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Anafvtica/ Studies on Phvto-asslsted Methods for Toxic Contaminants Removal
CHAPTER I SEPARATION OF Ni(ll) AND Cr(VI) FROM AQUEOUS
SOLUTION AND ELECTROPLATING WASTE BY COLUMN SORPTION TECHNIQUE USING BIOSORPTION
ABSTRACT
This study provides information on the removal of Cr(VI) and Ni(ll) by using two different
biomasses. In addition, a column was developed for the separation of nickel and chromium by
the binary mixture of them as well as from the electroplating waste. Chromium and nickel are
present in different types of industrial effluents, Especially electroplating waste, being
responsible for environmental pollution. Traditionally, the removal is made by chemical
precipitation. However, this method is not completely feasible to reduce the metal concentration
to levels as low as required by environmental legislation. Biosorption is a process in which solids
of natural origin are employed for binding heavy metals. It is a promising alternative method to
treat industrial effluents, mainly because of its low cost and high metal binding capacity. In this
work the chromium and nickel biosorption process by using two different biomasses at the same
time is studied. The work considered the determination of chromium-biomass equilibrium data
as well as nickel- biomass equilibrium data in batch system. These studies were carried out in
order to determine some operational parameters of metals sorption such as the time (5-150
minutes) required for the metal-biosorbent equilibrium, the effects of biomass dosage (1-10
g(L), pH (2-8) and initial metal concentration (1-500 mg(L). The results showed that pH has an
important effect on biosorption capacity. The optimum pH was considered as pH 3. Elution
studies were also investigated for both the metal ions Ni(ll) and Cr(VI). A single and mixed bed
column study for the separation of Ni(ll) and Cr(VI} from the binary mixture of Ni(ll) and Cr(VI} was
investigated. It was concluded that the adsorption is rapid and biosorption equilibrium was
established after about 30 minutes. The effect of various common ions such as Cl·, so.2·, Cd2•,
Mn2•, Cu2', were investigated. Under optimal conditions, the uptake capacities were calculated
for 250 mg/L of Ni(ll) and 250 mg(L of Cr(VI) were found as 18.5 mg/g and 29.55 mg/g
respectively
Analvtlcal Studies on Phyto-asslsted Methods for Toxic Contaminants Removal
INTRODUCTION
Heavy metals, especially Nickel and chromium can have serious effects on human and animal
health (National Research Council, 197 4; ATSDR, 1993; ATSDR, 2000; JARC, 1990). Beside the
health effects, heavy metals are non-renewable resources. Therefore, effective recovery of heavy
metals is as important as removal of them from waste streams.
Wastewater produced during electroplating is one of the main causes of contamination of the
natural environment with metal ions. The negative impact of waste streams containing heavy
metals upon the environment, has caused increasingly strict egulations. According to recent
regulations of USEPA(1997), for common metals facilities discharging 38,000 liters or more
process wastewaters (resulting from the process in which a ferrous or nonferrous basis material
is electroplated with copper, nickel, chromium, zinc, tin, lead, cadmium, iron, aluminum, or any
combination thereof) per day should not exceed 4.5 mgfl for Cu, 4.1 mgfL for Ni, 7.0 mg/L for
Cr, 4.2mgfl for Zn, 0.6mgfl for Pb and 1.2 mgfl for Cd.
Chromium is an important industrial metal used in diverse products and processes. At many
industrial and waste disposal locations, chromium has been released to the environment via
leakage and poor storage during manufacturing or improper disposal practices (Palmer and
Wittbrodt, 1991). The principal sources of chromium contaminated soils and groundwater are
electroplating, textile manufacturing, leather tanning, pigment manufacturing, wood preserving,
and chromium waste disposal, cement industries, tanning, water cooling, pulp producing, ore
and petroleum refining processes, production of steel and other metal alloys (U.S. EPA, 1997,
Barnhart, 1997).
The maximum levels permitted in waste water are 5 mgfl and 0.05 mgfl, for Cr(lll) and Cr(VI)
respectively. They exit as low levels in the environment. Cr(lll) apparently plays an essential role
in plant and animal metabolism. While Cr(VI) is directly toxic to bacteria, plants and animals. In
the WHO (1993) Guidelines for drinking-water quality, a health-based guideline value for nickel of
0.02 mgflitre was derived. The acceptable limit of Nickel in the industrial discharge limit in
wastewater is 2 mgfl (Sharma et al.,1992). Microorganism's uptake metal either actively
(bioaccumulation) and 1 or passively (biosorption) (Shumate and Strandberg, 1985; Andres et al.
1992: Fourest and Roux. 1992; Hussein et al. 2001; 2003;).
Methods reported for removal of Cr!VIl and Ni(l/)
The main separation techniques to treat spent electroless nickel bath are chemical precipitatiOn
(McAnally eta/., 1984; de Carvalho et al., 1995), ion exchange (Paker, 1983) and electrodialysis
(Li eta/., 1999). However, these methods are not cost effective and contribute to other problems
JQQ
Anal'{tlcal Studies on Phyto-asslsted Methods for Toxic Contaminants Removal
such as sludge disposal and extra chemical injection. Membrane technology had also gained its
popularity in metal recovery from industrial waste like reverse osmosis (Ujang and Anderson,
1995) and ultrafiltration (Bhattacharyya et al., 1989; Chaufer and Deratani, 1998). However
problems like high operation and maintenance cost for application of high pressure to the
system and pretreatment necessity have led to the production of nanofiltration (NF) membranes
[Peeters et al., 1996). Successful studies utilizing NF as tools for removal of heavy metals, which
are generally multivalent ions (Peeters et al., 1998; Ahn et al., 1999; Garba et al., 1999),
investigated the performance of NF (NTR-7250) in simulated nickel electroplating rinse water
environment and found that the rejection of Ni2+ in multi-salts systems was relatively high -
above 80%. However, there has not been any study reported on the performance of NF in the
real waste from Ni-P electroless plating industry.
Existing chemical treatment processes for the lowering of Cr(VI) concentrations generally involve
the aqueous reduction of Cr(VI) to Cr(lll) using various chemical reagents, with the subsequent
adjustment of the solution pH to near-neutral conditions, for the precipitation of the Cr(lll) ions
produced. However, these methods have been considered undesirable due to the use of
expensive and toxic chemicals, poor removal efficiency for meeting regulatory standards, and the
production of large amounts of chemical sludge (Kratochvil et al., 1998; Cabatingan, 2001).
The conventional methods which are commonly used for the removal of nickel from the aqueous
solution industrial effluents are physio-chemical methods, such as chemical precipitation,
chemical oxidation or reduction, electrochemical treatment, evaporative recovery, filtration, ion
exchange, and membrane technologies. These processes may be ineffective or expensive,
especially when the heavy metal ions are in solutions containing in the order of 1-100 mg
dissolved heavy metal ions/L (Volesky 1990a; Volesky 199Gb), Biological methods such as
biosorption/ bioaccumulation may provide an attractive to Physico-chemical methods for the
removal of heavy metal ions (Kapoor and Viraraghvan, 1995). But due to the operation demerits
and high cost of treatment some other methods are to be adopted.
The conventional methods for the removal of chromium from aqueous solution included,
chemical reduction, electro chemical treatment, ion exchange and evaporative recovery.
Different biosorbent reported for the removal of NiCIIl and CrNI)
According to literature study adsorbents have been investigated for removal of Ni(ll), some
adsorbents are presented in Table 5.1.
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Anaivtlcai Studies on Phvto-essisted Methods for Toxic Contaminants Removal
TABLE 5.1.
SOME ADSORBENTS USED FOR THE REMOVAL OF NICKEL.
S. No. Adsorbent used for the removal of Nl(ll} References
1 Sphagnum peat Viraraghavan and Drohamraju, 1993
2 Blast furnace slage Dimitrva, 1996
3 Apple waste Maranon and Sastre, 1991
4 Soyabeen and cottonseed husk Marshall et al., 1995
5 Peat nut husk carbon Periasamy and Namasivayam, 1995
6 Straw Larson and Schiernp, 1981
7 Treated saw dust and activated alumina Meena et al., 2003
8 Waste Fe(III)/Cr(lll) hydroxide Namasivayam and Ranganathan, 1994
Many types of biomass in nonliving from have been studied for their heavy metal uptake
capacities and suitability to be used as bases for biosorbent development. These include
bacteria (Strandberg et al., 1981; Scott and Karanjkar, 1992; Sag and Kutsal, 1995), fungi
(Tobin et al., 1984), fresh water algae (Crist et al., 1981), marine algae (Holan et al., 1993;
Fourest and Volesky 1997; Matheickal et al., 1997), Use of low cost material for the removal of
chromium are starch product (Wing, and Rayford, 1980), alumina (Gupta and Tiwari 1985), low
grade manganese ore and coconut shell (Prasad and Venkobochan 1988), Fly ash wollastonite,
tree barks, blast furnace flue dust, albizia lebbeck pods,coal char,(Baishakh and Pathaik., 2002).
Synthetic resin (Sengupta, 1986,), activated carbon (Perez-Candela et al., 1995) fly ash
wollastonite (Pandey et al., 1984), carbon slurry (Singh and Tiwari, 1997), inorganic sorbent
materials (Lehmann et al., 1999,), or the so-called biosorbents derived from dead biomass. Of
these, biosorbents are considered the cheapest, most abundant, and environmentally friendly
option. Because of these advantages, there has been extensive research exploring appropriate
biosorbents able to effectively remove Cr(VI), such as sawdust (Raji and Anirudhan 1998; Yu et
al., 2003; Acar and Malkoc,2004), moss peat (Sharma and Forster, 1993), agricultural
byproduct (Chun et al., 2004; Bishnoi et al., 2004), food industrial waste (Selva raj et al., 2003),
plants ( Zhao and Duncan 1997; Ucunet al., 2002)
In this chapter, selective removal and recovery of the nickel and chromium from an aqueous
solution was successfully developed.
________________________________________________________ 201
Analvtical Studies on Phvto-assisted Methods for Toxic Contaminants Ramo val
General description of biomass used for chromium removal
Botany
Amalaki is a small to medium-sized tree with a crooked trunk and spreading branches, the
grayish-green bark peeling off in flakes. The branch lets are glabrous or finely pubescent, 10-20
em long, usually deciduous; the leaves simple, subsessile and closely set along branchlets, light
green, resembling pinnate leaves. The flowers are greenish-yellow, borne in axillary fascicles,
giving way to a globose fruit with a greenish-yellow flesh and six furrows, enclosing a stone with
six seeds. Amalaki is native to tropical southeastern Asia, particularly in central and southern
India, Pakistan, Bangladesh, Sri Lanka, Malaysia, southern China and the Mascarene Islands. It
is commonly cultivated in gardens throughout India and grown commercially as a medicinal fruit
(Warrier et al., 1995; Kirtikar and Basu, 1935).
ScientificName : Embe/ica officina/is
Family: Euphorbiaceae
Common Name : Hindi:Amla, Bengali- Amlaki Tamil - Nelli
Telgu- Usirikai
Part used:
Fresh or dried whole fruit.
Description
The tree is a graceful ornamental, normally reaching a height of 60 ft (18 m) and, in rare
instances, 100 ft (30 m). Its fairly smooth bark is a pale grayish-brown and peels off in thin
flakes like that of the guava. While actually deciduous, shedding its branchlets as well as its
leaves, it is seldom entirely bare and is therefore often cited as an evergreen. The miniature,
oblong leaves, only 1/8 in (3 mm) wide and 1/2 to 3/4 in (1.25-2 em) long, distichously disposed
on very slender branchlets, give a misleading impression of finely pinnate foliage. Small,
inconspicuous, greenish-yellow flowers are borne in compact clusters in the axils of the lower
leaves. Usually, male flowers occur at the lower end of a growing branchlet, with the female
flowers above them, but occasional trees are dioecious. The nearly stemless fruit is round or
oblate, indented at the base, and smooth, though 6 to 8 pale lines, sometimes faintly evident as
ridges, extending from the base to the apex, give it the appearance of being divided into
segments or lobes. Light-green at first, the fruit becomes whitish or a dull, greenish-yellow, or,
more rarely, brick-red as it matures. It is hard and unyielding to the touch. The skin is thin,
translucent and adherent to the very crisp, juicy, concolorous flesh. Tightly embedded in the
center of the flesh is a slightly hexagonal stone containing 6 small seeds. Fruits collected in
South Florida vary from 1 to 11/4 in (2.5-3.2 em) in diameter but choice types in India approach
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Analytical Studies on Phy(o-asslsted Methods for Toxic Contaminants Removal
2 in (5 em) in width. Ripe fruits are astringent, extremely acid, and some are distinctly bitter.
Different Part of Amblica officanalis are shown in Figure 5.1
Origin and Distribution
The emblic tree is native to tropical southeastern Asia, particularly in central and southern India,
Pakistan, Bangladesh, Ceylon, Malaya, southern China and the Mascarene Islands. It is
commonly cultivated in home gardens throughout India and grown commercially in Uttar
Pradesh. Many trees have been planted in southern Malaya, Singapore, and throughout
Malaysia. In India, and to a lesser extent in Malaya, the emblic is important and esteemed, raw
as well as preserved, and it is prominent in folk medicine. Fruits from both wild and dooryard
trees and from orchards are gathered for home use and for market. In southern Thailand, fruits
from wild trees are gathered for marketing.
In 1901, the United States Department of Agriculture received seeds from the Reasoner
Brothers, noted nurserymen and plant importers of Oneco, Florida. Seeds were distributed to
early settlers in Florida and to public gardens and experimental stations in Bermuda, Cuba,
Puerto Rico, Trinidad, Panama, Hawaii and the Philippines. The fruits of these seedlings aroused
no enthusiasm until 1945 when Mr. Claud Horn of the Office of Foreign Agricultural Relations in
Washington, D.C., inspired by Indian ratings of the emblic as the "richest known natural source of
vitamin C", asked that analyses be made in Puerto Rico. A high level of ascorbic acid was found
and confirmed in Florida but interest quickly switched to the Barbados cherry (q.v.) which was
casually assayed and found to be as rich or richer when underripe. The ernblic was soon
forgotten. Some old trees still exist in southern Florida; others have been removed in favor of
housing or other developments. In 1954, the Campbell Soup Company in Camden, New Jersey,
requested 5 lbs (2.25 kg) of the fruits for study. They were sent, but no further interest was
evidenced. In 1982, several individuals asked for and were given seeds for planting in Australia.
They did not reveal whether the tree was desired for its own sake or for its fruits.
Medical research
Antioxidant
Like many of the rasayana botanicals, P. emblica displays pronounced adaptogenic properties,
and has been shown to be active in vivo against free radical damage induced during stress
(Rege, 1999). Although P. emblica is stated as one of the highest naturally occurring sources of
vitamin C (Katiyar, 1997), its antioxidant properties have also been attributed to the tannoid
complexes (emblicanin A [37%], emblicanin B [33%), punigluconin [12%] and pedunculagin
[14%] (Bhattacharya 1999). Overall, the antioxidant effect of Amalaki is significantly greater than
that of vitamin C alone.
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Analytical Studies on Phyto-asslsted Methods for Toxic Contaminants Removal
Anti-inflammatory
An extract of the leaf of P.emblica has been found to have significant anti-inflammatory activities
in carrageenan and dextran-induced rat hind paw oedema (Asmawi., 1993).
Antimicrobial
Aqueous and ethanol extracts of P.emblica have been found to be both antifungal and
antimicrobial in vitro, without any indication of cellular toxicity (Dutta, 1998; Ahmad., 1998).
Antiviral
A bioassay-guided fractionation of a methanol extract of the fruit of P. emb/ica (putranjivain A)
was isolated as a potent inhibitory substance on the effects of human immunodeficiency virus-1
reverse transcriptase (ei-Mekkawy et al., 1995).
Cancer
Nandi et al., report that the supplementation P.emblica to mice in vivo significantly reduced the
cytotoxic effects of a known carcinogen, 3.4-benzo(a)pyrene, in much smaller doses than the
carcingogen (1997). When an aqueous extract of P. emblica is administered prior to radiation
treatment, it has been found to have a protective effect upon radiation induced chromosomal
damage).
Digestive
Research conducted at the Amala Cancer Research Centre in Kerala, India, has found that an
extract of P. emblica significantly inhibited hepatocarcinogenesis induced by N
nitrosodiethylamine (NDEA) in experimental animals (Jeena, 1999}. In addition to its
hepatoprotective activities, P. emblica also appears to be functional in acute necrotizing
pancreatitis, reducing inflammation and the damage to acinar cells (Thorat, 1995}.
Immune
P. emblica has been found to enhance natural killer cell activity and antibody dependent
cytotoxicity in tumor bearing mice, enhancing lifespan to 35% beyond the control animals. An
aqueous extract of P. emblica has been shown to significantly reduce the cytotoxic effects of
sodium arsenite when administered orally in experimental animals (Biswas 1999).
Toxicity
No data found. Amalaki is widely consumed throughout India as a medicinal food.
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Analytical Studies on Phvto-asslsted Methods for Toxic Contaminants Removal
(b) (c)
(a)
(e)
(d)
(f)
FIGURE 6.1 DIFFERENT PART OF EMBLIC (PHYLLANTHS EMBLICA)IEMBELICA OFFICINALIS
Anafvtical Studies on Phvto-asslsted Methods for Toxic Contaminants Removal
Cardiovascular
The lipid lowering and antiatherosclerotic effects of P. emblica fresh juice, given in doses equal
to 5 mljkg over a 60 day period, was evaluated in cholesterol-fed rabbits. Serum cholesterol,
triglycerides, phospholipid and LDL levels were lowered by 82%, 66%, 77% and 90%,
respectively. Tissue lipid levels showed a significant reduction following P. emblica juice
administration, with the regression of aortic plaques and increased excretion of cholesterol and
phospholipids, compared to controls (Mathur et al., 1996). Researchers studied the effect of P.
emblica in normal and hypercholesterolaemic men aged 35-55 years to determine its effect on
total serum cholesterol. The supplement was given for a period of 28 days in the raw form. Both
normal and hypercholesterolemic subjects showed a decrease in cholesterol levels while taking
Amalaki, but two weeks after withdrawing the supplement the total serum cholesterol levels of
the hypercholesterolemic subjects rose almost to initial levels (Jacob et al., 1988). P. emblica
was found to reduce serum cholesterol, aortic cholesterol and hepatic cholesterol in rabbits, but
did not influence euglobulin clot lysis time, platelet adhesiveness or serum triglyceride levels
(Thakur, 1985). The effect of Amalaki on serum cholesterol was investigated in rabbits. After a
standard laboratory diet the rabbits were fed a combination of cholesterol and clarified butter,
and were divided into three groups: one which served as a control, the second which were also
given 10 mg of vitamin C daily, and one group that were given 1 g of Amalaki daily. Mean serum
cholesterol levels in all three groups rose to significantly higher levels by the end of the second
week, and continued to rise by the end of the third and fourth weeks except in those animals
given Amalaki, which demonstrated significantly lower mean serum cholesterol levels (Mishra,
1981).
Indications
Dyspepsia, gastritis, biliousness, hyperacidity, hepatitis, constipation, flatulent colic, colitis,
hemorrhoids, convalescence from fever, cough, asthma, skin diseases, bleeding disorders,
menorrhagia, anemia, diabetes, gout, osteoporosis, premature graying, alopecia, asthenia,
mental disorders, vertigo, palpitations, cardiovascular disease, cancer.
Contra indications
Acute diarrhea, dysentery (Frawley and Lad, 1986).
Medicinal uses
Amalaki is among the most important medicinal plants in the Ayurvedic materia medica, and
along with Haritaki and Vibhitaki forms the famous Triphala formula, used to cleanse the dhatus
of ama. pacify all three doshas. and act as a rasayana to promote good health and long life. A
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Analvtical Studies on Phyto-asslsted Methods for Toxic Contaminant§ Removal
synonym for Amalaki is Dhatri or 'nurse; indicating that it has the power to restore health like a
mother caring for her child. The fruit is the most commonly used plant part, and the fresh fruit is
preferred. An excision in the unripe fruit is made and the exudate collected Is used topically in
conjunctivitis (Kirtikar and Basu, 1935). The unripe fruits are also made Into pickles and given
before meals to stimulate the appetite in anorexia (Nadkarni, 1954). The fresh juice of the fruit
rnixed with ghrita is a rasayana, has a beneficial activity upon the intestinal flora, and is a
corrective to colon function. The fresh fruit is very hard to come by outside of the subcontinent,
and can usually be found in Indian markets for only a few weeks during the fall. The dried fruit is
used as a decoction to treat ophthalmia when applied externally, and is used internally as a
hemostatic and antidiarrheal (Nadkarni, 1954). The boiled, reconstituted dried fruit, blended into
a smooth liquid with a small quantity of gur added, is useful in anorexia, anemia, biliousness
dyspepsia, and jaundice. This is also an excellent restorative in chronic rhinitis and fever, with
swollen and dry red lips and rashes about the mouth. The dried fruit prepared as a decoction and
taken on a regular basis is useful in menorrhagia and leucorrhea, and is an excellent post
partum restorative. Similarly the Chakradatta recommends the fresh juice of Amalaki with
Amalaki churna, taken with ghee and honey as a vajikarana rasayana. In the treatment of
cardiovascular disease Amalaki is an excellent antioxidant botanical, used to treat all of the
cardiovascular effects of poorly controlled diabetes and insulin resistance, including diseases of
microcirculation such as macular degeneration. Amalaki is similarly taken in polluted urban
areas to keep the immune system strong. For coronary heart disease in particular Amalaki can
be combined with Arjuna, or non-Indian botanicals such as Hawthorn, and with Guggulu for
dyslipidemia. Taken with Guduchi, Katuka, and Bhunimba, Amalaki forms an important protocol
in the treatment of hepatitis and cirrhosis. Amalaki is also an important herb to consider to
protect the body against the deleterious effects of chemotherapy and radiation in conventional
cancer treatments. In combination with Chitraka, Haritaki, Pippali and saindhava, Amalaki
churna is mentioned by the Sharangadhara samhita in the treatment of all types of fever
(Srikanthamurthy, 1984; 2001). In the treatment of nausea, vomiting and poor appetite fresh
Amalaki is crushed with Draksha (Vitis vinifera) and mixed with sugar and honey (Sharma, 2002).
Amalaki fruit fried in ghee and reduced to a paste and mixed with kanjika (fermented rice water)
is applied over the head to treat nosebleeds (Srikanthamurthy, 1984 ). In the treatment of
agnimandya, edema, abdominal enlargement, hemorrhoids, intestinal parasites, diabetes and
allergies three parts Amalaki churna is mixed with the same amount each of Ajamoda
(Trachyspermum ammi), Haritaki and Maricha (Piper nigrum), with 1 part pancha lavana (the
'five salts,' i.e. saindhava, samudra, sambara, sauvarchala and vid lavana), macerated in
buttermilk until it has fermented (Sharma, 2002). Combined with equal parts Guduchi
(Tinospora cordifolia), Shunthi (Zingiber officinalis), Aragvadha (cassia fistula) and Gokshura
(Tribulus terrestris), dried Amalaki fruit is recommended by the Chakradatta as a decoction in the
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Analvtical Studies on Phy(o-asslsted Methods for Toxic Contaminants Removal
treatment of urinary tenesmus (Sharma, 2002). Amalaki Is the primary constituent of a complex
polyherbal lehya called Chyavanaprash that Is used as a rasayana, and In the treatment of
chronic lung and heart diseases, infertility and mental disorders (Sharma 2002). Another valued
rasayana that contains Amalaki, as the primary constituent is Brahma rasayana, giving the
person that takes it " ... the vigor resembling an elephant, Intelligence, strength, wisdom and right
attitude (Srikanthamurthy 1995). The dried fruit made into an oil and applied to the head, and
taken internally as a decoction or powder, is reputed to be useful in alopecia and adds luster and
strength to the hair. Similarly, the Chakradatta recommends a nasya of equal parts Amalaki and
Madhuka (Giycyrrhiza glabra), decocted in milk, in the treatment of alopecia (Sharma, 2002).
Both the fresh juice and crushed seeds are combined with Haridra (Curcuma longa) as an
effective treatment for diabetes (Sharma, 2002; Dash and Junius, 1983). The seeds are made
into a fine powder and mixed with equal parts powder of Ashvagandha (Withania somnifera) root
as a rasayana in the cold winter months (Nadkarni, 1954). For scabies and skin irritations the
seed is charred, powdered and mixed into sesame oil and applied externally (Nadkarni, 1954).
MATERIAL AND METHODS
Preparation of biomass for chromium removal
An appropriate body part of amala tree collected from the different areas of Chattisgarh. The
biomass was extensively washed with running tap water for 30 to 40 minutes to remove dirt and
other particulate matter followed by washing in double distilled water. The cut in small pieces.
The sample was dried first at sun light for seven days then immersed in hot water for 1 hr then
again the sample was washed with double deionized water and dried in an electric oven at 45°C
for over night, The dried biomass was ground in a laboratory blender and sorted by sieving using
the standard test sieves. The particle size used was 250 JJ. The Sample was stored in
desiccators and used for biosorption studies. The adsorbent has already being utilized for
chromium removal by Krishnamoothy and Joseph (2003). The procedure adopted by us was
different from theirs, in the leaching process.
Preparation of biomass for Nickel removal
The root of Calotropic procera was collected from the different areas of Durg Distt of Chattisgarh.
The biomass was extensively washed with running tap water for 30 to 40 minutes to remove dirt
and other particulate matter followed by washing in double distilled water. An appropriate body
part were removed and cut in small pieces. The sample was immersed in 1:1 HCI solution for 10
minutes then again the sample was washed with double deionized water and dried in an electric
oven at 600C for 2hr, and then it was kept at a temperature of 45°C for overnight. The dried
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Ana/vfica/ Studies on Phvfo-asslstad Mefhods for Toxic Coatamlnaqta Remove/
biomass was ground in a laboratory blender and sorted by sieving using the standard test sieves.
The particle size used was 250 ~- 100 gm of FBM was Immersed for 24hr in 1L 1:1 HN03. Then
the solution was filtered and washed properly with double deionized water. Washed sample was
dried at sooc for 1hr in an electric oven. The Dried sample was again dried at 35oc for 24hr and
stored in desiccators for use. Sample was stored in desiccators and used for biosorption studies.
Analysis of nickel
Nickel was analysed by hydride generation atomic absorption spectrophotometer with
background correction facility (HG-MS, Chemito-201) and occasionally by Dimethyl glyoxime
method using scanning UV-Visible spectrophotometer (Chemito-UV 2100) following the APHA
(American Public Health Association) standard solution and chemicals Apparatus and Materials.
The process of nickel is same as described in chapter IV.
Analysis of chromium
Chromium was analysed by hydride generation atomic absorption spectrophotometer with
background correction facility (HG-MS, Chemito-201) and occasionally by s-diphenyl carbazide
method using scanning UV-Visible spectrophotometer (Chemito-UV 2100) following the APHA
(American Public Health Association) standard solution and chemicals Apparatus and Materials.
The process of analysis of chromium is discribe below.
Atomic absorption spectrophotometer
The MS used Chemito (MS 201) is a single channel, double-beam instrument having a grating
monochromator, photo-multiplier detector, adjustable slits, a wavelength range of 357.9 to
359.4 nm. The burner used was special corrosion resistant metal as recommended by the
particular instrument manufacturer. The chromium hollow cathode lamp used was manufactured
by Photron, Australia.
Reagents
Analytical reagent grade chemicals (Merck, Germany/India) were used in all tests. The reagent
water used was deionized and double distilled, interference free water. All references to water in
the method refer to reagent water unless otherwise specified. Acid viz. HNOa. H2S04, and HCI etc.
were analysed to determine levels of impurities. The acid was used only when the method blank
was less than the detection limit ( < MDL).
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Analvtical Studies on Phvto-asslsted Methods tor Toxic Contaminants Removal
• Chromium stock solution (1000 mgtl)
Dissolve 3.735 gm potassium dichromate (K2Cr207) In 1000 ml with double distilled water.
• Intermediate Chromium solution
10 ml stock nickel solution was pipetted into a 100-ml volumetric flask and made up to
mark with deionized water. (1 ml = 100 IJg Cr).
• Standard chromium solution
10 ml intermediate chromium solution was pipetted into a 100-ml volumetric flask and
brought to volume with deionized water (1 ml =10 IJg Cr).
Procedure adopted in MS
0.00, 1.0, 2.0, 3.0 and 4.0 ml of standard chromium solution in 50 ml of uncontaminated
volumetric flask was taken out, and made upto mark with double distilled water. This yields
blank and standard solutions of 2, 4, 6, 8 IJ&'ml. (APHA, 1992). lnsrumental parameter
employed in HGAAS method is perented in Table 5.2.
TABLE 5.2.
INSTRUMENTAL PARAMETERS EMPLOYED IN HGAAS METHOD
Wavelength (nm)
Current (mA)
Flame
Parameter
Normal Working Range (mgtl)
Spectral band width (nm)
N2 flow rate (Litrejminute)
Value
357.9/ 452.4(Aiterative)
5-10
Air-Acetylene flame reducing (AAR)
2-8
0.5
0.4-1.0
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Analvtlcal Studies on Phyto-aul!ted Methods lor Toxic Contaminants Bemoval
Procedure adooted in UV- Visible spectrophotometer
In a series of uncontaminated conical flask 0.0, 1.0 2.0, 4.0, 5.0 ml of chromium standard
solution was pipetted. Include a 50.0 ml volumetric flask containing none as a reagent blank.
The sample containing not more than 50 ~g in 50.0 ml volumetric flask. To the blank and
standards and sample the following reagents were added in order with mixing after each
addition.
(2) 10 ml 5% sulphuric acid,
(2) 0.4ml phosphoric acid, and
(3) 4 ml diphenyl carbazide solution. Then made up to 50 ml with double distilled water and
allowed to stand for 5 minutes. Pored the solution in cuvette of I em cell and measured
the absorbance of solution at 540 nm on UV- Visible spectrophotometer. Prepared the
calibration curve and found the mg chromium equivalent to the observed optical density.
A typical calibration curve of chromium for AAS and UV-Spectrophotometer is shown in
Figure 5.2 and 5.3 respectively.
0.2
0.18
0.16
0.14
Cl) 0.12 IJ 1::
"' -e 0.1 0
"' .Q "': 0.08
0.06
y = 0.0406x + 0.0035
~ R2 = 0.9731
/ ? ~
# ~
~ 0.04
0.02 I I
0 I
2 4 6 8
Concentration of Cr(VI) mg/L
_.....Absorbance for Cr(VI) -Linear (Absorbance for Cr(VI))
FIGURE 5.2. A TYPICAL CALBRATION CURVE OBTAINED WITH HG-AAS.
211
Analytical Studies on Phvto·asslsted Mgthods for Toxic Contaminant! Rgmoval
<II ...
1.4
1.2
1
:; 0.8 -e ~ 0.6 -----.Q "'(
0.4
02 :.i·~ . -------- ----·-
0.2 0.4 0.8 1
Concentration of Cr(VI) mg/L
-""-Absorbance -Linear (Absorbance)
FIGURE 5.3. A TYPICAL CALIBRATION CURVE OBTAINED WITH UV·VIS.
Biosorption Experiments
With the objective of achieving an understanding of the process of biosorption to establish better
conditions for this process and to provide data based on biosorption, sorption experiments were
carried out using stock solutions of metallic Nickel and Chromium (99.99%, MERCK). in order to
study the effects of pH, contact time, biosorbent dosage and initial concentration of the heavy
metal in the process of removal of metallic Nickel and Chromium at a constant temperature. The
heavy metal concentrations were determined using an atomic absorption spectrophotometer
and occasionally by UV-VIS. All the biosorption experiments were conducted in 250 ml
Erlenmeyer flasks at room temperature (28°C) (Kapoor and Viraraghavan, 1998) In each
experiment 1 litre of binary mixture of Ni(ll} and Cr(VI) of 50 mg/L initial concentration was
treated with a specified known amount (by wt) of biomass (1g/L to 10g/L}, and the known pH for
a known period of time. Batch kinetic studies were first conducted using biomasses and to
determine the time needed for binding process to reach the equilibrium state. Based on kinetic
experiment results all experiments were conducted for a period of 30 minutes.
After the equilibrium was reached the adsorbent was separated from the metal solution by
whatman filter paper no 42. Then the the concentration of metal ions remaining in solution was
measured using Atomic Adsorption Spectrophotometer (CHEMIT0-201). All the experiments were
conducted in duplicate. Blank experiments were carried out simultaneously, indicate that no
prec1p1tation of metal ions occurred under the conditions selected. Biomass control indicates
212
Ana/vtica/ Studies on Phvto-asslatad Methoda for Tox{c ContamlnfQtf Bemovtl
that ther was no release of metal by biomass. The amount of metal ion In adsorbed by the
biosorbent was calculated by the equation:.
Where
Ci
Ce
m
qe
=
=
=
=
initial concentration of metal ion mgfL
Equilibrium concentration of metal ion mgfl
mass of adsorbent giL
Amount of metal ion adsorbed per gram of adsorbent
With a view to determining the influence of pH, chromium and nickel concentration, and biomass
concentration on the efficiency of biosorption determined.
Batch Elution experiments were also carried out to desorb bound from the biomass using five
different eluting agents HC\, NaCI, HN03, NaOH, Na2C03.
Column Mode Adsorption Studies
(Single column and mixed bed adsorption stvdy)
The column used for the removal of binary mixture of nickel and chromium under the continuous
flow conditions, was made up of Borosi\ glass. The outer diameter of column was 4.6 em and the
inner diameter of column was 4.1 em. The filter used in the column was 0.5 em thick
approximately 5 gm of biomass was packed into a column having a column height of 0.1 em. An
aqueous solution containing 50 mgfl binary mixture solution of Ni(ll) and Cr(VI) was first passed
through a column containing only the biomass responsible for Ni(ll) adsorption. Effluent sample
was collected for every cycle volume using a fraction collector (Gilson FC-203) and were analyzed
for Ni(ll) as well as Cr(VI) concentration by using Atomic Adsorption Spectrophotometer
(CHEMITO - 201). Then the solution containing Cr(Vl) was passed through another column
containing the biomass which was responsible for adsorption of Cr(Vl). Effluent sample was
collected for every cycle volume using a fraction collector (Gilson FC-203) and were analyzed for
Ni(ll) as well as Cr(VI) concentrations by using Atomic Adsorption Spectrophotometer (CHEMITO -
201). As per the results of batch experiments eluting agent was selected. Eluted biomass was
washed with distilled water for regeneration. The regenerated biomass was tested for Ni(ll) and
Cr(VI) uptake. Two cycles of metal ions loading and elution were conducted.
A mixed bed column was successfully developed in the laboratory, in which a single column
containing first the biomass responsible for Cr(VI) removal then the biomass for the adsorption of
213
Analytical Studies on Phyto-asslsted Methods for Toxic Cont!mln«Dtl Remoytl
Ni(ll). Both the biomasses were separated through a thin filter paper. A 50 ml binary mixture of
Ni(ll) and Cr(VI) of initial concentration 50 mg/L was passed through the column. The solution
coming out from the column was analysed for the both metal ions. Then the blomasses were
sepreted and by using the suitable eluting agent the metal get eluted as In the form of
concentrated acidic solution. Then the biomasses were washed with double distilled water for
the regeneration purpose.
Desorption Study
A known amount of biomass was taken into a 250 ml beaker. Batch kinetic studies were
conducted using biomasses to determine the time needed for the Ni(ll) and Cr(VI) binding
process to reach the equilibrium state separately. After the biosorption tests the biomass was
washed with deionsed water for 15 minutes and left in 15 ml different eluting agents for one
hour at 30°C in a beaker. The biomass was separated from the solution by filtration and washed
with deionized water until the pH of the filtrate reached 7. Then the recovered biomass was dried
in an electric oven at 60°C and the capacity to biosorb metal was determined. The biosorption
desorption cycle of Ni(ll) metal-biomass recovery and Cr(VI) metal-biomass recovery was
repeated two times in order to determine the biosorption capacity of recovered biomass.
Batch experiment were conducted to desorbs bound Ni(ll) and Cr(VI) from biomass using
different eluting agents such as NaOH, NaCI, Na2C03, HCI, HN03. Overall processes of adsorption
desorption and regeneration is presented in result and discussion.
FT-IR Method
The FT-IR Study of fresh biomass and metal loaded biomass of Calotropis procera and Embalica
offcinals using the detector DTGS KBr, Beamspilter KBr, Infrared source was done with Branch
Thermo Nicoler Nexus 670 Spectrometer. This FT-IR Study was done in Indian Institute of
Chemical Technology, Hydrabad.
RESULT AND DISCUSSIONS In this chapter, Successful attempt has been made for the separation of nickel and chromium
from contaminated effluent. Two local biomasses available in Chhattisgarh has been studied for
the ability to bind Cr(VI) and Ni(ll) under the room temperature time effects.
Ootimization of all Analvtical oarameters
Effect of pH on metal biosorption
Sorpt1on of heavy metals from aqueous solutions depends on properties of adsorbent and
molecules of adsorbate transfer from the solution to the solid phase. It has been also reported
214
Analytical Studies on Phyto·asslsted Methods for Toxic Contamlnsnts Removal
that biosorption capacities for heavy metals are strongly pH sensitive and that adsorption
increases as solution pH increases (The equilibrium Cr(VI) and Ni{ll) uptakes at various pH values
are presented in Figure 5.4. The effect of pH was studied by varying the suspension pH from 2 to
7. The initial metal ions concentration was 50 mg/L, using 5 giL of biosorbent dosage with 30
minutes of contact time. The results indicates that the biosorption initially increases, in case of
Cr(VI) increases up to pH 3. After the pH 4 increases in pH value decreases the percentage
removal of Cr(VI) up to the pH 7. It has been known that Cr2072· ions precipitate at pH's above 7,
and in the range between 3 to 4 the removal of Cr(VI) was the same. (By Literature study) can be
attributed to the positive surface charge gained depending on the adsorption of H' ions on the
biomaterial surface (Aksu et al., 1996). And in the case of Ni{ll) the removal was initially
increases with increase in pH value after the pH 3 the removal was decreases with increase in
pH value. The increase in percentage removal of metal ion due to increase in pH may be
explained on the basis of a decrease in competition between proton (H+) and positively charged
metal ion at the surface sites and also by decrease in positive charge near the surface which
results in a lower repulsion of the adsorbing metal ion (Meena et.al, 2004). Maximum
percentage removal of nickel was investigated at pH 3, which can be due to the formation of
M(OH) and M(OH)2 as hydrolyzed product. The lower solubility of these hydrolised species may be
another reason for maximum adsorption. So the optimum pH taken for both the metal ions were
pH 3.
Concentration of N1(ll) solution = 50 mg/L,
Concentration of Cr(VI) solution = 50 mg/L,
Temperature = 28oC,
120
100 - :;/-'_ ~ 0 80 e "' Q: ., 60 "" ~ c: "' 40 --------~ .t
20
0 2 3
Biosorbent dosage = 5 g/L,
Contact time= 30 minutes,
---~--------------
4 5 6 7
PH ~-~ Ni(ll) removal -.-Cr(Vl) removal
FIGURE 5.4. EFFECT OF pH ON BIOSORPTION OF Ni(ll) AND Cr(VI).
215
Analytical Studies on Phyto-asslsted Methods for Toxic Contaminants Removal
Effect of sorbent concentration
The effect of biosorbent dosages for both Ni(ll) and Cr(VI) were investigated at 28°C and
optimum pH value (pH 3) by varying the biosorbent concentration 1 giL to 10 giL. The results
shown are shown in Figure 5.5. It is apparent that the percent removal of Cr(VI) increases rapidly
with increasing concentration of the biosorbent, due to the greater availability of the
exchangeable sites or surface area at higher concentration of the sorbent. The maximum
removal of Cr(VI) was occured at 5 giL sorbent dosages. Further increase in concentration of
biomass does not show the significant changes upto 10 giL. And in the case of Ni(ll) shows that
there was an increase in percentage removal of metal ion with increase of absorbent dose. The
removal in this case was between ranges of 90-95%. Hence it can be inferred that the
Percentage removal of nickel and Cr(VI) using two biomasses increases gradually. According to
the results 5 giL of biosorbent dosage was considered as the optimum dose for the removal of
both Ni(ll) and Cr(VI).
Concentration of Ni(ll) solution = 50mg/L,
Concentration of Cr(VI) solution = 50mg/L,
pH =3,
120
100
Temperature= 28°C,
Contact time = 30 minutes,
-~ .--0 80 ~ II:
"' 60 Cl ~ 0::::
"' ~ 40 "' Q.
20
oL---------------------~------~--~ 0.5 1 1.5 2 3 5 10
Biosorbent Dosage in giL
--.:- Ni(il) Removal --Cr(VI) Removal
FIGURE 5.5. EFFECT OF 8/0SORBENT DOSAGE ON B/OSORPTION OF Ni(ll) AND
Cr(VI) AT pH 3.
216
Analvtica/ Studies on Phvto-assisted Methods for Toxic Contaminant! Removal
Effect of contact time
Kinetics and equilibrium are the two most important parameters to evaluate adsorption
dynamics. The effect of contact time on the nickel and chromium removal were Investigated for
an initial concentration of 50 mg/L Figure 5.6. Shows the variation of percent removal of metal
ions with contact time 5 to 150 minutes. It was investigated that the rate of removal of metal
ions initially increases with contact time. About 90% of the nickel and 100% of Cr(VI) adsorption
were attained within 30 minutes. Further increase in contact time decreases the percent
removal of Ni(ll) up to 120 min and further increase in contact time does not show significant
changes on the uptake due to the saturation of the adsorption process. And in the case Cr(VI)
further increase in contact time after 30 minutes does not show significant changes on the
uptake (i.e. 100%) due to the saturation of the adsorption process. So the optimum time
considered for both the metal ions was 30 minutes. For the determination of the kinetics,
Langergren equation was applied as follows;
log (q • .q) =log qe-Kao x t/2.303
Where
Kao - is the rate constant of adsorbent
q- the amount of metal ion adsorbed at timet mg/g
qe -the amount of metal ions adsorbed at equilibrium (mgt g)
Values calculated based on above equation and graph plotted between log (qe-q) and time in
minutes follow a linear relation which indicates that the kinetics of biosorption of Ni(ll) was of
first order kinetic. And in the case of Cr(VI) a straight line indicate that the adsorption was of first
order kinetics. Shown in Figure 5.7.
217
Analytical Studies on Phyto-asslsted Methods for Toxic ConfBmlnan(S Removal
Initial concentration of Cr(VI) 10n = 50mg!L,
Biosorbent Dosage = 5 giL, pH =3,
Temprature = 30°C, Initial concentration of Ni(ll) ion =50 mg/L,
120 ---- ~-
-------·--------------~. -----------
100 -~ 0 80 E ..
Q: g, 60 l!
!~'=-:.>------------__,_________. :S T -------·-'-.ao==="""lla~~~---.. ---------
" .. ~ ~
20 ---~-------------~---
0 -+,-----,--------,----,-----,----,-------,-----,----10 20 30 45 120 150 180 240
Contact Time in Minutes
---11---- Ni(ll) Removal __.._ Cr(VI) Removal
FIGURE 5.6. EFFECT OF CONTACT TIME ON BIOSORPTION OF Ni(/1) AND Cr(VI) AT
pH3.
0.8
0.7
0.6
~ 0.5 . • Q)
-!:!: 0.4 l:ll
..!2 0.3
0.2
0.1
0 5 10 15 30
Time in minutes
--- Ni(ll) Cr(VI) -Linear (Ni(ll)) -Linear (Cr(VI))
FIGURE 5. 7. THE STRAIGHT UNE FOR Ni(/1) AND Cr(VI) SHOWS THE KINETICS OF
BIOSORPTION IS OF FIRST ORDER AT pH 3.
218
Analytical Studies on Phvto-aglsfad Mefhods for Toxic Contaminants Removal
Effect of loading capacity of Ni(ll) and Cr(VI) for blosorptlon
The effect of initial metal concentration on Nl(ll) and Cr(VI) removal by using two different
biomasses are shown in Figure 5.8. The biosorbent dose, pH and standing time for the batch
experiment were fixed at 5 g/L, pH 3 and 30 minutes respectively. Increasing the initial
concentration of both metal ions in a batch study resulted in decreasing percentage of removal
because the biosorbent was approaching its saturation uptake capacity. In batch study the
removal for nickel was 90-42% and in the case of Cr(VI) the removal was 100 to78% when the
initial concentration of metal ions were increased from 5 to 250 mg!L.
pH; 3,
Temprature; 28°C, Biosorbent Dosage ; 5 giL,
Standing time; 30minutes,
Concentration of metal ions ; (1 - 500mg/L),
120
100 II
-~ 80 .. ~-. -------0 e Cll
a:: Cll 60 - -----tn ~ c: Cll
~ 40 ~
20
0 5 10 20 30 50 100 250
Concentration of Metal ion Solution in mg/L
--Ni(ll) Removal --cr(VI) Removal
500 1000
FIGURE 5.8. THE EFFECT OF INITIAL METAL ION CONCENTRATION ON
BIOSORPTION OF Ni(/1) AND Cr(V/) AT pH 3.
l
219
Analytical Studies on Phyto-asslsted Methods for Toxic Contaminants Removal
Effect of Common ions
The effect of co-occurring ions was studied in detail in this experiment. The ions considered are
chloride, sulphate, cadmium, manganese, and copper. It Is generally present in electroplating
waste. The concentration varies from the range of 5 to 500 mg/L.
Effect of Chloride ions on biosorption
The effect of chloride ions on the biosorption of Ni(\1) and Cr(VI) are presented in Figure 5.9. The
results clearly shows that the removal of metal ions decreased in the presence of chloride ion in
solution. The different concentration of chloride was varying between 5-500mg/L. The removal of
Ni(ll) decreased from 35 to 8%, with increase in concentration of chloride from 5 to 500 mg/L,
and in the case of Cr(VI) the percent removal was slightly increased from 22 to 48%, with
increase in the chloride dosage from 5 to 500 mg/L.
Initial concentration of Cr(VI) metal= 50 mg(l,
Concentration of chlonde ion range = 5-500 mg(l
Chromium Biosorbent Dosage = 5 g(L,
Standing Time= 30 minutes
Temperature = 2soc pH=3,
Nickel Biosorbent Dosage = 5 g(L, Initial concentration of Ni(ll) metal = 50 mg(L,
60
t: ---l .2 50 -----.l!l Q)
e 40 .... 0
---~~ -~ 30 0 e ~ 20 .... t: Q)
!:! 10 Q)
a.
0 5 10 20 40 50 100 250 500
concentration of chloride mg/L
__,.,__ % Removal Ni(ll} --% Removal Cr(VI}
FIGURE 5.9. EFFECT OF CHLORIDE ION ON BIOSORPTION AT pH 3.
220
Analytical Studies on Phyto-asslstfd Methods for Toxic Contaminants Removal
Effect of Sulphate ion concentration on the blosorptlon
The concentration of sulphate ion varied within the range of 5 to 500 mgtl. The result shown are
Figure 5.10, for both the biomasses. The results Indicate that the percentage removal of Ni(ll)
decreased with increase in sulphate ion concentration from 5-500 mgtL. And in the case of
Cr(VI) the removal increased from 20 to 60% with increase in the concentration of sulphate ions
from 5 to 500 mgtL.
pH =3
Chromium B1osorbent Dosage= 5 giL
Initial concentration of Ni(ll) metal = 50 mgtL
Standing Time= 30 minutes
70
II) 60 t: ~~-
.~ -.l!! 50 Cll
--- -----
E .... 40 0 -~ 0 30 E e -20 t:
- -~
/ .:;~--- --
/ -·lr
Cll ~ ~ 10 -----
0 5 10 20
Nickel Biosorbent Dosage = 5 g{L
Temperature = 28°C
Initial concentration of Cr(VI) metal =50 mgtl
Concentration of sulphate ion range = 5-500 mgtl
--
----- - .. ------~
/
~ ~
' '
40 50 100 250 500
Concentration of Sulphate ions mg/L
----c•-% Removal of Ni(ll) -+-% Removal of Cr(VI)
FIGURE 5.10. EFFECT OF SULPHATE ION ON BIOSORPT/ON AT pH 3.
I I
221
Analvtlca/ Studies on PhV(o-ass/sted Methods for Toxic Contaminants Removal
Effect of Cadmium ion on biosorption
The different concentration of cadmium was varying between 5-500mg!L The results are shown
in Figure 5.11. The result indicates that cadmium enhances the percentage removal of Ni(ll) as
well as Cr(VI) from the solution. When the cadmium ion concentration was 5 mg/L, 70% of Ni(ll)
and and 73% of Cr(VI) were removed. The removal of Ni(ll) was increased by increasing the
dosage of cadmium ion upto 40 mg/L. After 40 mg/L of concentration of cadmium decrease in
percent removal of Ni(ll) was observed. But in the case of Cr(VI) the percentage removal was
increased with increase in the cadmium ion concentration. After 50 mg/L of cadmium ion
concentration the removal of Cr(VI) was 83% and same up to 500 mgll of cadmium.
pH= 3
Chromium Biosorbent Dosage = 5 g/l
Initial concentration of Ni(ll) metal= 50 mg/L
Standing Time= 30 minutes
Nickel Biosorbent Dosage = 5 g/l
Temperature = 28°C
Initial concentration of Cr(VI) metal = 50 mg/l
Concentration of cadmium ion range= 5-500 mg/L
90-r-----------------------------------------,
... ~ 50 ~ 0 40
~ ... 30 -~ 20 ~
- ------------ ~~ ~------ ---~-
- ~- ----~----------------~--------1
--- ----~-
,r 10 -
QL-------------~----~--~----~--~--~
5 10 20 40 50 100 250 500
Concentration of Cadmium ion mg/L
--- % Removal of Ni(ll) % Removal of Cr(VI)
FIGURE 5.11. EFFECT OF CADMIUM ION ON THE 8/0SORPT/ON AT pH 3.
222
Analvtlcal Studies on Phvto-asslsted Methods for Toxic Contaminants Removal
Effect of Manganese ion on the biosorption
The effect of common ion manganese was investigated from the range of 5-1000 mg/L in
solution. The effect of manganese ion on the percentage removal of Ni(ll) and Cr(VI) are shown in
Figure 5.12. The results clearly indicate that the presence of manganese was playing a very
important role for the biosorption process. In the presence of manganese the removal of Ni(ll)
and Cr(VI) decreased sharply. In the case of Ni(ll) the percentage removal becomes zero with the
40 mg/L of manganese concentration. And in the case of Cr(VI) , initially the removal decreased
from 30 to 24% with increase in the manganese ion concentration from 5 to 40 mg/L, Then the
removal was increased upto 38% with 500 mg/L of manganese ion concentration.
pH= 3
Chromium Biosorbent Dosage = 5 g/L
Nickel Biosorbent Dosage = 5 giL
Temperature= 28°C
lnittal concentration of Ni(ll) metal = 50 mg/L
Standing Time= 30 minutes
Initial concentration of Cr(VI) metal = 50 mg/L
Concentration of manganese ion range = 5-500 mg/L
40.---------------------------------------,
~ 35 .!2 :a 30 Cll
e 25 ~ ... ~ 20 0 e 15 ~ ~ 10 ~ Cll 5 - -~
-----+--- -------- -
--{,.:·----;::- ---
---·---- j ~- -----\----~-----~----- -- .J
5 10 20 40 50 100 250 500
Concentration of Manganese ion mg/L
- ~ % Removal of Ni(ll} ----% Removal of Cr(VI}
FIGURE 5.12. EFFECT OF MANGANESE ION ON 8/0SORPT/ON AT pH 3.
223
Analytical Studies on Phvto-asslste(f Methods for Toxic Contaminants Removal
Effect of Copper ion on biosorption
The effect of metal ion copper was investigated from the range of 5-1000 mg/L in solution. The
effect of copper ion on the percentage removal of Ni(/1) and Cr(VI) is shown on Figure 5.13. The
results clearly indicate that the presence of copper was also playing an important role for the
biosorption process. In the presence of copper the removal of Ni(ll) and Cr(VI) was decreased
sharply. In the case of Ni(ll) the percentage removal was initially zero from 5 to 20 mg/L of
copper ion concentration. After increase in copper concentration above the 20 mg/L of removal
of Ni(/1) increased with increase in the dosage of copper ion from 40 to 500 mg/L, in solution.
And in the case of Cr(VI), there was increase in the percent removal of Cr(VI) from 18 to 54%,
with increase in the concentration of copper ion in solution from 5 to 500 mgll.
pH= 3
Chrom1um Biosorbent Dosage = 5 giL
Nickel Biosorbent Dosage = 5 giL
Temperature = 28°C
Initial concentration of Ni(ll) metal = 50 mg;L
Standing Time = 30 minutes
Initial concentration of Cr(VI) metal = 50 mg/L
Concentration of Copper ion range = 5-500 mg/L
-~~~~· ::=:2_"' _l ;7 ~
----/---1 1------------------ ----~
I ' I
---lll'~---~~----------------j
-'\---------~ '\
50 100 250 500
Concentration of Copper ion mg'L
« % Removal of Ni(IQ -1o-% Removal of Cr(VQ
FIGURE 5.13. EFFECT OF COPPER ION ON BIOSORPTION AT pH 3.
224
Analvtical Studies on Phyto-assfsted Methods for Toxfc Contamfnants Removal
Column Mode Adsorption Studies
!Single column and mixed bed adsorotion stydyl
In batch study the maximum removal of Ni(ll) was 90% and Cr(VI) was 99.9% (initial
concentration of both was 50 mg/L) was occurred at pH 3. A column was developed for the
removal of these metal ions. When An aqueous solution containing 50 mg/L binary mixture
solution of Ni(ll) and Cr(VI) was first passed through the column which contains only the biomass
responsible for Ni(ll) adsorption. Effluent sample was collected using a fraction collector and
were analyzed for Ni(ll) and Cr(VJ) concentration by using Atomic Adsorption Spectrophotometer
(CHEMITO - 201), then it was investigated that the Ni(ll) get almost completely adsorbed on the
biomass and only chromium remains in solution that mean 50 mg/L of Ni(ll) removed completely
and the removal of 50 mg/L of Cr(VI) after passing the first column was zero percent. The
solution containing Cr(Vl) was then passed through another column containing the biomass
which was responsible for adsorption of Cr(VI). Effluent sample was collected for every cycle
volume using a fraction collector and were analyzed for Ni(ll) and Cr(VI) concentrations by using
Atomic Adsorption Spectrophotometer. It was investigated that the removal of 50 mg/L of Cr(VI)
get almost completely after passing the column contains the biomass responsible for Cr(VI)
removal . The results indicates that the biomass which is responsible for Ni(ll) removal does not
remove Cr(VI), so the chromium remains in solution as it is. As the results of batch experiments
0.1 N HN03 was considered as a elution of Ni(ll) from the adsorbed biomass as well as taken for
the elution of Cr(VI) from the biomass too. Eluted biomass was washed with distilled water for
regeneration. The regenerated biomass was tested for Ni(ll) and Cr(VI) uptake.
A mixed bed column was successfully developed in the laboratory, in which a single column
containing both biomasses the lower layer contains Cr(VI) removal biomass and the upper layer
contains the biomass for Ni(ll) removal. First the biomass responsible for Cr(VI) removal then the
biomass for the adsorption of Ni(ll). Both the biomasses were separated through a thin filter
paper. 50 ml of binary mixture of Ni(ll) and Cr(VI) of initial concentration were 50 mg/L. The
solution coming out from the column was analysed for the both metal ions. The removal of 50
mg/L of Ni(ll) as well as Cr(VI) was removed completely. And 100% of Ni(ll) and 88% of Cr(VI) get
eluted using the suitable agents, separately. Over all process is presented in Figure 5.14. and
5.15.
225
Analvtlcal Studies on Phyto-assfsted Methods for Toxic Contaminants Removal
BIOSORPTION PROCESS OF SEPERATION OF N1(ll) AND Cr(VI) BY SEPARATE COLOUMN
lnctustrlal Effluent Contains Ni(ll} and Cr(Vt) Both 50 mglt
Nl(ll) Adsorbed on Biomass Cr{VI)
Remain in Solution
(250 iJ size)
'--- Effluent Free From Ni(ll}
I cr=~R=e=m=o=va=,~E=ff!=ci=et=,c=y="' Removal of Ni{l1)=100%
Compfete ,Removal
Nt(if}"" 50 Mgll
c~rv~~ .. _so Mglt ,_I
Remaining Solution Contains only Cr (VI)
,..50 mil
Cr (VI) Adsorbed on Biomass
(250 ~size)
Effluent Free From Ni(ll} as. Well as Cr{Vi)
Removal ofCr{VI)=100%
FIGURE 5.14. BIOSORPTION PROCESS OF SEPERATION OF Ni(ll) AND Cr(VI) USING
SEPARATE COLUMN.
226
Analvtlcal Studies on Phvto=asslst!d Methods for Toxic Contaminant! Removal
MIXED BED COLOUMN USING SEPERATION N1(ll) AND C1(VI) ON A SINGAL COLUMN
Industrial Emuent Contains
Ni(ll) and Cr(Vi)
Only Ni(ll) Adsorbed on the Biomass
(250 ~size)
Thin Filter Paper
Cr(Vi) Adsorbed on Biomass
(260 ~size)
Ni(ll) and Cr(VI) Free Effluent
Ci for Ni(ll)• 50 mgli
Ci for Cr(VI)•SO mgli
Removal Efficiency
Ni(lll"'100%
Cr(Vi)=100%
FIGURE 5.15. SEPERA TION OF Ni(/1) AND Cr(VI) USING A MIXED BED COLUMN.
Elution study
For the purpose of desorption five different eluting agents were chosen 0.1N HN03, 0.1N HCI,
0.1M Na2C03, 0.05 M NaOH, 0.2M NaCI. The results are presented in Figure 5.16. It clearly
shows that 0.1N HN03 was playing a good eluting agent. 100% of 50 mg/L of Ni(ll) get eluted
using 0.1N HN03, and 88% of Cr(VI) was recovered. By using 0.1 N HCI, 0.1M Na2C03 , the
elution of Ni(ll) was 65%and 20 % respectively. And by using 0.05 M NaOH and 0.2 M NaCI the
elution was zero. And in the case of Cr(VI) 54% with using 0.1 N HCI and 24% by using 0.1M
Na2C03 of elution was occurred.
Concentration ratio for different eluting agents is presented in Table 5.2.
Where Co = the concentration ratio
C = Initial concentration of ion
Co = concentration desorb
227
Analytical Studies on Phyto-ssslsted Methods for Toxic Contaminant§ Removal
Eluting Agent
0.1 NHNO,
High Concentration Ni(JI) Metal to Recovery
Concentration Ratio Cr-1 .
lntJal conce-ntration of Nl{i1)=50 mgn Concentration desorb Cd=50 mgll
Cd=100
Eluting Agent
0.1 N HNOJ
High Concentration CrM Metal to Recovery
Cd=88%
Concentration Ratio Cr=O.S8 lntial concentration of Cr{VJ}=44 ml
Concentration desorb Cd .. 50 mgll
FIGURE 5.16. PRROICESS OF ELUTION OF BINDED Ni(/1) AND Cr(VI) ON
BIOMASS USING A SUITABLE ELUTING AGENTS.
TABLE 5.2.
THE CONCENTRATION RATIO OF DIFFERENT ELUTING AGENTS FOR BOTH Ni(/1)
AND Cr(VI).
S.No. Initial Concentration of Eluting agents Concentration Concentration
metal ion (Ni(ll) and Cr(VI) ratio for Ni(ll) ratio for Cr(VI)
both in mg(L
1 50 0.1 N HN03 1 0.88
2 50 0.1N0.1 N HCI 0.65 0.54
3 50 0.1M Na2C03 0.2 0.24
4 50 0.05 M NaOH 0 0
5 50 0.2 M NaCI 0 0
228
Anafvtlcal Studies on Phvto-ass/sted Methods for Toxic Contaminants Removal
Interpretation of Infrared Spectra
An invaluable tool in organic structure determination and verification involves the class of
electromagnetic (EM) radiation with frequencies between 4000 and 400 cm-1 (wavenumbers).
The category of EM radiation is termed infrared (IR) radiation, and its application to organic
chemistry known as IR spectroscopy. Radiation in this region can be utilized in organic structure
determination by making use of the fact that it is absorbed by interatomic bonds in organic
compounds. Chemical bonds in different environments will absorb varying intensities and at
varying frequencies. Thus IR spectroscopy involves collecting absorption information and
analyzing it in the form of a spectrum.
FT-IR studies of fresh biomass and chromium loaded biomass of Embalica officina lis was taken.
The results Interpreted that a very broad peak in the region between 3100 and 3600 cm-1
indicates the presence of exchangeable protons, typically from alcohol, amine, amide or
carboxylic acid groups. The frequencies from 2800 to 2000 cm-1 are normally void of other
absorptions, a very strong peak around 1700 cm-1, indicates the carbonyl group, and the peaks
around 1200 cm-1 indicates the C-0 bond. This complex lower region is also known as the
"fingerprint region" because almost every organic compound produces a unique pattern in this
area - Therefore identity can often be confirmed by comparison of this region to a known
spectrum.
Structure of aromatic compounds may also be confirmed from the pattern of the weak overtone
and combination tone bands found from 2000 to 1600 cm-1, this strong band indicates either an
aldehyde, ketone, carboxylic acid, ester, amide, anhydride or acyl halide. A methyl group may be
identified with C-H absorption at 1380 cm-1. The carbonyl (C=O) absorption between 1690-1760
cm-1, C-H bending below 900 cm-1 was seen. C-H absorption between 3000 and 2850 cm-1 is
due to aliphatic hydrogens. A peak between the region 1340-1220 cm-1 indicates thestreching C
N in amine group. The absorption in the region 1390-1260 cm-1 shown the stretching of nitro
group present in biomass (Ashkenazy, et.al., 1997; Padmarathy, et. al., 2003).
FT-IR of fresh biomass and metal loaded biomass of Embalica officina/is is shown in Figure 5.17
and 5.18 respectevily. The shifting and possible functional groups present in biomass is
presented in Table 5.3.
On the bases of FT-IR spectra study it can be concluded that the biomass contains aromatic
compounds. The metal binding in biomass of Embalica officina/is takes place by the substitution
of amine, nitro and caroboxylic groups by the Cr(VI).
229
Analytical Studies on Phy(o-asslsted Methods for Toxic Contaminants Removal
TABLE5.3
FT-IR OF FRESH AND METAL LOADED BIOMASS OF EMBALICA OFFICINALIS.
SI.No. Fresh biomass Metal loaded Peak Reported Assignments cm-1 biomass cm-1 Intensity range
cm-1 1 3288.31 3287.98 Shift 3600-3200 N-H
containing amine or amide, or carboxylic acid may be present in biomass.
2 1720.08 1721.36 Shift 1690-1760 C-0 stretching in carboxylic acid
3 1619.74 1619.87 Shift 1660-1500 Streching in N02 group
4 1449.83 1450.35 Shift 1470-1350 Bending C-H in alkane
5 1327.13 1339.40 Shift 1470-1350 Bending C-H in alkane
6 1238.58 1239.40 Shift 1260-1000 C-0 satreching in acidic group
7 1114.96 1116.20 Shift 1260-1000 C-0 satrech i ng in acidic group
8 1058.45 1058.86 Shift 1340-1220 Stretching C-N in amine group
230
Analvtical Studies on Phvto-assisted Methods for Toxic Contaminants Removal
·:}-~ "' \ " ..
.. .. .. ..
\ \
\ \ \ /
\j • ~
Sample Narn. LOAOED-M 0835Gnn __ ,., Colleelton tim. Wed J~031!t:U 35 200l"IGMT .. 05 301
~ TllemloN!ColttNews810~ ~4cnt-J
FIGURE 5.17. FT·IR SPECTRA OF FRESH BIOMASS OF EMBALICA OFFICINALIS.
lndlali 1~mut. or c: .... &~ 1·~"dli!l~, ttydfiabad FilRAiloiylilo Rot>ort.
''"l ~t·----.....
l -~
"' \ .. I
..
.,
.,
..
..
\ \ ' \ i
'Ji
-~....,. UM.OADEI).A ...... ..__ ... ~ ..,_ Wid....,_ u 10 20 10 :zoa7 (OWT~ 30J ~ ""--fllallllt--fTOIIpacSOU'* ......., ·-1
- .... W...........~t)
. .. DleldDr DT08 ~ _ ... _ .. __ ...
. ...
FIGURE 5.18. FT-IR SPECTRA OF CHROMIUM LOADED BIOMASS OF EMBALICA
OFFICI NALlS.
231
Analytical Studies on Phyto-asslsted Methods for Toxic Contaminants Removal
CONCLUSION
In this study, the ability of the two different biomasses to remove Ni(ll) and Cr(VI) in synthetic
binary solution as well as electroplating waste has been demonstrated. In addition, a column
study was successfully done for the separation and recovery of Ni(ll) and Cr(VI) from the binary
mixture. This chapter concluding the following remarks:
The Calotropic procera and Embalica officinalis a plant biomass were investigated as a new
biosorbent of Ni(ll) and Cr(VI) from aqueous solution with 90% and 100% sorption efficiency of
Ni(ll) and Cr(VI) from 50 mg/L solution. Biosorption was rapid and equilibrium was achieved
within 30 minutes. It is concluded that adsorption was pH dependent and maximum adsorption
occurs at pH 3. According to Langergren equation the kinetic of Ni(ll) and Cr(VI) biosorption was
calculated as first order kinetic. Column type of biosorption was more efficient as compared to
batch mode adsorption study because of more close packing of adsorbent sites. Under optimal
conditions, the uptake capacities were calculated for 250 mg/L of Ni(ll) and 250 mg/L of Cr(VI)
were found as 18.5 mg/g and 29.55 mg/g respectively. Batch elution tests revealed that almost
complete elution of bounded Ni(ll) and 88% of Cr(VI) from the biomass could be achieved using
aqueous solution of 0.1N HNOa. A single and mixed bed column was successfully developed for
the separation of Ni(ll) and Cr(VI) from the binary mixture as well as from the electroplating
waste. The effect of various common ions such as Cl-, SQ42_, Cd2+, Mn2+, Cu2+, were investigated.
It was concluded that the presence of Mn2+ and Cu2+ played a serious interfere on the
biosorption. On the bases of FT-IR spectra study it can be concluded that the biomass contains
aromatic compounds. The metal binding in biomass of Embalica officinalis takes place by the
substitution of amine, nitro and caroboxylic groups by the Cr(VI).
Analvtical Studies on Phvto-asslsted Methods for Toxic Contaminant§ Removal
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