LING TAU CHUAN
FK 1997 7
OLIGOSPORUS BIOMASS
LING TAll CHllAN
Thesis Submitted in Partial Fulfilment of the Requirements for the Degree of Master of Science in the Faculty of Engineering,
Universiti Putra Malaysia.
ACKNOWLEDGEMENTS
FIrst of all, I wIsh to express my utmost thanks and appreCiatIOn to my
chamnan, Dr Fakhru'I-Razi Ahmadun and members of the SupervIsory
CommIttee, Dr Arbakanya ArIff and Dr Mohd All Hassan for theIr gUIdance
and enlIghtemng advIce throughout the duratIOn of thIS study
I also wIsh to express my smcere apprecIatIOn to Mr Rosh, Mdm
Renuga, Mdm Aluyah, Ms MadIhah and Ms Rosfanzan for theIr assIstance
and help dunng my laboratory work
Lastly, J wIsh to express my whole-hearted thanks to my famIly
members for gIvmg me support and love
11
Lead
Copper
CadmIum
AlumInIUm
Wastes
Membrane TechnologIes
FungI 14
EqUIlIbnum 18
Effect of BIOmass CharactenstIcs on BIOsorptIOn
CapacIty 23
Effect of Heavy Metal ConcentratIOn 29
Effect of Competmg CatIOns on Metals Uptake 30
Heavy Metal Recovery 3 1
RegeneratIOn and Repeated Use of BIOmass 33
MATERIALS AND METHODS
Expenments
CalculatIOn of Heavy Metals Uptake
RESULTS AND DISCUSSION
lsothenn
Scatchard "I ransfonnatIOn of The LangmUIr Plots of
BIOsorptIOn Data
CapaCIty
BlosorptlOn CapaCIty
DesorptIon of Metals from BIOmass
Heavy Metal Removal from Industnal Effluent
CONCLUSIONS AND RECOMMENDATIONS
3 Treatment Cost
5 Heavy Metal Accumulation by Yeast and Algae
6 Heavy Metal Accumulation by Fungi
7 The Composition of Liquid Medium Used to Cultivate Biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8 Effect of Lead Concentration in Solution on It Uptake by Powdered Rhizopus o/igosporus Biomass .................... .
9 Initial and Final pH for Heavy Metals Uptake
10 Effect of Copper Concentration in Solution on It Uptake by Powdered Rhizopus oligosporus Biomass .............. .
1 I Effect of Aluminium Concentration in Solution on It Uptake by Powdered Rhizopus oligosporus Biomass
12
13
Effect of Cadmium Concentration in Solution on It Uptake by Powdered Rhizopus o/igosporus Biomass
The Uptake Capacities of Various Metal by Powdered Rhizopus o/igosporus Biomass Derived from the Langmuir Model ............................................................ .
14 Maximum Biosorption Capacities of Various Micro- orgamsms
15 Effect of Biomass Concentration on Heavy Metals Uptake
VB
Page
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7
10
12
13
14
35
46
102
48
50
52
56
66
1 6 Effect of ImtIal Heavy MetallBIOmass RatIO on Heavy Metal Uptake 1 03
17 Heavy Metals Uptake by Powdered RhlZOpUS olzgoporu5
Biomass BIOsorptIOn Process m A StIrred Tank Reactor 104
1 8 Etfect of SolutIOn pH on Heavy Metals Uptake by Powdered RhlZOpUS o/igo5porus BIOmass 1 05
19 Optimum pH for BIOsorptIon Process by Several MICro- orgamsms 77
20 DesorptIOn of Metals From BIOmass 111
2 1 DesorptIOn of Heavy Metals from Powdered Rhcopus
ohg()poru<; BIOmass by DIfferent ConcentratIOn of Hydrochlonc ACId 84
22 DesorptIOn of Heavy Metals from Powdered Rhl::OPU5
ohgo5poru<; BIOmass by DIfferent ConcentratIOn of SodIUm Hydroxide 85
23 Heavy Metal Removal from Industnal Effluent 88
VIlI
FIGURE
2
3
4
5
6
7
8
9
EqUIhbnum BIOsorptIOn Isotherm of Lead by Powdered RhlZOpW olzg(),poru!> BIOmass ........................ .. ..... .
EqUIhbnum BIOsorptIOn Isotherm of Copper by Powdered RhlZOpUS ohgosporus BIOmass .............................. .
EqUIhbnum BIOsorptIOn Isotherm of AlummIUm by Powdered Rhl::OpUS ohgosporw BIOmass
EqUilIbrIum BIOsorptIOn Isotherm of CadmIUm by Powdered RhlZOpUS olzgosporus BIOmass ....... ......... .
Lmear LangmUIr Transformations of EqUIhbrIum BIOsorptIOn Isotherms
Lmear LangmUir TransformatIOns of EqUIlIbnum BIOsorptIOn Isotherms
ReCIprocal LangmUir Plot for Lead and Copper BIOsorptIOn Data by Powdered Rhz:::opus O/lgO,'POru,\ BIomass .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . .
RecIprocal LangmUir Plot for AlummIUm and CadmIUm BIOsorptIOn Data by Powdered RhlZOpUS olzgo!>poru!> BIOmass
Scatchard Plots of Lead and Copper BIOsorptIOn Data by
Powdered RhlZOpUS ohgosporus BIOmass .................... .
Scatchard Plots of AlummIUm and CadmIUm BIOsorptIOn Data by Powdered RhlZOpUS ohgosporus BIOmass
IX
Page
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39
47
49
1 3 Uptake of Heavy Metal wIth Increasmg BIOmass ConcentratIOn
14
Effect of Imttal Lead ConcentratIOn/BIOmass RatIO on Lead Uptake
Effect of ImtIal Copper ConcentratIOn/BIOmass RatIo on Copper Uptake
1 6 Effect of Imtlal AlummIUm ConcentratIOniBlomass RatIO on AlummIUm Uptake
1 7
1 8
1 9
on CadmIUm Uptake
The Profile of Heavy Metals Uptake by Powdered Rhcopu<, ofzgmporus BIOmass durmg SorptIOn Process m A StIrred Tank Reactor
Effect ot Solution pH on Lead Uptake by Powdered Rhcopu\ olrgosporus BIOmass
Effect of SolutIon pH on CadmIUm Uptake by Powdered Rhcopu\ ofzgosporus BIOmass
Effect of SolutIon pH on Copper Uptake by Powdered Rhcopu\ ohgosporus BIOmass
Effect of SolutIon pH on AlummIUm Uptake by Powdered Rhcopu!> olrgo!',poru\ BIOmass
Effect of SolutIOn pH on MaXImum Metals CapacIty by Powdered RhlZOpUS o/zgosporu<i BIOmass
DesorptIon of Heavy Metals from Powdered Rhl::OpU!> o!zgo<,porus BIOmass by Different ConcentratIOn of Hydrochlonc ACId and SodIUm HydroXIde
Heavy Metal Removal Capacity from AlummIUm
lndustnal Effiuent
Industnal Effiuent
Initial heavy metal concentration
Concentration of metal uptake per unit weight of biomass
Maximum concentration of metal uptake per unit weight of biomass in forming a complete mono-layer on cell surface
The volume of heavy metal bearing solution
Xl
Abstract of this thesis submitted to the Senate of Universiti Putra Malaysia in partial fulfilment of the requirements for the degree of Master of Science.
Chairman:
Faculty:
RHIZOPUS OLIGOSPORUS BIOMASS
The biosorption of several metals by powdered biomass of
Rhizopus o/igosporus was investigated. Cells of Rhizopus o/zgosporus were
cultured, harvested, washed, oven dried and mixed in solutions containing lead,
copper, cadmium and aluminium ions. After an equilibration period, the
biomass was separated from the metal bearing solution and the content of heavy
metals were determined by an Atomic Adsorption Spectrophotometer. The
biosorption of metal ions was increased with increasing initial concentration of
heavy metal. The heavy metal uptake capacity increased in the order: copper
(73.50 mg/g) > lead (60.90 mg/g) > cadmium (30.15 mg/g) > aluminium (26.60
mg/g). Langmuir Adsorption Model was suitable for describing the biosorption
of lead, cadmium, aluminium and copper. Reciprocal Langmuir
Transformation and Scatchard analysis revealed that different types of binding
sites are involved in the biosorption process. pH regulation of the process can
xu
enhance the bIOsorptIOn capacIty for all metals tested The optImum pH for
lead , cadmIUm, alUmIniUm and copper are 5, 4, 4 and 6 respectIvely The
posslbI ltty for desorbmg the metals from loaded bIOmass usmg HCI and NaOH
were tested The desorptIOn efficIency for HC! and NaOH mcreased WIth
Increasmg concentratIOn of HCl and NaOH HCl wass more efficIent than
NaOH The possIbI l Ity of removmg heavy metal from mdustnal wastes was
also mvestigated For electroplatmg wastes, the heavy metals uptake capacItIes
Increased m the order lead (0 44 mg/g) > cadmIUm (0 1 1 mg/g) > copper (0 09
mg/g) For alummIUm wastes, the heavy metals uptake capacItIes mcreased In
the order cadmIUm (0 1 2 mg/g) > copper (0 1 0 mg/g)
X111
Abstrak teslS yang dlkemukakan kepada Senat Umversltt Putra MalaYSIa untuk memenuhl sebahaglan danpada syarat untuk mendapat IJazah Master Sams
Pengerusl
Fakultl
Oleh
sel untuk menyerap beberapa logam sepertl plumbum, kadrmum, alummIUm
dan kuprum telah dlkaJI Sel RhlZOpUS ohgosporus dlkulturakan, dltual, dtbtlas
dengan au sulmg dan dlkenngkan dengan menggunakan oven Serbuk kenng
sel dltmdakbalaskan dengan larutan yang mengandungt kepekatan logam
tertentu Setelah mencapal keselmbangan, serbuk kenng sel akan dlpIsahkan
danpada larutan secara turasan Kandungan logam akhu akan dltentukan
dengan menggunakan AtomIC AdsorptIOn Spectrophotometer Adalah dldapatI
bahawa logam yang dlserap adalah bertambah dengan bertambahnya kepekatan
logam permulaan lumlah logam yang dlserap oleh sel dlsusun secara menalk
lalah kuprum ( 7350 mg/g) > plumbum (6090 mg/g) > kadmIUm (30 15 mg/g)
> alumInIUm (26 60 mg/g) LangmUIr AdsorptIOn Model adalah sesual untuk
menerangkan tlndak balas bIOserapan Int Anahsls RecIprocal Langmwr
XIV
terhbat dalam blOserapan Kawalan pH dldapatl dapat memperbanyakkan
Jumlah kuantltl logam yang dlserap pH yang optImum untuk plumbum,
kadmmm, aiummmm dan kuprum masmg-masmg lalah 5, 4, 4 dan 6 Logam
yang telah dlserap oleh sel Juga dapat dlkeluarkan danpada tapak aktlf sel
dengan menggunakan HCl dan NaOH Adalah dldapatl HCI leblh berkesan
Laglpun, sel Juga dapat menyerap logam-Iogam yang terdapat pada Slsa mdustn
Untuk Slsa electroplatmg, Jumlah logam yang dlserap dlsusun secara menalk
talah plumbum (044 mg/g) > kadmlUm (0 1 1 mg/g) > kuprum (009 mg/g)
Untuk slsa a\ummmm pula, Jumlah logam yang dlserap dlsusun secara menmk
lalah kadmmm (0 12 mg/g) > kuprum (0 ] 0 mg/g)
xv
INTRODlJCTION
The rapid pace of IndustnahsatlOn has Increased the number of heavy
metal polluting sources In the manufactunng sector slf,JT1IficantIy The main
heavy metals polluting sources are effluents from Industnes such as texti le
Industry, baSIC steel works, electroplating, battenes and metal fimshIng The
most common heavy metal contaminants are lead, cadmIUm, copper, chromIUm
and aluminIUm Two kinds of methods used to treat heavy metal waste
commercially now are phYSical and chemical processes However, bIOlogIcal
methods Increasmgly appear as an alternative to the chemical and phYSIcal
methods WhICh have been proven to be inefficient when used to treat high
volume but low metals concentratIOn effluents (Schmlechen et al , 1 992)
The dIverse phYSIologIcal metabolic and charactensttcs of micro­
orgamsms such as fungi, algae, bactena and yeast and theu abilIty to thnve In a
vanety of environment may be explOited for the purpose of removmg heavy
metals from aqueous mdustnal effluent and metals recovenng from Industnal
processes
2
A number of mechamsms take place dunng the removal of heavy metals
from aquatic solutIOns by these ITIlcroblal bIomass These mechamsms Include
complexatIOn, coordInatIOn, adsorptIon and IOn exchange These mechamsms
can be dIvIded Into two phases namely, passIve and act ive process Vanous
parameters such as bIOmass concentratIon, bIOmass charactenstIc, types of
heavy metals, heavy metals concentrat IOn, solut IOn pH and growth medIa affect
these mechamsms, thus affect Ing blOsorptlOn process
The aIms of thIs study are as follows
To mvestIgate the ablltty of powdered bIOmass of Rlll::opw o/rgosporus to
adsorb lead, cadmIum, copper and alummlUm
2 To study the effect of bIOmass concentratIOn and sol utlOn pH on blOsorptlOn
capacIty
3 To analyse the kmetIcs of blOsorptlOn of va no us heavy metals by powdered
bIOmass of Rhcopu\ ol!ymporus usmg several sorpt IOn Isotherms models
such as LangmUIr Model, Scatchard plots and RecIprocal transformatIOn of
the Langmulf model
4 To study the posslbI ltt Ies of desorbmg the metals from loaded bIOmass and
heavy metal removal from mdustnal effluent such as electroplat Ing wastes
and aiummmm wastes by bIOmass
CHAPTER II
LITERATtJRE REVIEW
Heavy Metal Pollution and Toxicity
Heavy metals are defined as metals havmg a denSIty greater than 5 gil or
havmg an atomIC number greater than that of Iron (Passaw et al , 1 96 1 ) Phipps
( 1 976) defined tOXIC heavy metals as 'elements WhICh have neIther an essential
nor benefiCIal but posItIvely catastrophIC effect on normal metabohc functIOns,
even when present m only small amounts Generally, they consist of forty
elements m the Pen odic Table except those m Groups I and I I Heavy metals
are WIdely used m textile, electroplatmg, basIc steel works and metal fimshmg
mdustnes Heavy metals enter our body through mhalatIOn, food cham and
dnnkmg water Several mIlhon peoples world-wIde suffer currently from sub­
chmcal heavy metals pOisonmg due to metal contammatlOn of foods and
beverages which were Identified as major contnbutors (Nnagu, 1 988) High
level heavy metal exposure can cause numerous dIsorders such as growth
retardatIOn, morbidity and pathological changes
3
4
Lead
Lead is one of the most useful heavy metals used in modern industries
such as batteries and electrical, electroplating, ceramic glazes and gasoline
industries. There are a variety of these industries in Malaysia. Despite its
value, lead is also a very toxic metal. Elevated levels of lead in marine
environment can be traced to industrial discharges from these industries (Table
1). These industries are the main polluter in the manufacturing sector and are
the industries have low compliance rate with the Environmental Quality
( Sewage and Industrial Effluents) Regulation 1979 (EnVironmental Quahty
Report 1994).
High-level lead exposure can cause neurological disorders such as
muscular tremor, fatigue and headache. Furthermore, it also can damage the
kidneys and nerves system. Low-level exposure can cause central systems
cause central nervous systems disorder. Exposure to small amounts of lead also
can seriously affect mental development.
5
Cases References
I Lead level as hIgh as 3 0 Ilg/g Almah et al ( 1992) accumulated In anchOVIes tissues It was found that lead level In Envi ronmental QualIty Report many nvers had exceeded the I 1994 Department of EnvIronment, Intenm NatIOnal Water QualIty I Malaysia (1995) Standards for class III , Lead was one of the main EnvIronmental QualIty Report 1993 polluter WhICh pol luted the Department of EnVIronment,
I manne enVIronment MalaysIa ( (994)
Copper
Copper IS mainly released Into the enVIronment by Industnal wastes and
thiS caused a senous health hazard Copper IS Widely used In electroplatmg,
metal fimshIng and chemical mdustnes (Chenmismoff, 1995) In MalaYSIa,
there are a lot of Industnes based on electromc and chemIcal processes
IneVItably, these Industnes has caused a pollutIOn problem Proper system to
treat the wastes from these Industnes are much deslfed Furthermore, the
IndISCnmInate dIsposal of effluent from these small and mediUm mdustnes Wil l
worsen the pollutIOn problem Cooper Ion IS released mto the water and finally
enter mto human body through the food cham It IS depoSIted m the pancreas,
bram and lIver WhICh cause "WIlson's dIsease" It was found that copper level
6
m several nvers m MalaysIa had exceeded the lntenm Nattonal Water QualIty
Standards for Class III (EnvIronmental Quahty Report, 1 994)
Cadmium
CadmlUm IS WIdely used m pamt pIgments, plashcs and electroplatmg
mdustnes (Chenmismoff, 1 995) The mIsmanagement of effluent from these
types of mdustry can cause a senous health hazard When cadmlUm enter mto
the human body It bounds to some soft tIssues such as kIdneys and hvers ThIS
wIl l cause senous long term and short term effects A dIsease known as "Itm­
Itm" m Japan IS assocIated WIth cadmlUm pOIsomng whIch caused multIple
fractures ansmg from osteomalacia (Murata et aI, 1 970) The mtensificatIOn of
mdustnalIsatIOn m Malaysia has mcreased cadmIUm pollutmg problem (Table
2)
7
Cadmium Pollution in Malaysia
Cases References Cadmium levels accumulated In BabJI et al ( 1986) fish tissues Increased slgmficantly CadmIUm levels were found to EnVIronment Quahty Report 1993 have exceeded the standard of 0 0 1 Department of Envlfonment, mg;1 In 3 nvers In Terengganu MalaysIa ( 1994 ) namely, Sungal Terengganu (0 0 1 7 mg/ I ), Sungm SetIU (0 024 mg/I) and Sungal Dungun (0 0 1 4 mg/I ) CadmIUm levels was found I n the Envlfonment Quality Report 1990 coastal waters of Malaysia (0 0 1 3 Department of Envlfonment, mg/I) MalaysIa (1991 ) CadmIUm level as high as 0 04 g/g Watanabe et al (1989) was found In nee In vanous areas of ASia
Aluminium
AlumInIUm IS one of the heavy metals Wldely used In alumInIUm
anodlslng Industry and electroplatIng Industry At present, treatment technology
for alumInIUm removal IS essentlally bmlted to chemical preCIpItatIOn by pH
adjustment However, mcreasmg publIc awareness of the detnmental
consequences aSSOCIated wlth the eXlstence of alumInIUm m the enVIronment
has led to slgmficant concern by the publIc (Wengtsson et ai, 1995)
Furthermore, alumInIUm hydroXide (Alum) IS normally used to treat water and
subsequently used as dnnkmg water The alum enhanced the sedImentatIOn
rate of suspended solids However, the alum reSidues left In tap water Wlll
8
cause health problem A lummlUm pOisonmg gIVmg nse to tremors, loss of
memory and Jerkmg have first reported m 1921 and there IS eVIdence that
alummlUm can be a neurotoxm (Albery, 1996)
Physical and Chemical Treatment of Heavy Metal Wastes
Carbon Adsorption
Heavy metals may be removed from aqueous waste wIth activated
carbon by adsorptIOn of the chemIcal substances on to a carbon matnx
However, the use of adsorptIOn by activated carbon need a hIgh capItal
mvestment and mefficient (Schmiechen et ai , 1992) The dIsposal of carbon
contammated wIth heavy metals can cause a senous Impact on enVIronment
Furthermore, the operatmg cost mvolved to reactivate carbon IS very hIgh For
example, energy reqUirements for systems employmg thermal reactIOn IS 14,000
- 18,600 KJIKg of carbon (Edward and Johnson, 1986)
Chemical Precipitation
carbonate (Na2C03) and calcIUm carbonate (CaC03) are a cheaper method
The energy consumptIOn and aSSOCiated costs are low as compared With other
9
methods However, thIS method IS judged that has mImmal potential for the
heavy metal pUrIficatIOn applIcatIOn (Schmiechen et ai , 1 992) This IS because
non target materIals are precIpItated together WIth the heavy metal thus
affectmg the heavy metal recovery process Furthermore, thIS process IS a tlme­
dependent phYSIcal process (Cheremisnoff, 1995)
Evaporation
EvaporatIOn IS the process that heats the lIqUids, vents the vapours and
concentrates the heavy waste Into a slurry fOrIn The major dIsadvantages of
evaporatIOn are hIgh capItal mvestment and operatmg cost It has been proven
to be mefficient m treatmg aqueous hazardous wastes contammg moderately
volatIle orgamc substances (Edward and Johnson, 1 986)
Incineration and Air Stripping
IncmeratIon IS a hIgh temperature OXIdatIOn process The aIr strIppmg IS
a process m WhIch water at elevated temperatures IS used to separate volatIle
components of a liqUid The major dIsadvantages of mCIneratIOn and aIr
strIppmg methods are the releases of addItIonal tOXIC materIals such as dIOxm