydroponic
experiment
Sediment soil
water
Artificially polluted
water
surface waters
Natural lake water
Artificially
contaminated water
abandoned mining and
sediment
artificially
contaminated
water
electric industries
waste water
artificially
contaminated
water
aquatic media
24 eutrophic lakes
local river
hydroponic system
Surface water
Artificially
contaminated water
Storm water
Artificially
contaminated water
Industrial wastewater
electroplating factory
wastewater
Artificially
contaminated water
Sediment and water
Gujarat wetland
Artificially
contaminated water
Fe, Mn,
Cu, Cd,
Pb, Cr
Fe,Zn,Cu,
Cr,Cd
Accumulation of Pb
increased Glutathiane
synthase
Suitable
Bioindicators or
bioaccumulator
3 Suitable
phytoremediators
Cd,Cu
Hyperaccumulator
Heavy
metals
Leersiahexandra
Cs
Sr
Mn,
Fe,Cu,Zn,
Pb
Cr
1-As and Cd
hyperaccumulator
2- Co,Cr and Fe
hyperaccumulator
3-Pb hyperaccumulator
Zn and Cd
hyperaccumulator
May be hyperaccumulator
for Pb2+
Cr,Cu,Fe,Mn,Ni,Pb, and
Zn hyperaccumulator
The roots are effective in
absorbing most of Cd and
Ni
These plants are the most
efficient plant for up taking
heavy metals
Ideal hyperaccumulator
For radionuclides
Harvested plant safely can
use for compost or
handicrafts
Hyperaccumulator
Callitriche cophocarpa
Cr
Suitable bioaccumulator
Eichhorna crassipes
Ipomea aquatic
Typha angustata
Lemna minor
Zn,Cu,Pb,
Ni, Co,Cd
Echonrnnia crassipes
Spirodela polyrhiza
Eichhornia crassipes
Spirodela polyrrhiza
pistia stratiotens
Myriophyllum
aterniflorum
1-Najas marina
2-Ceratophyllum
demersum
3-Vallisneria natanas
Alternantbera philoxeroids
Myriophyllum vercillatum
Pistia stratiotes L.
Eichhorna crassipes
Potamogeton natans
Alismaplantago aquatica
Filipendula ulmaria
Catharanthus roseus
heavy
metals
Pb,Cu,Cd
and Zn
heavy
metals
Cd,Ni
Cu,Zn,Pb
137
90
Chrysopagann zizanioides
Pb
200
(Roongtanakiat, 2009)
Faraji
Wastewater Treatment by Phytoremediation Methods
REFERENCES
Abdallah MAM (2012). Phytoremediation of heavy
metals from aqueous solutions by two aquatic
macrophytes, Ceratophyllum demersum and
Lemna gibba L. Environmental technology,
33(14): 1609-1614.
Abhilash P, Pand VC, Srivastava P, Rakesh P,
Chandran S, Singh N, Thomas A (2009).
Phytofiltration of cadmium from water by
Limnocharis flava (L.) Buchenau grown in freefloating culture system. Journal of hazardous
materials, 170(2): 791-797.
Abioye O, Agamuthu P, Aziz A (2012).
Phytotreatment of soil contaminated with used
lubricating oil using Hibiscus cannabinus.
Biodegradation, 23(2): 277-286.
Agunbiade FO, Olu-Owolabi BI, Adebowale KO
(2009). Phytoremediation potential of Eichornia
crassipes in metal-contaminated coastal water.
Bioresource Technology, 100(19): 4521-4526.
Ahmad, A., R. Ghufran and A. Zularisam (2011).
"Phytosequestration of metals in selected plants
growing on a contaminated Okhla industrial
areas, Okhla, New Delhi, India." Water, Air, &
Soil Pollution, 217(1-4): 255-266.
Ahmad F, Kan AU, Yasar A (2013) Comparative
Phycoremediation of Sewage Water by Various
Species of Algae. Proceedings of the Pakistan
Academy of Sciences, 50(2): 131139.
Alkorta I, Hernndez-Allica J, Becerril J, Amezaga I,
Albizu I, Garbisu C (2004). Recent findings on
the phytoremediation of soils contaminated
with environmentally toxic heavy metals and
metalloids such as zinc, cadmium, lead, and
arsenic. Reviews in Environmental Science and
Biotechnology, 3(1): 71-90.
Alkorta I, Hernndez-Allica J, Becerril J, Amezaga I,
Albizu I, Onaindia M, Garbisu C (2004).
Chelate-enhanced phytoremediation of soils
polluted with heavy metals. Reviews in
Environmental Science and Biotechnology,
3(1): 55-70.
Alkorta I, Hernndez-Allica J, Garbisu C (2004).
Plants against the global epidemic of arsenic
poisoning. Environment international, 30(7):
949-951.
Alley BL, Willis B, Rodgers J, Castle JW (2013).
Water depths and treatment performance of
pilot-scale free water surface constructed
wetland treatment systems for simulated fresh
oilfield
produced
water.
Ecological
Engineering, 61: 190-199.
Anamika S, Eapen S, Fulekar MH (2009).
Phytoremediation technology for remediation of
201
202
Faraji
Wastewater Treatment by Phytoremediation Methods
203
204
Faraji
Wastewater Treatment by Phytoremediation Methods
205
Submerged
Macrophytes:
Looking
for
Hyperaccumulators in Eutrophic Lakes.
Environmental science & technology, 47(9):
4695-4703.
Xue S, Chen Y, Reeves RD, Baker AJ, Lin Q,
Fernando DR (2004). Manganese uptake and
accumulation by the hyperaccumulator plant
Phytolacca acinosa
Roxb.(Phytolaccaceae).
Environmental Pollution, 131(3): 393-399.
Yamagata N (1979). Industrial emission of cadmium
in Japan. Environmental Health Perspectives,
28: 17.
Yang L, Wu Z, Wu J, Zhang Y, Li M, Lin Z,
Bauelos G (2013). Simultaneous removal of
selenite and electricity production from Seladen wastewater by constructed wetland
coupled with microbial fuel cells. Selenium in
the Environment and Human Health, 212.
Yifru DD, Nzengung VA (2008). Organic carbon
biostimulates rapid rhizodegradation of
perchlorate. Environmental Toxicology and
Chemistry, 27(12): 2419-2426.
Yoon J, Cao X, Zhou Q, Ma QL (2006).
Accumulation of Pb, Cu, and Zn in native
plants growing on a contaminated Florida site.
Science of the Total Environment, 368(2): 456464.
Zavoda J, Cutright T, Szpak J, Fallon E (2001).
Uptake, selectivity, and inhibition of
hydroponic treatment of contaminants. Journal
of environmental engineering, 127(6): 502-508.
Zhang XH, Liu J, Huang HT, Chen J, Zhu YN, Wang
DQ (2007). Chromium accumulation by the
hyperaccumulator plant Leersia hexandra
Swartz. Chemosphere, 67(6): 1138-1143.
Zhang X, Zhao FJ, Huang Q, Williams PN, Sun GX,
Zhu YG (2009). Arsenic uptake and speciation
in the rootless duckweed Wolffia globosa. New
Phytologist, 182(2): 421-428.
206
207
Abstract. Production of raw leachate from landfills regards as shortcoming for the sanitary landfills. Unprocessed landfill
leachate requires treatment prior disposal to the natural environment. In this work, leachate channeling, biological, and
physical-chemical treatment processes for treatment of formed landfill leachate were presented in details. Definite treatment
processes were resulted in high removal of pollutants such as ammonia (NH3-N), chemical oxygen demand (COD),
biochemical oxygen demand (BOD5), phenols, color etc. Practically, age of produced leachate have influence on the treatment
systems. Efficient treatment methods were explained for fresh, medium, and stabilized landfill leachates.
Keywords: Landfill, leachate, treatment, municipal solid waste, pollutants, removal efficiency
1. INTRODUCTION
Sanitary landfill is the most common municipal solid
waste (MSW) disposal method due to such advantages
as simple disposal procedure, low cost, and landscaperestoring effect on holes from mineral workings.
However, the production of highly contaminated
landfill leachate is a chief weakness of this system
(Aziz et al., 2010). The generation of highly
contaminated leachate that can seep into the ground
and contaminate the ground water, surface water, and
soil is principally a main negative aspect associated to
municipal sanitary landfill disposal method (Bashir et
al., 2012. Additionally, leachate is liquid contain large
amounts of organic compounds measured as chemical
oxygen demand (COD), biochemical oxygen demand
(BOD5), ammoniacal nitrogen (NH3-N), halogenated
hydrocarbons
suspended
solid,
significant
concentration of heavy metals, and inorganic salts
(Aziz, 2013; Bashir et al., 2012; Aziz et al., 2010;
Uygur and Kargi, 2004).
If not treated and disposed safely, landfill leachate
could be a major source of water contamination
because it could percolate through soil and subsoil,
causing high pollution to receiving waters. Thus, the
treatment of hazardous leachate constituents before
discharge has been made a legal requirement to
prevent pollution of water resources and to avoid both
acute and chronic toxicities (Aziz et al., 2011).
To reduce the negative impacts of discharged
leachate on the environment, several techniques of
water and wastewater treatment have been used,
including aerobic and anaerobic biological treatment,
chemical and electrochemical oxidation processes,
chemical precipitation, adsorption using various
2. LANDFILL LEACHATE
2.1 Types of leachate based on landfill design
According to Yamamoto, (2002) and Matsufuji et al.
(1993), in an anaerobic landfill, solid wastes are
dumped in an excavated area of a plane field, which is
filled with water in an anaerobic condition. Typically,
anaerobic sanitary landfills are recognized by its
sandwich-shaped cover. On the other hand, semiaerobic landfills have a leachate collection duct. The
opening of the duct is surrounded by air, and the duct
is covered with small crushed stones. Moisture
content in solid waste is small, and oxygen is supplied
to the solid waste from the leachate collection duct.
The schematic diagram of anaerobic and semi-aerobic
(Fukuoka method) landfills is demonstrated in Figure
1 (JICA, 2005). Characteristics of fresh landfill
leachates at semi-aerobic and anaerobic landfills are
given in Table 1.
208
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
209
Fig. 2: Diagram of landfill leachate treatment techniques, based on Abbas et al. (2009); Renou et al. (2008)
210
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
211
Table 1: Characteristics of raw leachate at semi-aerobic and anaerobic landfills (Aziz et al., 2010)
Semi- aerobic Pulau Burung site
No.
Intermittently aerated
Anaerobic
Averagea
1.2
483
Range
2.85-10.5
700-1800
Averagea
6.7
1200
Range
1-5.25
100-600
Averagea
2.6
300
Discharge limit b
1
2
Phenols (mg/L)
Total nitrogen (mg/L N-TN)
360-730
542
1145-2150
1568
130-1039
538
900-3200
2200
2900-7900
5233
400-2600
1283
Unaerated
Standard B
Range
0.35-2.07
200-700
Parameter
Kulim site
44-270
91
20-120
49
30-60
52
10-43.0
21
10.0-25
17
8.0-40
19
84-274
141
94-210
159
57-197
94
67-93
83
146-336
243
135-476
326
50
COD (mg/L)
600-1300
935
1680-4020
2345
630-2860
1892
100
10
11
BOD5/COD
pH
0.051-0.12
8.05-8.35
0.096
8.20
0.036-0.186
8.14-8.37
0.124
8.28
0.088-0.35
6.93-8.26
0.205
7.76
0.5
5.5-9
12
10.14-13.630
12.17
21.500-22.500
22.10
5.250-13.92
8.55
13
Turbidity (FAU)
600-3404
1546
149-211
180
490-4500
1936
14
1944-4050
3334
2310-4390
3347
1950-7475
4041
15
5138-7404
6271
8860-11084
9925
4520-10568
6336
16
906-2220
1437
374-1372
837
232-1374
707
100
17
2-29.5
7.9
0.9-8.8
3.4
0.6-11.4
5.3
18
0-3
0.6
0.01-2
0.5
0-1
0.2
19
Total coliform
<50
(0.77-0.85)x104
0.81x104
20
E-Coli
0.00
(0.18-0.22)x104
0.20x104
212
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
Table 2: Effectiveness of leachate treatment techniques versus leachate age (Abbas et al., 2009)
No.
Type of treatment
Medium (5-10)
Old (>10)
Good
Fair
poor
Good
Fair
poor
Aerobic processes
Good
Fair
poor
Anaerobic processes
Good
Fair
poor
Coagulation/flocculation
Poor
Fair
Fair
Chemical precipitation
Poor
Fair
Poor
Adsorption
Poor
Fair
Good
Oxidation
Poor
Fair
Fair
Stripping
Poor
Fair
Fair
10
Ion exchange
Good
Good
Good
11
Microfiltration
Poor
12
Ultrafiltration
Poor
13
Nanofiltration
Good
Good
Good
14
Reverse osmosis
Good
Good
Good
213
214
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
Anaerobic filter
Anaerobic filter method is a high rate system that
collects the advantages of other anaerobic methods
and decreases the shortcomings. The filtration process
may be down-flow or up-flow. Packed filter media
provides the mechanism for separating the solids and
the gas that are produced within the digestion process.
In an up-flow anaerobic filtration process, biomass is
retained as biofilms on the supporting material, such
as plastic rings (Nedwell and Reynolds, 1996). At
loading rates of 1.26-1.45 kg/m3/d of COD and for
different ages of landfill leachate, anaerobic filter
removed 90% of COD. Further, anaerobic filter
resulted in total biogas production ranged between
400 to 500 Lgas/kg COD destroyed and methane
content of 75% and 85% (Henry et al., 1987).
Anaerobic SBR
Anaerobic SBR is a type of suspended-growth
digester. Some studies have shown good
performances of anaerobic SBRs. These technologies
are able to obtain solid capture and organic lowering
in one reactor (Timur and Ozturk, 1999). Uygar and
Kargi (2004) used lab-scale SBR for the reduction of
nutrient from pre-treated leachate. The researchers
reported that, at the end of cycle time of 21 h,
sequential anaerobic/aerobic operations offered
removal efficiencies of 62% for COD, 31% for NH3-
215
Hybrid filter
Hybrid bed filter consists of an up-flow sludge
blanket at the bed and an anaerobic filter on the top.
This technique acts as a gas-solid separator and
improves solids retention without causing
channelling or short-circuiting. A hybrid bed filter
(consisted of anaerobic filter and up-flow anaerobic
sludge blanket reactor) with a filter volume of 2.75 L
and HRT of 2.4 d at temperature of 35 oC resulted in
removal of about 37.5 to 76 % COD from landfill
leachate (Timur and Ozturk, 1997). Nedwell and
Reynolds(1996) showed steady state COD removal
efficiencies of 81-97% under methanogenic digestion
was based on organic loading rate; and effective
treatment occurred up to a volumetric COD loading
rate of 3.75 kg COD/m3d1. One disadvantage of
hybrid bed filter, as well as anaerobic filter, is the
additional cost of the supporting media.
Fluidized bed filter
Imai et al. (1993) applied microorganism-attached
activated carbon fluidized bed technique for the
treatment of real landfill leachate containing
refractory organics and a high concentration of NH4N. They reported that the microorganism-attached
activated carbon fluidized bed method removed about
60% and 70% of refractory organics and nitrogen,
respectively. A number of researches on carbonassisted fluidized beds have been conducted (Gulsen
and Turan, 2004; Suidan et al., 1993). Suidan et al.
(1993) stated that about 82% of COD was removed
from leachate via fluidized bed reactor at temperature
of 35 oC and volume of 7.9 L.
3.3. Physical/chemical treatment
Physico-chemical processes are used along with the
biological processes generally to enhance treatment
efficiency or to enhance biodegradability when the
biological oxidation method is disadvantaged by the
occurrence of bio-refractory materials. A number of
physical/chemical treatment techniques which
includes coagulation/flocculation, flotation, chemical
precipitation, adsorption, ammonium stripping,
chemical oxidation, ion exchange, electrochemical
oxidation, and membrane filtration are used for
removing non-biodegradable (humic and fulvic acid)
and/or unwanted compounds (such as heavy metals)
from the landfill leachate (Abbas et al., 2009; Renou
et al., 2008; Zouboulis et al., 2004)
3.3.1. Coagulation/flocculation
Coagulationflocculation technique is considered as a
simple physicalchemical process in landfill leachate
treatment (Aziz et al. 2009; Ghafari et al., 2009). It is
216
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
3.3.2. Flotation
3.3.4. Adsorption
217
218
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
ii) Ultrafiltration
Ultrafiltration is a selective process utilizing pressures
up to 10 bar. This technique is efficient to remove
suspended matters either by direct filtration or with
biological treatment to replace sedimentation unit. It is
strongly dependant on the kind of material
constituting the membrane. Syzdek and Ahlert (1984)
proposed that this process might prove to be useful as
a pre-treatment method for reverse osmosis. It could
be employed to eliminate the larger molecular weight
components of leachate that tend to foul reverse
osmosis membranes (Bohdziewicz et al., 2001;
Rautenbach et al., 1996). COD removal of 50% was
obtained by using ultrafiltration alone (Bohdziewicz et
al., 2001)
Lastly, Tabet et al. (2002) reported that
ultrafiltration membranes have been successfully
employed in full scale membrane bioreactor plants by
combination of bioreactors and membrane technology.
High levels for landfill leachate treatment have been
obtained by using this method.
iii) Nanofiltration
Because of its unique properties between
ultrafiltration and reverse osmosis membranes,
nanofiltration has discovered a place in the
elimination of refractory organic compounds and
219
4. CONCLUSIONS
Design of landfill, age of landfill leachate, climate etc.
have great effect on leachate treatment. In this work,
detailed review on various treatment techniques were
explained. Results revealed that combined treatment
with domestic sewage, recycling, and biological
systems are efficient for processing young landfill
leachate. Commonly, physical-chemical treatment
methods are competent for treating medium and
old/stabilized leachates. Further, augmenting physical
and chemical methods or biological and physicalchemical processes enhanced treatment of stabilized
leachate.
REFERENCES
Abbas AA, Jingsong G, Ping LZ, Ya PY, Al-Rekabi
WS (2009). Review on landfill leachate
treatments. Journal of Applied Sciences
Research, 5(5): 534545.
Adlan MN, Palaniandy P, Aziz HA (2011).
Optimization of coagulation and dissolved air
flotation (DAF) treatment of semi-aerobic
landfill leachate using response surface
methodology (RSM). Desalination, 277(13):
7482.
Aghamohammadi N (2006). Semi-aerobic leachate
treatment using powdered activated carbon
augmented
activated
sludge
process.
Unpublished, M.Sc. thesis, School of Civil
Engineering, Universiti Sains Malaysia.
Ahn S, Congeevaram S, Choung YK, Park J (2008).
Enhanced phenol removal by floating fungal
populations in a high concentration phenolfed
membrane bioreactor. Desalination, 221: 494
501.
Ahn WY, Kang MS, Yim SK, Choi KH (2002).
Advanced landfill leachate treatment using an
integrated membrane process. Desalination,
149: 109l 14.
Akkaya E, Demir A, Karadag D, Varank G, Bilgili
MS, Ozkaya B (2010). Post-treatment of
anaerobically treated medium-age landfill
leachate.
Environmental
Progress
and
Sustainable Energy, 29(1): 7884.
Al-Hamadani YAJ, Yusoff MS, Umar M, Bashir
MJK, Adlan MN (2011). Application of
psyllium husk as coagulant and coagulant aid in
semi-aerobic landfill leachate treatment. Journal
of Hazardous Materials, 190: 582587.
Al-Rekabi WS, Qiang H, Qiang WW (2007). Review
on sequencing batch reactors. Pakistan Journal
of Nutrition, 6(1): 1119.
Al-Shamrani AA, James A, Xiao H (2002). Separation
of oil from water by dissolved air flotation.
220
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
221
222
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
223
224
225
1. INTRODUCTION
Design and analysis of experiments (DOE) have been
widely used in planning, analyzing and running
experiments in different areas of research, such as
wastewater treatment, food analysis, material
production and medication intake helping the
researchers to achieve the research objective with less
effort, cost and time. The application of DOE in
wastewater industries has increased since the
application of experimental design and analysis of
experiments enables us to collect data effectively and
reduce the error by excluding non-significant factor/s
in the experiment and effectively improves the results
to the target range. Three basic principles should be
considered in using experimental design, namely,
replication, randomization and blocking. Replication
allows experimenter to get an estimation of
experimental error and to increase the precision.
Randomization is the allocation of the experimental
materials and the order that the individual runs or
trials of experiment are to be carried out in random
manner. Furthermore, randomization eliminates bias
and to make sure independence among the
observations. Blocking technique is used to enhance
the accuracy by reducing or eliminates variability that
may affect the response (output) such as the difference
in skills of two or more operators and weather
conditions (rainy, cloudy, sunny) (Montgomery, 2012).
Researchers should provide clear objective of the
project before using experimental design, for instance
number of input variables and levels of each variable
(the region of each selected variable). As an example,
an outcome of an experiment includes the
identification of which factors contribute to overall
wastewater treatment process, for instance the factors
involved may include chemical dosing and total
retention time, while their levels may be 100g/L or
500g/L of chemical dosing and 3 days or 7 days for
the total retention time.
226
Lim et al.
Application of Optimization in Wastewater Treatment
3. FACTORIAL DESIGN
Factorial designs are designs consist of several factors
(input variables) that influence one or more responses.
The advantage of factorial designs is to study the
effect of several factors and the interaction between
different factors
simultaneously whilst
the
disadvantage appears when the number of factors
included in the study increases which result in
increasing of the number of experiments. General
factorial design studies experiments with more than
one factor; each has at least two levels while special
cases of factorial designs are two-level factorial
design 2k and three-level factorial design 3k.
xi
(1)
Example 3.1
Suppose a 25-1 two-level fractional factorial designs
with 16 runs were used to study the effects of
concentration of phenolic compounds, adsorbent
dosage, contact time, temperature and shaking speed
on phenolic compound removal (y) in wastewater.
The levels of each factor in coded and actual forms
are given in Table 1. The data for this experiment in
actual levels are given in Table 2.
Symbol
Levels
Actual
Coded
x1
20
40
-1
x2
0.10
0.30
-1
x3
120
300
-1
Temperature ( C)
x4
50
80
-1
x5
300
400
-1
227
Adsorbent
dosage
(g/100ml)
Contact
time
(hours)
Temperature (oC)
Shaking speed
(rpm)
% Removal by
phenolic
compounds
20
0.1
50
400
30.29
40
0.1
50
300
8.16
20
0.3
50
300
67.70
40
0.3
50
400
46.36
20
0.1
50
300
35.04
40
0.1
50
400
10.16
20
0.3
50
400
66.45
40
0.3
50
300
52.08
20
0.1
80
300
29.69
40
0.1
80
400
11.11
20
0.3
80
400
58.52
40
0.3
80
300
30.06
20
0.1
80
400
33.40
40
0.1
80
300
7.17
20
0.3
80
300
57.82
40
0.3
80
400
39.83
An ANOVA table can be built after excluding nonsignificant terms and analyze the result with only
three factors, concentration of phenolic compounds,
228
Lim et al.
Application of Optimization in Wastewater Treatment
DF
Sum of square
F-value
P-value
Main effects
6065.58
2021.86
173.85
0.000
2-Way interaction
131.83
43.94
3.78
0.059
3-Way interaction
10.47
10.47
0.90
0.371
Residual error
93.04
11.63
Pure error
Total
8
15
93.04
6300.92
11.63
It can be seen that three-factor interaction and twofactor interaction were insignificant whilst the main
effect for selected factors was significant. Two-factor
interaction will be included in the model since this
interaction is significant at p<0.07.
(2)
229
5. OPTIMIZATION
Optimization is a procedure to select the best target
output from a process. This selection is made from a
series of experiments testing from a range of values
and the combination of each all factors. Optimization
may be a maximizing, minimizing and to keep the
target within range depending on the objective.
5.1. Concept of optimization
Concept of optimization is to select a combination of
the levels of factors which will result in a product with
desirable properties. This means solving problems
involving the optimization of several responses
(output), which depends upon a number of factors or
sets of parameters (input). Each desirable output
requires a special setting of input factors. For instance,
in an experimental study to maximize dye adsorption
capacity of an adsorbent made from coconut husk, the
two responses involved are decoloration and COD
removal of the dye wastewater. It can be achieved by
having higher temperature and retention time and at
the same time, reducing the rotation speed and
concentration of dye. In this optimization process, an
attempt was made to fulfill the requirement of the
wastewater treatment plant discharge (maximize the
dye adsorption capacity to reduce the discharge of dye
concentration in wastewater) while at the same time
reduces the material used (chemical dosage), obtain an
energy saving condition and reduces the duration of
the runs and most importantly to save cost.
.
[ y L ]m
T L
D( y )
[ U y ]n
T U
if y L
if L y T
(4)
if T y U
if y U
Whereas, for a process response that requires a maximum yield, then the desirability function would be;
yL m
D ( y ) [
]
T L
(3)
if y L
if L y T
(5)
if y T
230
Lim et al.
Application of Optimization in Wastewater Treatment
Lastly, for a process response that requires a minimum yield, then the desirability function would be:
y U n
D ( y ) [
]
T U
if y T
if T y U
(6)
if y U
y = o + ixi
(7)
i=1
where, 0 , and i are regression coefficients, and
i 1
i 1
y 0 i xi ii xi2 ij xi x j (8)
i j
6.1. Model
The most commonly response surface models used to
fit the data are first-order and second-order
polynomial models.
6.1.1. First order model
In most experimental condition, the relationship
between the response or the yield and independent
factors are unknown. In order to obtain a suitable
approximation for the relationship, a linear function or
lower order polynomial is engaged. This function is
known as a first-order model. The first order model
with k variables is given in (7).
231
x2
-1
-1
1
1
0
0
-1.41421
1.41421
0
0
0
0
0
Factorial
Points
Axial
Points
Centre
Points
Example 6.1
Suppose a chemist would like to extract vegetable
oil by using supercritical CO2 from a sample prepared
Symbol
Levels
Actual
Coded
Pressure (MPa)
x1
27.58
48.26
-1
Temperature (C)
x2
40
80
-1
Time (min)
x3
45
70
-1
232
Lim et al.
Application of Optimization in Wastewater Treatment
Temperature (C)
Time
(min)
Percent yield
(%)
27.58
80
45
42.5
48.26
80
45
35.0
27.58
40
70
27.1
48.26
40
70
66.7
27.58
80
70
59.5
48.26
80
70
50.1
27.58
60
57.5
38.2
48.26
60
57.5
75.9
37.92
40
57.5
44.3
37.92
80
57.5
68.9
37.92
60
45
46.8
37.92
60
70
74.4
27.58
40
45
65.4
48.26
40
45
67.6
37.92
60
57.5
67.1
37.92
60
57.5
66.9
37.92
60
57.5
68.3
37.92
37.92
60
60
57.5
57.5
68.7
68.3
Sum of squares
3911.79
892.95
50.90
1200.73
663.93
296.65
Degree of Freedom
9
1
1
1
1
1
Mean
sum square
434.64
892.95
50.90
1200.73
663.93
296.65
F-value
13.25
27.22
1.55
36.60
20.24
9.04
P-value
<0.0003
<0.0006
<0.2444
<0.0002
<0.0015
<0.0148
TimeTime
10.30
10.30
0.31
<0.5888
PressureTemperature
13.42
13.42
0.41
<0.5383
785.76
119.00
119.00
4207.03
1
1
1
18
785.76
119.00
32.80
23.95
3.63
<0.0009
<0.0892
Source of variation
Model
Pressure
Temperature
Time
PressurePressure
TemperatureTemperature
PressureTime
TemperatureTime
Residual
Total
233
Fig. 2: Three-dimensional response surface diagram of percent yield as a function of pressure and temperature
x2
x3
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
234
Factorial
Points
Lim et al.
Application of Optimization in Wastewater Treatment
-1
-1
Example 6.2
A biopolymer clarifies turbid water added during
coagulation-flocculation process. The performance of
clarifying water is examined by using the turbidity
Center Point/
Intermediate
Symbol
Levels
Actual
Coded
pH
x1
-1
x2
0.1
1.0
-1
x3
10
50
-1
Cation concentration
(mM)
0.10
Biopolymer dosage
(mg/L)
30
Turbidity reduction
(%)
55.5
9
3
9
3
9
3
9
6
6
6
6
6
6
6
6
6
0.10
1.00
1.00
0.55
0.55
0.55
0.55
0.10
1.00
0.10
1.00
0.55
0.55
0.55
0.55
0.55
30
30
30
10
10
50
50
10
10
50
50
30
30
30
30
30
91.1
99.7
98.8
97.0
98.4
68.7
99.7
99.0
99.8
76.2
99.7
99.6
99.7
99.0
99.3
99.4
235
725.81
311.25
264.44
1
1
1
725.81
311.25
264.44
51.69
22.17
18.83
<0.0002
<0.0022
<0.0034
113.85
113.85
8.11
<0.0248
1.16
333.06
219.04
1
1
1
1.16
333.06
219.04
0.083
23.72
15.60
<0.7821
<0.0018
<0.0055
128.82
98.28
2783.39
1
7
16
128.82
9.18
<0.0191
Fig. 3: Three-dimensional response surface for turbidity reduction as a function of pH and concentration of cation
REFERENCES
Box GE and JS Hunter (1957). Multi-factor
experimental designs for exploring response
236
Lim et al.
Application of Optimization in Wastewater Treatment
237