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Environmental Chemistry for a Sustainable World 70
Inamuddin
Mohd Imran Ahamed
Eric Lichtfouse
Tariq Altalhi Editors
Remediation
of Heavy
Metals
Environmental Chemistry for a Sustainable
World
Volume 70
Series Editors
Eric Lichtfouse , Aix Marseille University, CNRS, IRD, INRA, Coll France,
CEREGE, Aix en Provence, France
Jan Schwarzbauer, RWTH Aachen University, Aachen, Germany
Didier Robert, CNRS, European Laboratory for Catalysis and Surface Sciences,
Saint-Avold, France
Environmental chemistry is a fast developing science aimed at deciphering
fundamental mechanisms ruling the behaviour of pollutants in ecosystems. Applying
this knowledge to current environmental issues leads to the remediation of
environmental media, and to new, low energy, low emission, sustainable processes.
The topics that would be covered in this series, but not limited to, are major
achievements of environmental chemistry for sustainable development such as
nanotech applications; biofuels, solar and alternative energies; pollutants in air,
water, soil and food; greenhouse gases; radioactive pollutants; endocrine disruptors
and other pharmaceuticals; pollutant archives; ecotoxicology and health risk;
pollutant remediation; geoengineering; green chemistry; contributions bridging
unexpectedly far disciplines such as environmental chemistry and social sciences;
and participatory research with end-users.
The books series will encompass all scientific aspects of environmental
chemistry through a multidisciplinary approach: Environmental Engineering/
Biotechnology, Waste Management/Waste Technology, Pollution, general,
Atmospheric Protection/Air Quality Control/Air Pollution, Analytical Chemistry.
Other disciplines include: Agriculture, Building Types and Functions, Climate
Change, Ecosystems, Ecotoxicology, Geochemistry, Nanochemistry,
Nanotechnology and Microengineering, Social Sciences. The aim of the series is to
publish 2 to 4 book per year. Audience: Academic/Corporate/Hospital Libraries,
Practitioners / Professionals, Scientists / Researchers, Lecturers/Tutors, Graduates,
Type of books (edited volumes, monographs, proceedings, textbooks, etc.). Edited
volumes: List of subject areas the series will cover: • Analytical chemistry, novel
methods • Biofuels, alternative energies • Biogeochemistry • Carbon cycle and
sequestration • Climate change, greenhouse gases • Ecotoxicology and risk
assessment • Environmental chemistry and the society • Genomics and environmental
chemistry • Geoengineering • Green chemistry • Health and environmental chemistry
• Internet and environmental chemistry • Nanotechnologies • Novel concepts in
environmental chemistry • Organic pollutants, endocrine disrupters • Participatory
research with end-users • Pesticides • Pollution of water, soils, air and food •
Radioactive pollutants • Remediation technologies • Waste treatment and recycling
• Toxic metals
Remediation of Heavy
Metals
Editors
Inamuddin Mohd Imran Ahamed
Department of Applied Chemistry, Zakir Department of Chemistry, Faculty
Husain College of Engineering and of Science
Technology, Aligarh Muslim University
Aligarh Muslim University Aligarh, India
Aligarh, India
Tariq Altalhi
Eric Lichtfouse Department of Chemistry, College
Aix Marseille University, CNRS, IRD, of Science
INRA, Coll France, CEREGE Taif University
Aix en Provence, France Taif, Saudi Arabia
© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland
AG 2021
This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether
the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of
illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and
transmission or information storage and retrieval, electronic adaptation, computer software, or by similar
or dissimilar methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors, and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
editors give a warranty, expressed or implied, with respect to the material contained herein or for any
errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional
claims in published maps and institutional affiliations.
This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Foreword
Water will become more and more vital in the context of climate change, pollution,
industrialisation, and the future circular economy. Epidemiological and eco-
toxicological studies have shown that heavy metals have adverse impacts on living
organisms in both terrestrial and aquatic environments, in particular with genotoxic,
carcinogenic, mutagenic, and teratogenic effects, even at trace levels. Heavy metals
are both of natural and human origin, yet the human activity sources are rising fast
with industrialisation. Unlike organic pollutants, heavy metals do not degrade in
nature and thus must be removed, or their toxicity must be inactivated. Remediation
methods include ion exchange, membranes, reverse osmosis, filtration, electrodialy-
sis, precipitation, electrochemical process, biological treatments, coagulation/floc-
culation, and adsorption.
This book presents advanced knowledge on the sources, analysis, abatement, and
remediation of heavy metals, with focus on water and wastewater. Adsorbents
include nanomaterials, adsorbents, biowaste, and chelating materials, whereas tech-
niques include nanotechnology assisted treatments, membrane adsorption, advanced
oxidation processes, and eco-engineering. Chapter 1 gives an overview of the most
used analytical methods for the determination of heavy metals in water, with special
emphasis on modern developments regarding detection techniques, sample prepara-
tion, and their combinations. Additionally, the importance and latest developments
related to the speciation analysis of heavy metals are discussed in depth, along with
relevant examples and future perspectives in the field. Chapter 2 discusses the use
of by-products and waste from olive tree cultivation, olive recollection, and olive oil
extraction as low-cost materials in the removal of heavy metals from aqueous media.
Chapter 3 discusses different types of magnetic sorbents for heavy metal ion reme-
diation. The focus is on eco-friendly ferrite magnetic nanocomposite sorbent having
a high remediation rate. Case studies are illustrated based on oil palm fibres, cellu-
lose, and Ceiba pentadra as the recently developed metal-oxide composites based
on agrowastes. Chapter 4 details two-dimensional materials for heavy metal
removal. The major focus is given to communicate structures, mechanisms, and
applications of the two-dimensional materials for heavy metal removal. Chapter 5
addresses electrodialysis-based processes, focusing on electroplating and mining
v
vi Foreword
Natural landscape in New Caledonia showing the absence of plants on reddish soils that contain
naturally high contents of nickel, cobalt, chromium, and manganese. Observed living plants have
developed unique strategies to live in the presence of toxic metals. (Copyright: Eric Lichtfouse 2015)
activities. The feasibility of recovering nickel, copper, zinc, and chromium for reuse
in electroplating processes, as well as copper and zinc recovery from mining pro-
cessing solutions, is discussed.
Chapter 6 discusses the adsorption-mediated removal of heavy metal ions from
contaminated water using novel metal oxide nanostructures. High surface area, sur-
face charge, and porosity in metal oxides are the prime requisites for efficient
adsorption and removal of metal ions. The quantification of adsorption is described
with Freundlich and Langmuir isotherms. Chapter 7 presents the application of
organic and inorganic ion exchange materials for the removal of heavy metals from
water resources and industrial wastewaters. Fundamentals of the ion exchange pro-
cess and examples on the removal of various heavy metals with ion exchangers are
discussed. Chapter 8 outlines conventional wastewater treatment and potential low-
cost methods for the removal of toxic heavy metals from wastewaters. Advanced
approaches include bionanotechnology, emerging membrane technology, and low-
cost sorbents using zeolites and metal organic frameworks for efficient and eco-
nomical techniques. Chapter 9 presents nanomaterials as adsorbents for remediation
of water laden with heavy metal cations, with numerous examples. Chapter 10
reviews the origin, fate, and health hazards of the riverine contaminants, and then
the application of ecoengineered systems for remediation of the polluted rivers.
Foreword vii
Laboratory scale and on-site hybrid integrated treatment technologies for river bio-
remediation are detailed. Chapter 11 discusses ballast water releases from ships and
their impacts on the local marine environment as the result of transporting various
invasive aquatic species. Management options and available treatment techniques,
which can be ship or port based, are reported.
Chapter 12 details sources and effects of hexavalent chromium pollution with a
focus on carcinogenic properties. Cr(VI) removal techniques are presented, for
example chemical and electrochemical methods, ion exchange with membrane sep-
aration, adsorption, biosorption, nanozerovalent iron adsorption, and microbial
remediation. This chapter also highlights the advantages and disadvantages of pop-
ular chromium removal processes and recent advances in microbial remediation of
Cr(VI). Chapter 13 discusses the impact of heavy metals on biological systems, and
metal removal using various technologies. Chapter 14 discusses the merits and
demerits of conventional processes used for the removal of heavy metals from
water. Recent advances in removal are explained in detail, with focus on opportuni-
ties and challenges. Chapter 15 presents different modification techniques used to
increase the adsorption capacity of sugarcane bagasse, with emphasis on process
parameters such as initial concentration of metal, pH, and amount of biosorbent in
mono- and multi-component systems. Adsorption capacity, isotherm models, and
kinetic models are reported. Chapter 16 reviews the use of chelating materials such
as membranes, nanomaterials, polymers, resins, surfactants, chitosan, covalent and
metal organic frameworks, and hybrid materials to remove heavy metals from water.
Chapter 17 presents metal sources and transportation in environmental media, and
mitigation strategies.
ix
x Contents
xi
xii About the Authors
journal citation award by the Essential Indicators. He is world XTerra vice cham-
pion and has won the ITU cross triathlon world bronze medal in the age category.
Tariq Altalhi, PhD, joined the Department of Chemistry at Taif University, Saudi
Arabia, as assistant professor in 2014. He received his doctorate from the University
of Adelaide, Australia, in the year 2014 with Dean’s Commendation for Doctoral
Thesis Excellence. He became head of the Chemistry Department at Taif University
in 2017 and vice dean of the Science College in 2019, a position he still holds. In
2015, one of his works was nominated for the GreenTec Awards from Germany,
Europe’s largest environmental and business prize, amongst top 10 entries. He has
co-edited various scientific books. His group is involved in fundamental multidisci-
plinary research in nanomaterials synthesis and engineering, characterisation, and
their application in molecular separation, desalination, membrane systems, drug
delivery, and biosensing. In addition, he has established key contacts with major
industries in the Kingdom of Saudi Arabia.
Chapter 1
Analytical Methods for the Determination
of Heavy Metals in Water
1.1 Introduction
The rapid evolution of technology and industry is, without a doubt, one of the defin-
ing aspects of modern-day society. Although its influence in our everyday life is
ever present, its impact on the environment is usually ignored or understated by the
general public. Even though natural sources of chemical, physical and pathogenic
polluting agents exist, anthropogenic influence from human activities has a much
more significant impact on water, soil and air contamination (Rhind 2009). In par-
ticular, water bodies are extremely susceptible to direct contamination from indus-
trial, urban and agricultural activities. An estimate of 2 million tons (the approximate
weight of the entire human population) of sewage and industrial and agricultural
waste are discharged into the world’s water every day (WWDR 2003); among these,
the problem of heavy metal waste disposal is of paramount importance, since their
applications in technological industries are continually growing (Sharma 2014).
Even though there is not a widely accepted definition for the term, “heavy metals”
is usually applied to a group of metal elements which are known to be toxic to
humans and ecosystems at low concentrations (Dufus 2002). Furthermore, the
health threats represented by heavy metals exceed aqueous organisms, since they
have the tendency of bioaccumulating in organisms; thus, by means of trophic
chains, contamination is transferred to non-aqueous organisms.
Therefore, it is clear that the detection and quantification of heavy metals in
water samples is one of the main areas of interest in analytical chemistry. Precise
and accurate measurements allow for the evaluation of the present situation and
historical records permit the estimation of future trends concerning contamination
and necessary courses of action for its control. Furthermore, it is widely known that
the toxicity, bioavailability and environmental transport mechanisms of several
heavy metals (e.g. arsenic, mercury, lead) are highly dependent on their oxidation
state, thus making the determination of each metal species fundamental, indepen-
dently of the total concentration of the metal or metals under study (Bakirdere
2013). Moreover, the total concentration of heavy metals in aqueous samples is
usually below the parts per million (ppm, mg/L) or parts per billion (ppb, μg/L)
levels (Crompton 2015). This, in addition to the fact that the concentration of each
species is only a fraction of the total, translates into the need of highly sensitive and
selective analytical methods for the quantification and speciation analysis of heavy
metals and, in several cases, the development of sample pre-treatment methods
prior to said determinations.
In this chapter, an overview of the analytical techniques that have been most used
for the determination of heavy metals in aqueous samples is presented. Special
emphasis will be made on recent developments concerning modern environmental
aspects, such as nanoparticle contamination. Furthermore, several novel sample
preparation techniques are discussed.
1 Analytical Methods for the Determination of Heavy Metals in Water 3
Heavy metal analysis in waters has been very well benefited from innovative ana-
lytical methodologies. Up to date, this has evolved from the identification and quan-
tification of the total concentration of a given element to the identification, separation
and quantification of the different chemical species. The term speciation has become
extremely popular and is frequently used in studies related to the distribution of a
chemical element in its different forms or species (Templeton and Fujishiro 2017).
Therefore, the development of highly selective and sensitive analytical methodolo-
gies for the identification and determination of toxic and/or essential elemental spe-
cies constitutes one of the main demands on modern analytical chemistry (Clough
et al. 2018). The knowledge on the different chemical species of an element, as well
as their stability and dissociation kinetics is of vital importance, due to the high
dependence between elemental species and toxicity, bioavailability, bioaccumula-
tion, mobility and biodegradability (Achterberg et al. 2019). To cite an example,
tellurium -an increasingly popular element for the construction of solar panels- is
widely recognized as a toxic heavy metal, but the fact that the toxicity of its tetrava-
lent species is ten-fold higher than that of its hexavalent species is not much dis-
cussed in the literature (Zare et al. 2017).
The concept of speciation thus turns out to be extremely important in water pol-
lution studies, since it provides information related with the bioavailability and tox-
icity of a given element (Cornelis and Nordberg 2007). It is evident that the
determination of the different chemical forms in which an element can be present in
water samples is a fundamental need in order to obtain exact results on the risk of
exposure to certain toxic elements and, on the other hand, to establish nutritional
requirements for those which are essential at low concentrations (Bakirdere 2013).
Such is the case of chromium, which exists in nature in two stable oxidation states:
Cr(III) and Cr(VI), with completely different biological and physiological proper-
ties. Cr(III) is essential for living organisms, playing an important role in metabolic
processes, enhancing the activity of enzymes stimulating the synthesis of choles-
terol and fatty acids. On the other hand Cr(VI) is a toxic and carcinogenic agent,
which makes the differential quantitation of these species of paramount importance
(József et al. 2019).
Consequently, the ongoing development and application of cutting-edge analyti-
cal methodologies involves the coupling of highly efficient sample preparation
methods, e.g. solid and liquid microextractions or chromatographic methods, with
sensitive elemental detection techniques, such as atomic absorption spectrometry or
inductively coupled plasma-mass spectrometry. These are crucial activities in mod-
ern analytical chemistry in order to achieve a high level of elemental speciation
analysis based on the identification and quantification of species at trace concentra-
tion levels (μg/L or even lower) (Kocot et al. 2016). In all cases, a great distinction
of different chemical species is needed by means of physical, chemical or biological
processes, for an unequivocal identification.
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—
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Hän ei vastannut.
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rusottivat hänen olkapäänsä ja hoikat, lempeät käsivartensa. —
Miksihän minä näin kääriydyin? Onhan täällä muutenkin kuuma, ja
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Tyttö nauroi niin että oli siihen läkähtyä ja pyyteli häntä ojentaen
käsiään. Sitten äkkiä luisti lattialle, lankesi polvilleen ja koettaen
tarttua hänen käteensä, rukoili:
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— Odota!
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Hän ei ymmärtänyt.
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Kirjailijani sanoo: olet järkesi menettänyt, siksipä hän onkin konna.
Pysy sinä vain rehellisenä.
— Ei tepsi?
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— Entä sitten?
Siinä istui hän, joka ei tiennyt muuta kuin kyllä ja ei, käsivarsiin
nojaten ja hitaasti liikutellen silmiään, ikäänkuin elämänsä toisesta
päästä toiseen. Ja hajosi elämä, kuten huonosti liimattu lukittu
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sielunsa. On häpeällistä olla hyvä…
— Ja ne toiset?
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*****
*****
— Kauhistuttaa, Ljuba!
‒ Ei rakkaani, kyllä on. Et pelkää, sepä hyvä, mutta älä kutsu sitä.
Se ei ole tarpeellista.
— Minä lähden.
— Lähdet? —
Naurahti katkerasti.
— Anna lompakkoni.
Antoi sen.
— Entä kello?
— Pelästyitkö?
— Pelästyitkö?
— Kuinka?
— Miksi?
Lukko jo narahti.
— En.
Nainen alkoi iloisena hääriä. Hän riisui häntä kuin lasta, päästeli
auki hänen kengännauhojaan, silitteli hänen päätään, hänen
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Äkkiä katsahtaen hänen kasvoihinsa tyttö kauhistui:
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siemauksin. Alkoi yskiä.
— Ei tee mitään. Kyllä sinä opit hyvin juomaan, sen huomaa heti.
Olet kunnon poika. Miten iloinen olenkaan!
— Mitävarten?