Separation of Transition Metals and Chelated
Complexes in Wastewaters
Philip C.W. Cheung and Daryl R. Williams
Department of Chemical Engineering, Imperial College, London SW7 2AZ, United Kingdom; philip.cheung@imperial.ac.uk (for
correspondence)
Published online 24 November 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.12065
This review responds to the ongoing needs of wastewater
engineers tasked with treating aqueous solutions containing
chelated complexes of metal ions, of which nickel citrate in
electrodeless plating and copperEDTA in electronic chip
board manufacturing are two key examples. Because of the
presence of these sequestering agents, metallic ions cannot be
readily precipitated by alkalinity, making a compelling case
for the discovery of alternative methods of treatment. This
review is a critical appraisal of the varying degrees of success
in separation process strategies deployed for the recovery of
metallic ions under such challenging chemical conditions.
Guidance is provided on making progress toward satisfactory
industrial solutions to surmount these difficulties. V C 2014
American Institute of Chemical Engineers Environ Prog, 34: 761783,
2015
Keywords: wastewater treatment, metal complexes, electro-
less and electroplating, dyes, circuit board manufacturing,
radioactive wastes, tannery wastes
INTRODUCTION
Since 1916, complexation of metallic ions in aqueous sol-
utions by various ligands has been used in industry for many
purposes. The first patent for an electrodeless nickel-plating
solution containing citrate anions, a chelating agent, was
issued in 1916 to Roux [1]. The applications of chelating
agents have since grown, and engineers have endeavored to
discover the most effective methods to treat the resulting
wastewaters containing such chemical entities. However, dur-
ing the treatment of plating wastewaters, most of the prob-
lems posed by chelated complexes of transition metallic ions
are caused by the protective action of the ligands them-
selves, which prevent precipitating the metallic ions when
alkalinity is increased.
Henry [2] acknowledged that Chelators and stabilizers
make it difficult to reduce the electrodeless metal content by
alkaline precipitation, and he recommended sulfide precipi-
tation. However, the difficulty encountered by sulfide precip-
itation was already reported by Ku and Peters [3], with Allen
and Gurol [4] adding, Frequently, the concentration of ions
at the point where the precipitant stream contacts the waste
far exceeds the solubility product [and] the initially high con-
centration (of total ions) can result in a large number of
nuclei and small particles, since the rate of precipitate forma-
tion is much faster than the rate of mechanical mixing to
provide homogenous solutions, [these scenarios are] not the
C 2014 American Institute of Chemical Engineers
V to occur in an open water pond was inversely proportional
Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
optimum for a waste treatment process. Peters and Ku [5]
further reported poor zinc removal as Zn(OH)2 when tartrate
ions were present. Hu et al. [6,7] reported inhibition of pre-
cipitation of Ni(II) ions by alkali in the presence of gluco-
nate. Kim et al. [8] reported that the presence of just 1 ppm
of fully protonated EDTA in their wastewaters considerably
hindered the sulfide precipitation of Ni and Zn. These exam-
ples are some of the many problems posed by complexation.
This review summarizes the current attempts to overcome
some of the problems encountered during treatment using
various techniques. Eighteen different types of treatment
methods were identified from the literature (up to May
2014), as summarized in Table 1.
DESCRIPTION OF TREATMENT TECHNOLOGIES
Photolysis
Direct Photolysis and Fenton-Like Redox Systems
Zepp et al. [9] studied the photolysis of Fe(III) citrate,
oxalate, and phosphate separately in H2O2(aq) as a step pre-
ceding the classical dark Fenton reaction.
UV
Fe31 Ln2 ! Fe21 1Ln212 ;
k5436 nm
where L is one of the ligands just mentioned, with * denot-
ing its excited state of the separated ligand. Balzani and Car-
assiti [10] speculated that the most likely mechanism of the
above reaction is one of ligand-to-metal charge transfer,
resulting in Fe(III) to Fe(II) reduction, and CO2 evolution.
The Fe21 ion then donates an electron to an antibonding
molecular orbital between the two oxygen atoms of a mole-
cule of HOAOH, splitting it to produce a hydroxyl free radi-
cal, itself a powerful oxidizing agent, thus:
Fe21 ! Fe31 1OH2 1HO
Using sunlight, Dudeney and Tarasova photolysed the
iron oxalate complex [FeIII(C2O4)3]32 in aqueous solution of
pH 5 2. Iron was present in sand destined for glass making,
and when the sand was leached in a column by oxalic acid
in aqueous solution, the iron oxalate-chelated complex was
formed [11]. The leachate contained 80700 ppm of iron.
Fe(II)C2O42H2O was precipitated as yellow crystals. The
time required for photolytic decomposition of Fe(III) oxalate
May 2015 761
Table 1. Types of wastewater treatment methods for metal
complexes.
Methods References
Photolysis [935]
Ozonolysis [3642]
Oxidation by H2O2 [4349]
Catalytic oxidation by H2O2 [5052]
Oxidation by sodium hypochlorite [5355]
Simultaneous photolysis and oxidation [47,5664]
Oxidation by Mn(VII): the Hanford story [6594]
Electrodeposition [9598]
Simultaneous electrodeposition [99101]
of metal and ligand destruction
Electromembrane separation [102104]
Electrodialysis [105]
Hollow fiber membrane separation [106108]
Ultrafiltration and nanofiltration [109117]
Froth flotation [118126]
Ion exchange [127131]
Adsorption [132197]
Biodegradation [198214]
Hybrid treatment methods [215221]
to the duration and intensity of sunlight. Dudeney and Tara-
sova also hypothesized that decomposition of the Fe com-
plex was achieved through direct photon absorption by the
Fe(III) complex itself followed by a ligand-to-metal electron
transfer [11], a scenario supported by Hislop and Bolton [12].
Zhan et al. [13] favored an indirect photolysis model with the
production of HO as a preceding step and also showed that
the overall rate of photolysis increases with decreasing pH.
Li et al. [14] wrote an article similar to the publication of
Zhan et al. emphasizing the degradation of organic pollu-
tants in natural waters by a Fenton-like system (Fe31/H2O2/
UV) in the presence of oxalate and various iron oxides, with
the iron oxides acting as photocatalysts or photosensitizers.
To decolorize three metal azo dyes Acidol Yellow, Acidol
Grey, and Acidol Scarlet, Triphathi and Chaudhuri [15]
used a Fenton-like process composed of sunlight, Fe(III)
oxalate, and H2O2, with 92% decolorization of the waste-
water after 90 min of exposure to sunlight.
Copestake and Uri [16] photolysed [CoIII(C2O4)3]32 to pro-
duce Co21, CO2, and oxalate ions. Using aprotic, nonaqu-
eous solvents, Joosten and DOlieslager [17] found no
difference in the initial step of photolysis of [CoIII(C2O4)3]32,
whether carried out aerobically or anaerobically, and that the
first step of the photochemical reaction is analogous to that
carried out in water. Porter et al. [18] provided the most thor-
ough discussion of the intimate mechanism of the photo-
chemistry of some metaloxalato complexes, including
[CoIII(C2O4)3]32, a fully deprotonated Co(III) complex.
The direct photolysis of the 1:2 metalligand chelate
between Eu31 and tetrahydrofuran1,2,3,4-tetracarboxylic
acid by using ultraviolet light has been demonstrated by
Beitz [19]. The chelating agent was used in a solvent extrac-
tion process to remove trivalent metal ions from liquid
nuclear waste while suppressing the removal of UO221 ions
[19]. The ligand was destroyed with accompanying evolution
of CO2, thus rendering europium easier to remove.
Titanium(IV) Oxide-Assisted Decompositions
Titanium(IV) oxide (TiO2) and a handful of other metallic
oxides have been popular solid matrixes on which products
resulting from photodegradation can be adsorbed from aque-
ous solution. A coating (e.g., Au or Pt) on TiO2 itself may
exercise some catalytic effect, which participates and facili-
tates the photolysis of adsorbed species. The monograph
762 May 2015 Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
Electrochemistry for the Environment is an excellent intro-
duction and description of the subject [20]. The following are
some examples of TiO2-assisted photolysis from wider
literature.
Chen et al. [21] photolyzed [UVIEDTA]22 (50 ppm of ura-
nium ions) by ultraviolet radiation and deposited several ura-
nium species onto the surfaces of TiO2 and Pt-coated TiO2
particles suspended in water. Park et al. [22] extended this
TiO2 method to separate Fe(III) and Cu(II) ions chelated by
EDTA. The photoreduction resulted in a mixture of Fe(II)
and Fe(III) oxides, Cu2O, and metallic copper, all adsorbed
onto a TiO2 matrix. In the investigation of a related subject,
Yang et al. [23] reported that adsorption of Cu(II)EDTA onto
TiO2 was strongly influenced by pH, ionic strength, and the
type of background electrolytes (see also Ref. 24); they
found that excess EDTA in solution decreases the amount of
adsorption of copper ions onto TiO2. Kocot et al. [25]
observed that the photolysis of [FeIIIEDTA(H2O)]2 in the
wavelength range 254365 nm yielded a variety of products
including Fe(II) species. Lee et al. [26] proposed that ZnO
nanoparticles adsorb more Pb(II) and Cu(II) ions from their
EDTA complexes than TiO2.
Li et al. [27] fabricated a series of gold-coated TiO2/ITO (a
mixture of titanium dioxide and indium tin oxide) films and
studied their role in the photocatalytic (PC) and photoelec-
trocatalytic (PEC) degradation of bisphenol A [BPA,
(CH3)2C(C6H4OH)2]. They reported some interesting insights,
Compared with a TiO2/ITO film, the degree of BPA degra-
dation using the AuTiO2/ITO films was significantly higher
in both the PC and PEC processes [27]. Wang et al. [28] irra-
diated and degraded the dye Brilliant Red X-3B by ultravio-
let photons, the photocatalyst being nanoparticles of TiO2
deposited on carbon nanotubes by a modified solgel
method. Similar work was undertaken by Gao et al. [29,30].
Yu et al. [31] also managed to control the thickness of TiO2
on the carbon nanotubes during fabrication. Pandey and Pra-
kash [32] examined in great detail the effect of variable
nanogeometry of titanium oxidegold nanocomposite on the
electrochemical sensing of hydrazine. Ramrez-Santos et al.
[33] discovered that five layers of porous films of TiO2
deposited on ITO was detrimental to the process of remov-
ing Cu21 ions from their cyano complexes because the layers
acted as barriers to the electron transfer necessary for photo-
chemical reactions to occur. Zhao et al. [34] successfully
recovered Cu21 from their EDTA complexes in a tubular
PEC reactor using a TiO2/Ti mesh anode. Kim et al. [35]
built a photoelectrochemical cell and convincingly demon-
strated the feasibility of achieving the twin purpose of
decomposing organic materials in wastewaters and recover-
ing metals. In construction, they used WO3 as the photocata-
lyst on the anode because it responds better under solar
light irradiation than TiO2 (which is well known to be only
able to absorb a narrow range of visible light in the absence
of any surface modifications such as doping) [35].
Ozonolysis
Andreozzi et al. [36] demonstrated that manganese as
Mn(II) oxalate can be oxidized to higher oxidation states by
ozone. The decomposition step was established as that of
the Mn(III) complex, with the splitting of the oxalate moiety
into two CO2 molecules. (Note that each carboxylic group
contributes an oxygen atom for chelation; Figure 1.)
Shambaugh and Melnyk [37] carried out ozonolysis of the
EDTA chelates of Mn, Cd, Ni, and Pb, reporting that the
decomposition rates were an order of magnitude faster
than that of unbound EDTA. Games and Staubach [38]
attempted to compare the rates of ozonation of unbound
and chelated nitroloacetic acid (NTA, of Mg, Cu, and Zn);
however, the results were inconclusive. Morooka et al. [39]
ozonolysed the EDTA chelates of Mg, Zn, and Cu and found
that the rate of decomposition was in the following order:
Mg > Zn > Cu. Gilbert and Hoffmann-Glewe [40] also com-
pared the rates of ozonolysis of 1:1 EDTA chelates, studying
the rate of degradation of EDTA (1023 mol dm23) by ozone
in the presence of metallic ions. They found that 75% of all
chelate types decomposed in 30 min, except that of Fe(III).
The presence of Ca and Cd ions made no difference to the
rate of decomposition of the EDTA moiety, and the rate of
ozonolysis of Fe(III)EDTA was only about half that of all
other metalEDTA chelates [40]. (Figure 2 illustrates that the
metallic ion is six-coordinated by EDTA in most of the com-
plexes mentioned above.)
El-Raady et al. [41] reported scarcely any degradation of
citric acid in the concentration range 0.51 3 1022 mol
dm23, at pH 5 2, in the absence of metallic ions; however,
increasing the pH to 5.5 in the presence of Mn21 ions
Figure 1. Metaloxalate complex.
Figure 2. Anionic and neutral metalEDTA complexes, with
charge depending on pH.
Figure 3. Schematic representation of ozonation pilot plant in the Department of Civil Engineering, Imperial College, London,
UK [42]. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]
Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
resulted in 80% destruction of citric acid. At pH 5 7, Fe21,
Ti41, and Co21 also catalyzed the destruction of 6070% of
the citric acid [41]. Resolving these differences, however,
require mechanistic elucidation on the molecular level. At
universities all over the world, experimental ozonation plants
are built to research ozonation as a means of treating waste-
water. One such system used extensively at the Imperial Col-
lege of Science and Technology (London, UK) is illustrated
in Figure 3.
Oxidation by H2O2
Using a batch reactor, Sundstrom et al. [43] experimented
with simulated wastewaters from cleaning operations of
steam generators. The liquids contained Fe31 (9.4 3 1022
mol dm23), Cu21 (4.9 3 1023 mol dm23), NH41 (1.36 mol
dm23), and EDTA (1.2 3 1021 mol dm23) [43]. More than
95% of all chelating ligands were destroyed within 12 h,
under the conditions of pH between 4 and 5, a 20:1 molar
ratio of H2O2 to EDTA, and a temperature range 4060 C.
The metals were removed by precipitation, after which the
residual metal concentration in aqueous solution was
claimed to be less than 1 ppm (1025 mol dm23). Sund-
strom et al. [43] then compared their experimental results
with those of Evans and Nott [44], who studied the ozonation
of simulated iron and copper cleaning wastes. A 4-h ozona-
tion of the iron solvent at an initial pH of 8.8 yielded a 63%
reduction in EDTA. The performance of ozone on the copper
solution improved EDTA destruction, achieving an 88%
reduction in 4 h.
Two further examples in which H2O2 was used to treat
wastewaters containing chelated complexes are worth men-
tioning. By reacting wastewaters from the manufacturing of
liquid crystal display units with H2O2 in a continuous flow
tubular reactor in the temperature range 400605 C, at 25
MPa, Veriansyah et al. [45] recovered chromium as its oxides.
Fu et al. [46] treated a solution of Ni(II)EDTA first by Fen-
tons reaction and then by a combination of Fentons reac-
tion and ultrasound. The removal of nickel ions from
solution was 95.4% in the form of Ni(OH)2 in the presence
of iron hydroxides [46].
Treating wastewaters arising from electroless nickel plat-
ing by classical Fenton and Fenton-like reagents has been
problematic. In the course of intended nickel deposition on
surfaces, hyposphosphite [H2P(I)O2]2 (phosphorous in oxida-
tion state 11) is the ingredient which affects the Ni(II) !
May 2015 763

Figure 4. A tridentate metal citrate complex. [Color figure
can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
Ni(0) reduction; however, its presence in wastewaters will
continuously deprive a Fenton system of the free radical HO
due to its oxidation to become phosphite [HP(III)O3]22 and
phosphate [P(V)O4]32, and these oxyanions of phosphorous
will form insoluble [Fe(II)HPO3]0 and [Fe(III)PO4]0 respec-
tively. It is highly likely that phosphorous species in waste-
waters are competing with the chelated complexes of nickel
citrate in aqueous solution for the free radical HO to the
extent that the treatment process can be severely limited.
Huang et al. [47] tackled the problem by deploying the so-
called Fered-Fenton system, whereby externally applied elec-
trodes generated Fe21(aq) ions in situ, the cathodic reaction
being Fe31 1 e2 ! Fe21, with the result that citrate anions
were decomposed. In a similar fashion, work done by Shih
et al. [48] showed that 95% of chemical oxygen demand
(COD) and 99.9% of nickel were removed by a Fered-Fenton
system. Liu et al. [49] recovered high-purity iron phosphate
from wastewaters arising from electroless nickel-plating baths
to be used as a raw material for the manufacturing of
lithium ferric phosphate batteries.
Catalytic Oxidation by H2O2
Attempts to degrade several metal chelates at 60 C, using
H2O2, with metallo-tetrasulfo-phthalo-cyanines as catalysts
met with mixed results [50]. The chelants were as follows:
methylphosphonic acid, NTA, EDTA, diethylenediaminepen-
taacetic acid (DTPA), and b-alaninediacetic acid. EDTA was
reported as the most degradable relative to the rest. Of all
the chelates, iron, manganese, and sodium complexes were
most degradable, whereas zinc, copper, and calcium com-
plexes were more difficult to oxidize [50]. Englehardt et al.
[51] attempted, with some success, to develop a Fenton-like
oxidation system, by using steel wool (iron at zero oxidation
state) and air, to attack the EDTA moiety and to precipitate a
number of metals and metalloids. Quici et al. [52] showed
that photolysis of citric acid in the presence of Fe31(aq) and
H2O2 proceeded at a much enhanced rate over that of heter-
ogeneous photocatalysis using nearUV light and TiO2.
Oxidation by Sodium Hypochlorite
Schlegel [53] reported limited success in attempting to
extract metals from their chelates using hypochlorite ions.
The nickel and copper chelates of citrate, EDTA, gluconate,
tartrate, and oxalate ions were all very resistant to degrada-
tion [53]. As the citrate moiety contains a hydroxyl (AOH)
group, the ligand can be either bidentate or tridentate. In the
latter case, the oxygen atom on the AOH group (attached to
carbon atom number 3; Figure 4) donates electrons to the
central metal ion to form a coordinate (covalent) bond; the
other two donating oxygen atoms are from the nearest car-
boxylic groups, carbons labeled with numbers 5 and 6 (Fig-
ure 4). The U.S. Army Corps of Engineers [54] was of the
764 May 2015 Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
opinion that citrate is a quaridentate ligand; however, a 1:1
(Nicitrate) complex in aqueous solution with all four func-
tional groups formally bonded to the Ni(II) ion has yet to be
identified. Nonetheless, elucidation of mechanisms of oxida-
tion of these complexes must be preceded by determination
of the actual structure of the complex in question.
The (patented) work of Isamu and Shigeru [55] seemed to
be relatively more successful than Schlegels attempt
described above [53]. Electrodeless plating wastewater was
treated using hypochlorite. The chelate to be decomposed
was an EDTA complex of nickel. The wastewater contained
up to 200 ppm Ni21; however, below 20 ppm, the waste-
water required doping with nickel sulfate, chloride, and
nitrate to initiate the process! The patent claimed that the
concentration of Ni21 in the clarified liquid was 2 ppm and
below. In the same patent, the workers also produced data
on treating an aqueous solution containing all the EDTA che-
lates of Cr, Ni, Cu, Zn, Cd, and Pb (10 ppm of each metal) in
three separate experiments: straightforward addition of (a)
Ca(OH)2 to pH 5 11; (b) CaCl2 and adjustment to pH 5 11;
and (c) addition of FeCl2 and adjustment to pH 5 11.
Simultaneous Photolysis and Oxidation
On the basis of the work of Lipin and Masyutin [56],
Adams et al. [57], and of Schaefer and Asmus [58], Huang
et al. [47] examined the efficacy of the Fe21/H2O2 (Fenton
solution), the UV/Fe21/H2O2 (photo-Fenton), and the elec-
trolysis/Fe21/H2O2 (electro-Fenton) systems to remove citrate
from electrodeless nickel-plating baths, in the presence of
hypophosphite H2PO22 ions, with mixed results [47]. The
combined electrolysis and Fenton method was most effec-
tive, removing 95% COD in 7 h. The work implied severe
competition for HO between citrate and hypophosphite
ions, slowing down the overall decomposition of the Ni
complex. In similar experiments, Lipin and Masyutin [56]
showed that the rate of reduction of nickel ions increased as
the concentration of hypophosphite ions was increased in
solution, whereas citrate ions had the opposite effect.
Tucker et al. [59] studied the effectiveness of destruction
of the EDTA chelates of Co(II) and Cu(II) by a mixture of
four oxidants, namely, Cl2, HOCl, ClO2, and H2O2, while the
reaction solution was being irradiated by UV. They argued
that this method was the most effective in degrading EDTA
of initial concentration 7 3 1025 mol dm23. Oxidation with-
out irradiation, and irradiation in the absence of oxidants,
were not as effective (Figure 5; Ref. 59). Although this treat-
ment resulted in the loss of chelation ability of EDTA, the
fate of metal ions thereafter was not described.
Kunz et al. [60] examined the effect of UV light and H2O2
(1022 mol dm23) on unchelated EDTA (1023 mol dm23),
reporting 90% destruction after 6 min of treatment [60]. It
was perhaps a confirmation of this finding when Ghiselli
et al. [61] demonstrated that photolysis (UV, 366 nm) of
Fenton-like aqueous systems degraded EDTA far more effec-
tively than mere Fenton-like systems without UV irradiation,
the metallic ions in both cases being those of Fe and Cu. In
the 2004 endeavor, the solutions of interest stood at pH 5 3,
which meant that a substantial proportion of EDTA ions
remained as unbound ligands. Contrarily, in highly alkaline
solutions, the predominate amount of negatively charged
EDTA moieties are bonded to the transition metal ions when
the mole ratio (metal:ligand) is 1:1 [62]. The direct photolysis
of H2O2 leading to the formation of hydroxyl radicals, and
perhaps coupled with a concomitant photodegradation of
free EDTA, are evidenced. The oxidative power afforded by
the Fenton system itself cannot be disregarded; Ghiselli et al.
[61] showed that when Cu21 was substituted for Fe21, degra-
dation of EDTA was much reduced. It is difficult to envisage
the oxidation of Cu(II) to a higher state. It must be noted
 Table 2. Hanford tankwaste: total radioactivities in liquids
and solids [67].

Radionuclide Radioactivity (Curies)

60
Co 1.35 E14
63
Ni 3.09 E15
90
Sr 8.90 E17
90
Y 8.90 E17
99
Tc 3.22 E14
137
Cs 8.88 E17
137m
Ba 8.39 E17
151
Sm 1.04 E16
239
Pu 2.53 E14
240
Pu 6.18 E13
241
Pu 8.60 E14
241
Am 9.77 E14

cies (e.g., residual plutonium). The liquid in some of the

Figure 5. Kinetic data of EDTA destruction [59].
that it may be possible for Fe(II) to be oxidized while com-
plexed. Engelmann et al. [63] demonstrated that the 1:1 iron
complexes of EDTA, DTPA, and citrate clearly induce the
reduction of H2O2. However, Kishimoto et al. [64] discov-
ered that the extent to which Fenton systems were inhibited
to degrade 1,4-dioxane in the presence of oxalate and EDTA
decreased as solution pH fell below 6, that is, as the degree
of complexation also deceased at lower, acidic pH values,
implying that only unchelated Fe(II) ions can be oxidized
further.
Oxidation by Mn(VII): The Hanford Story
Liquid Waste at the Hanford Reservation, Washington (USA)
Wastewaters currently stored at the Hanford Reservation
(Washington State) are a legacy of the Manhattan Project of
World War II. The wastes were generated from processes
that recovered uranium and plutonium from irradiated
nuclear fuel but left fission products and other transuranic
metals in high-level waste. These wastes exist as liquid
supernatants, sludge (insoluble solids), and crystalline salt
cakes of variable composition depending on their source
[65], held in underground holding tanks collectively known
as the tank farm. The sludge waste is the most radioactive.
The volume of waste stored at Hanford is about 57 million
U.S. gallons, a formidable amount of wastewater requiring
treatment. The U.S. Department of Energy (DOE; Ref. 67)
listed the major radionuclides in these tankwastes (Table 2).
A general description of the inventory up to the year 1993,
published by Curtis [66], included inorganic, nonradioactive
elements.
During the 1960s and 1970s, 90Sr was recovered from
some of the tankwaste for production of sealed sources. Sep-
aration of 90Sr involved its extraction by a mixture of organic
solvents and stripping with an aqueous solution of EDTA/
HEDTA and glycolate salt. Raffinates and other wastes from
the process were returned to the underground storage tanks.
The returned liquid returned inevitably introduced complex-
ants into the tank waste, solubilizing many constituents from
the sludge, including radioactive 60Co and transuranic spe-
tanks now contains these radioactive nuclides.
Using capillary electrophoresis, Ballou et al. [68] deter-
mined the lower detection limit of the following chelating
agents in Hanford tankwastes, that is, in the range 12 3
1025 mol dm23 (Table 3; see also Ref. 66 for the great poten-
tial for chelation of radionuclides cited therein).
In addition, Sharma et al. [69] identified citric and glycolic
acids in Hanford tankwaste, in addition to the already listed
chelating agents by Ballou et al. [68].
Challenges in the 21st Century
Commenced in 2012, a Waste Treatment and Immobiliza-
tion Plant (WTP) at Hanford has been under construction by
the contractor Bechtel National Inc. to treat and immobilize
the tank waste into glass (a process known as vitrification).
This Vit Plant is scheduled for commissioning in 2018. Pub-
lic announcements by PennEnergy [70], the U.S. DOE [71]
and Bechtel [72] reported latest progress.
Long-term problems that the U.S. EPA aim to address
include the potential environmental and health hazards posed
by the isotope 99Tc, listing emission sources including facilities
that treat or store radioactive waste [73]. 99Tc has a fission
product yield of 6.0507% for fission of 235U by thermal neu-
trons [74], and the possibility of long-distance transport of the
aqueous species [TcVIIO4]2 has been raised by Harrison and
Phipps [75] and Tagami [76]. The U.S. EPA has issued a pleth-
ora of regulations to limit the discharge of radioactive ele-
ments, including 99Tc [73], and these regulations will,
inevitably, drive postclosure disposal site performance and are
likely to remain a topic of considerable debate at Hanford for
years to come (the U.S. EPA has published 151 papers on the
subject matter of radiation protection of the Yucca Mountain
site, the latest one on May 1, 2014; see Ref. 77). Moreover,
Hanfords so-called high-complexant wastes (from which the
transuranic elements must be separated) also exhibit poor 99Tc
ion-exchange performance, indicating coexisting species such
as [TcVIIO4]2 and [TcI(CO)3(H2O)3]1 [78]. In high-complexant
tanks such as AN-107 and AN-102, the overall redox reaction
TcVII ! TcI involved a number of inorganic and organic con-
stituents. This is a complex scheme of reactions resulting in
solid, hydrated TcIVO2 as a stable intermediate.
A research and development program identified potas-
sium permanganate KMnO4 as the agent that provides a pre-
cipitate with physical properties most amenable to efficient
separation. Therefore, 90Sr and transuranic elements will be
precipitated by KMnO4 and separated by gravity and filtra-
tion. Many U.S. DOE reports published from 2000 to 2007
have documented oxidative precipitation and leaching of

Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep May 2015 765
Table 3. Aminocarboxylic acid ligands used in the nuclear industry [68].
EDTA HEDTA
strontium and transuranic elements from wastewaters and
sludge [7989].
On March 26, 2014, the U.S. DOE publicized its plans for
long-term storage for cesium and strontium at the Hanford
site. The departments new goal, as of January 2013, is to
have a repository sited by 2026 and to begin operations by
2048. Therefore, long-term stewardship of the capsules will
require interim storage until final disposal can be achieved,
no earlier than 35 years from now [90]. Recent plans call for
dechelation and precipitation of 90Sr and transuranic metals
to be performed in the tank farm itself rather than the WTP.
Duncan et al. (of Washington River Protection Solutions,
WRPS) [91] reported that Tanks 241-AN-102 and 241-AN-107
supernatants contain soluble 90Sr and transuranic elements
that require removal prior to vitrification according to speci-
fications and regulations. In addition, the concentration of
organic materials including complexants is so high in the
two tanks that they are now identified as complexant con-
centrate tanks. Evaluations of the recovery of 90Sr and trans-
uranic species by permanganate are documented in their
157-page report. Before further processing is possible, the
residence time of the reaction mixture is now estimated at
up to 12 months, a much longer time period than the hours
and days originally envisaged at the WTP [91].
Design and construction of the high-level waste vitrifica-
tion plant of the WTP has been on hold since early 2014 for
the review of the safety of designs and practices, and Farrell
[92] had already addressed plans and potential problems for
restarting the engineering of the High-Level Waste facility at
the WTP [92]. In a parallel development, on March 21, 2014,
the Washington State Department of Ecology [93] issued an
administrative order to the U.S. DOE and its contractor WRPS
to take steps to empty a failed double-shelled tank on the
site within 11=2 years.
Ojovan and Lee [94] at the Imperial College (London, UK)
have just written a tome titled Immobilisation of Nuclear
Waste, which is the latest and the most comprehensive
monograph on the technology. It is indispensible for anyone
interested in the subject [94].
Electrodeposition
In an attempt to remove metal ions from solution by elec-
troplating, the cathodic reaction being Mn1 1 ne2 5 M(s),
Gabe and Walsh [95] designed a rotating cylinder electrode
reactor but reported that ligands such as CN2 and S2O322,
when complexed to Cu(II) and Ag(I) ions, respectively,
significantly affected [retarded] the cathodic reaction. For the
nickel electroplating and wastewater engineering commun-
ities, however, it is very encouraging that the same Professor
David Gabe of Loughborough University (UK), an expert in
both fields, published with Wang et al. [96] an article concern-
ing the speciation of cations in electroplating baths containing
nickel chloride, sulfate, and sulfamate. Knowledge of the
major species will improve the plating process and greatly
facilitate wastewater treatments. When the maximum amount
of nickel is deposited on target surfaces, waste is minimized.
Ju et al. [97] and Shanhong Lan et al. [98] used a method
called interior microelectrolysis to liberate Cu(II) ions from
766 May 2015 Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
DTPA EDDA NTA
their EDTA complexes. It is clear from these publications that
the resulting precipitate is an iron-floc. Is it possible that this
will be classified as a hazardous waste in itself? If recovering
copper for recycling and reuse is not the objective, then is it
possible to add iron salts to the wastewater at alkaline pH to
form the floc? It is well known that EDTA is used in chela-
tion therapy for patients with metal poisoning, as the EDTA
will block the chemical reactions of bare metallic ions (e.g.,
lead poisoning). If the metalEDTA complex thus formed is
nontoxic, why not simply landfill the iron-floc containing the
metalEDTA complexes? These aspects must be addressed.
Simultaneous Electrodeposition of Metal and Ligand
Destruction
Kusakabe et al. [99] used a packed-bed electrode cell to
treat a simulated wastewater containing the Cu(II)EDTA
complex. The anode packings were platinum-plated titanium
pellets, whereas the cathode packings were graphite par-
ticles. The concentration of copper in solution was 1 3 1022
mol dm23. The treated solution had a copper concentration
of the order 1025 mol dm23, and the COD of the solution
decreased by 60% [99]. In a similar fashion, Yeh et al. [100]
attempted to decompose Cu(II)EDTA in wastewater from an
electrodeless plating operation by electrodepositing copper
at the cathode and destroying EDTA at the anode. It was
claimed that the iron anode dissolved and Fe(OH)2 formed,
which acted as a coagulant for the removal of residual cop-
per ions in the aqueous phase. An application of an electro-
motive force (e.m.f.) of 15 V in a pH 5 9 solution of
concentration 1 3 1022 mol dm23 of the copper chelate
halved the total concentration of Cu21 ions in 20 min [100].
Earlier work by Johnson et al. [101] listed the breakdown
product as oxalic acid, iminodiacetic acid, glycine, and CO2
in a system in which EDTA was electrolysed using a Pt
anode in an acidic sulfate bath.
Electromembrane Separation
While examining waste effluents generated by ion-
exchange operations, Etzel and Tseng [102] attempted to
separate Ni21, Cu21, and Zn21 from their chelates. They
reported that electrodeposition of Cu and Zn from their
chelate complexes was partially achieved but no electrode-
position of Ni film was possible in the presence of EDTA,
NTA, and CIT [102]. Juang and Lin [103] continued further
the work of Etzel and Tseng [102] by investigating the effects
of current density, initial catholyte pH values, NaNO3 con-
centration in the analyte, and initial chelate concentration in
the catholyte on the electrolytic recovery of Cu21 and citrate.
They reported that increasing the current density decreased
the current efficiency due to evolution of H2. Recovery of
Cu21 ions and current efficiency were maximized at
pH 5 2.2, with the additional requirement that a minimum
concentration of NaNO3 of 0.1 mol dm23 was needed to
avoid citrate precipitation. They recommended that the mini-
mum concentration of Cu(II) citrate in the feed should be
0.02 mol dm23 for the current density to be greater than
50% and that the recovery of copper was found to be
greater than 96% when the applied current density was 139
A m22.
Safari et al. [104] carried out a speciation exercise on envi-
ronmental samples containing both Cr(III) and Cr(VI) spe-
cies, by using dual electromembrane extraction followed by
complexation with ammonium pyrrolidinedithiocarbamate
before the quantification by high-performance liquid
chromatography. Both complexation and speciation chemis-
tries are very interesting here [104].
Electrodialysis
Green et al. [105] investigated the feasibility of using elec-
trodialysis to recover nickel and copper from citrate electro-
plating solutions of pH 12. They found that 12% of the total
metals were removed in 45 h using the cationic exchange
membrane Nafion-112, whereas commercially available
cation-exchange membranes could not readily achieve
removal of the anionic chelates or unchelated metal cations
from these baths [105].
It is worth noting that when using the concept of mem-
brane equilibria, there is an essential difference between the
separation of a free metallic ion such as Na1(aq) from an
ionizable salt, for example, the sodium salt of biologically
important polyelectrolytes such as nucleic acids and proteins,
and the attempt to separate a chelated transition metallic ion
such as Ni21 from another biologically significant ion such as
citrate. Dialysis is based on the principle that a membrane
allows free passage of small particles in true solution through
it while retaining particles of colloidal dimensions. If the sol-
vent on the exit side of the membrane is continuously
removed and replaced by fresh solvent from the bulk of the
liquid, the particles escaping through the membrane are
removed, while further transfer through the membrane is
maintained by the concentration difference, and thus the col-
loid is separated. In electrodialysis, removal of ions is
enhanced by an electric field. The solution containing the
macroparticles is placed between two membranes with pure
solvent on either side, and an electromotive force is imposed
between electrodes placed in the solvent compartments. It
remains to be seen whether a metal chelate will decompose
in the applied electric field and whether the metal will sepa-
rate from its ligand.
Hollow Fiber Membrane Separation
Juang and Huang [106] attempted to model mass transfer
phenomena of the extraction of aqueous Cu(II) species in
the presence of an equimolar amount of EDTA, through a
microporous hollow fiber membrane, into a nonaqueous sol-
vent system of AliquatV R 336 (the quaternary ammonium salt:
tri-n-octyl-methyl-ammonium chloride) in kerosene.
Lin and Juang [107] used a microporous hollow fiber
membrane to separate Cu21 ions from EDTA. Solutions of
Cu(II)EDTA (1023 to 1022 mol dm23) were fed through the
membrane, extracting the complex into the kerosene phase,
which was then re-extracted into an aqueous solution of
HCl. Concentrations of the amine and HCl were 0.10.3 mol
dm23 and 0.24.0 mol dm23, respectively. The result chosen
for presentation and discussion was the reduction of the con-
centration of copper ions from 0.05 to 0.02 mol dm23 within
1 h. These workers also carried out experiments to deter-
mine optimal conditions for the extraction. It was found that
in the feed flow rate range studied (1.44.3 cm3 s21), the
rate of extraction increased with an increasing influx rate of
Cu(II)EDTA [107].
Yang and Kocherginsky [108] studied the mass transport
phenomena associated with the successful separation of cop-
per amine complexes from wastewaters by hollow fiber-
supported liquid membrane systems. The wastewater
(pH 5 7.25) arose from the etching of printed circuit boards
Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
with aqueous ammonia, containing 5.6 3 1023 mol dm23 of
Cu21 ions, and all ammonia species totalling 0.4 mol dm23,
that is, a massive excess of ammonia ligands was present.
The carrier for the transport process was LIX 54 (a com-
mercially available, multicomponent organic liquid whose
main ingredient is 1-phenyldecane-1,3-dione) diluted with
kerosene (33% v/v). It was found that the rate-determining
step for mass transfer was probably the formation of com-
plexes between the inorganic amine copper complexes with
their organic carriers and the decomposition of these com-
bined inorganicorganic complexes.
Ultrafiltration and Nanofiltration
Between 2006 and 2012, a research group at the University
of Oulu (Oulu, Finland) systematically investigated the per-
formance of a separation process known as micellar-
enhanced ultrafiltration (MEUF) to remove toxic metals from
wastewaters. In 2006, then doctoral candidate Junkal
Landaburu-Aguirre, in the Department of Process and Envi-
ronmental Engineering, introduced the main theme of her
research program: the role of surfactants and polymers in
forming micelles and macromolecular complexes, respectively,
with metallic ions in aqueous solutions [109]. These sizeable
miceller and polymeric species, which sequester the target
metallic ions, were retained, whereas purified water passed
through the membranes. Using Zn21 ions and the surfactant
sodium dodecyl sulfate (SDS), and cellulose membranes of
area 0.00418 m2 as the model MEUF system for investigation,
Landaburu-Aguirre et al. [110] reported on the controlling
parameters of ultrafiltration in batch mode. The factors exam-
ined were as follows: operating pressures of 1 and 3 bars (i.e.,
1 3 105 and 3 3 105 Nm22); nominal molecular weight limit
(NMWL, also called molecular weight cutoff) of 3000 (3 kDa)
and 10,000 (10 kDa); zinc feed concentrations set at 0.5 3
1023 and 3 3 1023 mol dm23; and SDS feed concentration of
8.3 3 1023 mol dm23 (critical micelle concentration), and
twice this value. The group made three major findings:
1. Pressure and NMWL positively affected the permeate flux.
Concentration polarization was not encountered with the
10-kDa membrane (relative flux 5 1, i.e., the fluxes of
wastewater and pure water are the same), but appeared
with the 3-kDa membrane (relative flux 5 0.8). In this
study, concentrations of SDS (in the range examined) in
the feed had a negligible effect on flux.
2. An increase in SDS concentration enhanced the amount of
Zn21 retained, as more Zn-trapping micelles formed. Sig-
nificantly, when the mole ratio of surfactant-to-metal ratio
exceeded 5, rejection coefficients edged close to 99%.
3. Variations in pressure and NMWL within the experimental
ranges had no effect on the rejection coefficient. Further-
more, using a process analytical tool called response sur-
face methodology, Landaburu-Aguirre et al. [111]
successfully modeled and optimized the performance of
MEUF in the treatment of wastewaters containing Zn and
Cd ions. They stated that maximum permeate flux with
good membrane operational stability is concluded to be
achieved using the highest NMWL membrane and highest
pressure, substantiating results they reported in 2009.
Landaburu-Aguirre et al. [112] then published the results
of their collaborative work with a fertilizer manufacturing
company that is interested in recovering phosphorous from
drainage waters contaminated with Cd and Cu. The separa-
tion was successful: phosphate anions passed through the
membrane, whereas the metallic ions were retained [112].
Continuing this work, Landaburu-Aguirre et al. [113] reported
that although secondary pollution resulting from surfactant
monomers that are not retained traditionally posed a prob-
lem in MEUF operations, the phenomenon was not a prob-
lem in their work. In another study, Landaburu-Aguirre et al.
May 2015 767
[114] identified a significant barrier to the commercialization
of MEUF to treat wastewaters arising from the fertilizer man-
ufacturing industries, noting that the key problem yet to be
solved is to find a proper pretreatment process [for the
wastewaters]. The calcium content in the wastewater pro-
vided a challenge, as it precipitated the surfactant. Therefore,
we had to apply the surfactant as a pretreatment measure.
This method will not be feasible in larger scale, due to the
prohibitive cost of SDS pretreatment. Therefore, further
research is required before this technology is feasible in an
industrial scale. Gong and Zhao [115] reviewed
conventional and emerging separation technologies for the
recovery of phosphorous in wastewaterschemical precipi-
tation, crystallization, ligand exchange, adsorption, magnetic
separation, and nanotechnologies were all discussed.
In separate experiments, Liu et al. [116] encapsulated
Cu21 ions by anionic and cationic surfactant micelles of SDS
and cetyl pyridinium chloride (CPC) respectively, and sub-
jected the resulting micellar solutions (which contained a
concentration of 7.1 3 1024 mol dm23 of Cu21) to ultrafiltra-
tion under 2 bars, with the conclusion that the performance
of the anionic surfactant SDS was unsatisfactory, implying
that the cationic CPC was the more efficacious agent.
Balanya et al. [117] showed that Cu21 ions in solution can
be separated from their citrate ligands at pH 5 2 by acid-
resistant membranes (of pore size 45 mm). Filtration pressure
varied from 2 to 14 bars.
Froth Flotation
Froth flotation is one of the most frequently deployed
mineral processing technologies, and its operational princi-
ples have been found to be applicable to wastewater treat-
ment and materials recycling. From the mid- to late-1980s,
Brooks [118120] examined the suitability of several techni-
ques, including froth flotation, to treat various waste types,
reporting some treatment systems to be more effective than
others. In their discussion of environmental applications of
flotation, Rubio et al. [121] were confident that flotation
would be incorporated as a technology in the minerals
industry to treat these wastewaters and, when possible, to
recycle process water and materials. These pioneering dis-
coveries led to hopes that froth flotation also might develop
into full-scale unit operations to recover useful and valuable
metallic elements from wastes of the metal finishing, textiles,
and tanning industries and that pilot plants were built all
over the world to ascertain the feasibility of this technology.
Ion Flotation
In ion flotation, a homogeneous solution is rendered
heterogeneous subsequent to the addition of a soluble sur-
factant with an electrical charge opposite to that of specific
ions, forming an insoluble complex molecule. The surfactant
acts as both frother and collector, facilitating the attachment
of the target species onto the air bubbles. The bubbles are
forced through the solution and separated from the bulk of
the solution in the foam phase. In a successful application of
this technique, an acidic electroplating waste containing
Ni(II), Cu(II), Zn(II), and Cd(II) ions, chelated by citrate and
EDTA, was treated by Leu et al. [122]. The process involved
exchanging the ligands with surfactants functioning as
ligands followed by an electrically induced froth flotation of
these metalsurfactant chelates to the liquidair interface.
The total metal ion concentration in each experiment was 1
3 1023 mol dm23, and the metals were assumed to be fully
chelated. Sodium ethyl-dithiocarbamate (C2H5NHCS22Na1)
and potassium ethylxanthate (C2H5OCS22K1) were tried as
surfactants. The authors concluded that the carbamate was
the best surfactant, with removal efficiencies in the vicinity
of 80% for each of the metals studied [122].
768 May 2015 Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
Development of Flotation Agents with Metal-Chelating Abilities
Singh [123] wrote a valuable review article based on his
knowledge of froth flotation and his own work. Aspects of
this study included the discussion of his stepwise research
protocol and chelation chemistry on the surface of solid min-
eral particles. This article is important in the development of
theoretical aspects of froth flotation. Eleven flotation agent
systems were tabulated together with their suitability for spe-
cific ore types, for example, the akyl or aryl derivatives of
phosphonic acids were suggested as flotation agents for the
minerals fluorite, barite, calcite, apatite, wolframite, chromite,
cassiterite, and monazite and for the ores fluorite, phosphate,
and tin. In addition, six other chelating agents were listed for
their function as depressants in various ore-processing sit-
uations (i.e., certain components in an ore are preferentially
suppressed to enhance separation) [123]. The motivation for
this research originated from the need to extract metals from
ores of increasing complexities, demanding new additives
for the separation process of flotation.
Huang et al. [124,125] demonstrated that chitosan from
crustacean shells was found to selectively depress chalcopy-
rite (copper sulfide), whereas galena (lead sulfide) was
floated by xanthate. At pH 4, the recovery of galena was up
to 95%, whereas that of chalcopyrite was 30% when flotation
tests were carried out on mixtures of chalcopyrite and
galena. They also suggested that Chitosan could potentially
be used in differential CuPb sulfide separation to replace
the hazardous inorganic depressants such as cyanide, dichro-
mate, and sulfur dioxide [124,125].
Cui et al. [126] performed detailed instrumental analysis of
metal complexes formed by bastnaesite (which contains
cerium) and oxides of rare earth metals. The froth collector
was n-octanohydroxamate. They demonstrated that the inter-
action between mineral and collector can be examined with
a combination of Fourier transform infrared spectroscopy
(FTIR), Raman spectroscopy, X-ray photoelectron spectros-
copy, and scanning electron microscopy (SEM) [126].
Ion Exchange
Juang et al. [127] attempted to remove Mn21, Co21 and
Ni , and Sr21 ions (each separately chelated by citrate,
21
NTA, and EDTA) from aqueous solution in a simulation of
chemical cleaning water used to wash the boilers of nuclear
power plants. A fixed-bed, strong-acid (from the sulfonic
acid ASO3H group) ion-exchange resin called Amberlite IR-
120 was used for the absorption of these ions. The authors
did not specify the concentration of the metallic ions in the
water to be treated, but mentioned that ion-exchange meth-
ods are suitable for solutions with 10 mM concentrations of
metallic cations. Ninety percent of these ions were removed
in acidic medium (pH 5 2), but in alkaline media (pH 5 9),
only 20% of any of the ions were removed. Sr21 alone was
successfully removed at pH 5 9, even when chelated [127].
Adsorption isotherms for Ni21 ions on the cationic
exchange resin called Purolite NRW-100 (with sulfonic acid
groups ASO3H) was reported by Juang et al. [128] to be
Langmuirian in shape. The simulated solution used for the
work was dilute with respect to all components (in mM):
0.8511.9 mM of Ni21 and of citrate, 1.1 mM of H2PO42, and
11.2 mM of NH41, concentrations typical of rinse water of an
electrodeless plating system [128].
Ku and Chen [129] and Chang et al. [130] claimed that
Cu21 from its EDTA- and DTPA-chelated complexes were
adsorbed onto iron powders and that Fe(II)EDTA made its
appearance in aqueous solution from which the copper ions
were extracted.
Hasegawa et al. [131] reported on the adsorption charac-
teristics of 32 metallic ions in the presence of up to 100-fold
excess of aminocarboxylate ligands, on various adsorbents,
with mixed results. The effects of pH, stability constants, and
analyte flowrate over the adsorbing media were discussed
[131].
Adsorption
In the most general term, adsorption is a process whereby
a component accumulates at an interface between two
phases, for example, the solidliquid. The driving force for
adsorption is the reduction in interfacial tension between the
liquid and the solid adsorbent as a result of the adsorption
of chemical species on the surface of the solid. Schiewer and
Volesky [132] very broadly bracketed the applicability of
adsorptionwhen the target species to be removed is of
mass concentration less than 100 mg L21 (100 ppm).
Latest Developments in Biosorbents
Davis et al. [133] defined biosorption as a process
whereby the solid matrix designated for the adsorption of
target materials is of biological origin, regardless of the meta-
bolic status of its cells, that is, dead microbes can be
included in this category.
Although Slokar and Le Marechal [134] were still debating,
in their review article, whether ion-exchange methods
were adequately versatile in removing a great number of
dyes from wastewaters, a parallel but different trend of treat-
ment strategy was already marinating in the minds of peers.
For example, Ho and McKay [135] listed many naturally
occurring materials as adsorbents. They include orange peel,
banana pith, peanut hulls, water hyacinth roots, moss, Fomi-
topsis carnea (most probably the dead fungus), and last but
not least, activated carbon from a lignocellulosic waste mate-
rial called Core Pith Carbon (which had no economic value
and posed disposal problems) [135]. Hao et al. [136] listed
under the heading Adsorption many materials such as
bagasse pith, teak wood bark, rice husk, cotton waste, coal,
hair, bentonite clay, and silica as adsorbents for waste dyes.
Producing adsorbents from readily available natural mate-
rials, at low cost, was the subject of many recent literature
reviews. For example, Sud et al. [137] and Demirbas [138]
reviewed the use of agricultural waste materials to sequester
metallic ions from wastewaters. Other notable studies were
published by Mohd Salleh et al. [139], Geetha and Belagali
[140], and Rangabhashiyam et al. [141]. Below are just a few
interesting examples of natural materials deployment, prolifi-
cally reported.
Silk: Silkworms produce two groups of proteins,
fibroin and sericin, during the pupa phase of the natural life-
cycle of the moths. The main component of sericin, called
Ser 1, is made up of repetitive units of Ser- and Thr-rich
38 amino acid residues [142]. Fibroin, the desired commer-
cial product, is obtained following its separation from sericin,
and sericin is discarded as a waste. However, Chen et al.
[143] demonstrated that Sericin displayed large capacity for
the adsorption of Acid Yellow (AY) and copper(II)
phthalocyanine-3,40 ,400 ,4000 -tetrasulfonic acid (CuPc), with
adsorption capacities of 3.1 and 0.35 mmol g21,
respectively. Agarwal and Bhushan [144] also synthesized
nanoparticles from sericin and proposed medicinal and skin-
care applications for them.
Bacteria: Paraneeiswaran et al. [145] reported that the
bacteria Pseudomonas aeruginosa SPB-1 was a very effective
adsorbent for [CoIII(EDTA)]2 from aqueous solution, with
maximum adsorption at pH 5 7 and regeneration of biosorb-
ent at pH 5 1. Adsorption capacity was maintained at 80%
even after the fourth cycle of adsorption/desorption. They
also suggested that bioremediation of moderately radioactive
waste containing 60Co chelated to EDTA is possible [145].
Seaweed: Vijayaraghavan et al. [146] compared the
absorbtivities of three seaweeds, namely, Turbinaria (brown
Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
algae), Sargassum (brown algae), Ulva (green algae), for a
laboratory waste mixture containing the ions of eight metallic
elements: Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II),
and Pb(II), totalling 0.016 mol dm23. They found that Turbi-
naria (conoides) was the best adsorbent removing 3.20 3
1023 and 3.01 3 1023 mol of metallic ions per gram of the
seaweed.
Banana and Orange Peels: Hossain [147] used banana
peels to adsorb Cu21(aq) of concentration 1000 ppm, or
16 mM. They claimed that the banana skins can be regener-
ated seven times without compromise of adsorption effec-
tiveness [147]. Hashemian et al. [148] used activated carbon
made from agricultural waste orange peel to remove success-
fully two azo dyes (Violet B and Violet 5R) from aqueous
wastes.
Coconut, Almond, and Walnut Shells: Bernard et al.
[149] used activated carbon prepared from coconut shells to
adsorb Cu(II), Fe(II), Zn(II), and Pb(II) ions from electroplat-
ing wastewaters. Aliabadi et al. [150] adsorbed the dye
Rhodamine B on almond shell [150], whereas Shah et al.
[151] managed to remove the same dye from industrial efflu-
ents using walnut shells pretreated by various techniques.
Xanthates and Chitosan: Chang et al. [152] devised a
two-stage adsorption system to treat wastewaters at pH 5 4
containing Cu21 ions (501000 ppm) as copper nitrate. Xan-
thate materials were the absorbents, which form a chelated
complex with the copper ions. The first column contained
insoluble peanut shell xanthate (IPX), and the second col-
umn contained insoluble starch xanthate (ISX). The result
was that the concentration of copper ions in the final efflu-
ent was 0.6 ppm, below the statutory limit for discharge in
Taiwan. Shaheen et al. [153] compared the relative effective-
ness with which Cd(II), Cu(II), Pb(II), and Zn(II) ions are
removed from wastewaters by a variety of low-cost adsorb-
ents, including chitosan, egg shells, humate potassium, and
sugar beet factory lime and discovered that chitosan was the
most efficient.
Shrimp, Crab, and Mussel Shells: Ahmed et al. [154]
used the chitosan component of shrimp shells to adsorb
aqueous uranium species [(UVIO2)(OH)]1 and found that the
shell flakes were 85% effective. Niu and Volesky [155]
adsorbed the negatively charged inorganic complexes chro-
mate [CrO4]22, vanadate [VO4]32, and gold-cyanide
[Au(CN)2]2 onto the positively charged amide groups lining
the shells of Ucides crabs (a genus of mangrove crabs in
South America; see also Ramrakhiani et al. [156] for the bio-
sorption of [Cr2O7]22 by inactivated biomass of the fungus
Termitomyces clypeatus). For the simultaneous adsorption of
the aqueous ions of eight metallic elements (Cd, Co, Cu, Cr,
Mn, Ni, Pb, and Zn), Vijayaraghavan and Balasubramanian
[157] compared the adsorptive performance of crab shells,
chitosan, activated carbon, ion-exchange resin, peat, saw-
dust, bagasse, Turbinaria conoides, Sargassum sp., and Ulva
sp. and found that crab shells were the best. El Haddad
et al. [158] used ecofriendly calcined mussel shells to
adsorb Rhodamine B and two other textile dyes Alizarin
Red S and Orange II [158].
Cellulose Biopolymers: Kalidhasan et al. [159] used a
combination of instrumental methods of analysis, namely,
FTIR, SEM, energy-dispersive X-ray, and solid-state 13C
nuclear magnetic resonance to study the mechanism of
adsorption of the diphenylthiocarbazone complex of Cr(VI)
in acidic medium, concluding that cellulose is an effective
adsorbent of Cr complex under acidic conditions.
Clay Minerals as Adsorbents
Using bentonite clay with a negative surface charge, Tahir
and Naseem [160] removed 93% of Cr(III) ions from diluted
samples of liquid wastes collected from 18 tanneries. Mala-
misa and Katsoua [161] examined the adsorption of aqueous
May 2015 769
Zn(II) and Ni(II) ions on natural and modified zeolite, ben-
tonite, and vermiculite. They concluded that the adsorbate
type, solution pH, metal concentration, and ionic strength as
well as the adsorbent type and concentration are usually the
most influential parameters. Solution temperature, mineral
grain size, and agitation speed also seem to affect the proc-
ess [161]. Liu et al. [162] prepared a zeolite modified with
N,N-dimethyl dehydroabietylamine oxide and discovered that
the sorption of Congo Red greatly improved from that of
unmodified natural zeolite.
Modified Membranes as Sorbents for Wastes from Surface-Coating
Industries
Membranes coated with strong chelating agents have
become fashionable as sorbents for metallic ions present in
wastewaters arising from surface-finishing operations. Song
et al. [163] coated a polyvinylidene fluoride membrane sup-
port with melamine and DTPA (MA-DTPA) with the objective
of adsorbing Ni(II) ions. The workers attempted to establish
the efficacy of this membrane experimentally, by studying
two main types of plating solutions: (1) one in which organic
acids such as citric, succinic, and lactic, which exhibit metal-
sequestration ability, are present as part of the recipe of a
commercial plating solution; and (2) the so-called ternary
plating solutions, in which the deposited coating on steel or
chromium is an alloy of three elements, namely, Ni-Co-P, Ni-
Cu-P, or Ni-Zn-P. The initial concentration of Ni(II) ions in
every sample tested was 50 mg L21 (0.85 mM). It was found
that the presence of Ca(II), Fe(III), and NH41 ions in all
these solutions, up to a concentration of 1 mM, significantly
reduced the adsorption of Ni(II) ions by 24%, 7.7%, and
15%, respectively. The presence of citric, succinic, and lactic
acids up to a concentration of 1 mM also reduced the
adsorption of Ni(II) ions by 12.9%, 11%, and 6.1%, respec-
tively. In the ternary systems, interference of Ni(II) adsorp-
tion was quite severe. When the molar concentration of
Fe(II), Co(II), Cu(II), or Zn(II) neared that of the initial con-
centration of Ni(II), that is, to a 1:1 molar ratio, the removal
of Ni(II) from aqueous solution depreciated by 40.3%, 37.3%,
51.5%, and 31.8%, respectively. This sorption process is by
no means a failure if all these metallic elements in addition
to nickel are to be removed as part of a pollution abatement
exercise.
Metal Azo Complex Dyes and the Tanning Industry
Many metal azo complex dyes are chelated complexes of
a metallic ion such as Cr(III), Co(II/III), Ni(II), and Cu(II)
and one or two dye molecules. Chromium-azo dyes are rou-
tinely used in the tannery and other industries. Puntener and
Koller [164] patented the use of 1:2-chrome complex dyes
(one Cr atom chelated by two organic azo dye molecules)
for dyeing leather or furs. For dyeing wool, Slokar and Le
Marechal [134] asserted that metal complex dyes are the most
favored. An example of a 1:2 chromium azo dye is shown in
Figure 6 [165].
It is important to note that the same types of metal com-
plexes can have multiple applications. For instance, phthalo-
cyanine metal complexes have been used as dyes for much
of the 20th century [166]; however, the same type of com-
pounds are now catalysts for many economically important
reactions in the 21st century [167].
Environmental Risks in Perspective
P
untener [168] carried out a Risk Assessment of Leather
Dyestuff and concluded that The environmental risk posed
by a colorant can be defined in both its inherent ecotoxicity
and the concentrations attained in the environmental com-
partments. There is an increasing body of circumstantial evi-
dence indicating that the portion of colorants entering the
environment is ultimately degradable either by biological or
770 May 2015 Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
Figure 6. Structure of the 1:2 chromium azo dye Acid Black
172 [165]. [Color figure can be viewed in the online issue,
which is available at wileyonlinelibrary.com.]
photochemical pathways. He was of the opinion that a
wastewater containing 0.110 ppm of a colorant is not of
ecotoxicological concern, but the problem is with the
esthetics of the receiving body of water of a waste stream
with any concentration > 10 ppm of colorants, as the colora-
tion will be visible and cause public concern. He also
described a sequential treatment process for dye wastewaters
in tanneries, of which sorption is a step [168].
Treatment of Tanning Wastes
Fahim et al. [169] successfully adsorbed Cr(III) hydroxy
species [Crx(OH)y]1/2 from tanning wastes onto activated
carbon made from wastes from the sugar industry. Mohan
et al. [170] also adsorbed similar species from tanning efflu-
ents by activated carbon made from waste coconut shells
and a commercially available activated carbon fabric cloth.
Sahu et al. [171] removed Cr(III) ions from tannery waste-
water by the cation-exchange resin Indion 790, but
reported that the sorption process was very sensitive to bulk
solution pH such that beyond pH 3.5 extraction of chromiu-
m(III) drastically decreased from 92% to 76%. El-Sherif et al.
[172] reported 99% removal of Cr(III) from tannery waste
with cystein-modified polymer nanofibers. Fabbricino et al.
[173] adsorbed Cr(III) ions from tannery wastes onto ground
shrimp shells and referred to the very important reminder
from Fabiani et al. [174], The recovery of chromium from
sludge produced during wastewater treatment does not nec-
essarily mean that it can be reused in a new tanning process.
In fact, the use of recovered chromium instead of new chro-
mium can lower the quality of the produced leather and tan-
nery operators are normally opposed to this practice. To
place the treatment of chromium-laden tannery wastewaters
in perspective, the research worker will benefit from com-
paring different approaches to solving similar problems. For
example, Paschoal et al. [175] successfully deployed PEC oxi-
dation to treat wastewaters containing the leather dye Acid
Red 151, Cr(VI) species, and an anionic surfactant. It was
claimed that complete decolorization was achieved, with
95% removal of the original total organic carbon loading and
removal of more than 98% Cr(VI) from the wastewater [175].
Walsh and OHalloran [176] showed that the ligands bind-
ing chromium in a wastewater were proteins, amino acids,
and other organic acids, such as oxalate, ascorbate, citrate,
glutamate, albumin, and casein, and that chromium specia-
tion changed after release of effluent from a tannery into an
estuary in Ireland [177]. In earlier attempts of speciation,
however, Stein and Schwedt [178] reported that both Cr(III)
and Cr(VI) species were present in tannery waste; however,
in practice, it was difficult to determine the entire speciation
profile, qualitatively and quantitatively, as chromium species
were distributed amongst many phases, including colloidal
materials. This difficulty did not deter efforts by Burbridge
et al. [179] to investigate chromium speciation in pore waters
of river sediments in Lake Ontario (Ontario, Canada). The
site of interest was the property of a large former tannery,
into which Cr-contaminated effluent was discharged over a
55-year period, and where extremely high Cr concentrations
have been found in the sediments. Analysis revealed the
absence of Cr(VI) species, suggesting the ubiquitous pres-
ence of reductants in sediments [179].
The research of Baccar et al. [180], which focused on the
adsorption of potential pollutants, revealed a systematic
methodology to be emulated. In 2009, this group used the
waste material that originated from the olive oil manufactur-
ing industry (in Tunisia) as a precursor of activated carbon
for adsorption. The carbon surface was oxidized with per-
manganate [MnVIIO4]2, which is itself reduced to MnIVO2,
which then adsorbed aqueous Cu(II) ions. They reported
that the uptake of copper ions was enhanced by a factor of
3 when compared with activated carbon that has not been
treated by permanganate [180]. Baccar et al. [181] then
treated an industrial wastewater containing Lanaset Grey
G, a mixture of metal complex dyes, using olive-waste
cakes as an adsorbent. The adsorption capacity of the sor-
bent for Lanaset Grey G was found to be 108.7 mg g21 of
adsorbent and was better than the capacity of a commercial
activated carbon [and that] the presence of other compo-
nents, commonly used in the textile industrial bath, did not
affect the uptake extent of the target dye by the activated
carbon. Activated carbon made from olive-waste cakes was
shown to be a promising adsorbent for the efficient removal
of metal complex dyes [181]. (Da^assi et al. [182] also decol-
orized Lanaset Grey G by white-rot fungi.) Baccar et al. [183]
demonstrated that activated carbon made from olive-waste
cakes was effective in removal of dyes from tannery waste
containing a chromium complex dye called Black Dycem
TTO.
Celekli and Bozkurt [184] confirmed that pumpkin husks
are good adsorbents for the metal azo dye Lanaset Red G.
Recent research into the use of modified chitosan as an
adsorbent saw the publication of a series of articles by Repo
et al. [185188], on removing metallic ions and their EDTA
complexes from aqueous solution. Koody nska [189] also
successfully adsorbed the chelated complexes of Cu(II),
Zn(II), Cd(II), and Pb(II) with polyaspartic acid onto
chitosan.
Adsorption of Metal Complex Dyes by Bacteria, Fungi, and Algae
The kingdom of microorganisms is constituted of bacteria,
fungi, algae, protozoa, and viruses. They are grouped
together by virtue of their small sizes only, and not by their
diverse and versatile physiologies. Some microorganisms
such as viruses, bacteria, and protozoa are notoriously small,
a fraction of a millimeter. Algae and fungi, however, have
relatively large-sized relatives: the brown algae known as the
giant kelp, Macrocytis pyrifera, has been observed to grow
to 45 m long [190,191]. The ability of bulk materials originat-
ing from bacteria, algae, and fungi to adsorb metallic ions is
well known. Das et al. [192] explained the physical chemistry
of adsorption in terms of the diverse chemical compositions
on the cell walls of these microorganisms, which allow them
to bind a variety of metallic ions.
Bacteria: Dimicri et al. [193] screened halophilic pro-
karyotes, isolated from the Turkish Camalt Saltern (the larg-
est coastal solar saltern on the Aegean Sea), to identify those
resistant to some metal azo dyes used in the textile industry
so that the dyes could be decolorized in wastewaters. They
Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
found that only the bacterium Halobacillus sp. C-22 was
resistant to the two dyes of interest, Lanaset Navy R and
Lanaset Brown B (Cr-dyes). The first dye decolorized very
rapidly, almost 50% in 10 min, and the later one was 96%
decolorized after 78 h [193].
The kinetics and mechanism of biosorption of the metal
complex dye Acid Black 172 (see Figure 6) by live and
heat-treated Pseudomonas sp. strain DY1 was studied by Du
et al. [165]. After discovering that heat-treated bacteria
adsorbed the dye more effectively than live bacteria, they
explained the following phenomena: Amine groups played
a major role in the biosorption of Acid Black 172. Moreover,
heating of the biomass significantly increased the permeabil-
ity of the cell wall so that the dye could enter into the cells
and be adsorbed to intracellular proteins [165].
Fungi: Aksu and Balibek [194] investigated the effect of
salinity (NaCl) on the adsorptive ability of the fungus Rhizo-
pus arrhizus on the cobalt complex anionic dye Yellow RL.
The three most important parameters for successful adsorp-
tion were found to be initial pH of the dye solution, dye
concentration, and amount of salt. It was found that pH 5 2
was an optimum condition for adsorption; adsorption of
dyes with concentrations to 1000 ppm was not a problem.
The workers also reported that increasing salinity had an
adverse effect on adsorption, For 500 mg L21 initial dye
concentration, in the absence of salt, the amount of dye
adsorbed on fungal sorbent was 130.0 mg g21, at an initial
adsorption time of 1 h. However, as salt concentration rose
to 50 g L21, in a similar initial time period (1 h), the equilib-
rium uptake of Yellow RL by dried fungus was only 93.5 mg
g21 [194].
Yang et al. [195] studied the biosorption of Acid Black
172 (Cr-dye) and Congo Red from aqueous solution by
autoclaved, dried, and ground biomass from the fungus
known as Penicillium YW 01. The two dyes are used exten-
sively in China in the textiles and tanning industries. They
found that intraparticle (i.e., pore) diffusion was the rate-
determining step of adsorption for both dyes [195]. Xin et al.
[196] reported 99.7% removal of Cu-complex reactive dye
C.I. Reactive Blue 21 from aqueous solution, at original
mass concentration 400 mg L21 (400 ppm), after 2 days of
bioaccumulation of the dye by Penicillium oxalium pellets
and hypothesized a mechanism of the process.
Algae: Cobas et al. [197] tested the adsorption prowess
of the algae F. vesiculosus on simulated tanning dye solu-
tions. The aqueous solutions contained potassium dichro-
mate (thus the [Cr2O7]22 ion) and four leather dyes: Sella
Solid Blue, Special Violet, Burdeuox, and Sella Solid
Orange, all mixed together. In addition, they discovered
that the adsorptive ability of the algae could be enhanced by
treatment with calcium chloride [197].
Biodegradation
Metal Carboxylate-Chelated Complexes
White and Knowles [198] attempted to degrade chelated
complexes formed by metallic ions and NTA by the bacteria
Mesorhizobium sp. NCIMB 13524 isolated from a mixed cul-
ture of soil bacteria. (Mesorhizobium is a genus of nitrogen-
fixing bacteria. NCIMB is the abbreviation for the National
Collection of Industry and Marine Bacteria, a UK national
culture collection wherein bacteria are isolated. The number
13524 identifies its strain.) It was found that the bacteria com-
pletely degraded free NTA in solutions containing the NTA
complexes of the ions of Mn, Fe, Co, Ni, Cu, and Zn, in phos-
phate buffer (which sequesters metals), within 224 days of
incubation at 30 C. In a nonsequestering buffer, copper inhib-
ited the growth of bacteria and NTA degradation, suggesting
that only the free NTA was degraded. Moreover, in the
May 2015 771
presence of the noncomplexing buffer, the NiNTA complex
was not degraded and CoNTA was only 18% degraded.
This may suggest that the metalNTA complex itself is difficult
to biodegrade relative to the free NTA ligand. It must be added
that at pH 5 7 (the pH of these experiments), the phosphates
of transition metals are only sparingly soluble in water,
thereby freeing the NTA moiety to remain in solution.
Biodegradation seems to be relatively less successful
with citrato complexes. In a letter to Nature, Francis et al.
[199] demonstrated convincingly that the 1:1 complexes
formed between the anionic citrate moiety and several metal-
lic cations cannot be decomposed by the citrate-metabolizing
bacterium Pseudomonas fluorescens (ATTC no. 52241), a
microbe which this group isolated from leachate samples
collected from a low-level radioactive waste disposal site in
West Valley, New York. In one experiment, it was shown
that the Cu(II)citrate complex was not degraded at all after
40 h. However, free citric acid (in the absence of metallic
ions) was totally degraded after about 20 h, and the addition
of citric acid to a solution containing the 1:1 complex
resulted in the degradation of the free acid. The same resist-
ance was exhibited by the 1:1 citrato complexes of Fe21,
Cd21, Pb21, and [UO2]21. The 1:1 complex [Ni-cit]2 formed
by Ni21 and triply ionized citric acid was 70% degraded,
whereas the two 1:1 complexes of Fe31, namely, the biden-
tate [Fe(OH)2(cit)]22 and the tridentate [Fe(OH)(cit)]2, expe-
rienced 100% and 16% degradation, respectively, a mixed
result. Through experimentation and review of literature,
Brynhildsen and Allard [200] explained that the inability of
the bacterium Klebsiella oxytoca to degrade the citrate com-
plexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II),
and Al(III) was not due to problems of transport of these
complexes across cell membranes, but rather to the inhibi-
tion of the enzyme aconitase to convert citrate to isocitrate.
Puzon et al. [201] also demonstrated beyond doubt that the
two bacteria Ralstonia eutropha JMP-134 and Pseudomonas
aeruginosa pAO1 readily degraded the free ligands citrate,
malate, and histidine, but not the Cr(III) complexes of these
ligands. They cited the work of Means et al. [202,203] to sub-
stantiate their general argument that chelated complexes of
metallic ions and organic ligands (e.g., 60CoEDTA is an exam-
ple of interest to them) are recalcitrant to biodegradation in
the short term. Mattuck and Nikolaidis [204], Farmer et al.
[205], and Icopini and Long [206] all reported the resistance of
chelated metal complexes to biodegradation.
Qian et al. [207] claimed that although Pseudomonas alca-
liphila degraded only 15% of nickel citrate complexes in
aqueous solution, addition of excess free citrate ligands led
to an increase in pH of solutions and aided the partial disso-
ciation of the complex, leading to further biodegradation.
They claimed that addition of Fe31 also facilitated the Ni
removal process, as Fe(III) formed a complex with the citrate
ligand, thereby displacing Ni(II) ions. In addition, they main-
tained that Fe(III) ions will coprecipitate with Ni(II) ions and
detoxify them [207].
Maszenan et al. [208] reviewed the literature on the sub-
ject matter of Bioremediation of wastewaters with recalci-
trant organic compounds and metals by aerobic granules
and commented especially on the management of wastes
containing radioactive nuclides chelated by the aminocarbox-
ylic acids NTA and EDTA. They had no illusions regarding
the difficulty of treating these wastes [208]. In this expose,
Maszenan et al. [208] cited the work of Bolton et al. [209]
and Thomas et al. [210], showing that the practice and
understanding of biodegradation did not significantly
improve between 1996 and 2011.
Metal Complex Dyes
Blanquez et al. [211] attempted to decolorize wastewaters
containing Lanaset Grey G, which is a mixture of several metal
772 May 2015 Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
complex dyes (Cr and Co). In this instance, biodegradation
seemed to have been successful by the white-rot fungus Tra-
metes versicolor, a mushroom. The bioreactor was operated
under the conditions whereby laccase (i.e., oxygen oxydore-
ductase, one of the ligninolytic enzymes) was produced. The
solutions were 90% decolorized. In addition, 54.7% Cr and
68.1% Co that were originally chemically bound to dye mole-
cules were freed from bondage and released into liquid
medium. Kalpana et al. [212] also used a white-rot fungus,
Irpex lacteus, to biomediate the sulfonated chromium com-
plex dye Isolan Dark Blue 2SGL-01. The results were excel-
lent: 100% decolorization was achieved after 96 h of
treatment. The process functions well at a wide range of pH
values (59) and ambient temperatures (2035 C). Further
efforts to decolorize textile effluents were made by Li and
Guthrie [213] who removed colorations caused by metal azo
dyes Irgalan Grey GLN, Irgalan Black RBLN, and Irgalan
Blue 3GL by anaerobic biodegradation. Whole bacterial cells
of Shewanella J18 143 were used for the exercise.
Dhal et al. [214] described the biogeochemical life cycle
chromium with a diagram showing the oxidation of the com-
plex Cr(III)citrate by MnIVO2. The resulting products were
Cr(VI) and Mn(II) species, with the return of the citrate moi-
ety, intact, to the environment or so the diagram implied.
The reaction needs further investigation.
Hybrid Treatment Methods
Metal Azo Dyes Wastewaters
Adams et al. [215] achieved the dual objectives of decolor-
ization of wastewaters containing the metal azo dyes Acid
Black 52 (Cr) and Direct Blue 80 (Cu) and the release of
these metallic ions from their dye complexes. Three oxida-
tion systems were experimented on, namely, (i) O3, (ii) O3
and H2O2, and (iii) O3 and UV [215]. Yu et al. [216] used
ClO2 as an oxidant for the successful decolorization of waste-
waters containing Acid Chrome Blue K.
Soil Washing and Remediation
Di Palma et al. [217] treated soil wash waters containing
0.05 mol dm23 metallic ions (either Pb21 or Cu21) and
0.05 mol dm23 EDTA at pH 5 7.3. The first step was to con-
centrate the solution by evaporating 75% of the water by
heating. They suggested two methods of further treatment.
The first, acidifying the concentrated solution, recovered 93%
EDTA as a precipitate. NaOH was then added to coprecipi-
tate the iron and one of the other metals. In the second
method, they added ferric chloride to the concentrated solu-
tion, substituting Fe31 for the divalent metallic ion. The addi-
tion of sodium phosphate precipitated the lead or copper
phosphate. More than 90% of both Pb21 and Cu21 ions were
removed. The addition of NaOH precipitated iron and left
NaEDTA in solution to be recovered.
Deng et al. [218] reported that the rate of photoreduction
of Cr(VI) to Cr(III) increased in the presence of an algae
called Chlorella vulgaris. The complexants present were
EDTA, carbonate, and hydrogen phosphates.
Biosorption and Bioreduction of Cr(VI) Species from Electroplating
Wastewater
Ye et al. [219] used a mixture of Candida lipolytica (a
yeast) and dewatered sewage sludge to adsorb and subse-
quently reduce Cr(VI) from electroplating wastewaters (with
total Cr: 1550 ppm), to Cr(III), with promising results.
Simultaneous Dye Decolorization and Hydrogen Fuel Production
Mona et al. [220,221] demonstrated that it was possible to
decolorize the two highly toxic metal azo dyes Reactive Red
198 and Crystal Violet containing Cr(VI) and Co(II), and
produce gaseous hydrogen in the process, by the
cyanobacterium Nostoc linckia which originated from a tex-
tile mill oxidation pond.
DISCUSSION OF LIMITATIONS OF TREATMENT SYSTEMS
The 18 separation techniques described above are now
analyzed, and six potential problem areas are identified.
These must be taken into account when choosing an optimal
treatment system for a specific wastewater.
Heating and Odor Problems
Heating a wastewater to dryness to retrieve all dissolved
components is extremely energy intensive and inevitably
leaves films of solid deposits that may be difficult to remove
from heating elements. If a volatile component such as
ammonia (as ligands and buffers) is evolved, direct heating
is best avoided as its odor is usually unbearable to workforce
and neighbor alike. None of the other treatment methods
mentioned in this article, except for Mn(VII) oxidation,
included the application of heat, which has to be applied to
accelerate the oxidation of recalcitrant components in alka-
line Hanford tank wastes. In the case of sulfide precipitation,
the method is still practiced in many countries including the
United States and Canada; however, emission of H2S from
sewer networks results in objectionable odors and corrosion
of pipes. Nonetheless, it has already been demonstrated that
sulfide precipitation is not an effective method of treatment
in the presence of chelating agents [4,6,7].
Concentration Limits of Treatment Methods
For a successful separation process, thermodynamics
demand that the formation constant of the metal and the
functional group on an ion-exchange adsorbent must be
greater than that of the metalligand pair in the wastewater.
There is no report of successful removal of Co21 from a
solution, for instance, of Co(II)EDTA (1 3 1023 mol dm23
for the sake of argument) by ion exchange, with the elution
of free EDTA ions alone. The formation constant of the
cobalt complex is of the order 1018 mol dm23 in alkaline sol-
utions! Equally important to ascertain is the ion-exchange
capacity of each commercially available ion-exchange resin.
Method Effectiveness
Photolysis
It is an extremely good idea to degrade organic com-
pounds using sunlight. However, in personal communica-
tions, Dudeney and Tarasova [11] have pointed out that on
certain days when sunshine is lacking in London, it took 5
days to split the iron(III) oxalate complex in a 10-L solution,
circulated in an open channel exposed to sunlight.
Electrodialysis
Electrodialysis is an established process whereby saline
waters are rendered potable by separating the distinct ions
under the influence of an electric field. It is normally carried
out through a membrane stack of alternating cation-
exchange membranes and anion-exchange membranes, with
a cathode and anode applying the electric field on opposing
sides. The salt solution is fed to all of the intermediate gaps.
Under the influence of the electric field, cations pass through
the cation-exchange membranes, and anions through the
anion-exchange membranes in opposite directions. The
result is that ions are depleted in alternate cells, whereas the
remaining cells experience a net concentration. The depleted
streams form the desalinated product. However, unlike
Na1(aq) and Cl2(aq) ions, species such as [Ni(citrate)]n2 of
similar concentrations may not be separated readily by elec-
trodialysis. At low pH values, when the proportion of che-
lated metal ions is lower than that in alkaline solutions,
Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
separation of unchelated Ni21 from the bulk of the solution
may be possible. In comparison with electrodialysis, it may
be recalled that Green et al. [105] used an anionic exchange
membrane to remove the nickel citrate complex from solu-
tion, but did not separate the metal from the ligand. The
concentration of the untreated nickel citrate solution was
0.7 mol dm23, in the vicinity of the concentration used in
the electrodialysis experiments [105].
Electroplating and Electromembrane Separation
The studies reviewed on these techniques reported unsuc-
cessful attempts to affect separation, although no explanation
was offered. However, the apparent success with electromem-
brane separation achieved by Juang and Lin [103] was prob-
ably due to the fact that at low pH 5 2.2, Cu21 may not be
strongly complexed by citrate because of the protonation of
the anion, therefore neutralizing some charges and reducing
the electrostatic attraction between cations and anions.
Design and Operational Considerations
In UV treatment, Reina [222] reported that very poor
transmissivity (of UV light) has been identified as an opera-
tional problem in large-scale treatment plants for water
supplies.
In the case of electrodialysis, concentration polarization
results in an increased power requirement without an appre-
ciable performance enhancement. There is a value of current
that produces a depletion of ions on the feed side of the
membrane because the ions are being transferred through
the membrane faster than they can be transported from the
membrane to the solution. Increase in resistance occurs not
only because there are no ions to transfer the current at the
membrane boundary but also because the excess current is
used to split water into H1 and OH2 ions, and the increase
in pH on the concentrating side of the membrane results in
scaling and fouling by precipitation of various substances. In
the electrodialysis of wastewaters containing metallic cations,
the metallic hydroxide and carbonate may precipitate on the
membrane, as the solubility of these substances is sensitive
to pH changes [223]. Frequent cleaning of the membranes
becomes necessary.
Chemical Feasibility
Some of the chemical and biochemical methods of treat-
ment discussed above witnessed kinetics and mechanisms
that are both difficult to study and to control; these problems
were reported in earnest by the respective workers. Some of
the issues raised in their work are discussed further here.
Fenton Reactions
1. Glaze and Kang [224] reported that the half-life of HO
free radicals in treatment systems is of the order 1026 s,
which meant that concentrations of the free radicals in
aqueous solution will not exceed 10212 mol dm23 at any
one time. Because the concentrations of chelated com-
plexes in plating waste solutions are in the vicinity of 0.7
1 mol dm23 [105], the initial mole ratio of oxidant to
reductant will be about 11012. A treatment process of this
type probably would be very lengthy, notwithstanding the
lack of knowledge of the speed of the rate-determining
step(s) of these free radical mechanisms.
2. Photoreduction of Fe(III) to Fe(II) must be extremely effi-
cient not only to sustain the attack on the target complex
but also to make sure that all Fe ions remain complexed.
This efficiency may be limited by kinetic considerations.
Because the formation constants of Fe(II) chelates are gen-
erally smaller than those of Fe(III), it is important to avoid
releasing unchelated Fe21 ions into the bulk of the
May 2015 773
 solution as they will be oxidized to Fe31 ions by HO (and
by dissolved O2) very rapidly, with the undesirable result
that iron oxides/oxyhydroxides precipitate.
3. The complex which encapsulates the iron atom must
retain its structural integrity while being attacked by HO
radicals, when Fe(II) is being oxidized to Fe(III) by H2O2.
It was once thought that ironEDTA would be the ideal
complex; however, Walling et al. [225] have shown that
decomposition of H2O2 catalyzed by the ironEDTA com-
plex led to destruction of EDTA itself, a drawback also
noticed by Halliwell and Gutteridge [226]. The synthetic
work of Sienko et al. [227] may be of good aid here. They
prepared the stable ion [FeIII(C2O4)3]32 by oxidizing FeII(-
C2O4).2H2O with H2O2 in the presence of potassium oxa-
late. H2O2 oxidized Fe(II) to Fe(III) without oxidative
decarboxylation of the oxalate anions.
4. The iron complex must remain in aqueous solution while
the target complex is destroyed, and the central metallic
ion released and precipitated in some insoluble form. The
iron complex must also remain in aqueous solution to
avoid contaminating the target precipitate.
5. Traditionally, one of the main disadvantages of Fenton
treatment is that it produces too much iron sludge which
needs disposal. A lot of effort is made toward developing a
new Fenton Family of wastewater treatment methods,
with the minimization of disposal sludge as one of its main
objectives. The organization known as GreenTec [228] has
produced a user-friendly and readable summary of these
developments. One of the latest Fenton methods developed
toward the same end was proposed by Hanson et al. [229].
Ozonolysis
Although the empirical results of ozone treatment
obtained by various workers have already been presented in
the Ozonolysis and the Oxidation by H2O2 sections, sev- strated convincingly the resistance of a large number and
eral additional factors may limit the successes of ozonation.
First is the known phenomenon whereby ozonation of aque-
ous solutions of soluble organic compounds typically results
in the corresponding organic acids [230], that is, carboxylic
acids are the end products of ozonation and will react or
fragment extremely sluggishly.
Second, and closely related to the previous point, is
whether the mass transfer of ozone gas into the bulk of the
solution is adequate to affect a specific chain of redox reac-
tions between chelated complexes and ozone, to completion,
in an acceptable time scale. To be sure, ozonation of waste-
waters as a means of treatment on an industrial scale is well
known, and by the turn of the last century, there were more
than 2000 such installations worldwide for the treatment of
potable water [231]. Is the knowledge and conventional wis-
dom regarding disinfection of various waters including sew-
age, especially the chemical feasibility and rate of mass
transfer of ozone molecules into the bulk of the solution,
adequate to extract metallic ions chelated by the large selec-
tion of organic and inorganic ligands available commercially?
Third, the speciation of ozone as a function of pH
requires consideration. Hoigne and Bader [232] reported that
in acidic solutions, the chief oxidant is triatomic ozone O3,
whereas in alkaline solutions, or in the presence of H2O2 or
UV light, oxidation by HO radicals predominate. Kinman
[233] determined the maximum solubility of O3 molecules in
water at 20 C to be 1.2 3 1022 mol dm23. Similar to the sit-
uation of very low concentrations of HO radicals described
above, the problem of the mole ratio of O3 to target species
also arises, albeit the ratio is a relatively more favorable
1:100. (c.f. Existing water treatment plants typically operate
in the range 2 3 1026 to 2 3 1025 mol dm23 of O3 concen-
tration, as reported by the U.S. EPA in 2001 [230], thereby
depreciating the 1:100 ratio by 3 to 4 orders of magnitude!)
774 May 2015 Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep
Biodegradation
Francis et al. [199] demonstrated convincingly that
although unbound citric acid was totally degraded after
about 20 h by the citrate-metabolizing bacterium Pseudomo-
nas fluorescens (ATTC no. 52241), the 1:1 metalcitrate com-
plexes of Cu(II), Fe(II), Cd(II), Pb(II), and of the complex
cation [UO2]21 were recalcitrant to decomposition. The addi-
tion of citric acid to a solution containing the 1:1 complex
resulted only in the degradation of the free acid. However,
[Ni(C6H5O7)]2 was 70% degraded, whereas two Fe(III)
citrate complexes, the bidentate [Fe(OH)2(C6H5O7)]22 and
the tridentate [Fe(OH)(C6H5O7)]2, experienced 100% and
16% degradation, respectively. These results show that the
identities of the metallic ions, their oxidation states, and the
presence of secondary ligands are factors crucial to
biodegradation.
The work of White and Knowles [198] drew attention to
the importance of whether the pH buffer used in experimen-
tation is a competing ligand itself. Unbound NTA was com-
pletely degraded in solutions containing the NTA complexes
of a number of first-row transition metal ions in the presence
of phosphate ions (which bind metallic ions and precipitate
them). With a nonsequestering buffer, however, Cu21 inhib-
ited the growth of bacteria and NTA degradation, suggesting
that only the free NTA was degraded. In the presence of the
noncomplexing buffer, the NiNTA complex was not
degraded and CoNTA was only 18% degraded. This sug-
gests that the metalNTA complex is difficult to biodegrade
relative to unbound NTA.
Puzon et al. [201] demonstrated beyond doubt that the
free ligands citrate, malate, and histidine are easily biode-
graded, but not their Cr(III) complexes. Earlier works of
Means et al. [202,203] on the biodegradation of cobaltEDTA,
Brynhildsen and Allard [200], Mattuck and Nikolaidis [204],
Farmer et al. [205], and Icopini and Long [206] all demon-
variety of chelated complexes to biodegradation.
PRACTICAL SUGGESTIONS FOR FUTURE RESEARCH
The overall objectives of implementing any treatment sys-
tem for wastewaters must be clearly defined, commencing
from the earliest conception of a novel technological idea.
The end products (and their amounts) of an industrial-scale
treatment system or combination of systems must be known
in advance. It is highly desirable to recover the metallic com-
ponents of wastewaters in an immediately reusable form, or
in a form that can be processed easily for recycling, espe-
cially when landfilling options for hazardous wastes are
severely limited by legislation. It may be possible to reuse
the treated water, depending on its quality; in any case, the
wastewater must be treated to sewerable standards. These
objectives should constitute part of a waste-minimization
program in any factory. It is hoped that this literature review
will encourage researchers to incorporate the following activ-
ities in any further work on the subject of treatment of
wastewaters containing chelated complexes of transition
metals.
1. The composition and concentration of all metallic species
must be determined by appropriate instrumental methods
of analysis, together with speciation diagrams generated
by extensive and well-maintained computer databases,
expressing speciation as a function of pH. The speciation
exercise will mark the commencement of the treatment
plan, as it provides the first data necessary for a full mass
balance of metallic species. Especially with carboxylic
and aminocarboxylic acids, sequestration of metallic ions
is least effective in extremely acidic solutions, that is, the
thermodynamic formation constants of metal complexes
are a strong function of pH [62]. Is it possible to over-
come the hindrance experienced by Green et al. [105]
Figure 7. Hydroxycarboxylic acids considered to be used as ligands in various industries. [Color figure can be viewed in the
online issue, which is available at wileyonlinelibrary.com.]

while using electrodialysis, as metallic ions and ligands are
already well separated in acidic solutions? How well does
electroplating applied to an acidic solution perform in rela-
tion to an equivalent solution in alkaline solution? The opti-
mum pH value or pH range for a specific surface-finishing
operation must be meticulously predetermined, applied
consistently on production lines, and tightly controlled
throughout the plating. The same respect for the impor-
tance of pH control must be rendered to the treatment of
wastewaters originating therefrom.
In certain cases, it is possible to render a solution alkaline
to precipitate metallic ions even though they may be com-
plexed. It has been found that addition of ammonia to cer-
tain copper-plating baths is beneficial to the overall plating
process, for example, Rafizadeh et al. [234] proposed
replacing the highly toxic cyanide by ammonia as a com-
plexing agent in copper plating. The addition of excess
alkali results in the precipitation of the pale blue gel of
copper hydroxide [235]:
CuNH3 4 H2 O2 21 aq 1 2OH2 or the operating parameters can mitigate the issuing of these
1 2H2 O
CuH2 O4 OH2 s # 14NH3
After washing the blue gel free from ammonia, the suspen-
sion can be boiled in the open air, decomposing the hydrox-
ide to form the black CuO [236]:
CuH2 O4 OH2 gel ! CuO s # 15H2 O GC-MS, UVvisible spectroscopy, and cyclic voltammetry.
With any metalligand pair (ML), therefore, it is necessary to
investigate the stability of the chelated complex (a) as func-
tion of pH at room temperatures, (b) as a function of tem-
perature, up to the boiling point of the wastewater, and (c)
as a function of the combined effect of pH (both acidic and
alkaline) and temperature.
Research in the field of industrial chemistry proposed many
low-molecular-weight hydroxy-carboxylic acids as chelators
of metallic ions, the ML pairs being targeted for surface fin-
ishing (plating) or otherwise. Figure 7 shows the most com-
monly encountered and their molecular structures.
2. On-line monitoring of operational characteristics must be
implemented throughout industrial processes. Whatever the
separation process chosen for the treatment, the pH and
temperature of the wastewater must be monitored through-
out the treatment process, and the optimum values of these
two parameters must be identified. This is important, as it
will affect both the speciation and solubility of the target
compound, and in turn, the performance of the treatment
process. The head space of a reaction vessel must be moni-
tored to detect the presence of any noxious gases. This will
determine whether a change in the solution chemistry and/
gases, without compromising prescribed treatment objec-
tives. The treated liquor must be tested for standards of sew-
erability, if the water is not reused in-house.
3. When a suitable advanced oxidation process has been
identified to extract dissolved metallic ions, it is important
to investigate the sequence of physicalchemical events
of the redox reactions using analytical methods such as
The chemistry of redox reactions that fragment and/or
detach ligands, leading to the release of metallic ions and
proceeding in parallel with coagulation of colloidal

Environmental Progress & Sustainable Energy (Vol.34, No.3) DOI 10.1002/ep May 2015 775
 particles and their sedimentation, are highly complex
phenomena.
If MnVII is the oxidant of choice for inducing precipita-
tion, it will be reduced to the insoluble oxides MnIVO2 and
MnIIO, and these will inevitably coprecipitate with target
metallic compounds. Such an operation can be carried out if
recycling of various metals for reuse is not the aim, as in the
case of Hanford, where the goal is to vitrify the waste to be
buried in stable geological formations. However, if recycling
is the goal, the reduced species must be soluble, staying in
aqueous solution so as to not contaminate the target metallic
species to be precipitated as a solid.
4. Physical properties and morphologies of precipitated sol-
ids require investigation. Is the precipitate composed of
very fine powders, granules, or crystals? What is the size
distribution in a population of such aggregates? What are
the bulk densities and settling times of these solids? What
is the time scale of crystallization? These parameters indi-
cate the appropriate unit operations to be deployed for
separating the solid and liquid phases. Is sedimentation
of solids so rapid that the clarified liquid can be conven-
iently decanted? Or should filtration of suspended solids
commence as soon as chemical reactions are completed?
With many colloids and solids, the size distribution of
particles changes as they are partially dewatered (e.g.,
they aggregate into larger particles and/or consolidate
into denser forms). Is drying in fluidized beds an option?
Should solids be dried in an oven or by waste heat gen-
erated from other processes? These questions and their
answers are integral to a successful wastewater treatment
system.
CONCLUSIONS
This review highlights the difficulties faced by many
industries in the treatment of wastewaters containing che-
lated complexes of metallic ions. Eighteen methods of sepa-
rating metallic ions from wastewaters, with their approaches
and limitations, are identified from the literature. These
become pointers for future research protocols that may
develop treatment systems leading to the recycling and reuse
of the metallic components of these wastes. Some sugges-
tions to achieve this end in treatment plants are also
outlined.
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