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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