Equilibrium and kinetic modelling of cadmium(II) biosorption byC.

vulgaris in a batch system:

effect of temperature

The biosorption of cadmium(II) ions to C. vulgaris studied in a batch system with respect
to the temperature, initial pH and initial metal ion concentration. The algal biomass exhibited the
highest cadmium(II) uptake capacity at 20C, at the initial pH value of 4.0 and at the initial
cadmium(II) ion concentration of 200 mg l1. Biosorption capacity decreased from 85.3 to 51.2
mg g1 with an increase in temperature from 20 to 50C at this initial cadmium(II) concentration.
Freundlich and Langmuir isotherm models were tried to represent the equilibrium data of
cadmium(II) biosorption depending on temperature. Equilibrium data fitted very well to both the
models in the studied concentration range of cadmium(II) ions at all the temperatures studied.
The pseudo first- and pseudo second-order kinetic models were also applied to experimental
data assuming that the external mass transfer limitations in the system can be neglected and
biosorption is sorption controlled. The results showed that cadmium(II) uptake process followed
the second-order rate expression and adsorption rate constants decreased with increasing
temperature. Using the second-order kinetic constants, the activation energy of biosorption was
also evaluated.

Chemosphere
Volume 54, Issue 7, February 2004, Pages 951967
Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial
activated carbon modified with oxidizing agents and/or chitosan

In this study, the technical feasibility of coconut shell charcoal (CSC) and commercial
activated carbon (CAC) for Cr(VI) removal is investigated in batch studies using synthetic
electroplating wastewater. Both granular adsorbents are made up of coconut shell (Cocos
nucifera L.), an agricultural waste from local coconut industries. Surface modifications of CSC
and CAC with chitosan and/or oxidizing agents, such as sulfuric acid and nitric acid,
respectively, are also conducted to improve removal performance. The results of their Cr
removal performances are statistically compared. It is evident that adsorbents chemically
modified with an oxidizing agent demonstrate better Cr(VI) removal capabilities than as-received
adsorbents in terms of adsorption rate. Both CSC and CAC, which have been oxidized with
nitric acid, have higher Cr adsorption capacities (CSC: 10.88, CAC: 15.47 mg g1) than those
oxidized with sulfuric acid (CSC: 4.05, CAC: 8.94 mg g1) and non-treated CSC coated with
chitosan (CSCCC: 3.65 mg g1), respectively, suggesting that surface modification of a carbon
adsorbent with a strong oxidizing agent generates more adsorption sites on their solid surface
for metal adsorption.

Water Research
Volume 33, Issue 11, August 1999, Pages 24692479
A review of potentially low-cost sorbents for heavy metals

The use of low-cost sorbents has been investigated as a replacement for current costly
methods of removing heavy metals from solution. Natural materials or waste products from
certain industries with a high capacity for heavy metals can be obtained, employed, and
disposed of with little cost. Modification of the sorbents can also improve adsorption capacity. In
this review, an extensive list of sorbent literature has been compiled to provide a summary of
available information on a wide range of potentially low-cost sorbents, including bark, chitosan,
xanthate, zeolite, clay, peat moss, seaweed, dead biomass, and others. Some of the highest
adsorption capacities reported for cadmium, chromium, lead and mercury are: 1587 mg Pb/g
lignin, 796 mg Pb/g chitosan, 1123 mg Hg/g chitosan, 1000 mg Hg/g CPEI cotton, 92 mg
Cr(III)/g chitosan, 76 mg Cr(III)/g peat, 558 mg Cd/g chitosan, and 215 mg Cd/g seaweed.

Title : Low-Cost Sorbents: A Literature Summary.

The capital and regeneration costs of activated carbon and ion exchange media suggest
that better process economics may be achieved with disposable sorbents for the treatment of
metals-contaminated water and waste streams. An extensive literature search was conducted to
identify potentially inexpensive sorbents that could be disposed, rather than regenerated, after
use. The literature indicates that many materials with this potential are readily available, either
as process by-products or in their natural form. The most promising sorbents identified in this
literature search will be tested at bench scale with synthetic metal solutions.

Reverse osmosis applied to metal finishing wastewater

The electroplating industry is a great water consumer and, as a consequence, one of the
biggest producers of liquid effluent. The metal finishing industry presents one of the most critical
industrial waste problems. There is therefore growing interest in developing methods for
reclaiming metals from plating waste stream and recovery of water using membrane technology
[1,2]. The application of reverse osmosis (RO) to the global effluent from the electroplating
industry has been studied in this paper. The results obtained show that there is 7595%
recovery of water and nearly total removal of metals in the permeate.

Removal of arsenic from groundwater using low cost ferruginous manganese ore

A low cost ferruginous manganese ore (FMO) has been studied for the removal of
arsenic from groundwater. The major mineral phases present in the FMO are pyrolusite and
goethite. The studied FMO can adsorb both AS(III) and As(V) without any pre-treatment,
adsorption of As(III) being stronger than that of As(V). Both As(III) and As(V) are adsorbed by
the FMO in the pH range of 28. Once adsorbed, arsenic does not get desorbed even on
varying the pH in the range of 28. Presence of bivalent cations, namely, Ni 2+, Co2+,
Mg2+ enhances the adsorption capability of the FMO. The FMO has been successfully used for
the removal of arsenic from six real groundwater samples containing arsenic in the range of
0.040.18 ppm. Arsenic removals are almost 100% in all the cases. The cost of the FMO is
about 5056 US$ per metric tonne.

Changes in the Biochemical Oxygen Demand Procedure in the 21st Edition of "Standard
Methods for the Examination of Water and Wastewater"
The dilution biochemical oxygen demand (BOD) test has widespread application for
design and operation of wastewater treatment processes, evaluating the quality of natural
waters, and assessing the effect of wastewater discharges on these waters. While
standardization of the BOD-measuring method has become of prime importance in maintaining
dependable data acquisition, changes are made as needed in response to questions raised by
analysts and to accommodate new applications. The purpose of this article is to describe
changes that have been incorporated in the 20th and 21st editions of "Standard Methods for the
Examination of Water and Wastewater" (APHA et al., 1998 and 2004). These changes include
changes in text format to clarify the procedural steps, allowance for use of bottle sizes ranging
from 60 mL or larger, improvements in quality-control procedures, and improvements in the
method of calculating BOD. Other changes include allowance for the use of allylthiourea for
nitrification inhibition and broadening the source of seed that can be used for inoculation of BOD
samples.

Removal of heavy metal from industrial wastewater using chitosan coated oil palm shell
charcoal

This research focuses on understanding biosorption process and developing a cost

effective technology for treatment of heavy metals-contaminated industrial wastewater. A new
composite biosorbent has been prepared by coating chitosan onto acid treated oil palm shell
charcoal (AOPSC). Chitosan loading on the AOPSC support is about 21% by weight. The shape
of the adsorbent is nearly spherical with particle diameter ranging 100~150 m. The adsorption
capacity of the composite biosorbent was evaluated by measuring the extent of adsorption of
chromium metal ions from water under equilibrium conditions at 25C. Using Langmuir isotherm
model, the equilibrium data yielded the following ultimate capacity values for the coated
biosorbent on a per gram basis of chitosan: 154 mg Cr/g. Bioconversion of Cr (VI) to Cr (III) by
chitosan was also observed and had been shown previously in other studies using plant tissues
and mineral surfaces. After the biosorbent was saturated with the metal ions, the adsorbent was
regenerated with 0.1 M sodium hydroxide. Maximum desorption of the metal takes place within
5 bed volumes while complete desorption occurs within 10 bed volumes. Details of preparation
of the biosorbent, characterization, and adsorption studies are presented. Dominant sorption
mechanisms are ionic interactions and complexation.

Water Research
Volume 26, Issue 4, April 1992, Pages 469472

A series of different functionalized biopolymers were prepared and their comparative

efficiencies for removing lead (II) and copper (II) ions from water at part per million
concentrations determined. The biopolymers evaluated included cellulose, alginic acid, chitin,
chitosan and carrageenan. Besides the base biopolymers, the carboxymethyl and hydroxamic
acid derivatives of these materials were prepared and tested as well. Terephthalic acid and its
hydroxamic acid derivative and a state of the art ion exchange resin, Chelex 20 (Bio-Rad),
were also tested as controls. It was found that, generally, the hydroxamic acid derivatives were
the most efficient at removing both metals at a number of different starting ion concentrations
although no one material was found to be the best under all experimental circumstances.

Chemosphere
Volume 55, Issue 1, April 2004, Pages 135140
Preparation of alginatechitosan hybrid gel beads and adsorption of divalent metal ions

Naturally occurring polysaccharides such as alginic acid and chitosan have been
recognized as one of the most effective adsorbents to eliminating low levels of heavy metal ions
from waste water stream. The present study intended to use alginic acid and chitosan
simultaneously, which are expected to form a rigid matrix structure of beads due to electrostatic
interaction between carboxyl groups on alginic acid and amino groups on chitosan, and to
prepare alginatechitosan hybrid gel beads. This could be achieved for the first time by using
water-soluble chitosan, which was obtained by deacetylating chitin to 3639% degree. The
water-soluble chitosan dissolved in water could remain in solution in the presence of sodium
alginate, and the homogeneous solution of chitosan and alginate was dispensed into a
CuCl2 solution to give gel bead particles. The resultant beads were then reinforced by a crosslinking reaction of aldehyde groups on glutaraldehyde with amine groups on the chitosan. The
cross-linking reaction made the beads durable under acidic conditions. The adsorption of Cu(II),
Co(II), and Cd(II) on the beads was significantly rapid and reached at equilibrium within 10 min
at 25 C. Adsorption isotherms of the metal ions on the beads exhibited Freundlich and/or
Langmuir behavior, contrary to gel beads either of alginate or chitosan showing a step-wise
shape of adsorption isotherm.

On the Modification and Characterization of Chemical Surface Properties of Activated Carbon:

In the Search of Carbons with Stable Basic Properties

Differences between the surface chemical properties of hydrogen- and nitrogen-treated

samples of an activated carbon were quantified using several complementary techniques.
Calorimetric studies conducted at 303 K revealed that the sample treated in N2 at 1223 K
adsorbs a great deal of oxygen with unusually high differential heats. In fact, both the quantity
and the heat of adsorption increased when the treatment temperature was raised from 773 to
1223 K. In contrast, samples treated in H2 adsorbed less and less O2 as the temperature of
treatment was raised; after treatment at 1223 K, virtually no O 2 adsorption occurred. At the
same time the H/C ratio in the H2-treated samples decreased with increasing treatment
temperature. Point of zero charge measurements revealed that only H 2 treatments at high
temperature (>1073 K) create basic (hydrophobic) surfaces which are stable after prolonged air
exposure. These findings are consistent with the notion that the removal of oxygen in the form
of CO and CO2 during high-temperature N2 treatment leaves unsaturated carbon atoms at
crystallite edges; these sites are very active for subsequent oxygen adsorption. In contrast,
high-temperature H2 treatment accomplishes three tasks: (a) it also removes surface oxygen;
(b) it stabilizes some of the (re)active sites by forming stable CH bonds; (c) it gasifies the most
reactive unsaturated carbon atoms. The relative contributions of these three effects depend on
the temperature of H2 treatment. The carbon surface resulting from high-temperature
H2 treatment is stable against subsequent O2 adsorption in ambient conditions.

Modified activated carbon for the removal of copper, zinc, chromium and cyanide from
wastewater

Modified activated carbon are carbonaceous adsorbents which have tetrabutyl

ammonium iodide (TBAI) and sodium diethyl dithiocarbamate (SDDC) immobilised at their
surface. This study investigates the adsorption of toxic ions, copper, zinc, chromium and
cyanide on these adsorbents that have undergone surface modification with tetrabutyl
ammonium (TBA) and SDDC in wastewater applications. The modification technique enhance
the removal capacity of carbon and therefore decreases cost-effective removal of Cu(II), Zn(II),
Cr(VI) and CN from metal finishing (electroplating unit) wastewater. Two separate fixed bed
modified activated carbon columns were used; TBA-carbon column for cyanide removal and
SDDC-carbon column for multi-species metal ions (Cu, Zn, Cr) removal. Wastewater from
electroplating unit containing 37 mg l1Cu, 27 mg l1 Zn, 9.5 mg l1 Cr and 40 mg l1 CN was
treated through the modified columns. A total CN removal was achieved when using the TBAcarbon column with a removal capacity of 29.2 mg g 1 carbon. The TBA-carbon adsorbent was
found to have an effective removal capacity of approximately five times that of plain carbon.
Using SDDC-carbon column, Cu, Zn and Cr metal ions were eliminated with a removal capacity
of 38, 9.9 and 6.84 mg g1, respectively. The SDDC-carbon column has an effective removal
capacity for Cu (four times), Zn (four times) and Cr (two times) greater than plain carbon.

Title : Low Cost Sorbents Screening and Engineering Analysis of Zeolite for Treatment of
Metals Contaminated Water and Soil Extracts

Heavy metals contamination is an environmental problem at Army installations engaged

in firearms training and munitions production. Weathering and corrosion of expended munitions
and leaching from wastewater lagoons, landfills and bum pits, has resulted in heavy metals
contamination of the soil at these facilities. Transport of metals to the groundwater has been
confirmed in some locations, requiring treatment of the groundwater at the site. Certain
treatment processes for contaminated soil produce metals laden extracts, which also require
treatment before reuse or disposal. Low cost sorbents with a high affinity for metals that can be
disposed after use may provide an economic alternative to ion exchange and activated carbon.
Metals sorption capacity is reported in the literature for a variety of natural materials and
industrial byproducts. This information is useful in identifying potentially useful sorbents, but is
limited to the specific conditions studied. Of primary interest are those sorbents with a
demonstrated affinity for the metals of interest, that are inexpensive and readily available, and
that require no modification prior to use. A field ready sorption technology for treatment of
metals-contaminated water and waste streams was the principal objective of this work unit.

Use of Activated Carbon for the Recovery of Chromium from Industrial Wastewaters

A technique for the removal and recycling of hexavalent chromium from electroplating industries
was developed. It involves a two-phase process which consists of (1) the use of an activated
carbon bed for the accumulation of chromium onto the surface of activated carbon followed by
(2) the regeneration of the carbon leading to a concentrated chromium solution with potential for
reclamation or reuse within the plating operation. Results from continuous ow experiments
showed that in excess of 99% chromium removal efficiency can be achieved. It was also
revealed that regeneration of the exhausted carbon under acidic conditions recovered chromium
in the trivalent state with concentrations as high as 3 g dm~3, more than 12 times the inuent
concentration. The adsorption capacity of the activated carbon was found to increase with
successive cycles of adsorption/regeneration. However, when regeneration was achieved under
alkaline conditions, the chromium was recovered in the hexavalent state with concentrations as
high as 84 g dm~3, in excess of 33 times the chromium inuent concentration. In addition,
under caustic regeneration conditions, the data showed that the adsorption capacity in this case
decreases with the increased number of exhaustion cycles. Mass balance calculation for both
acid and caustic regeneration indicated that in both cases the regeneration process was
incomplete with a recovery efficiency averaging around 50%. In an attempt to maximise the
recovery efficiency, a combination of caustic followed by acid regeneration was applied to the
exhausted activated carbon and the results led to a drastic improvement in the total recovery
process (8598%). These results clearly show that activated carbon is a viable candidate for the
removal and recovery of chromium from electroplating industries. The critical advantage in the
use of activated carbon is (1) the ability to regenerate and thus prepare a concentrated
chromium solution for potential reclamation or recycle to the plating operation, and (2) the
potential of avoiding the generation of hazardous sludge for land disposal.

Removal of chromium from water and wastewater by ion exchange resins

Removal of chromium from water and wastewater is obligatory in order to avoid water
pollution. Batch shaking adsorption experiments were carried out to evaluate the performance of
IRN77 and SKN1 cation exchange resins in the removal of chromium from aqueous solutions.
The percentage removal of chromium was examined by varying experimental conditions viz.,
dosage of adsorbent, pH of the solution and contact time. It was found that more than 95%
removal was achieved under optimal conditions. The adsorption capacity (k) for chromium
calculated from the Freundlich adsorption isotherm was found to be 35.38 and 46.34 mg/g for
IRN77 and SKN1 resins, respectively. The adsorption of chromium on these cation exchange
resins follows the first-order reversible kinetics. The ion exchange resins investigated in this
study showed reversible uptake of chromium and, thus, have good application potential for the
removal/recovery of chromium from aqueous solutions.

Adsorption of Cu(II) and Cr(VI) ions by chitosan: kinetics and equilibrium studies
R Schmuhl, HM Krieg, K Keizer
The ability of chitosan as an adsorbent for Cu (II) and Cr (VI) ions in aqueous solution
was studied. The experiments were done as batch processes. Equilibrium studies were done on
both cross-linked and non-cross-linked chitosan for both metals. Cr (VI) adsorption behaviour
could be described using the Langmuir isotherm over the whole concentration range of 10 to
1000 mgl-1 Cr. The maximum adsorption capacity for both types of chitosan was found to be 78
mgg-1 for the non-cross-linked chitosan and 50 mgg-1 for the cross-linked chitosan for the Cr
(VI) removal. For the Cu (II) removal the Freundlich isotherm described the experimental data
over the whole concentration range of 10 to 1000 mgl-1 Cu (II). The maximum adsorption
capacity for both types of chitosan can be estimated to be greater than 80 mgg-1. Cr (VI)
removal was the highest at pH 5 but pH did not have a large influence on Cu (II). From these
results it is clear that the adsorption of heavy metals is possible with chitosan, but that with this
method, end concentrations of below 1 mgl-1 can hardly be obtained.

Removal of Heavy Metal from Contaminated Water by Biopolymer Crab Shell Chitosan
M.S. Rana, M.A. Halim, S. Safiullah, M. Mamun Mollah, M.S. Azam, M.A. Goni, M. Kamal
Hossain andM.M. Rana

The study focuses on potential of using crab shell chitosan as a low-cost biosorbent, for heavy
metals removal from aqueous solutions in an adsorption filtration system. Chitosan was
synthesized from chitin by the treatment of strong alkali solution under reflux condition and
chitin was extracted from crab shell followed by decalcification and deproteinization treatment.
Spectrometric (AA and UV) method was employed to detect the heavy metals concentration.
Prepared 10 mg L-1 solutions of zinc, lead, cadmium, cobalt, nickel, chromium, manganese and
iron were passed through the 5 g of chitosan separately and it was found that chitosan was
excellent adsorbent in removing mentioned heavy metals. The removal efficiency of chitosan
was in the following order Mn>Cd>Zn>Co>Ni>Fe>Pb>Cr. The result also showed that the time
required for 100% breakthrough of prepared chitosan for Mn and Zn was approximately 27 and
23 h whereas it was only 16 h for both Cr and Pb, respectively. The research revealed that
prepared chitosan showed better removal performance for Mn, Cd, Zn whereas the removal
efficiency was satisfactory for Co, Ni and Fe but it exhibited relatively least performance for Pb
and Cr.

Modified crab shell particles for the removal of lead[II] ions from aqueous solutions

By: Ramalingham Senthilkumar, Josephraj Jegan, Puthugramam Venkitakrishnan

Ramachandra Iyer, Manickam Velan
Courtesy of International Journal of Environment and Waste Management
(IJEWM)Published:Apr. 9, 2012

The ability of crab shell particles to remove lead[II] was evaluated in a batch reactor and
in a fixedbed column. The binding of lead[II] by crab shell was found to be affected significantly
by pH, with maximum sorption capacity 714 mg/g observed at pH 4. The sorption isotherm of
lead[II] on crab shell particles was modelled by the application of Langmuir followed by Sips,
RedlichPeterson and Freundlich. The kinetic data followed pseudosecondorder kinetics. A
glass column (2 cm I.D and 35 cm height) was used to study the continuous lead[II] biosorption
performance of crab shell particles with different bed heights.
Keywords: biosorption, crab shells, kinetics, packed bed column, lead removal, Portunus
sanguinolentus, crab shell particles