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Biodegradable chelating agents for industrial, domestic, and agricultural applications-a review


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Aminopolycarboxylates, like ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), are chelating agents widely used in several industrial, agricultural, and domestic applications. However, the fact that they are not biodegradable leads to the presence of considerable amounts in aquatic systems, with serious environmental consequences. The replacement of these compounds by biodegradable alternatives has been the object of study in the last three decades. This paper reviews the most relevant studies towards the use of environmentally friendly chelating agents in a large number of applications: oxidative bleaching, detergents and cleaning compositions, scale prevention and reduction, remediation of soils, agriculture, electroplating, waste treatment, and biocides. Nitrilotriacetic acid (NTA), ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic acid (IDS) are the most commonly suggested to replace the nonbiodegradable chelating agents. Depending on the application, the requirements for metal complexation might differ. Metal chelation ability of the most promising compounds [NTA, EDDS, IDS, methylglycinediacetic acid (MGDA), L-glutamic acid N,N-diacetic acid (GLDA), ethylenediamine-N,N'-diglutaric acid (EDDG), ethylenediamine-N,N'-dimalonic acid (EDDM), 3-hydroxy-2,2-iminodisuccinic acid (HIDS), 2-hydroxyethyliminodiacetic acid (HEIDA), pyridine-2,6-dicarboxylic acid (PDA)] with Fe, Mn, Cu, Pb, Cd, Zn, Ca, and Mg was simulated by computer calculations. The advantages or disadvantages of each compound for the most important applications were discussed.
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Biodegradable chelating agents for industrial, domestic,
and agricultural applicationsa review
Isabel S. S. Pinto &Isabel F. F. Neto &
Helena M. V. M. Soares
Received: 14 September 2013 / Accepted: 23 January 2014 /Published online: 20 February 2014
#Springer-Verlag Berlin Heidelberg 2014
Abstract Aminopolycarboxylates, like ethylenediaminetet-
raacetic acid (EDTA) and diethylenetriaminepentaacetic acid
(DTPA), are chelating agents widely used in several industrial,
agricultural, and domestic applications. However, the fact that
they are not biodegradable leads to the presence of consider-
able amounts in aquatic systems, with serious environmental
consequences. The replacement of these compounds by bio-
degradable alternatives has been the object of study in the last
three decades. This paper reviews the most relevant studies
towards the use of environmentally friendly chelating agents
in a large number of applications: oxidative bleaching, deter-
gents and cleaning compositions, scale prevention and reduc-
tion, remediation of soils, agriculture, electroplating, waste
treatment, and biocides. Nitrilotriacetic acid (NTA),
ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic
acid (IDS) are the most commonly suggested to replace the
nonbiodegradable chelating agents. Depending on the appli-
cation, the requirements for metal complexation might differ.
Metal chelation ability of the most promising compounds
[NTA, EDDS, IDS, methylglycinediacetic acid (MGDA), L-
glutamic acid N,N-diacetic acid (GLDA), ethylenediamine-
N,N-diglutaric acid (EDDG), ethylenediamine-N,N-
dimalonic acid (EDDM), 3-hydroxy-2,2-iminodisuccinic acid
(HIDS), 2-hydroxyethyliminodiacetic acid (HEIDA),
pyridine-2,6-dicarboxylic acid (PDA)] with Fe, Mn, Cu, Pb,
Cd, Zn, Ca, and Mg was simulated by computer calculations.
The advantages or disadvantages of each compound for the
most important applications were discussed.
Keywords Chelating agents .Biodegradability .Industry .
Chelating agents are widely used in many industrial, domestic,
and agriculture applications due to their ability to complex
metals. Over the last decades, they have been used in several
applications, such as scale and corrosion inhibitors, pulp, paper
and textile production, cleaning and laundry operations,
prevention/inhibition of the growth of microorganisms, soil
remediation, wastes and effluents treatment, agriculture, metal
electroplating and other surface treatments, tanning processes,
cement admixtures, photography, food products, pharmaceuti-
cals, and cosmetics (Knepper 2003; Nowack and VanBriesen
2005). These compounds are mainly used with two different
purposes: (1) to remove critical metals that can affect the effi-
ciency of the process or (2) to avoid metal precipitation and
ensure an essential amount for the good operation of the process.
Among the various chelating agents available,
organophosphonates and aminopolycarboxylates (APCs)
stand out as they are good metal chelators with a good
quality/price ratio. APCs, such as ethylenediaminetetraacetic
acid (EDTA), diethylenetriaminepentaacetic acid (DTPA),
nitrilotriacetic acid (NTA), and also organophosphonates like
diethylenetriamine penta(methylene phosphonic acid)
(DTPMP), hydroxyethylidenediphosphonic acid (HEDP),
and nitrilotrimethylenephosphonic acid (NTMP) are the most
common chelating agents used in the world (Knepper 2003;
Nowack and VanBriesen 2005). In the last decades, discussion
about their environmental consequences has been raised. The
biodegradation of EDTA, DTPA, and organophosphonates is
Responsible editor: Philippe Garrigues
Electronic supplementary material The online version of this article
(doi:10.1007/s11356-014-2592-6) contains supplementary material,
which is available to authorized users.
I. S. S. Pinto :I. F. F. Neto:H. M. V. M. Soares (*)
1REQUIMTE, Departamento de Engenharia Química, Faculdade de
Engenharia, Universidade do Porto, Rua Dr. Roberto Frias,
4200-465 Porto, Portugal
Environ Sci Pollut Res (2014) 21:1189311906
DOI 10.1007/s11356-014-2592-6
very limited, and they can only be biodegraded in very partic-
ular conditions, with specific isolated bacterial strains (Bucheli-
Witschel and Egli 2001; Nörtemann 2005); still, these com-
pounds do not obey the Organization for Economic Co-
operation and Development (OECD 1992) criteria for biode-
gradability (Knepper 2003). To reduce their concentration in
industrial effluents, additional treatments such as advanced
oxidation processes, which have been reviewed (Sillanpää
and Pirkanniemi 2001; Sillanpää et al. 2011), are necessary.
The understanding of the chemistry of the chelates in
natural waters is essential to predict the fate of these com-
pounds in the environment (Nowack 2002). EDTA is not toxic
for mammals and is used in cosmetics and pharmaceuticals
with no harmful effects in human life (Nowack and
VanBri e s e n 2005), but its strong ability to form metal com-
plexes, together with its persistency in the environment, re-
sults in a perturbation of the natural metal speciation in the
environment. The presence of chelating agents in water solu-
bilizes heavy metals from the sediments and soils, enhancing
its mobility, which can increase the presence of metals in
water supply systems. The exposure of humans, animals,
plants, and microorganisms to heavy metals raises concern
due to their toxic effects. The metal complexes of EDTA
themselves have been found to be more toxic than the free
form of the ligand (Sillanpää and Oikari 1996). Mobilized
metals can include radioactive ions from contaminated soils or
disposal sites, with all the harmful effects associated with
them (Nörtemann 2005). Chelating agents also have an effect
on the liberation of phosphorous due to the dissolution of
metal phosphates that contribute to an increase of microor-
ganisms in water (Oviedo and Rodriguez 2003).
NTA (Fig. 1) was the first chelating agent to be synthesized
and it is widely used. Although it is biodegradable, its usage is
controversial because it is moderately toxic to humans and
mammals and suspected to induce kidney toxicity and tumors
(Bahnemann et al. 1998; Ebina et al. 1986). The present
concentrations of NTA in the environment are lower than the
thresholds determined for these effects (Bucheli-Witschel and
Egli 2001), but its use cannot be increased substantially.
Other biodegradable chelating agents, such as
ethylenediaminedisuccinic acid (EDDS) and iminodisuccinic
acid (IDS), started to be considered and studied as alternatives
in the 1980s, especially to substitute phosphonates in deter-
gents and cleaning compositions, but also in the bleaching
industry and as peroxide stabilizers. EDDS (Fig. 1) can exist
in three stereoisomer forms but only the S,S-isomer is consid-
ered biodegradable according to the OECD guidelines
(Schowanek et al. 1997; Takahashi et al. 1997). Most of the
works concerning the application of EDDS consider the bio-
degradable isomer that will be only identified as EDDS
throughout this work. It is commercialized by Innospec Inc.,
UK as Enviomet
. IDS (Fig. 1), also known as (N-1,2-
dicarboxyethyl)-D,L-aspartic acid, has three stereoisomers as
well, but, unlike EDDS, all of them were proven to be biode-
gradable (Hyvonen et al. 2003). IDS is commercialized by
Lanxess under the name Baypure CX 100, and its synthesis
process is considered environmental-friendly, with no gener-
ation of off-gases or effluents (Kolodynska 2011).
The search for alternative chelating agents, more environ-
mentally friendly, is very important, and several works
concerning the various applications have been published in
the last two decades. The new compounds must be biodegrad-
able, to avoid harmful consequences for the environment, but
also have good chelating abilities and be economically viable.
This is a critical point since most of the biodegradable
complexants have low or moderate stability constants when
compared to EDTA and DTPA. For each application, the
assessment of the best compounds must take into consider-
ation the metals that need (or not) to be complexed, pH range,
and compound characteristics, like solubility and stability in
different conditions, protonation, and stability constants.
Besides EDDS and IDS, there is a group of other APCs
(Fig. 1) that are recurrently mentioned in the literature as
possible substitutes of the traditional chelating agents. The
correlation between the structure and respective biodegrad-
ability has been studied; most of the molecules represented in
Fig. 1have one nitrogen atom, which makes them more easily
biodegraded, while the presence of tertiary amines in EDTA
and DTPA molecules makes them difficult for biodegradation
(Nörtemann 2005).
Methylglycinediacetic acid (MGDA) has a good stability
in a wide pH range and is classified as ready biodegradable
according to OECD (1992) criteria. MGDA commercial name
is Trilon® M and is produced by BASF (2007).
L-Glutamic acid N,N-diacetic acid (GLDA) is classified as
ready biodegradable and has no toxic effect on biotic systems
or human health (Borowiec et al. 2009). This ligand is
marketed on commercial scale by AkzoNobel with the name
Dissolvine® GL-38 (AkzoNobel 2010).
Ethylenediamine-N,N-diglutaric acid (EDDG) and
ethylenediamine-N,N-dimalonic acid (EDDM) are two che-
lators, members of the same homologous series of EDDS.
EDDG biodegradability was assessed by Lanham et al.
(2011). Synthesis and biodegradability of EDDM were stud-
ied by Aoki and Hara (2002).
Chelating agent 3-hydroxy-2,2-iminodisuccinic acid
(HIDS) is biodegradable and presents low toxicity (Nippon
2013). The compound is produced and commercialized by
Nippon Shokubai.
2-Hydroxyethyliminodiacetic acid (HEIDA), also com-
monly referred as ethanoldiglycinic acid (EDG), has proven
to be biodegradable (Lynn et al. 1975). Two companies sell
this compound: Dow, as VERSENEHEIDA, and Akzo
Nobel under the name Dissolvine® EDG.
Pyridine-2,6-dicarboxilic acid (PDA), also known as
dipicolinic acid, contains a pyridine ring and is biodegradable
11894 Environ Sci Pollut Res (2014) 21:1189311906
according to the OECD guidelines (Martins et al. 2014). It is a
naturally occurring compound, as it constitutes ~10 % of the
dry weigh of Bacillus species spores. Due to its structure, it
tends to chelate metals in a proportion of 2:1 (ligand/metal),
improving the stability of the complex.
Protonation and stability constants (as log β) for several metals
of interest are presented for the APCs mentioned in Table 1.
The present work attempts to give an overview of the
studies where the practical application of biodegradable che-
lating agents was considered and experimented. The biode-
gradability of the chelating agents is not considered funda-
mental in industries like cosmetics, food processing, and
pharmaceuticals, where the compound is used in smaller
quantities. Almost no studies regarding this problematic were
found; therefore, these usages were not object of review in the
present work. Requirements of chelation abilities differ de-
pending on the goal of the application. For the group of
compounds more recurrent in recent literature (EDDG,
and PDA), computer chemical simulations were performed to
assess their ability to chelate metals, using conditions relevant
for the applications discussed in order to make a standardized
comparison between them.
Applications using biodegradable chelating agents
Oxidative bleaching processes
Chelating agents are widely used in pulp and paper as well as in
textile industries and the current preference for bleaching pro-
cesses free from chlorine (total chlorine-freeTCF) might
increase their usage. TCF bleaching processes are usually based
on oxygen chemicals, e.g., hydrogen peroxide and peroxy
acids. Transition metals, such as Mn, Fe, and Cu catalyze the
decomposition of peroxy compounds, thus its presence in pulp
and cotton affects the efficiency of bleaching and increases
process costs. On the other hand, complexation of Mg must
be minimized because its presence is beneficial for the process.
EDTA and DTPA are the most used chelating agents to control
thepresenceofmetalsandcanbe applied in a pretreatment
stage prior to bleaching or as stabilizers in the actual bleaching
stage. The metals are then removed, as metal complexes, in the
dewatering stage (Ni and Liu 2000),anddischargedintothe
aquatic resources. The quantity of chelant used in the pretreat-
ment stage is usually between 1 and 6 kg/ton of pulp.
EDDS and IDS are the two biodegradable chelating agents
that appear more often associated to pulp bleaching processes.
Fig. 1 Molecular structure of the
biodegradable chelating agents:
nitrilotriacetic acid (NTA),
ethylenediaminedisuccinic acid
(EDDS), iminodisuccinic acid
(IDS), methylglycine diacetic acid
(MGDA), L-Glutamic acid N,N-
diacetic acid (GLDA), 2-
hydroxyethyliminodiacetic acid
(HEIDA), ethylenediamine-N,N-
dimalonic acid (EDDM),
acid (EDDG), 3-hydroxy-2,2-
iminodisuccinic acid (HIDS), and
2,6-pyridine dicarboxylic acid
Environ Sci Pollut Res (2014) 21:1189311906 11895
Tabl e 1 Protonation and overall stability constants of EDTA, NTA, IDS, MGDA, GLDA, EDDG, EDDM, HIDS, HEIDA, and PDAwith Fe, Mn, Cu,
Pb, Cd, Zn, Ca, and Mg ions, at 25 °C, in μ=0.1 M
H+LHL 9.5 9.5 10.1 10.0 9.9 9.4 9.5 9.7 9.6
8.7 4.7
2H + L H
L 15.6 12.0 17.0 14.2 12.4 14.4 16.3 16.3 13.7
10.9 6.7
3H + L H
L 18.3 13.8 20.8 17.5 13.9 17.9 20.5 19.0 16.8
4H+ L H
L 20.3 15.0 23.9 19.4 20.4 3.3 21.1 18.9
5H + L H
L 21.8 25.3 20.5
M+LML 25.1 16.0 20.1
11.6 10.9
24.0 17.1
M+H+LMHL 26.4 17.0 17.8
17.7 11.6 12.2
M+LML 13.9 7.3 9.0 7.3
6.7 8.4 6.8
5.5 5.0
10.4 9.0 8.5
M+H+LMHL 17.0 13.7
M+LML 18.8 12.7 18.7 12.9
15.5 15.9 12.6
11.8 9.1
17.4 15.8 16.4
M+H+LMHL 21.9 14.3 25.0 17.3
7.4 3.5 7.6 2.5
3.1 1.6
M+LML 18.0 11.5 12.7 9.8 12.1
8.5 11.1 10.2
9.4 8.7
M+H+LMHL 20.8 15.0 16.0 16.3
14.4 15.3 14.3
M+LML 16.5 9.8 10.9 8.3 10.6
8.8 7.6
7.4 6.4
14.5 12.4 10.9
M+H+LMHL 19.4 14.6 13.0 15.0
3.3 -1.5 0.1
M+LML 16.5 10.4 13.6
10.2 11.1 9.8
8.4 6.4
14.2 12.0 10.9
M+H+LMHL 19.5 17.3
4.9 0.3 2.3
M+LML 10.7 6.3 4.6 4.3 7.0
2.6 5.4 4.8
4.7 4.4
8.8 7.4
M+H+LMHL 12.8 11.5 3.6 11.7
M+LML 8.8 5.5 6.0 5.5 5.8
3.0 4.9 3.4 2.3
M+H+LMHL 12.8 11.9 4.3 11.5
Values from NIST Database (Martell and Smith 2004) unless otherwise indicated
Orama et al. 2002
Hyvonen et al. 2003
BASF 2007
Begum et al. 2012a
AkzoNobel 2010
Begum et al. 2012b
Tak e t al. 1971
Hyvonen and Aksela 2010
Nippon 2013
11896 Environ Sci Pollut Res (2014) 21:1189311906
Renvall et al. (1997) and Chauveheid et al. (1999)suggesta
general formula for chelating agents to be applied in the
pretreatment of the pulp and both EDDS and IDS are in
accordance with the formula proposed. Employing a chelant
dose of 2 kg/ton of pulp, Mn concentration in the filtrate was
3.0 ppm using EDDS at optimum pH (6.57.0), which was
10 % below the value obtained for EDTA and DTPA (Renvall
et al. 1997). For Fe, similar results were obtained for EDDS,
EDTA, and DTPA, with metal concentrations of 2.0 ppm in
the filtrate. For both metals, when IDS was used, the removal
was 50 % below the traditional chelants. After the bleaching
step, no significant differences were found for brightness;
however, hydrogen peroxide consumption was usually lower
for DTPA. Experiments for stabilization of hydrogen peroxide
showed that in the presence of EDDS and IDS, the peroxide
was mostly degraded in the first 15 and 60 min, respectively,
but in the presence of EDTA or DTPA, it was still stable after
90 min.
Jones and Williams (2001) focused on the problem of
finding biodegradable alternatives in the pulp and paper in-
dustry, through computer chemical simulations. The lower
affinity of EDDS and IDS for Ca makes them promising
alternatives for replacing EDTA.
Giles and Dixon (2009) proposed a bleaching pretreatment,
at pH 47.5 with a mixture of biodegradable and nonbiode-
gradable chelating agents. According to this work, the mixture
of chelating agents resulted in a better brightness than it would
be expected from the results using similar amounts of each
chelating agent alone. For instance, DTPA and EDDS, when
used alone under the same experimental conditions, resulted
in a brightness of 66.0 and 63.9, respectively, after the perox-
ide stage. When applied together in a ratio of 30:70, the
obtained brightness was 66.9. The biodegradable com-
pounds suggested are EDDS, MGDA, GLDA, and IDS
and can be combined with DTPA, EDTA, or DTPMP.
Even though these formulations still contain nonbiode-
gradable chelating agents, the combination of both types
of chelants can be a solution for obtaining good chelat-
ing and bleaching results combined with a more envi-
ronmentally friendly process since lower amounts of
nonbiodegradable chelating agents are used.
Recently, PDA and MGDA were tested experimentally
in a pretreatment of paper pulp, at pH 57(Pintoetal.
2014). In these experiments, a consistency of 70 kg of
dried pulp/m
hydrogen peroxide and peracetic acid, was used. Mn
was totally removed from the pulp with both ligands
studied and EDTA, but MGDA at 3.7×10
bilized up to 70 % of Mg. On the other hand, PDA at
M was more selective and a removal of only
37 % of Mg was achieved. Similarly, NTA (7.0×10
and EDDM (4.5×10
M) removed Mn efficiently with a
good selectivity over Mg (Neto et al. 2014).
Detergents and cleaning compositions
Chelating agents found in detergents, both used for laundry or
dishwashing, are frequently added to the composition to soft-
en water by inactivating Ca and Mg ions, which are the major
metal ions that contribute to hardness. Hard water has negative
effects in cleaning applications due to precipitation of min-
erals that accumulate in the washing machines or in other
objects. Chelating components inactivate Ca and Mg ions by
sequestration, leaving them soluble. Phosphonates have been
extensively used in detergents, but they pose some environ-
mental concerns. There are also cases where compounds are
added to laundry detergents with peroxy-based bleaching
agents to chelate heavy metals in order to stabilize the solution
(Baillely et al. 1994).
The target metal ions must be complexed between pH 7
and 12, which is the typical pH of cleaning and washing
operations. Considering the large quantity of chelating agents
used in cleaning compositions, which can be up to 30 wt.%,
this is a crucial application where biodegradable alternative
chelating agents should be used.
PDA was added as a builder in dishwashing (De Ridder
1983; Frankena 1988) and laundry (Boskamp 1990)compo-
sitions due to its ability to sequester Ca ions. In the experi-
ments performed by De Ridder (1983), the capacity of se-
questering Ca, using 0.15 g/L of chelating agent, was mea-
sured by weighting the insoluble Ca deposit in glass slides.
EDTA and NTA had better performances with formation of
4.1 and 3.6 mg of solid deposit, respectively. PDA was also
effective (formation of 4.5 mg of deposit) when compared to
the situation where no chelating agent was used (7.4 mg of
deposit). These results could still be improvedby changing the
concentration of other components in the detergent. The ad-
dition of 2.0 % of PDA in a laundry detergent had a significant
effect on avoiding the reduction of the fabrics reflectance after
10 washes (Boskamp 1990).
In recent years, MGDA and GLDA studies in cleaning
applications became more frequent. MGDA alone showed a
good ability to inhibit scale formation due to calcium or
magnesium carbonate precipitation (Dailey et al. 2011).
When different compositions of the builder were tried, it was
verified that this parameter can be more or less affected
depending on the compounds and quantities present. MGDA
or GLDA can be present in a detergent composition together
with citrate and carbonate. Citrates are weaker chelants, but
mixed with a stronger chelating agent, can also sequester
hardness metals as they act as an alkaline buffer (Jefferis and
Zack 2011).
Another purpose for the addition of chelating agents to
cleaning compositions is to chelate heavy metal ions (Fe,
Mn, Cu) present in stains to enhance their removal (Palladini
2007;Pike1996). Palladini (2007) suggested detergent for-
mulations containing one biodegradable chelating agent (IDS
Environ Sci Pollut Res (2014) 21:1189311906 11897
or GLDA) pointing out the importance of both sequestration
of hardness and heavy metal ions.
composition at two concentrations (3.3 and 6.7 %) was studied
for the removal of organic stains at pH 9.8 (Hartman and
Perkins 1987). For some types of stains, the addition of chelant
does not make any difference; grape juice and tea were better
removed in the presence of EDDS while grass and bacon
removal was higher with EDTA. In general, higher concentra-
tion of chelating agent led to better removal of the stains.
For the rinse aid composition, proposed by Pike (1996), the
compounds must chelate heavy metals, preferentially at pH
lower than 7 to improve the removal of stains. In fact, these
pH conditions usually enhance bonding with heavy metals
instead of Ca and Mg for the majority of the chelating agents.
EDDG and hydroxypropylenediamine disuccinic acid
(HPDDS) were used, but since the purpose of using chelants
was the complexation with heavy metals during the rinsing
cycle of the dishwasher, phosphonates were also present to
soften water.
HEIDA salts have been compared to EDTA salts in a
composition with 3.2 % of chelating agent for hard surface
cleaning (Crump and Wilson 2011). The cleaning of soiled
tiles, where the soil contained Fe, Ca, and Mg was measured
by the number of strokes necessary to remove 90 % of the soil.
Even though HEIDA stability constants are significantly low-
er, HEIDA and EDTA potassium salts showed similar
cleaning efficiency (with 19 strokes each).
The use of HEIDA was also proposed by Giles and Dixon
(2012) in a dishwashing composition mostly free of bleaching
agents and phosphate builders. A second chelating agent,
biodegradable or not, could be added maintaining the total
concentration at 15 %. Compositions with mixtures of chelat-
ing agents gave better results on the removal of tea stains than
compositions with just one chelating agent, with an increase
of the cleaning score value up to 30 %.
Scale prevention and removal
The hardness ions present in the water used in industrial
processes lead to the formation of scale in metallic surfaces
of equipments, especially in heat exchanging processes. These
incrustations decrease the efficiency of heat transmission,
increase pressure drop, and promote the corrosion of the
equipment (Simpson et al. 1999). The removal of these de-
posits can be very costly, time consuming, and harmful to the
environment due to the use of strong acids and alkalis (Zack
et al. 2012). Chelating agent solutions can be used to prevent
and/or remove scale from the equipments.
In circulating aqueous systems for steam generating and
cooling, chelating agents can be added to the water. The
stability of GLDA (at 13 % in the treatment solution) and
EDDS (at 9.3 % in the treatment solution) and their ability to
avoid metals precipitation were tested at high temperatures
(216235 °C) and pressures (2131 bar) to assess their use in
water systems (Charkhutian et al. 2004,2006). The stability of
both compounds decreases for higher temperatures and pres-
sures. The anti-precipitation effect was tested, at pH 10, for
Ca, Mg, and Fe separately and with the three metals together.
When the three cations were mixed and tested at 216 °C and
21 bar, the results were similar between both ligands, with
more than 80 % of Mg and Ca and around 50 % of Fe
remaining in solution instead of precipitating. GLDA showed
better results for the solutions containing only one metal,
especially for Mg and Fe, while Ca showed a good stability
in solution with both compounds.
Aqueous solutions containing biodegradable chelating
components, such as MGDA and GLDA, can be used as oil
field chemicals. In this case, the solutions are preferentially
acidic or neutral and the main goal is to dissolve calcium
carbonate scale and other subterranean carbonate formations
to increase permeability and enhance the withdrawal of oil or
gas (De Wolf et al. 2009,2012). In the case of very acidic
solutions, GLDA showed a better solubility in aqueous acids
than other chelants.
For control and removal of Ca and Mg deposits at alkaline
pH in a steam generator, NTA and EDDS were suggested as
biodegradable alternatives, along with some nonbiodegrad-
able compounds (Richardson et al. 2012). Zack et al. (2012)
tested MGDA at pH close to neutrality, with the addition of
different acids, to dissolve calcium carbonate. In the presence
of methanesulfonic acid, the increase of MGDA concentration
from 0 to 8.7 % improved the scale dissolving capacity from
26.6 to 43.7 %.
The formation of Ca scale is also a major problem in the
pulp and paper industry, both in pulping and bleaching stages.
The presence of Ca in alkaline bleaching stage can lead to
precipitates, mainly oxalate and carbonate that accumulate in
the equipment, forming scale that is hard to remove. The
presence of chelating/sequestering agents, such as EDTA
and DTPA, can help to increase the solubility of calcium
oxalate (Elsander et al. 2000; Moore et al. 2012).
Biodegradable alternatives must be good Ca chelators forming
soluble and stable complexes. Pinto et al. (2014) considers
PDA as a possible Ca chelator to prevent the formation of
scale during pulp bleaching, since about 90 % of the Ca
present in the pulp is removed during the pretreatment.
Remediation of soils
The presence of toxic metals in the soils has become a
major concern due to industrial and agricultural practices,
inappropriate waste disposal, and increasing urbanization.
Heavy metals cannot be mineralized or decomposed; there-
fore, human intervention is needed to remove them from
the soils.
11898 Environ Sci Pollut Res (2014) 21:1189311906
Soil washing and flushing
In situ and ex situ remediation techniques have been studied
(Lestan et al. 2008), and chelating agents can be applied in
both techniques. In situ techniques include phytoremediation
and soil flushing. Ex situ methods usually consist of soil
washing to separate contaminants and the use of chelating
agents is less disruptive for the soils than acid washing.
According to some authors, the chelating agents must have
low biodegradability to allow recycling and reuse of the
washing solution (Dermont et al. 2008;Lestanetal.2008),
thus reducing treatment costs. Nevertheless, a fast biodegra-
dation rate of the ligand in this application is not convenient
because removal of metals from the soil cannot occur or be
inefficient. EDDS biodegradation studies in soils showed a lag
phase up to 11 days and proved that degradation was effective
even in polluted soils (Tandy et al. 2006). Meers et al. (2008)
compared the biodegradability of EDDS in three different
soils and concluded that the time of degradation differed
significantly due to different durations of the lag phase. The
type of soil is important in biodegradation and can be related
to EDDS recovery and reuse in remediation of soils.
Chelants must also have low toxicity to soil microorgan-
isms, which is not observed for EDTA (Epelde et al. 2008;
Kos and Lestan 2003), and the metal complexes should not
adsorb on the solid surfaces (Dermont et al. 2008). The ligand/
metals ratio must be higher than 1, to maximize the metals
removal, especially due to interferences of other cations pres-
ent in the soil (Fe, Mn, Ca, Al and Mg). The low selectivity of
EDTA caused by strong chelation with interfering cations is a
disadvantage in this process (Dermont et al. 2008).
In the middle 90s, PDA was considered for soil remediation
applications (Pb and Cd extraction and recovery), although it
was not mentioned as a biodegradable alternative in the respec-
tive studies (Macauley and Hong 1995; Hong and Chen 1996).
The extraction of Pb from soil with PDA 1 mM was above
80 % in four consecutive experiments using reused PDA
(Macauley and Hong 1995). Efficiency of extraction was com-
parable to EDTA, but PDA has the advantage of forming
weaker chelates, which makes the release of extracted Pb easier.
Heavy metals extraction from soils was studied using an ex
situ washing procedure (Vandevivere et al. 2001). EDDS
achieved extraction efficiencies of Pb, Zn, Cu, and Cd be-
tween 70 and 90 % as long as the contact time was sufficient
(1 to 6 days, depending on the metal) and pH higher than 7 in
order to avoid Fe interference.
Tan dy e t al. (2004) studied EDDS, NTA, IDS, and MGDA
for the extraction of Cu, Zn, and Pb and verified that the best
time for the experiments was 24 h; longer times only enhanced
Fe extraction without improving the other metals efficiency.
Although extractions of Cu and Pb were better using EDTA
(values above 80 % of extraction), EDDS, at pH 7, was
considered the best compromise between extraction of Cu,
Zn, and Pb (>60 % at chelant/metal=10) with reduced loss of
Ca and Fe.
Studies performed by Polettini et al. (2006) were focused on
the efficiency of the extraction of Cd, Cu, Pb, and Zn from soils
using different treatment durations. NTA, citric acid, and
EDDS were compared with EDTA. EDDS showed extraction
efficiency of target metals comparable to EDTA. EDDS also
had the advantage of reducing the co-extraction of metals from
the soil matrix, like Ca, Mg, and Fe to values below 10 %.
Yang et al. (2012) concluded that pH 5.5 led to better
extraction than pH 8.0, using EDDS, especially for Zn (64.4
vs. 53.3 % at 1.26 mol EDDS/kg soil) and Cd (52.2 vs.
37.2 %). These conclusions are contrary to the work of
Vandevivere et al. (2001), where pH above 7 evidenced better
results. These facts suggest that the optimal pH is dependent
of soil characteristics, namely the quantity of interfering metal
cations and the way how metals are coordinated to the soil.
Comparison between batch and column experiments on the
efficiency of EDDS for extracting Cu, Zn, and Pb showed that
Zn and Pb are equally extracted while Cu was affected in
column leaching (Hauser et al. 2005). The importance of
performing experiments in column is that this method is more
practical and economical to upscale. It was observed that
short-time experiments were more adequate for EDDS to
maximize the recovery and reuse of the ligand because longer
processing led to loss of compound due to biodegradation. For
simulating an in situ soil flushing situation, Mancini et al.
(2011) used column tests, comparing EDDS with EDTA for
Pb, Cu, Ni, Cd, and Zn mobilization. EDDS presented a better
mobilization capacity for Cu, Ni, and Zn, while EDTA gave
better results for Cd and Pb.
Several chelants (EDDS, IDS, MGDA, GLDA, and HIDS)
in 0.05 M solutions were compared in the treatment of a soil
(1:10 w/v) contaminated with Cd, Cu, Ni, Pb, and Zn at pH 4,
7, and 10 (Begum et al. 2012c). In general, extractions were
enhanced at pH 4. At this pH, the metal extraction perfor-
mance of GLDA for all metals studied was better (Cd 84 %,
Cu 94 %, Pb 54 %, Zn 62 %, and Ni 39 %) than for the other
biodegradable options and even better than EDTA for Ni and
Cu. At pH 7, metal extraction efficiencies decreased but
GLDA was still the best biodegradable option. These results
cannot be explained by the stability constants of the metal
complexes but probably by the way how metals are coordi-
nated to the soil. In order to guarantee homogeneous condi-
tions in the study, the same research group compared EDDS,
GLDA, and HIDS with EDTA on the treatment of artificially
contaminated reference soils (Begum et al. 2013). Chelant/
metal molar ratio and solution pH were varied, and results
showed that GLDA had the better extraction efficiency for the
lower chelant concentration (0.01 M). A better performance of
GLDA than EDTA was obtained, at pH 4, except for Pb,
which is consistent with a previous work of the same authors
(Begum et al. 2012c). At higher pH, EDDS performance is
Environ Sci Pollut Res (2014) 21:1189311906 11899
better than GLDA but none of the biodegradable chelating
agents is able to achieve the same efficiency as EDTA on the
extraction of Pb.
Plants have the ability to uptake metals that have no biological
function (Rahman et al. 2011). Since the remediation of large
areas by soil washing can be very costly, the use of plants to
accumulate heavy metals arises as a possible solution to
extract contaminants and restore the fertility of the soil. The
metals must be uptaken from the soil, transported from roots
to shoots, and accumulated in aboveground parts of the plants
(Rahman et al. 2011). After harvesting, the plants are burned
to produce energy and metals are recycled from the residues
(Kos and Lestan 2003). Chelating agents are used to increase
the solubility and mobilization of the metals, making them
bioavailable for plants (Nowack and VanBriesen 2005). The
main concern of using nonbiodegradable chelating agents is
their persistence in the soils that leads to the leaching of heavy
metals into underground waters.
EDDS has been the most studied alternative for EDTA in
phytoextraction. Studies performed with EDDS by Kos and
Lestan (2003), Luo et al. (2005), Epelde et al. (2008), and
Evangelou et al. (2007) for different plant species showed that
EDDS is more efficient than EDTA for Cu and Zn uptake but
less efficient for Pb. However, plant growth was affected by
EDDS, evidencing some toxicity. EDDS toxic effects were
not observed in other studies (Komarek et al. 2010;Meers
et al. 2005), which means that EDDS toxicity is dependent on
plant species and experimental conditions, such as, pH, type
of soil, presence of other metals, etc. The study performed by
Meers et al. (2005) also showed that metals mobilization
decreased with time when EDDS was used. This behavior
was not observed for EDTA and can be explained by the
higher biodegradability of EDDS.
Shilev et al. (2007) studied NTA and EDDS to enhance the
accumulation of Cd, Pb, and Zn in maize and sunflower. The
results revealed that the efficiency depends on the plant spe-
cies. For instance, Cd was more efficiently accumulated in the
leaves of sunflower in the presence of NTA (5 mmol/L) and
EDDS was better for maize. In addition, no negative effects in
soil bacteria and fungi were observed, which is an advantage
over EDTA. Freitas and Nascimento (2009) and Araújo and
Nascimento (2010) concluded that NTA toxicity to the plants
was significant but lower than EDTA, while Pb leaching
results showed that NTA caused no environmental effects,
unlike EDTA (Araújo and Nascimento 2010).
Cao et al. (2007) compared Pb and Zn phytoextraction by
ornamental flowers using EDDS and MGDA in dosages of 4
and 8 mmol/kg of soil. Both of the ligands showed an effective
increase in Pb accumulation in leaves as well as a benefic
contribution for bacterial activity in the soil. In the case of Zn,
metal accumulation was independent from the use of chelating
agents. EDDS and MGDA showed some toxicity to the plant
causing death at maximum dose. The application of MGDA to
a primrose species showed an effective Cu extractions and
increase in foliar concentration and plant growth (González
et al. 2011).
Iron-chelating agents for agriculture
Iron is an important nutrient for plant growth, and its deficien-
cy is one of the causes of chlorosis in plants. Chlorosis leads to
loss in the fruit quality and yield, lack of the green color in the
leaves, and in extreme cases, the death of the plant
(Rodriguez-Lucena et al. 2010). The deficiency of Fe in plants
is caused by Fe poor bioavailability, especially in calcareous
soils (Shenker and Chen 2005). Above pH 7, Fe species are
mainly insoluble and cannot be taken by the plants; thus,
chelating agents can be added to the soil in order to make
the Fe already present bioavailable or supplied to the plant as
Fe-chelates in fertilizers solutions (Lucena et al. 2008; Villen
et al. 2007). EDTA and DTPA complexes are often used in
liquid formulations; however, for calcareous soils,
ethylenediamine-N,N-bis(1-hydroxyphenylacetic) acid
(EDDHA) is the most used because of its even higher stability
constant of the FeL complex, which allows complexation at
higher pH (Lopez-Rayo et al. 2009; Shenker and Chen 2005).
The use of IDS chelates (Fe, Mn, Zn and Cu) in fertigation
and hydroponics formulations resulted in healthy plants
(Lucena et al. 2008). The same compound was tested in a
foliar spray composition though this technique was not as
The ability of the chelating agents to improve the mobility
of Fe in the soil is important to increase the bioavailability of
Fe for a plant. HIDS and EDDS showed a higher apparent
mobility followed by GLDA, EDTA, MGDA, and IDS at
pH 10 (Hasegawa et al. 2011). Results were related to the
growth of radish sprouts that showed the same trend. Authors
claim that stability constant of the FeL complex influences the
movement of Fe in the growth medium but the stability
constants in Table 1do not show the same trend.
At pH< 7 and 0.25 M of chelant, HIDS was more efficient
on the Fe uptake and plant growth than EDTA, EDDS, and
IDS (Rahman et al. 2009). HIDS is considered an effective
option to replace nonbiodegradable chelating agents in agri-
culture and Fe uptake due to the good experimental results as
an iron chelator and plant growth and its stability in severe
conditions (Hasegawa et al. 2011). The very fast biodegrada-
tion is also shown as an advantage by some authors
(Hasegawa et al. 2011,2012). However, this property can be
seen as a disadvantage for agricultural purposes since the
ligand should have some resistance to degradation in order
to increase the period of action of fertilizers and fulfill its
purpose as metal chelating agent (Shenker and Chen 2005).
11900 Environ Sci Pollut Res (2014) 21:1189311906
EDDS was compared with DTPA and EDTA as a Fe-
chelate source in a liquid fertilizer for the production of
marigold and extractant of metals from peat medium. Plants
treated with Fe-EDDS solution showed enough Fe in the
leaves for a normal growth (Albano 2008).
Other applications
Electroplating Electroless deposition of Cu into metallic sur-
faces can be done in the presence of complexing agents to
stabilize the metallic ions in solution by avoiding its precipi-
tation as metal hydroxide in the alkaline baths. The most
common complexants used in plating industry are EDTA
and tartrate salts. Performance of biodegradable chelating
agents, such as EDDS and NTA, has been also tested in
electroplating of Cu (Macmillan 1996; Pauliukaite et al.
2006; Simpson et al. 1999; Wilson and Crump 1994). The
stability of the electroless plating solution containing EDDS
was comparable to the situation where EDTA was used and
the rate of Cu deposition was very favorable (Macmillan
1996). From this study, it could be concluded that the use of
EDDS fulfilled the requirements for the industry and can
replace EDTA in existing plating systems.
Wast e t re atm e nt Sewage sludge can be recycled as fertilizer
for land because of its large content of organic substances and
also nitrogen and phosphorus content. However, the toxicity
of the heavy metals present in the sewage is a risk to human
health and plants (Zhang and Zhang 2012). Heavy metals in
sewage sludge can be removed by chelating agents, before its
reuse as a fertilizer. Zhang et al. (2008) and Zhang and Zhang
(2012) studied the use of EDDS to extract Cu and Zn from
sewage sludge. Zhang et al. (2008) observed that, within the
pH range of 410, both EDDS and EDTA had a good and
equivalent performance for extracting Cu from the sewage
sludge. Zhang and Zhang (2012) showed that the extraction
efficiency of Zn, using EDDS, was comparable to the extrac-
tion efficiency obtained with EDTA at pH between 5 and 9.
Spent hydrodesulphurization catalysts, used in petroleum
refineries, contain metals that must be extracted and recycled
to avoid their deposition in the environment. This is common-
ly done by acid or alkaline leaching but EDTA has also been
used (Goel et al. 2009; Pinto and Soares 2013). EDDS
(Chauhan et al. 2012) and NTA (Pinto and Soares 2013)have
been studied in the removal of Mo and Ni from these catalysts;
however, the metal recoveries were not as high as with EDTA
due to the lower stability constants of these ligands.
Indium is a rare metal employed in the fabrication process
of liquid crystal display (LCD) panels. The quantity of spent
LCD panels is increasing worldwide and they can be a sec-
ondary source of indium (Hasegawa et al. 2013a,b).
Hasegawa et al. (2013a) studied the use of NTA, IDS, and
HIDS to extract indium from spent LCD. NTA showed to be
comparable with EDTA at optimal conditions (acidic medium,
temperature 120 °C, and the pressure of 50 bar).
Biocides Some specific metal ions possess biocidal properties
and can be used for stabilization, inhibition, or reduction of the
growth of microorganisms when associated to a chelating
agent (Borkow et al. 2010). Several formulations containing
various biodegradable chelating agents, such as citric acid,
salicylic acid, NTA, EDDS, MGDA, and GLDA, have been
reported in the literature for cleaning and disinfection (Back
et al. 2003; Ploumen and Borgmann-Strahsen 1991; Romano
et al. 2000), herbicidal, fungicidal, or algaecide purposes
(Samarajeewa and Taylor 2011). Back et al. (2001) described
a method to control microbial growth in the water of climate
control systems where salicylic acid and NTA were found to
be effective.
Assessment of potential application of chelating agents
by computer calculations
In order to better understand the ability of the biodegradable
chelating agents for the applications described in this review,
computer simulations were performed and major conclusions
are pointed out in Figs. 2and 3and in the supplementary data
found in online resources 1and 2. For assessing the potential
of each chelating agent for a specific application, the target
metals to be chelated and the pH range should be considered
in the computer simulations. Briefly:
1) In paper pulp and textile TCF bleaching processes, there
is a need to form strong complexes of Fe, Mn, and Cu
while leaving Ca and especially Mg uncomplexed. In the
case of a pretreatment process before bleaching, the pH
range might vary between 4 and 8. Additionally, during
the bleaching stage, chelants are also useful in the stabi-
lization of the peroxide solution itself; this process is
typically performed between pH 9 and 12.
2) To avoid scale formation in industrial cooling or heating
systems, as well as for using in the detergents, it is
important to complex Ca and Mg ions between pH 6
and 12.
3) The remediation of metal-polluted soils implies the solu-
bilization of contaminant metals, usually Pb, Cd, Cu, and
Zn, while reducing the extraction of cations that are
important for plant growth and soil quality (Fe, Mn, Ca,
and Mg). In ex situ remediation, pH might be varied
between 4 and 10 while for phytoremediation, a narrower
interval is preferred (68).
4) In the case of agricultural practices, the main goal is to
increase Fe uptake by plants mainly in calcareous soils;
so, ligands must complex Fe to enhance its mobility at pH
higher than 7.
Environ Sci Pollut Res (2014) 21:1189311906 11901
According to the aims to be fulfilled when chelating agents
are used in these major applications, two different computer
simulations were performed. In the first case, the selectivity of
each chelating agent to transition metals in medium with
Fig. 2 pH range, calculated by
chemical simulations, for which
there is at least 80 % of metal
complexed. Chemical simulations
were performed assuming the
simultaneous presence of one
chelating agent (L) at a [L]/[M]
ratio of 5 (solid color line)and10
(dashed color line) and the pres-
ence of all metal ions
([Cd]=[Cu]=[Fe]=[Mn]= [P-
b]= [Zn]=10
M) with an ex-
cess of Ca and Mg ions
([Ca]=[Mg]=1 ×10
0 2 4 6 8 10 12 1402468101214
% Complexed Metal
Fig. 3 Amount, in percentage, of Ca (a) and Mg (b)complexedwith
NTA (yellow), EDDS (gray), IDS (pink), MGDA (green), GLDA
(orange), EDDG (blue), EDDM (brown), HIDS (violet), HEIDA (light
blue), PDA (red) and EDTA (black). Chemical simulation were per-
formed assuming the simultaneous presence of Ca, Mg and each chelat-
ing agent, with a [L]/([Ca] + [Mg]) ratio of 2, [Ca]= [Mg]=10
11902 Environ Sci Pollut Res (2014) 21:1189311906
excess of Ca and Mg ions was evaluated. In the second case,
the ability of compounds to complex Ca and Mg ions at a high
concentration was assessed. Metal chemical speciation calcu-
lations were performed using MINEQL+ Version 4.5
(Schecher and McAvoy 2003), a computer program that gen-
erates chemical equilibrium concentrations of all species be-
ing considered in the model by the program reactions.
Computational simulations were performed in aqueous medi-
um in the pH range between 0 and 14 and the studied chelating
HIDS, IDS, MGDA, NTA, and PDA. The first simulation was
performed in the presence of all transition metals (MFe, Mn,
Cu, Pb, Cd, and Zn), and one chelating agent (L), in a situation
of excess of Ca and Mg ions. Two different conditions were
tested, [L]:[M] ratios of 5 and 10 with [M]=2×10
each transition metal, except Ca and Mg. The concentration of
Ca and Mg ions was 1× 10
M for each metal ion.
In the second simulation, the presence of Ca and Mg with
one chelating agent was assessed. The concentration of che-
lating agent was twice the sum of Ca and Mg ions, [L]=
2([Ca]+[Mg]), where [Ca]= [Mg]=1×10
M. The main re-
sults taken from the first and second computer simulations are
represented in Figs. 2and 3,respectively.
Figure 2shows the pH range at which the chelating agent
complexes more than 80 % of the respective transition metal
(Fe, Mn, Cu, Pb, Cd, and Zn) in a medium with Ca and Mg in
excess. The results for EDTA are also shown to allow an easy
comparison with the most usual situation. Despite the good
ability of all compounds to complex transition metals, EDTA
chelates most metals in a larger pH range, especially Fe, Mn,
and Pb.
For paper pulp and textile bleaching process, considering
only the pH range and the metals to be chelated, we can
conclude that NTA, EDDS, MGDA, and PDA could be used,
which is in line with the literature (Chauveheid et al. 1999;
Moore et al; 1997;Netoetal.2014; Pinto et al. 2014; Renvall
et al. 1997; Seccombe and Dournel 2007). For EDDM, al-
though stability constants for Fe were not found, a recent
study showed that this compound could be a potential alter-
native to this process (Neto et al. 2014). As Giles and Dixon
(2009) suggested, a mixture of biodegradable and nonbiode-
gradable chelating agents can be an interesting option. The
combination of GLDA, IDS, or HIDS with EDTA can over-
ride the lack of affinity of GLDA, IDS, and HIDS to Fe ions.
In soil remediation process, NTA and EDDS could be used;
however, these ligands can only be used at alkaline pH to
avoid the removal of Fe, as it was mentioned by Vandevivere
et al. (2001)andTandyetal.(2004). Also IDS, HIDS,
HEIDA, PDA, MGDA, EDDG, and GLDA could be used
and experimental studies have already been performed
(Arwidsson et al. 2010; Begum et al. 2012c,2013; Cao et al.
2007; Macauley and Hong 1995; Tandy et al. 2004). The
conclusion obtained from these studies is that none of the
biodegradable options has a good performance for removing
Pb as EDTA. This fact is justified by the evident stronger
ability of EDTA to complex this metal.
According to the speciation simulations, only NTA could
be an interesting option to increase Fe bioavailability in agri-
culture using the higher [L]:[M] ratio simulated. Despite the
poor chelation ability evidenced by the computer simulations,
different researchers described that some of these chelating
agents could be possible options (Albano 2008;Hasegawa
et al. 2011,2012;Lucenaetal.2008).
Figure 3shows the percentage of Ca (Fig. 3a)andMg
(Fig. 3b) complexed over the pH range in a solution with only
Ca and Mg and one chelating agent. These simulations were
performed in order to understand the possibility of using the
chelating agents to avoid scale formation or to be applied in
detergents. The computer simulations suggest better results
with the use of NTA, MGDA, and GLDA. Both MGDA and
GLDA are frequently suggested in the literature for these
applications due to their high potential to complex with Mg
and Ca ions (Charkhutian et al. 2004,2006;DeWolfetal.
2009; Palladini 2007;Zacketal.2012). PDA and HEIDA
The search for more environmentally friendly chelating agents
to replace traditional EDTA and DTPA resulted in numerous
studies in the last two decades. Most of the research regards
areas where there is a large consumption of chelating agents,
such as paper pulp bleaching, detergents and cleaning, scale
prevention, soils remediation, and agriculture.
Many biodegradable compounds, like NTA, EDDS, IDS,
have been suggested as potential alternatives and some of
them are now marketed to be used at industrial scale. EDDS
has been widely studied in different applications and, in some
cases (e. g. detergents), used at commercial scale. In the last
decade, the various papers and patents, where MGDA and
GLDA were studied, pointed out the use of these compounds
as biodegradable substitutes in main industries.
Computer simulations, based on stability constants of
complex formation, show the difficulty of finding an alter-
native biodegradable compound with chelation ability as
good as EDTA. However, the requirements depend on the
purpose and, in some cases, a more selective chelation is
preferred, which can be an advantage for the biodegradable
With the aim of replacing nonbiodegradable chelating
agents in industrial and agriculture applications, the need to
find efficient and low-cost alternatives and optimize processes
still remains.
Environ Sci Pollut Res (2014) 21:1189311906 11903
Acknowledgments This work was financially supported by FEDER
funds through the Programa Operacional Factores de Competitividade
COMPETE and national funds by FCT-Fundação para a Ciência e
Tecnologia within the project PTDC-AAC-AMB-111206-2009. One of
us (Isabel F.F. Neto) acknowledges a grant scholarship financed by the
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... Although it is biodegradable, its usage is controversial because of its organ toxicity. 18 In artificial nucleases, NTA as a metalchelator cleaves DNA primarily by metal-bound ROS, and therefore, incorporation of these metal complexes in artificial nucleases has shown to provide more controlled delivery of ROS to targeted genes. 7,19 Copper forms watersoluble and chemically stable chelate with NTA at a neutral pH, thereby its toxicity, assimilation and accumulation in organisms changed to a greater extent. ...
... 20 The exposure of copper take place in occupational settings of the metallurgic industry via effluent in soil and water where it may occasionally be found in the chelated form with nitrilotriacetate (NTA), as a part of dental amalgams, dental casting alloys, and some intrauterine contraceptive devices (IUDs). 6,7,17,18 It has been reported that copper is gradually and constantly introduced as a corrosion product of IUDs, causing increment in 8-OH-dG and mitotic indices in hepatic and renal tissues of rats, and implying that the corrosion products of copper implants may be harmful to many tissues. 20 This necessitates a risk evaluation of copper-related hazards. ...
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Earlier we have shown that exposure to copper-nitrilotriacetate (Cu-NTA) manifests toxicity by generating oxidative stress and potent induction of proliferative reaction in the liver and kidney. In the study, we look at the impact of nitroglycerin (GTN) administration on Cu-NTA-induced oxidative stress and hyperproliferative response in the liver and kidney. GTN administration intraperitoneally to male Wistar rats after Cu-NTA administration intraperitoneally caused substantial protection against Cu-NTA-induced tissue injury, oxidative stress and hyperproliferative response. Cu-NTA administration at a dose of 4.5 mg/kg body weight produces significant (p < .001) elevation in biochemical parameters including aspartate aminotransferase (AST), alanine aminotransferase (ALT), blood urea nitrogen (BUN) and creatinine (CREA) with a concomitant increase in microsomal lipid peroxidation. Along with these alterations, we discovered a substantial increment in [3H]thymidine incorporation into hepatic and renal DNA synthesis (p < .001). Cu-NTA-induced tissue damage and lipid peroxidation in hepatic and renal tissues were inhibited by GTN treatment in a dose-dependent manner (p < .05-0.001). Furthermore, GTN can suppress the hyperproliferative response elicited by Cu-NTA by down-regulating the rate of [3H]thymidine incorporation into hepatic and renal DNA (p < .01-0.001). Protective effect of GTN against Cu-NTA was also confirmed by histopathological changes in liver and kidney. This result suggests that GTN may serve as a scavenger for reactive oxygen species (ROS) and reduces toxic metabolites of Cu-NTA, thereby avoiding tissue injury and oxidative stress. Further, administration of NO inhibitor, NG-Nitroarginine methyl ester (L-NAME), exacerbated Cu-NTA induced oxidative tissue damage and cell proliferation. Overall, GTN reduces Cu-NTA-induced tissue damage, oxidative stress, and proliferative response in the rat liver and kidney, according to these findings. On the basis of the above results, present study suggests that GTN may be a potential therapeutic agent for restoration of oxidative damage and proliferation to liver and kidney.
... Coordination compounds, in particular metal chelates, are widely used in industry, household activities, and agriculture [1], for water treatment [2], land reclamation [1,3,4], in medicine [5][6][7], biochemistry [8], pharmacy [9], as food supplements [10][11][12], as parts of new materials, in microelectronics [13], and in many other fields of science and technology. Chelates play an important role for living organisms and plants: hemoglobin, chlorophyll, and vitamin B12 are chelates. ...
... Coordination compounds, in particular metal chelates, are widely used in industry, household activities, and agriculture [1], for water treatment [2], land reclamation [1,3,4], in medicine [5][6][7], biochemistry [8], pharmacy [9], as food supplements [10][11][12], as parts of new materials, in microelectronics [13], and in many other fields of science and technology. Chelates play an important role for living organisms and plants: hemoglobin, chlorophyll, and vitamin B12 are chelates. ...
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Brief characterization is given for periods of the hundred-year history of application of coordination compounds (chelates) based on chromophoric organic reagents (ORs) for the spectrophotometric and luminescent determination of metal ions. Four periods can be distinguished: detection of the efficacy, synthesis of the first ORs for metal determination, and development of the theoretical fundamentals for their action; period of targeted synthesis of ORs, systematic research of the coordination of metal compounds to ORs, and extensive use in chemical analysis; period of modification of the ORs in solution and on the sorbent surface; and period of application of liquid and solid nanoplatforms and supramolecular processes for enhancing the properties of coordination compounds of metals with organic analytical reagents. The achievements and application areas for each period are given. INTRODUCTION Coordination compounds, in particular metal che-lates, are widely used in industry, household activities, and agriculture [1], for water treatment [2], land reclamation [1, 3, 4], in medicine [5-7], biochemistry [8], pharmacy [9], as food supplements [10-12], as parts of new materials, in microelectronics [13], and in many other fields of science and technology. Chelates play an important role for living organisms and plants: hemoglobin, chlorophyll, and vitamin B12 are che-lates. For more than 100 years, chelates have been widely used in analytical chemistry for titrimetric, photometric, luminescent, atomic absorption, and electrochemical analysis [14-17], chemical test methods [18], and for masking, separation, and preconcen-tration techniques such as extraction [19], gas liquid and high performance liquid chromatography (HPLC) [20-22], and sorption preconcentration [23-25]. It is noteworthy that in molecular spectrom-etry methods (spectrophotometry and luminescence), metal chelates formed by chromophore ligands are used most often, whereas in other determination methods and for separation and preconcentration this is not required. This communication proposes periodization of research in the synthesis, study of properties, and application of coordination compounds of metals in
... Owing to these difficulties in using conventional strong mineral acids, we have recently proposed a novel chemical stimulation method using chelating agents to selectively dissolve rock-forming minerals in geothermal environments and enhance the permeability of rock fractures (Watanabe et al., 2021). Among various types of chelating agents, eco-friendly compounds, such as N- N',, and readily biodegradable N, N-bis(carboxymethyl)-L-glutamic acid (GLDA), are suitable for use in natural environments (Pinto et al., 2014;Mahmoud et al., 2017;Wang et al., 2021Wang et al., , 2022. The dissolution rates of rock minerals can be sufficiently high even in weakly acidic aqueous solutions because of the combined effects of the chelating agent and hydrogen ion attacks on minerals (Fredd and Fogler, 1998). ...
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Chemical stimulation of geothermal reservoirs via selective mineral dissolution with eco-friendly chelating agents has been recently proposed as a novel method complementary to hydraulic stimulation. In our previous study, we demonstrated rapid and significant permeability enhancement accompanied by the creation of voids due to the selective dissolution of biotite in fractured granite at 200 °C under confining stress. However, the process of permeability enhancement and its optimum pH have not been investigated yet. In this study, we present the results of the stimulation experiments conducted on fractured granite at 200 °C under confining stress using a 20 wt% aqueous solution of the sodium salt of the chelating agent, N, N-bis(carboxymethyl)-l-glutamic acid (GLDA), at pH 1–8. The permeability enhancement was the highest at pH 4, at which preferential flow paths connecting the voids caused by biotite dissolution were observed. With decreasing and increasing pH, silica precipitation and suppressed selective dissolution of biotite, respectively, became more significant, accompanied by a decrease in permeability enhancement. Our findings suggested that the optimum pH was a combination of two pH values suitable for the creation of stress-resistant preferential flow paths by selective mineral dissolution of biotite and for the accelerated dissolution of quartz, which could not be achieved by the chelating agent. The successive use of first pH 4 and then pH 8 resulted in a more than 2-fold permeability enhancement in 4 h. Therefore, our study has strengthened the possibility and effectiveness of the new chemical stimulation method to facilitate the extensive use of enhanced geothermal systems worldwide in future.
... Iminodisuccinic acid salts belong to the group of aminopolycarboxylate chelating agents and are considered medium-strong chelators able to replace EDTA for masking alkaline earth or heavy metal ions. In fact, iminodisuccinic salt has been applied as an environmentally friendly metal-chelating ligand in industrial applications [20,21]. Consequently, IDS was used in many applications, such as detergent formulations, anticorrosion products, pulp and paper production, ceramics, textiles, photochemical processes, fertilizers, bleaching agent stabilizers and water softeners, thanks to its superior ecological profile [22,23]. ...
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Background: The disinfection process represents an important activity closely linked to the removal of micro-organisms in common processing systems. Traditional disinfectants are often not sufficient to avoid the spread of food pathogens; therefore, innovative strategies for decontamination are crucial to countering microbial transmission. This study aims to assess the antimicrobial efficiency of tetrapotassium iminodisuccinic acid salt (IDSK) against the most common pathogens present on surfaces, especially in food-borne environments. Methods: IDSK was synthesized from maleic anhydride and characterized through nuclear magnetic resonance (NMR) spectroscopy (both 1H-NMR and 13C-NMR), thermogravimetric analysis (TGA) and Fourier Transform Infrared (FTIR) spectroscopy. The antibacterial activity was performed via the broth microdilution method and time-killing assays against Escherichia coli, Staphylococcus aureus, Salmonella enterica, Enterococcus faecalis and Pseudomonas aeruginosa (IDSK concentration range: 0.5-0.002 M). The biofilm biomass eradicating activity was assessed via a crystal violet (CV) assay. Results: The minimum inhibitory concentration (MIC) of IDSK was 0.25 M for all tested strains, exerting bacteriostatic action. IDSK also reduced biofilm biomass in a dose-dependent manner, reaching rates of about 50% eradication at a dose of 0.25 M. The advantages of using this innovative compound are not limited to disinfecting efficiency but also include its high biodegradability and its sustainable synthesis. Conclusions: IDSK could represent an innovative and advantageous disinfectant for food processing and workers' activities, leading to a better quality of food and safer working conditions for the operators.
... To overcome these disadvantages of conventional strong mineral acids, a recent study proposed the use of chelating agents to selectively dissolve rock-forming minerals in geothermal environments and to enhance rock fracture permeability. Among the various types of chelating agents, environmentally friendly compounds, such as N-(2-hydroxyethyl)ethylenediamine-N, N', N'-triacetic acid (HEDTA) and readily biodegradable N, N-bis(carboxymethyl)-L-glutamic acid (GLDA), were found to be suitable for use in natural environments (Mahmoud et al., 2017;Pinto et al., 2014;Wang et al., 2021Wang et al., , 2022. Even in weakly acidic aqueous solutions, minerals have high dissolution rates due to the combined effects of the chelating agent and hydrogen ions (Fredd and Fogler, 1998). ...
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Chemical stimulation using environment-friendly chelating agents (e.g., readily biodegradable GLDA) was recently shown to rapidly and substantially enhance the permeability of fractured granite, without creating mineral precipitation. This study examined the effectiveness of such stimulation in volcanic rocks through flooding experiments conducted with a pH 4 GLDA solution on fractured dacitic, andesitic, and basaltic rocks from geothermal fields in El Salvador at 200 °C under confining pressure. Results showed substantial permeability enhancement of up to 4.3-fold in 2 h, where the magnitude of enhancement depended mainly on the initial proportion of Fe-rich phenocrysts, which dissolved to form voids.
... To tackle the problem of becoming secondary pollution sources, scientists have monitored the use of biodegradable chelants during the past three decades. They have found that, unlike non-biodegradable chelants, biodegradable chelants reduce the movement of heavy metals in soil or leaching of heavy metals because these chelants undergo degradation with time (Pinto et al. 2014). But considering the nonpolluting nature of biodegradable chelants, scientists recommend these compounds for environmental reclamation ). ...
The contamination of lands and water by heavy toxic metal(loid)s is an environmental issue that needs serious attention as it poses a major threat to public health. The persistence of heavy metals/metalloids in the environment as well as their potentially dangerous effects on organisms underpins the need to restore the areas contaminated by heavy toxic metal(loid)s. Soil restoration can be achieved through a variety of different methods. Being more cost-effective and environmentally sustainable, phytoremediation has recently replaced traditional processes like soil washing and burning. Many plants have been intensively explored to eliminate various heavy metals from polluted soils through phytoextraction, which is a commonly used phytoremediation approach. The ability of chelants to enhance phytoextraction potential has also received wide attention owing to their ability to elevate the efficiency of plants in removing heavy metal(loid)s. Chelants have been found to improve plant growth and the activity of the defense system. Several chelants, either non-biodegradable or biodegradable, have been reported to augment the phytoextraction efficiencies of various plants. The problem of the leaching of heavy metal(loid)s and secondary pollution caused by non-biodegradable chelants can be overcome by the use of biodegradable chelants to an extent. This review is a brief report focusing on recent articles on chelate-assisted phytoextraction of heavy metal (loids) As, Cd, Cu, Cr, Hg, Ni, Pb, U, and Zn.
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Kraft mill effluents are characterized by their content of suspended solids, organic matter and color due to the presence of lignin, lignin derivatives and tannins. Additionally, Kraft mill effluents contain adsorbable organic halogens and wood extractive compounds (resin acids, fatty acids, phytosterol) and show high conductivity due to the chemical compounds used in the digestion process of pulp. Currently, Kraft mills are operating under the concept of a linear economy and, therefore, their effluents are generating serious toxicity effects, detected in daphnia, fish and biosensors. These effluents are treated by activated sludge and moving bed biofilm systems that are unable to remove recalcitrant organic matter, color and biological activity (toxicity) from effluents. Moreover, under climate change, these environmental effects are being exacerbated and some mills have had to stop their operation when the flows of aquatic ecosystems are lower. The aim of this review is to discuss the treatment of Kraft pulp mill effluents and their impact regarding the current practices and future perspectives towards sustainability under climate change. Kraft pulp mill sustainability involves the closure of water circuits in order to recirculate water and reduce the environmental impact, as well as the implementation of advanced technology for these purposes.
Recently, biodegradable aminopolycarboxylic acid chelating agents have attracted attention as an alternative to environmentally persistent chelating agents such as ethylenediamine-N,N,N′,N′-tetraacetic acid. However, the detection of chelating agents requires complexation with metals or derivatization by esterification reagents, and their direct detection using the currently available analytical methods still represents a challenge. Herein, we describe a direct analytical method for the biodegradable chelating agents ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2′-iminodisuccinic acid, methylglycine-N,N'-diacetic acid, and N,N-bis(carboxymethyl)-l-glutamic acid, via ultra-performance liquid chromatography/electrospray ionization quadrupole/time-of-flight mass spectrometry. Satisfactory retention and separation with a good peak shape were successfully achieved using a metal-free hydrophilic interaction liquid chromatographic column. The calibration curves showed good linearity in the range of 1.0–50 μM with correlation coefficients greater than 0.9988. The detection limits ranged from 0.04 to 0.12 μM. Furthermore, the developed method could be applied to the quantitative analysis of the four chelating agents in biodegradation and photodegradation experiments at the laboratory level. The proposed method, which offers the advantages of quickness, sensitivity, and requiring no complicated pretreatment steps, is expected to contribute significantly to the practical analysis of chelating agents in environmental water samples.Graphical abstract
Accidental releases of highly saline produced water (PW) to land can impact soil quality. The release of associated salts can clog soil pores, disperse soil clays, and inhibit plants and other soil biota. This study explores a novel remediation technique using ferrocyanide to enhance the evaporative flux of soil porewater to transport dissolved salts to the soil surface, where crystallization then occurs. The addition of ferrocyanide modifies crystal growth that enhances salt transport, allowing salt efflorescence on the soil surface and physical removal. Release sites were simulated through beaker sand column experiments using two PWs collected from the Permian Basin. PW composition altered efflorescence, with up to ten times as much ferrocyanide required in PWs than comparable concentrations of pure NaCl solutions. The addition of EDTA reduced dissolved cation competition for the ferrocyanide ion, improving PW salt recovery at the soil surface. The speciation model, PHREEQC, was used to predict the onset of salt precipitation as a function of evaporative water loss and model the effect of aqueous ferrocyanide and EDTA speciation on efflorescence. The results highlight the utility of predictive modeling for optimizing additive dosages for a given release of PW.
A new concept of removal and recovery of heavy metals and simultaneous regeneration and reuse of ethylenediamine-tetraacetic acid (EDTA) in soil washing effluent containing metal-EDTA complexes is proposed, which is used to remediate heavy metal contaminated soil. To achieve this goal, soil washing approach coupled with rectangular wave asymmetrical alternative current electrochemistry (RW-ACE) equipped with amidoxime-functionalized electrodes (Ami-CF) is employed. With high hydrophilicity and strong binding affinity, Ami-CF could specifically compete for heavy metals over EDTA under electric field. RW-ACE system is found successfully to achieve the non-destructive decomplexation of heavy metal-EDTA, and then regenerate EDTA for highly recycling, which saves as high as 98.9% EDTA consumption compared with conventional washing method. Moreover, more than 90% of heavy metals are recovered and deposited on the electrode with a majority of them existed as zero-valence state as evidenced by XPS. The RW-ACE method is universal for various heavy metals such as Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ in an authentic contaminated soil, and the loss of soil nutrient is very limited. Along with long-term assessment and operation cost estimation, the RW-ACE method is a sustainable remediation approach for the heavy metal polluted wastewater and soils, and easily scaled up for field practice.
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Heavy‐metal soil pollution is a common environmental problem all over the world. In the induced phytoextraction process plants can transport and translocate to their above‐ground tissues significant concentration of contaminants. Since some heavy metals are mostly presented in non‐soluble state, the application of chelating agents is needed. In this study we introduced into the rhizosphere of maize (var. Kneja 530) and sunflower (var. Favorit) plants 1 and 5 mmol l−1 of EDDS and NTA, and 5 g kg−1 of nutrients to enhance the accumulated concentrations of cadmium, lead and zinc. The fraction of CaCl2‐extractable metals increased incrementing the concentration of chelates. This was clearly pronounced for all the metals in the treatments with NTA and for Pb in those with EDDS. Generally, under all the experimental conditions the accumulated heavy‐metal concentrations were found to be significantly higher than in the control. Thus, in the case of higher concentration of NTA and EDDS, the accumulated Cd in the leaves of sunflower was found to be threefold higher. The highest accumulation of Pb in the leaves of maize was observed when nutrients were added (62 mg kg−1). On the other hand, negative effects of the used chelating agents on soil bacteria and fungi at plant harvest were not observed. Moreover, when nutrients were added, the number of studied microorganisms significantly increased.
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Anthropogenic chelating agents of the types aminopolycarboxylates and phosphonates are ubiquitous in the environment. In this chapter we describe these compounds and present the most important representatives and their uses. Typical concentrations in natural systems (e.g., surface and ground waters, wastewaters, and drinking water) are described along with a brief summary of their potential effects in the environment. The increasing interest in and research on these compounds is evaluated in terms of publication volume and topic area.
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The aim of this work was to study the application of two biodegradable chelating agents, pyridine-2,6-dicarboxylic acid (PDA) and methylglycinediacetic acid (MGDA), in the treatment of the pulp, prior to hydrogen peroxide bleaching. Such compounds must remove transition metals (Mn, Fe and Cu) from pulp, that catalyze the degradation of hydrogen peroxide, and Ca, which is also problematic due to the formation of precipitates that accumulate in the equipment. Computer simulations were first performed to study the best conditions for metal complexation, and optimum pH was defined as 5–5.5 for PDA and 6.5–7 for MGDA. Metals removal from the pulp, as well as the subsequent bleaching process (Q-P1-Paa-P2), were tested experimentally, and performances were compared to ethylenediaminetetracetic acid (EDTA). PDA removed both Mn and Ca efficiently, leaving most Mg in the pulp after first chelation stage, while MGDA had a lower Ca removal, even using a higher pH and concentration. Residual hydrogen peroxide and kappa number after peroxide stages showed a similar bleaching efficiency between the studied compounds and EDTA.
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ABSTRACT: The aim of this work was to study the ability of two biodegradable chelating agents, nitrilotriacetic acid (NTA) and ethylenediiminopropanedioic acid (EDDM) to complex metals, in the treatment of the pulp, prior to a totally chlorine free (TCF) bleaching process, and compare with the ethylenediaminetetraacetic acid (EDTA) performance. Firstly, speciation efficiency index (SEI) was calculated by computer simulations in order to evaluate the best pH conditions for metal chelating removal: pH range 6.5-7.0 for NTA and EDDM and pH range 5-5.5 for EDTA. After implementation of the bleaching Q-P1-Paa-P2 sequence, NTA and EDDM removed transition metals (Cu, Fe and Mn) from the pulp more selectively than EDTA. The treatment with either NTA or EDDM resulted in a final bleached pulp with residual lignin contents similar to the one obtained with EDTA. A higher peroxide consumption was recorded when EDDM was used, while equivalent peroxide consumptions were registered when NTA or EDTA were applied.
Bleaching compositions comprising a peroxy compound and ethylenediamine-N,N'-disuccinic acid or salts thereof are provided. The bleaching compositions show good bleach stability in aqueous solution and are particularly useful in bleach processes conducted, at least in part, at temperatures > 60 C. The compositions also possess good storage stability. The bleaching compositions may be used in the bleaching of cellulosic fibrous material and synthetic textiles and are also useful components of detergent compositions.
Formation of oxalic acid during bleaching of softwood kraft pulp was studied. The bleaching agents used were oxygen, hydrogen peroxide, chlorine dioxide, peracetic acid, and ozone. Formation of oxalic acid increased linearly with the reduction in kappa number. However, bleaching with peracetic acid produced less oxalic acid than the other bleaching agents. In ozone bleaching, about one-third of the oxalic acid formed is adsorbed on the pulp and not released until pulp pH is increased during a later stage, where it could combine with calcium ions to produce a calcium oxalate scale.
Literature suggests that ethylene-diamine-tetraacetic acid (EDTA) has been proved as a successful chelating agent for the extraction of metals from soils and spent catalysts. EDTA, however, is quite persistent in the environment due to its low biodegradability, thus its use becomes a matter of environmental concern. Therefore, to minimize the potential environmental risks, a new chelating agent [S,S]-ethylene-diamine-disuccinic-acid ([S,S]-EDDS) can be considered as an environmentally benign substitute for EDTA due to its easy biodegradation capability. The present study focuses on the effectiveness of biodegradable chelating agent [S,S]-EDDS for extraction of nickel from the spent catalyst of fertilizer industry. Experiments were carried out in batch mode under reflux conditions and process design parameters were optimized to maximize the extraction efficiency. Ni extraction of 84% was attained at optimum reaction condition in one cycle run. Dechelation of Ni-EDDS complex was performed at pH 5 where more than 96% EDDS was recovered. Results of the present study were compared with the previously studied chelating agent EDTA at optimum reaction conditions reported in literature. It was observed that [S,S]-EDDS requires a narrower pH range as compared to EDTA for chelation–dechelation process. Thus milder reaction conditions were employed for metal extraction using EDDS which is favorable to select the material of construction of equipment, in addition to the added advantage of biodegradability. Kinetic study was also performed for the noncatalyzed extraction process using shrinking core model and the process was found to be diffusion controlled under experimental conditions.