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Application of
Advanced Oxidation
Processes
Edited by
Ciro Bustillo-Lecompte, Jose Colina-Márquez and
Lars Rehmann
Printed Edition of the Special Issue Published in Processes

www.mdpi.com/journal/processes
Application of Advanced Oxidation
Processes
Application of Advanced Oxidation
Processes

Editors
Ciro Bustillo-Lecompte
Jose Colina-Márquez
Lars Rehmann

MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade • Manchester • Tokyo • Cluj • Tianjin
Editors
Ciro Bustillo-Lecompte Jose Colina-Márquez Lars Rehmann
Ryerson University Universidad de Cartagena Western University
Canada Colombia Canada

Editorial Office
MDPI
St. Alban-Anlage 66
4052 Basel, Switzerland

This is a reprint of articles from the Special Issue published online in the open access journal
Processes (ISSN 2227-9717) (available at: https://www.mdpi.com/journal/processes/special issues/
Advanced Oxidation).

For citation purposes, cite each article independently as indicated on the article page online and as
indicated below:

LastName, A.A.; LastName, B.B.; LastName, C.C. Article Title. Journal Name Year, Article Number,
Page Range.

ISBN 978-3-03936-888-4 (Hbk)

ISBN 978-3-03936-889-1 (PDF)


c 2020 by the authors. Articles in this book are Open Access and distributed under the Creative
Commons Attribution (CC BY) license, which allows users to download, copy and build upon
published articles, as long as the author and publisher are properly credited, which ensures maximum
dissemination and a wider impact of our publications.
The book as a whole is distributed by MDPI under the terms and conditions of the Creative Commons
license CC BY-NC-ND.
Contents

About the Editors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Ciro Bustillo-Lecompte, Jose Colina-Marquez and Lars Rehmann

Special Issue: Application of Advanced Oxidation Processes
Reprinted from: Processes 2020, 8, 867, doi:10.3390/pr8070867 . . . . . . . . . . . . . . . . . . . . . 1

Luis Andrés Betancourt-Buitrago, Aracely Hernandez-Ramirez, Jose Angel Colina-Marquez,

Ciro Fernando Bustillo-Lecompte, Lars Rehmann and Fiderman Machuca-Martinez
Recent Developments in the Photocatalytic Treatment of Cyanide Wastewater: An Approach to
Remediation and Recovery of Metals
Reprinted from: Processes 2019, 7, 225, doi:10.3390/pr7040225 . . . . . . . . . . . . . . . . . . . . . 5

Ernesto Pino-Cortés, Silvio Montalvo, César Huiliñir, Francisco Cubillos and Juan Gacitúa
Characteristics and Treatment of Wastewater from the Mercaptan Oxidation Process:
A Comprehensive Review
Reprinted from: Processes 2020, 8, 425, doi:10.3390/pr8040425 . . . . . . . . . . . . . . . . . . . . . 29

Juan C. Ramı́rez Orejel and José A. Cano-Buendı́a

Applications of Electrolyzed Water as a Sanitizer in the Food and Animal-By Products Industry
Reprinted from: Processes 2020, 8, 534, doi:10.3390/pr8050534 . . . . . . . . . . . . . . . . . . . . . 53

Guoqiang Rong, Mengdi Xu, Dongyue Wang, Xiahui Gui and Yaowen Xing
Effect of Heating Oxidation on the Surface/Interface Properties and Floatability of
Anthracite Coal
Reprinted from: Processes 2019, 7, 345, doi:10.3390/pr7060345 . . . . . . . . . . . . . . . . . . . . . 73

Wen-Tien Tsai, Po-Cheng Huang and Yu-Quan Lin

Reusing Cow Manure for the Production of Activated Carbon Using Potassium Hydroxide
(KOH) Activation Process and Its Liquid-Phase Adsorption Performance
Reprinted from: Processes 2019, 7, 737, doi:10.3390/pr7100737 . . . . . . . . . . . . . . . . . . . . . 83

Denis Leybo, Marat Tagirov, Dmitry Arkhipov, Elizaveta Permyakova, Evgeny Kolesnikov
and Denis Kuznetsov
Effect of Initial Salt Composition on Physicochemical and Structural Characteristics of
Zero-Valent Iron Nanopowders Obtained by Borohydride Reduction
Reprinted from: Processes 2019, 7, 769, doi:10.3390/pr7100769 . . . . . . . . . . . . . . . . . . . . . 95

Yu Hou, Jimei Qi, Jiwei Hu, Yiqiu Xiang, Ling Xin and Xionghui Wei
Mesoporous Mn-Doped Fe Nanoparticle-Modified Reduced Graphene Oxide for Ethyl Violet
Elimination: Modeling and Optimization Using Artificial Intelligence
Reprinted from: Processes 2020, 8, 488, doi:10.3390/pr8040488 . . . . . . . . . . . . . . . . . . . . . 111

Mauricio Chiliquinga, Patricio J. Espinoza-Montero, Oscar Rodrı́guez, Alain Picos, Erick R.

Bandala, S. Gutiérrez-Granados and Juan M. Peralta-Hernández
Simultaneous Electrochemical Generation of Ferrate and Oxygen Radicals to Blue BR
Dye Degradation
Reprinted from: Processes 2020, 8, 753, doi:10.3390/pr8070753 . . . . . . . . . . . . . . . . . . . . . 143

S. Alejandro Lozano-Morales, Graciela Morales, Miguel Ángel López Zavala, Augusto

Arce-Sarria and Fiderman Machuca-Martı́nez
Photocatalytic Treatment of Paracetamol Using TiO2 Nanotubes: Effect of pH
Reprinted from: Processes 2019, 7, 319, doi:10.3390/pr7060319 . . . . . . . . . . . . . . . . . . . . . 157

v
Lili Wang and Xiaowei Liu
Degradation of Aqueous Polycyclic Musk Tonalide by Ultraviolet-Activated Free Chlorine
Reprinted from: Processes 2019, 7, 95, doi:10.3390/pr7020095 . . . . . . . . . . . . . . . . . . . . . 167

Xiaofang Sun, Huixuan Chen, Zhengyu Liu, Mengfei Zhou, Yijun Cai, Haitian Pan and
Luyue Xia
Investigations on Ozone-Based and UV/US-Assisted Synergistic Digestion Methods for the
Determination of Total Dissolved Nitrogen in Waters
Reprinted from: Processes 2020, 8, 490, doi:10.3390/pr8040490 . . . . . . . . . . . . . . . . . . . . . 183

vi
About the Editors
Ciro Bustillo-Lecompte (Ph.D.) has a multidisciplinary background in the areas of civil,
environmental, and chemical engineering. He completed his Bachelor of Engineering at the
University of Cartagena, Colombia, in 2008 and obtained his MASc (2012) and PhD (2016) at Ryerson
University, Canada. Ciro is a certified Professional Engineer (PEng), Environmental Professional (EP),
a Fraternal Member of the Canadian Institute of Public Health Inspectors (CIPHI), and a 2017–2018
Queen Elizabeth Scholar (QES). He is currently an Associate Member in the Environmental Applied
Science and Management Graduate Programs and Lecturer in the School of Occupational and Public
Health at Ryerson University. He has co-authored over 20 peer-reviewed scientific papers, as well
as several conference proceedings, chapters and books. His research interests include advanced
oxidation processes, advanced treatment of water and wastewater, waste minimization, water reuse,
water, soil and air quality, energy and resource recovery, and heterogeneous catalysis.

Jose Colina-Márquez (Ph.D.) has been an Associate Professor in the Chemical Engineering
Department at the University of Cartagena since 2010. He obtained his B.Sc. in Chemical Engineering
at the University of Atlantico (1996) and his M.Sc. and Ph.D in Chemical Engineering at the University
of Valle (2008 and 2010, respectively). Currently, he is leading the Research Group of Modeling and
Applications of Advanced Oxidation Processes, that aims to solve water detoxification issues using
these technologies. He is also a member of the Editorial Committee of the Revista Ingenieroa y
Competitividad (University of Valle, 2012) and a member of the Editorial Committee of the Revista
Ciencias e Ingenieria (University of Cartagena, 2011). He was awarded with the “Magna cum laude
grade” for his PhD studies, granted by the University of Valle (2010), and “Junior Researcher of the
year”, granted by the Colombian Society of Catalysis (2012).

Lars Rehmann (Ph.D.) obtained a PhD in Chemical Engineering in 2007 at Queen’s University
after completing his undergraduate degree at the Technical University Braunschweig, Germany and
his Masters work at Tottori University in Japan. He completed an NSERC post-doctoral fellowship at
the University of Manchester, UK (2007–2009) holding a Canada/UK Millennium Research Award.
He is an Associate Professor in the Department of Chemical and Biochemical Engineering at Western
University, as well as a Visiting Professor at the RWTH Aachen, Germany and a Fellow of the
Alexander von Humboldt Foundation. He is an accomplished and heavily cited researcher in the field
of biochemical and environmental engineering. His research has resulted in over 70 peer-reviewed
articles published in leading journals in his field, as well as three patent applications and the
foundation of a spin-off company. Since his appointment at Western (May 2009) he has attracted
over 4M USD in funding and has established research facilities centered around highly automated
bio-processing from the micro-scale to pilot scale; with infrastructure unique in Canada. His research
largely focuses on the fermentative production of platform chemicals and fuels from waste biomass,
as well as recombinant protein production.

vii
 processes
Editorial
Special Issue: Application of Advanced
Oxidation Processes
Ciro Bustillo-Lecompte 1, *, Jose Colina-Marquez 2, * and Lars Rehmann 3, *
1 School of Occupational and Public Health, Ryerson University, 350 Victoria Street, Toronto,
ON M5B 2K3, Canada
2 Department of Chemical Engineering, Universidad de Cartagena, Sede Piedra de Bolívar, Avenida del
Consulado 48-152, Cartagena 130015, Colombia
3 Department of Chemical and Biochemical Engineering, Western University,
Thompson Engineering Building, London, ON N6A 5B9, Canada
* Correspondence: [email protected] (C.B.-L.); [email protected] (J.C.-M.);
[email protected] (L.R.)

Received: 16 July 2020; Accepted: 16 July 2020; Published: 18 July 2020

Advanced oxidation processes (AOPs) are nowadays not only considered as a complementary
treatment option but as an attractive alternative to conventional methods. AOPs are often used
to improve the biodegradability of wastewaters, as well as in the inactivation of pathogenic
microorganisms. This Special Issue focuses on the “Application of Advanced Oxidation Processes”
and covers recent progress and trends in AOPs. A total of eleven papers constitute this Special Issue,
covering different aspects of the application of AOPs. Three review papers provide comprehensive
appraisals on the state-of-the-art of AOPs in industrial applications, while eight research papers cover
specific technologies for wastewater treatment, dye decolorization, and nanotechnology applications.
The first review explores different photocatalytic processes used for the treatment of gold
mining wastewater with an emphasis on cyanide wastewater applications [1]. In this review,
Betancourt-Buitrago et al. [1] investigate the effectiveness of photocatalytic processes in the removal of
free cyanide via oxidative pathways, where the need for more studies—with respect to the presence
of complexed cyano-metallic compounds in photoreactors, the requirement of modifying selectivity
using electron donors as scavengers of unwanted radicals, as well as the use of unconventional UV
LED lamps as a growing field in photoreactors design—is highlighted.
The second review summarizes the advantages and disadvantages of different treatment methods
of spent caustic wastewater from the mercaptan oxidation process in the oil industry [2]. Moreover,
Pino-Cortés et al. [2] describe the characteristics of spent caustic and its environmental impacts,
followed by an analysis of current neutralization processes to improve biodegradability.
The last review by Ramírez Orejel and Cano-Buendía [3] highlights the advantages of using
electrolyzed water in the food industry. The authors describe the characteristics of electrolyzed water
and explore the main applications of electrolyzed water in the food industry, specifically in animal
products derived from poultry, cattle, swine, and fish for sanitation, cleaning and disinfection.
The first of the eight research papers presented in this Special Issue examines the effect of heating
oxidation on the surface/interface features and floatability of anthracite [4]. The changes in surface and
interface of coal particles were confirmed by Rong et al. [4] using scanning electron microscopy (SEM),
Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS).
The second research paper explores the potential of cow manure to produce highly porous activated
carbon (AC) using a potassium hydroxide (KOH) activation process at different temperatures for the
removal of methylene blue from an aqueous solution [5]. Based on the XPS and FTIR observations,
Tsai et al. [5] concluded that the AC from cow manure has a strong interaction with the cationic
compound (i.e., methylene blue) due to its large pore properties and oxygen-containing complexes on
the surface.

Processes 2020, 8, 867; doi:10.3390/pr8070867 1 www.mdpi.com/journal/processes

Processes 2020, 8, 867

The following two research papers are related to nanotechnology applications. Leybo et al. [6]
investigated the effect of ferric and ferrous salts on the structural characteristics and physicochemical
properties of nanoscale zero-valent iron samples synthesized by borohydride reduction. Samples
were characterized by SEM, transmission electron microscopy, X-ray diffraction, and low-temperature
nitrogen adsorption. Leybo et al. [6] showcase the synergistic action of nanoscale zero-valent iron and
ferrihydrite leading to higher Pb2+ ion removal from water via borohydride reduction of iron from
sulphate salt.
On the other hand, Hou et al. [7] synthesized mesoporous Mn-doped Fe/rGO nanocomposites
by a co-precipitation method and investigated the ultrasonic-assisted removal of ethyl violet (EV)
from synthetic wastewater. Artificial Intelligence (AI) models were combined with response surface
methodology (RSM) to optimize the removal efficiency of Mn-doped Fe/rGO nanocomposites for EV.
The Mn-doped Fe/rGO nanocomposite demonstrated its potential for the removal of dyes in water
due to its facile synthesis, large adsorption capacity, high specific surface area, and excellent magnetic
properties [7].
The last four research papers cover specific technologies for wastewater treatment and dye
decolorization. The study by Chiliquinga et al. [8] explores the simultaneous production of the ferrate
ion and free radicals on a boron-doped diamond (BDD) anode surface. Further, it examines the
generation of both species in two different electrolytes with the addition of different concentrations of
iron sulphate, and the effect of the current density on the degradation of a textile dye. Results showed
fast degradation rates of up to 98% of colour reduction in 60 min of treatment with a COD reduction of
over 60% [8].
Similarly, Lozano-Morales et al. [9] evaluated the photocatalytic degradation of nanostructured
TiO2 catalysts under UV-C radiation and the effect of the pH of paracetamol suspensions on the overall
degradation efficiency. The photocatalytic oxidation degraded up to 99% of the paracetamol at a pH of
6.5, a value at which adsorption was favoured, leading to higher efficiency and exposure times below
100 min, where no traces of metabolites were detected [9].
Another study explores the use of UV-activated free chlorine and investigates the degradation
efficiency of the Aqueous Polycyclic Musk Tonalide [10]. Besides, Wang and Liu [10] identified primary
contributors and intermediates, described the toxicity profile of the Aqueous Polycyclic Musk Tonalide,
and evaluated the influence of natural organic matter, common anions and cations in the degradation.
Finally, the study by Sun et al. [11] compared UV/O3 , US/O3 , and UV/US/O3 processes based
on the digestion time and conversion rate of standard N-compounds, and investigated the influence
of temperature, pH, the concentration of O3 , mass flow rate, UV intensity, US frequency, and power
on digestion efficiency. Results showed that the UV/US/O3 process had the best digestion efficiency
under optimum conditions of pH = 11, O3 mass flow rate of 3200 mg/h, reaction temperature of
30 ◦ C, digestion time of 25 min, 18 W UV lamp power, 20 kHz and 75 W of US frequency and power,
respectively, for a wastewater conversion rate over 99% and total dissolved nitrogen in the range of
1.0–4.0 mg/L.
These diverse contributions provide sustained evidence of the large variety of applications of
AOPs as well as demonstrating a promising future of the research fields of photocatalysis, UV/O3 ,
electrochemical oxidation, sonolysis, nanotechnology in AOPs, the development of novel catalytic
material, heating oxidation, UV-activated free chlorine, electrolyzed water, industrial wastewater
treatment, and resource recovery, among other applications.
To conclude, the guest editors would like to thank all the authors for their valuable contributions;
their efforts and contributions are highly appreciated. State-of-the-art applications of AOPs presented
in this Special Issue may serve as valuable references for future research in this ever-evolving field.

2
Processes 2020, 8, 867

Author Contributions: Writing-review & editing, C.B.-L., J.C.-M., and L.R. All authors have read and agreed to
the published version of the manuscript.
Acknowledgments: The guest editors would like to acknowledge the authors who collaborated and contributed
with their research towards this Special Issue.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Betancourt-Buitrago, L.; Hernandez-Ramirez, A.; Colina-Marquez, J.; Bustillo-Lecompte, C.; Rehmann, L.;
Machuca-Martinez, F. Recent Developments in the Photocatalytic Treatment of Cyanide Wastewater:
An Approach to Remediation and Recovery of Metals. Processes 2019, 7, 225. [CrossRef]
2. Pino-Cortés, E.; Montalvo, S.; Huiliñir, C.; Cubillos, F.; Gacitúa, J. Characteristics and Treatment of Wastewater
from the Mercaptan Oxidation Process: A Comprehensive Review. Processes 2020, 8, 425. [CrossRef]
3. Ramírez Orejel, J.; Cano-Buendía, J. Applications of Electrolyzed Water as a Sanitizer in the Food and
Animal-By Products Industry. Processes 2020, 8, 534. [CrossRef]
4. Rong, G.; Xu, M.; Wang, D.; Gui, X.; Xing, Y. Effect of Heating Oxidation on the Surface/Interface Properties
and Floatability of Anthracite Coal. Processes 2019, 7, 345. [CrossRef]
5. Tsai, W.; Huang, P.; Lin, Y. Reusing Cow Manure for the Production of Activated Carbon Using Potassium
Hydroxide (KOH) Activation Process and Its Liquid-Phase Adsorption Performance. Processes 2019, 7, 737.
[CrossRef]
6. Leybo, D.; Tagirov, M.; Arkhipov, D.; Permyakova, E.; Kolesnikov, E.; Kuznetsov, D. Effect of Initial Salt
Composition on Physicochemical and Structural Characteristics of Zero-Valent Iron Nanopowders Obtained
by Borohydride Reduction. Processes 2019, 7, 769. [CrossRef]
7. Hou, Y.; Qi, J.; Hu, J.; Xiang, Y.; Xin, L.; Wei, X. Mesoporous Mn-Doped Fe Nanoparticle-Modified Reduced
Graphene Oxide for Ethyl Violet Elimination: Modeling and Optimization Using Artificial Intelligence.
Processes 2020, 8, 488. [CrossRef]
8. Chiliquinga, M.; Espinoza-Montero, P.; Rodríguez, O.; Picos, A.; Bandala, E.; Gutiérrez-Granados, S.;
Peralta-Hernández, J. Simultaneous Electrochemical Generation of Ferrate and Oxygen Radicals to Blue BR
Dye Degradation. Processes 2020, 8, 753. [CrossRef]
9. Lozano-Morales, S.; Morales, G.; López Zavala, M.; Arce-Sarria, A.; Machuca-Martínez, F. Photocatalytic
Treatment of Paracetamol Using TiO2 Nanotubes: Effect of pH. Processes 2019, 7, 319. [CrossRef]
10. Wang, L.; Liu, X. Degradation of Aqueous Polycyclic Musk Tonalide by Ultraviolet-Activated Free Chlorine.
Processes 2019, 7, 95. [CrossRef]
11. Sun, X.; Chen, H.; Liu, Z.; Zhou, M.; Cai, Y.; Pan, H.; Xia, L. Investigations on Ozone-Based and UV/US-Assisted
Synergistic Digestion Methods for the Determination of Total Dissolved Nitrogen in Waters. Processes
2020, 8, 490. [CrossRef]

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

3
 processes
Review
Recent Developments in the Photocatalytic Treatment
of Cyanide Wastewater: An Approach to Remediation
and Recovery of Metals
Luis Andrés Betancourt-Buitrago 1 , Aracely Hernandez-Ramirez 2 , Jose Angel Colina-Marquez 3, *,
Ciro Fernando Bustillo-Lecompte 4 , Lars Rehmann 5 and Fiderman Machuca-Martinez 1
1 Escuela de Ingeniería Química, Universidad del Valle, Calle 13 #100-00. Cali A.A. 25360, Colombia;
[email protected] (L.A.B.-B.); fi[email protected] (F.M.-M.)
2 Facultad de Ciencias Químicas, Universidad Autónoma de Nuevo León, San Nicolás de los Garza 64570,
Mexico; [email protected]
3 Department of Chemical Engineering, Universidad de Cartagena, Sede Piedra de Bolívar, Avenida del
Consulado 48-152, Cartagena A.A. 130001, Colombia
4 Graduate Programs in Environmental Applied Science and Management, and School of Occupational and
Public Health, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, Canada;
[email protected]
5 Department of Chemical and Biochemical Engineering, Thompson Engineering Building, Western
University, London, ON N6A 5B9, Canada; [email protected]
* Correspondence: [email protected]

Received: 6 March 2019; Accepted: 15 April 2019; Published: 20 April 2019

Abstract: For gold extraction, the most used extraction technique is the Merrill-Crow process, which
uses lixiviants as sodium or potassium cyanide for gold leaching at alkaline conditions. The cyanide
ion has an affinity not only for gold and silver, but for other metals in the ores, such as Al, Fe, Cu, Ni,
Zn, and other toxic metals like Hg, As, Cr, Co, Pb, Sn, and Mn. After the extraction stage, the resulting
wastewater is concentrated at alkaline conditions with concentrations up to 1000 ppm of metals.
Photocatalysis is an advanced oxidation process (AOP) able to generate a photoreaction in the solid
surface of a semiconductor activated by light. Although it is well known that photocatalytic processes
can remove metals in solution, there are no compilations about the researches on photocatalytic
removal of metals in wastewater with cyanide. Hence, this review comprises the existing applications
of photocatalytic processes to remove metal and in some cases recover cyanide from recalcitrant
wastewater from gold extraction. The use of this process, in general, requires the addition of several
scavengers in order to force the mechanism to a pathway where the electrons can be transferred to
the metal-cyanide matrices, or elsewhere the entire metallic cyanocomplex can be degraded by an
oxidative pathway.

Keywords: UV-LED; photoreactors; mining wastewater; cyanide; metal removal

1. Introduction
Gold has always had a high value since prehistoric times as ornaments in rituals, and it occupies
an essential role in the world economy. By mid-2017, the world gold reserves were around 33,450 metric
tons, with a demand of 4337 tons in 2016, destined for jewelry (47%), technology (7%), investments
(36%), and central banks (9%) [1].
The gold exploitation depends on the way it is present in minerals, and its extraction can be done
in the acid phase (pH < 3) with thiourea, thiocyanate, chlorine, aqua regia, ferric chloride; in neutral
phase with thiosulfate, halogens, sulfuric acids, bacteria; and in alkaline phase (pH > 10) with cyanide,
ammonium cyanide, ammonium, sulfur, and nitriles [2,3]. However, the practical application of these

Processes 2019, 7, 225; doi:10.3390/pr7040225 5 www.mdpi.com/journal/processes

Processes 2019, 7, 225

processes is limited to extraction in the alkaline phase using cyanide because of its high selectivity
with respect to gold [4–6].
Latin America and the developing countries exhibit one of the primary gold and silver exploitation
scenarios based on the leaching of ores with solvents, such as sodium cyanide (NaCN)—The
Merrill-Crowe Process. In this extraction process, the gold-concentrated effluent is later taken
to a precipitation stage with the use of zinc, called cementation [7]. The wastewater resulting from this
process is rich in heavy and non-heavy metals, poor of gold, and it contains dissolved silver, which is
very harmful to the environment [8]. The mining wastewater is well known to be the predominant
cause of pollution problems in surface water bodies (lakes and rivers). The problems, such as death,
due to poisoning, lead poisoning; cancer, due to chromium, blindness and congenital malformations,
are attributed to the contamination of surface and underground water sources [9]. Furthermore, heavy
metals in these waters could be bioaccumulated and present biomagnification causing serious health
effects, due to their high levels of toxicity [10–12]. Besides, mining wastewaters can show problems
of metal mobility and local cyanide release where they are stored; mining wastewaters are directly
discharged to tailings ponds for periods of three to six months where degradation is expected by the
sun (photolysis and evaporation) [13].
In large-scale operations, wastewater treatment is carried out with highly oxidizing processes,
such as chlorination, sulfur dioxide, hypochlorite oxidation, electrolytic oxidation, ozonation, use
of hydrogen peroxide, high thermal transformation, biological treatments, adsorption on activated
carbon, among others, usually at high oxidation conditions and operation cost [14].On the other hand,
advanced oxidation processes (AOPs) have the advantage of removing liquid and recalcitrant gaseous
matrices by non-selective chemical species. Among these processes, heterogeneous photocatalysis
(HPC) has received considerable attention as a promising technology, able to use renewable energy
from the sun. It is conventionally defined as the acceleration of the rate of a chemical reaction, induced
by the absorption of light by a catalyst or coexisting molecule. This definition of photocatalysis may be
the most widely accepted as it encompasses all aspects of the field, including photosensitization [15].
HPC is one of the AOPs that allows the elimination of toxic compounds in a non-selective
pathway, due to the generation of oxidizing species, such as the hydroxyl radical (• OH), perhydroxyl
radical (HOO• ), superoxide (O2 •– ), and photogenerated holes (h+), transforming recalcitrant and toxic
molecules into biodegradable or less harmful compounds [16]. Photocatalytic processes not only are
applied to oxidize recalcitrant organic matter, but also to promote reduction reactions. Some examples
are the photoreduction of benzaldehyde to benzyl alcohol, metallic ions, such as Fe3+ , Cr6+ , Hg2+ ,
Cu2+ , inorganic nitrogen and carbon dioxide to formic acid, simulating part of artificial photosynthesis.
The photocatalytic reduction represents an option when traditional oxidative pathways are not
feasible and when the nature of semiconductor is able to transfer electrons at a high energy level on its
conduction band. Although the current applications of large-scale photocatalytic processes are scarce,
different assessments have been made for the contamination associated with gold mining wastewaters.
In this review, different photocatalytic processes used for the elimination of synthetic and real cyanide
matrices of gold extraction are explained and described.

2. Production and Characterization of Cyanide Wastewater

Cyanidation is used when gold is in the pyrite form and is not extractable by physical separation
methods. This process is carried out through the use of sodium cyanide in the alkaline phase and with
an excess of oxygen, as shown in Equation (1) [17]. Once Au is extracted from the ores, the gold is
precipitated by adding Zn (cementation), replacing the gold of the aurocyanide ion with zinc cyanide
and precipitating it in metallic form, as indicated in Equation (2). Although the efficiency of the process
is in the order of 99%, the wastewater has metal cyano-complexes strong acid dissociable (SAD), such
as iron, copper, and cobalt, as well as weak acid dissociable (WAD), such as nickel, silver, zinc, and
arsenic [14].

6
Processes 2019, 7, 225

Leaching or cyanidation:

4Au + 8NaCN + O2 + 2H2 O → 4Na[Au(CN)2 ] + 4NaOH (1)

Cementation:

2NaAu(CN)2 + 4NaCN + 2Zn + 2H2 O → 2Na2 Zn(CN)4 + 2Au↓ + ↑H2 + 2NaOH (2)

Table 1 shows the metallic and semi-metallic cyano-composites, sorted by the logarithms of their
stability constants. Thus, the most unstable compound corresponds to the hydrogen cyanide in the gas
phase; the easily dissociable WAD corresponds to complexes of Cd, Zn, Ag, Ni, Cu, Cr, and the most
stable SAD correspond to complexes of Fe, Au, Co. The stability of strong complexes makes necessary
the use of tailings ponds for removing them by solar-evaporation [18].

Table 1. Stability of cyano-metallic complexes [19].

Group Species Toxicity [20] Stability Constant (Log Kn )

CN− High n.a.
Free cyanide
HCN(g) 9.2
NaCN, KCN, Ca(CN)2 ,
Simpler compounds:
Hg(CN)2 , Zn(CN)2 , High n.d.
Easily soluble
CuCN, Ni(CN)2 , AgCN
Weak complex Cd(CN)2− 4 Intermediate 17.9
(WAD—Weak Acid Cd(CN)− 3 n.d.
Dissociable) Zn(CN)2− 4 19.6
Ag(CN)− 2 20.5
Ni(CN)2−4 30.2
2−
Cu(CN)3 21.6
Cr(CN)3−6 n.a.
Cr(CN)3−6 n.a.
Strong complexes
(SAD—Strong Acid Fe(CN)4−
6 35.4
Dissociable)
Fe(CN)3−
6 Low 43.6
Au(CN)− 2 38.3
Co(CN)3−6 High 64.0
Unstable inorganic SCN− , CNO− High n.d.
Acetonitrile,
Aliphatic organic acrylonitrile, adiponitrile, Intermediate n.d.
propionitrile

On the other hand, weak complexes are easily hydrolyzable by changing the pH of the solution.
In principle, weak complexes tend to be destroyed over three months with or without photolysis;
however, strong complexes, such as Fe(CN)6 3– , Co(CN)6 3– remain over time, turning these waters into
recalcitrant. Additionally, degradation products, such as NH3 /NH4 + , NO2 – , NO3 – , CNO– , sulfates,
and carbonates are formed by the slow rupture of cyano-metallic complexes. Thus, the resulting
wastewater (concentrated by these complexes) is not suitable for being poured into surface bodies of
water [13,21].

3. Existing Treatment Options

The existing treatment options of oxidative processes for the treatment of cyanide wastewater,
such as natural attenuation [18,22], chemical oxidation [23], thermal treatments, precipitation, biologic
oxidation [24–27], and ionic adsorption [28], are well documented [18]. Nonetheless, strictly
photocatalytic treatments are scattered, and there is no clarity of existing photocatalytic processes
applications for degradation of cyanide complexes.

7
Processes 2019, 7, 225

Figure 1 shows a relational diagram constructed with VOS Viewer® using technology watch
tools [29] on the main topics related to cyanide. In this figure, it is observed that the relationship
with the word “photocatalysis” is not very broad. However, it appears related to “activated carbon”
and “titanium dioxide” (in yellow). Likewise, other technologies appear, such as: “Biodegradation”,
“ozone”, “hydrogen peroxide”, “electroplating”, and “adsorption”. For this review, some applications of
photocatalytic processes used in the degradation of this type of cyano-metallic wastewater are depicted.

Figure 1. Keyword correlation map. Database: Web of Science. 464 documents. Date of consultation:
22 February 2018. Built with VOSViewer v1.6.7.

4. Photocatalytic Treatment Alternatives

4.1. Classic Oxidative Photocatalysis

AOPs are generally based on mechanisms capable of producing profound changes in the chemical
structure of pollutants. Heterogeneous Photocatalysis (HPC) is a photochemical AOP where redox
reactions are promoted by the interaction of a semiconductor catalyst and photons, generating active
species able to degrade recalcitrant organic matter to allowable concentrations for final discharge [30].
Figure 2 shows the photocatalytic mechanism on a TiO2 particle. The photocatalytic process
initiates when a semiconductor is irradiated by photons (from solar or artificial light) whose energy is
equal or greater than the band-gap energy (Eg) of the semiconductor, promoting the electrons from
the balance band to the conduction band. Then, the electrons at the conduction band can react with
the adsorbed oxygen on the semiconductor surface to form superoxide radicals (O2 •– ), and other
radicals with water, such as the perhydroxyl (HOO• ) or generating reduction reactions by the direct or
indirect transfer with adsorbed compounds. On the other hand, the holes in the balance band can
react with the adsorbed water generating hydroxyl radicals (• OH), characteristics of the AOPs [31].
Conversely, it has also been evidenced that hydroxyl radicals are obtained by reduction of H2 O2 and
not by direct oxidation of water adsorbed on the catalyst surface [32]. Furthermore, the holes in the
valence band can react directly with other adsorbed molecules as sacrificing agents oxidizing them to
simpler substances [32]. This final step is the most argued mechanism in the photocatalytic treatment
of recalcitrant molecules.

8
Processes 2019, 7, 225

Figure 2. One electron reduction steps of oxygen to hydroxyl radical and two electron oxidation steps
of water to H2 O2 . Adapted from Reference [32].

In the case of the cyanide, the use of different catalysts, such as titanium dioxide, nickel oxide,
zinc oxide, platinum, zirconium, cadmium, and cobalt, have been studied for removing potassium
cyanide and sodium cyanide [33–50].
In general, all the photocatalytic evaluations are carried out using the oxidative chemical pathway
that works in the presence of oxygen. This process transforms the adsorbed substances in less toxic
compounds (nitrates, carbonates, carbon dioxide, and nitrogen). Table 2 shows the most applied
processes in matrices containing synthetic cyanide solutions of KCN and NaCN. It can be noticed that
the initial concentrations oscillate around 100 ppm of CN– (3.2 mM CN– ). Moreover, photocatalytic
degradation with doped TiO2 and ZnO has been evaluated, with the main doping agents of Ce,
Ag, Zn, Pt, and Co. These photocatalysts have achieved degradations of free cyanide (over 8 and
10%) in oxic conditions and with artificial radiation using UV-C (light emitting diodes) LED light.
The photocatalytic evaluations in batch and continuous reactors for degradation of organic cyanide
compounds show how they have degraded and mineralized acetonitrile (CH3 CN) in the gaseous and
liquid phase, obtaining better results with the gas phase [47].
Other combinations for free cyanide involve combined treatments of oxidation processes,
such as photocatalysis/ozone/electrolysis/electrocoagulation that achieved degradations greater than
90% [51–59]. Although in those photocatalytic evaluations, more than 90% of the substrate was removed.
Most of them were carried out with synthetic solutions of pure free cyanide, which does not address
the issue related to the metal-cyanide complex remediation at laboratory scale, as shown in Table 2.
The photocatalytic degradation of free cyanide is summarized in Figure 3. As mentioned before,
the oxidation is carried out by different pathways: Oxidation by holes (h+ ), oxidation by superoxide
(O2 •− ) and oxidation by hydroxyl radicals (• OH). The reaction of CN− with radicals transforms it
into cyanate (CNO– ), ammonium (NH4 + ), nitrates (NO2 – , NO3 – ) and carbonates (HCO3 – , CO3 2– ).
Although these photocatalytic treatments were used for the degradation of free cyanide, all applications
were limited to synthetic solutions. Complexing agents like the metals in the ores represent the main
problem of mining wastewater.

9
 Table 2. Photocatalytic treatments applied to free cyanide matrices.

Degradation/Reaction
Year Substance [C0 ] Source of Light Wavelength Type of Reactor Catalyst Main Findings
Time
Achieve total degradation to nitrates and
KCN 14 W UV Hg Low Compact Square
1992 360 nm 100%/60 min TiO2 P25 cyanates. They find the CO2 in air bubbling as
[100 ppm] Pressure batch reactor
harmful for the photocatalytic mechanism [33]
Processes 2019, 7, 225

NaCN, NaCNO [3.85 Solar 100%/4.1 Einstein Total degradation with solar light, but kinetics
1999 Solar light CPC pilot scale TiO2 P25
mM] spectrum accumulated is only related to accumulated energy [34]
1.5 mmol/h H2 The process produced hydrogen and cyanate
NaCN 450 W, 700 W Hg
2001 UV-A Laboratory Batch produced at 70 ◦ C NiO/TiO2 from cyanide as a photocatalytic strategy of
[666 ppm CN− ] high-pressure lamp
and 700 W remediation [50]
Free Cyanide, phenol,
atrazine, EPTC, photo Fenton and
Solar Pilot-scale PSA–Solar Several experiments applied at a solar pilot
2002 dichloroacetic acid, Solar 100%/N.D. photocatalysis
spectrum platform of Almeria plant in Almeria with successful results [60]
and Cr(VI) among applications.
others.
Achieved geometry optimization using the
KCN 150W Hg medium Supported TiO2 on
2002 >300 nm Batch cylindrical 47%/2 h TiO2 /SBA-15 support SBA. However, degradation resulted
[100 ppm] pressure lamp SBA-15 and MCM-41
low [43]
Achieved a low degradation of free cyanide
NaCN 150W Hg Medium TiO2 Sol-gel method on
2002 n.a. Batch cylindrical 50%/350 min exploring a novel geometry configuration on
[100 ppm CN− ] pressure four different support
the TiO2 distribution [48]

10
Although total degradation was achieved,
authors argue the photonic efficiency is very
NaCN
2003 n.a. n.a. n.a. 100%/420 min TiO2 P25 low and radical recombination occurred. They
[3.85 mM]
propose a very detail degradation kinetic
mechanism [61]
450 W They determine the interaction of CN− with
KCN binaural pyrex batch
2004 High-pressure Hg >300 nm n.a. TPA/TiO2 , Cs-TPA/TiO2 holes and electrons photogenerated. The Cs
[50 ppm] with intern lamp
lamp resulted in photocatalytic inhibition [62].
CH3 CN (gas and Annular photoreactor TiO2 anatase for gas,
500 W Hg medium 21%/4 g gas phase Photocatalytic activity was low, and free
2005 liquid) 365 nm steady state for liquid and TiO2 P25 for the
pressure lamp 35%/5 g liquid phase cyanide ions remain in solution [47]
[24 mM] and gas phase liquid phase
NH3 , HCOOH, CN−
from Electric Power
100% CN
Plant wastewater Requires addition of H2 O2 to enhance
2007 150 W Hg lamp 190–280 nm Batch cylindrical 90% NH3 TiO2 P25 + H2 O2
[10 ppm CN− , 1700 photocatalytic degradation [45]
100% HCOOH/10 min
HCOOH, 150 ppm
NH3 ]
 Table 2. Cont.

Degradation/Reaction
Year Substance [C0 ] Source of Light Wavelength Type of Reactor Catalyst Main Findings
Time
Apply an optimization methodology to
Recirculating
KCN 400 W Hg UV optimize the photonic efficiency of the
2007 >300 nm cylindrical 5%/100 min Sol-gel TiO2 /SiO2
[45 ppm CN− ] Lamp photoreactor. However, a very low
Processes 2019, 7, 225

photoreactor
photodegradation was evidenced [63]
Evaluated the photocatalytic degradation with
Three photocatalysts
three photocatalysts and with the addition of
KCN 400 W Hg medium Cylindrical with were evaluated: TiO2
2007 >300 nm 95%/60 min O3 . A good degradation was achieved but the
[40 ppm CN− ] pressure lamp reflector P25, DBH TiO2 ,
addition of O3 instead O2 resulted in
nanometric TiO2 .
photocatalytic inhibition [59]
The authors proposed an intrinsic kinetic model
KCN 80 W and 36 W Cylindrical of cyanide degradation with an accurate fitting
2008 UV-A n.a. TiO2 P25, TiO2 /SiO2
[3.85 nM] Low-pressure lamp photoreactor of experimental data. The study was more
kinetic than a photocatalytic evaluation [64]
200 W/cm2
of solar The evaluated the effect of solar light using a
NaCN, gasification
spectrum Cylindrical Fresnel lens to concentrate energy. They
2008 plant wastewater Solar light 100%/90 min TiO2 P25.
concentrated photoreactor required the addition of H2 O2 to achieve total
[10 ppm CN− ]
with a mineralization of free cyanide [46]
Fresnel Lens

11
The process reduced ferrate(VI) and oxidated
cyanate in a Fe(VI)-TiO2 -UV-NCO− system.
KCNO, Fe+4
Borosilicate glass 80% cyanate However, the role of the TiO2 in the degradation
2008 [1 mM CNO− ] n.a. UV-A TIO2 P25
cylindrical degradation/120 min was not specified. The possible
[1 mM Fe+4 ]
reduction-oxidation mechanism for Fe+4
reduction was not clarified [65]
The degradation was done using 10.5 mM
15 W Hg EDTA as a hole scavenger. Addition of EDTA
2008 KCN [100 ppm CN− ] UV-A Cylindrical batch 100%/350 min TiO2 P25
low-pressure lamp evidenced an increase in the cyanide oxidation
to CNO− [49]
They evaluate and compared the scaling-up
process from laboratory to pilot plant, using
400 W and 36 W
2009 KCN [30 ppm CN− ] 365 nm Annular reactor 100%/120 min TiO2 /SiO2 supported TiO2 . Total elimination of cyanide
Blacklight lamp
was achieved in both systems. Propose a scaling
up methodology for photoreactors [66]
 Table 2. Cont.

Degradation/Reaction
Year Substance [C0 ] Source of Light Wavelength Type of Reactor Catalyst Main Findings
Time
TiO2 nanoparticles It is proposed a recovery technique using
NaCN Cylindrical glass coupled with an electrocoagulation after a typical photocatalytic
2009 450 W Halide lamp UV-A 90%/30 min
[400 ppm] batch electrocoagulation cyanide degradation. A study of TiO2 reuse was
Processes 2019, 7, 225

recovery also performed [54]

Doping relations of 2% Ce-ZnO calcined at 500
◦ C. This photocatalyst works better in the

Ce-ZnO sonochemical visible region. There is an excess of light

2010 KCN [250 ppm] 8 W Hg lamp 365 nm Batch cylindrical 40%/100 min
impregnation applied to the system, which could mix the
photocatalysis with the photolysis effect on
CN− degradation [35]
KCN Batch cylindrical Ag-ZnO sonochemical Ag-ZnO was found to be three times better than
2010 8 W Hg Lamp 365 nm 86%/90 min
[11 mM CN– ] Reactor impregnation synthesis ZnO pure [36]
Photocatalytic activity was demonstrated but
150 W halide and 8
2011 KCN [10 mM] 365 nm UV Annular batch reactor 16%/150 min ZnO-TiO2 with important radiant field losses in the
W Hg UV lamp
photoreactor [37]
Pt-TiO2 -
150 W fluorescent Batch cylindrical hydroxyapatite. Hydroxyapatite enhanced the photocatalytic
2013 KCN [100 ppm] 450 nm 98%/60 min
lamp reactor Prepared by Sonic behavior of bare suspended TiO2 [38]
method.

12
Pt/ZrO2 -SiO2 prepared
150 W fluorescent Evaluated the effect of catalyst load on the
2013 KCN [100 ppm] 450 nm Batch annular reactor 100%/20 min by a photo-assisted
lamp reactor [39]
deposition method.
Co-TiO2 -SiO2 prepared
Obtained the best catalyst load obtained at 0.08
KCN 150 W fluorescent Batch cylindrical 100%/360 min by a photo-assisted
2014 450 nm g/L and a decreased in the TiO2 band-gap with
[100 ppm] blue lamp reactor 96%/240 min method and
the total elimination of CN− [41]
impregnation.
Not Demonstrated the possibility of using LED as a
Submerged
NaCN specified. source of UV light in a photocatalytic treatment.
2015 UV-LED cylindrical LED 100%/>600 min TiO2 P25
[30 ppm] UV-A UV-B The most efficient was UV-C, due to photolytic
photoreactor
UV-C effect [21]
They found carbon nanotubes beneficial for
KCN 500 W Xe bulb
2015 >420nm Pyrex reaction cell 100%/60 min MWCNT/Au-TiO2 photocatalytic degradation in the presence of
[100 ppm] lamp
oxygen and visible light [67]
 Table 2. Cont.

Degradation/Reaction
Year Substance [C0 ] Source of Light Wavelength Type of Reactor Catalyst Main Findings
Time
CeO2 /KLTO enhanced the photocatalytic
KCN
2015 700 W Xenon lamp n.a. Pyrex reaction cell 100%/5 h CeO2 /KLTO activity compared to a photolytic effect at
[100 ppm]
750W/m2 [68]
Processes 2019, 7, 225

Photocatalytic activity resulted enhanced with

KCN 150 W Blue Horizontal cylinder
2015 >400 nm 100%/30 min S-TiO2 the addition of S, being 0.3 wt %S-TiO2 the most
[100 ppm] fluorescent lamp annular batch reactor
efficient with visible light [69]
The Ag was beneficial for the photocatalytic
KCN 150 W Blue
2016 >400 nm Pyrex cell reactor 100%/60 min Ag-Sm2 O3 activity by 90% more than bare Sm2 O3 . The
[150 ppm] fluorescent lamp
catalyst is useful up to 5 times cycles [70]
The Pt addition to Ti-Al-MCM41 resulted in 10
CN− 150 W Blue Pyrex glass
2016 n.a. 100%/70 min Pt/Ti-Al-MCM-41 times more efficient the suspended TiO2
[100 ppm] fluorescent lamp cylindrical
photocatalytic activity [71]
25 W metal halide 0.5wt%Zn-CuPc enhanced cyanide degradation.
KCN 365 nm and Pyrex glass
2018 lamp, and UV 100%/350 min ZnO-CuPc However, the TiO2 P25 still showed faster
[30 ppm] 400–700 nm cylindrical
Lamp kinetic of degradation [72]
Nanotubes exhibited good photocatalytic
NaCN activity, but it was the dissolved oxygen played
2019 300 W Xe lamp >400 nm Quartz batch reactor 90%/150 min g-C3 N4 − Nanosheets
[0.18 mM CN− ] the most important role in the oxidation of
cyanide in visible light [73]

13
B-ZnO enhanced photocatalytic activity
Pyrex glass
2019 KCN [10 ppm] Xe lamp 400–800 nm 89%/120 min B-ZnO compared to bare ZnO with visible light at low
cylindrical
cyanide concentrations [74]
Processes 2019, 7, 225

Figure 3. Photocatalytic scheme of free cyanide in a TiO2 particle. Adapted from Reference [21].

It is well-known that the application of photocatalytic processes for chemical remediation and
disinfection via hydroxyl radicals and holes oxidation has shown promising results. However, it is
possible to develop other types of photodegradation without direct oxidation. Since photocatalysis is
a redox process, the transformation of metallic ions and inorganic substances using the conduction
band (holes) instead the valence band (electrons) can be developed. This pathway depends on the
conduction and valence band energy level in the catalyst, the redox potential of the inorganic substance
and the pH of the solution. In most cases, the electron transfer to a substrate is favored in the absence
of oxygen in a process called reductive photocatalysis. Reductive photocatalysis has been applied
to substances with oxidation states similar to CO2 , such as CCl4 , which could hardly enhance the
oxidation of carbon via interaction with holes. Another example is the removal of transition metals in
the solution given their multivalences when the oxidation potential is very similar to the valence band
value [32].

4.2. Photoreduction of Metals

Photoreduction of metals was one of the first motivations for developing photocatalytic processes,
and it was intended to be applied for precious metals exploitation. The main differences between
photocatalysis with inorganic substances and photocatalysis with metals are (1) There are greater types
of states excited by the participation of metal orbitals and ligands, (2) Conversion from one state to
another is not always efficient, (3) Some excitations are achieved in the visible spectrum, (4) Heavy
metals form strong spin pairing in the orbitals, generating stable and long-tripled states, and (5) The
modular structure of the complexes does not allow radicals attacks, due to the organic substances.
However, the excitation process by electron transfer can occur by direct transfer of the electron from
the conduction band to substrates adsorbed on the surface of the catalyst; or indirect reduction by the
formation of a radical product of the oxidation of organic molecules of low repulsion with the complex.
Similarly, the presence of metals, such as Tl, Pb or Mn in solution has demonstrated their reductive
ability of metals in solution [75].
Photoreduction processes require the absence of molecular oxygen for avoiding the formation
of superoxide radical by transfer of the electron promoted to the conduction band. Furthermore,
the efficiency of the reducing mechanism can be improved by the action of a sacrificing agent that
is more selective for hydroxyl (• OH), hole (h+ ), and perhydroxyl (HOO• ) oxidant radicals, so that
recombination is avoided and the probability of reducing other species adsorbed on the catalyst
increases [76]. This reductive mechanism can decrease the oxidation state of inorganic ions and metals
in solution, leading to smaller forms or their zero-valence state. This promotes the precipitation on
the semiconductor surface; nevertheless, it is required that the standard potential of the level of the
conduction band of the electron is sufficiently negative for generating the reduction half-reaction of the
metal [77].

14
Processes 2019, 7, 225

Figure 4 shows the different conduction and valence bands of some metal sulfides and oxides with
semiconductor properties. The standard potentials (NHE) of the conduction bands (upper) and valence
bands (lower) of each semiconductor are depicted. For the semiconductors with a conduction band
more negative than the H+ /H2 redox couple potential, the predominant mechanism is the reduction of
adsorbed species; those are known as reductive semiconductors. In the opposite, for semiconductors
with a balance band more positive than the H2 O/O2 redox couple, are considered oxidative catalysts,
generating oxidation reaction to adsorbates as its predominant mechanism.




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As it can be seen in Figure 4, the sulfides of La, Zn and Mn have conduction bands more negative
than the H+ /H2 redox potential, whereas metal oxides, such as Zr, Ni and BiTiO3 have valence bands
more positive for the H2 O/O2 potential. Depending on the reduction potential of the metal or inorganic
ion in solution, the most suitable semiconductor will be selected for a photocatalytic desired reaction.
The most applied semiconductor catalyst in photocatalytic processes is the TiO2 ; however, it appears
in three different crystalline forms: Anatase, rutile, and brookite. From them, anatase and rutile
are the most used crystalline phases in photocatalytic processes and the most commonly used in
photocatalytic applications.
Few studies reported the photocatalytic reduction of metals in cyanide complexed matrices.
Table 3 shows some studies related to metallic cyano-complexes using photocatalytic processes. The
first evidence of solar-assisted TiO2 photocatalysis studies with real mining wastewater by using As,
Fe, Hg, Cu, and Zn complexed for precipitating metals, reported that three days were needed for
free cyanide elimination and 17 days to achieve 99% of Hg and As removal [44]. Other studies were
focused on the degradation of complex in synthetic samples and studied the degradation of Cu, Ni, Fe,
Co, Pb, Cr, Au, and As cyano-complexes.

15
 Table 3. Photocatalytic treatments of metallic cyano-complexes.

Type of Removal/Reaction
Year Matrix Light Source Wavelength Catalyst Main Finding
Photoreactor Time
Real mining wastewater
Cu(CN)3 2– [22 mM]
Zn(CN)4 2– [300 mM]
Processes 2019, 7, 225

Solar 99% metal All metal was removed with the formation
1995 Fe(CN)6 4– [5.2 mM] Solar light Dish PVC TiO2 P25
spectrum removals/17 days of metal-hydroxides and nitrate [44]
Fe [29 mM]
Hg [11 mM]
As [16 mM]
The photocatalytic activity was evaluated
using two different support for TiO2 . The
Fe(CN)6 3− 150W Hg high Pyrex batch 50%/350 min for
2002 >300 nm TiO2 MCA-41, SBA-15 porous SBA-15 resulted in better
[0.64 mM] pressure lamp photoreactor SBA-15/TiO2
degradation of Fe(CN)6 3− but also for the
free cyanide mineralization [48].
TiO2 resulted in a better way to destroy
4W Hg low 100%/1.5 h solar Fe(CN)6 3− , however resulting wastewater
2003 Fe(CN)6 3− [1 mM] mercury lamp and >300 nm Cylindrical batch radiation, 77%/6 h TiO2 sol-gel was rich in cyanate and incomplete
solar light UV Lamp oxidation was observed. Solar light
exhibited better degradation rates [80].
400 and 700 W
halide lamp Batch cylindrical TiO2 in Raschig rings Evaluated four different methods and the
2004 CuCN [90 ppm CN– ] UV 100%/180 min

16
medium pressure reactor support hydrothermal was the best [81].
Hg
Batch annular The ratio Cu:CN influences photocatalytic
NaCN, Cu(CN)3 2– [1 mM 100 W high
2004 228–420 nm reactor bench 100%/150 min TiO2 P25 degradation. A 10:1 ratio was the best for
NaCN], [10 mM Cu(CN)3 2– ] pressure Hg lamp
scale. the process [82]
The recovery of free cyanide is made adding
methanol as • OH acceptor. Thus, oxidation
150 W medium of CN– to CNO– is avoided. The
2005 AuCN2 – [75 mg/L AuCN2 − ] 365 nm Beaker 86%/240 min TiO2 /L
pressure Hg lamp cyano-complex AuCN2 − is the electron
acceptor and Au0 is deposited on the TiO2
particles [83]
 Table 3. Cont.

Type of Removal/Reaction
Year Matrix Light Source Wavelength Catalyst Main Finding
Photoreactor Time
The maximum degradation was about 70%
TiO2 P25, TiO2 /SiO2
[Fe(CN)6 ]3– and [Fe(CN)6 ]4– 150 W Hg of the cyano-complex. It requires additional
2005 >320 nm Beaker 70%/240 min prepared by sol-gel and
[100 ppm CN– equivalent] medium pressure treatment. Iron complexes contaminated the
Processes 2019, 7, 225

hydrothermal method.
semiconductor [84]
KCN, K3 (Fe(CN)6 ),
Different methods of support were
KAu(CN)2 [3.85 mM KCN; 150 W Hg TiO2 /GrSiO2 ,
2005 365 nm Beaker n.d. evaluated, 60% of TiO2 /SBA-15 performed
0.64 mM K3 (Fe(CN)6 ); 0.38 medium pressure TiO2 /SBA-15.
better for iron-complex degradation [85]
mM KAu(CN)2 ]
There is an enhancement in the cyanate
CNO− [0.5 mM] Fe(IV) Spectro line UV-A
2008 365 nm Beaker 80%/120 min TiO2 P25 Degussa degradation related to the presence of
[1 mM] lamp
ferrate [65]
Although the study demonstrates the ability
Real Wastewater from Energy 200–280; of a pilot plant for cyanide degradation, it
2009 UVA UVC Pilot photoreactor 100%/15 min FeSO4 , H2 O2
Plant 320–400 nm only is evaluated the degradation of free
cyanide and not of its complexes [57]
15 W Hg Cylindrical Nickel removal was shown to be achievable
KCN, Co(CN)6 3– , Ni(CN)4 2– Ni:90%/180 min,
2013 low-pressure n.d. borosilicate TiO2 P25 suspension by photocatalysis; however, cobalt removal
[100 μM] Co: 30%/180 min
lamp. reactor is more challenging [86]

17
Synthesized photocatalyst could degrade
free cyanide and dissolved Co, Pb, Cr.
KCN, Co, Pb, Cr [100 ppm Blacklight lamp Annular
2013 365 nm 100%/180 min TiO2 /SiO2 sol-gel. However, the evaluation of metal
CN– , Co, Pb, Cr] and blue light photoreactor
photo-removal was not done in the presence
of cyanide [87]
Using UV-LED at 30W/m2 in a mini CPC
Mini CPC UVLED
2018 Fe(CN)6 3− [100 ppm] 30 W UV-LED 300–400 nm 70%/20 min TiO2 P25 resulted better for recovery of cyanide
photoreactor
instead remediation [88]
Configuration resulted useful for light
UV baffled flat harvesting, but it is required more UV
2018 Fe(CN)6 3− [100 ppm] 5W UV-LED 300–400 nm 60%/90 min TiO2 P25
plate reactor Power since the complex was not complete
degraded [89]
Processes 2019, 7, 225

Generally, the main characteristic of these photocatalytic treatments is the use of UV lamps with a
high irradiation capacity (about 150, 400 or 700 W) and in some cases metals are recovered by reducing
them to their zero valence state [37–41,46–48,50,54,59,62,63,66,81–86,90]. Nevertheless, photocatalytic
processes for stable metallic cyano-complexes destruction are not yet fully effective for the treatment
of mining wastewater, due to the presence of metal re-oxidation-redissolution and photocatalyst
poisoning by deposition.
It is known the role of chemisorbed oxygen in photooxidation reactions. The TiO2 chemistry
depends on the O2 coverage, temperature and the characteristics of the semiconductor crystalline phase.
Those studies are performed using molecules, such as Ar, Kr, N2 , CO, CH4 in order to understand their
interaction with the adsorbed oxygen using a photon stimulated desorption. This technique has been
used to understand and monitor photochemical processes occurring on the surface of photocatalyst [91].
Although these methods require specialized equipment, practical applications require more investment.
A simpler method to understand the global mechanism is related to scavengers’ addition to the bulk of
the photocatalytic system.
In the case of metallic-cyanide matrices, the addition of scavengers increases the selective
photoreduction of the metals (charge transfer efficiency) without oxidizing the free cyanide. Thus,
several acceptors have been used as electron donors for hydroxyl, perhydroxyl, and holes. This
selectivity enhancement was used to precipitate Ag from a solution of sodium cyano-argentate and
sodium aurocyanide [83].
Table 4 shows examples of the main acceptors with which the mechanism studies on photocatalytic
degradations in several matrices have been carried out. Compounds, such as NaF, have been used
to inhibit the adsorption effect on the semiconductor particle and demonstrate the importance of the
degradation reaction in bulk and not on its surface [92]. Moreover, the application of radical scavengers
has been used to determine the main pathway that affects the photocatalytic degradation and to study
the selectivity for certain radicals.

Table 4. Several radical scavenger agents used in a typical photocatalytic degradation.

Scavengers Compound
Glucose [93]; formic acid, sulfuric acid [9,94]; sodium
oxalate [95]; ammonium oxalate [96,97];
Holes (h+ ) 4-methylimidozal [98]; EDTA [97,99,100]; KI
[92,100,101]; NH4 + [102]; oxalic acid and methylene
blue [103]
t-butanol [92,96,99]; isopropyl alcohol [97]; methanol
Hydroxyl radical (• OH) [100,104]; ethanol [101]; acetonitrile [101]; KBr [105];
terephthalic acid [106]
Fe3+ , Cu2+ , Ag+ [106,107]; AgNO3 [96]; Cr6+ [95];
Electrons on the conduction band (e− )
KIO3 [102], (S2 O8 )2− [92]
Superoxide radical (O2 •− ) Benzoquinone [96,97]

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Processes 2019, 7, 225

4.3. Application of Traditional Photoreactors and LEDs in Mining Wastewater

Sunlight and UV lamps (as natural and artificial photon source, respectively) have been used
directly on photocatalytic processes with several reactor geometries, such as compound parabolic
concentrators (CPC), flat plates, spinning-discs, submerged lamps and microchannel among other
systems, in order to harvest light energy [108]. Nevertheless, available sunlight radiation is very
variable and depends on the weather condition, geography, time of the day and year. Reversely, UV
lamps as a source of UV photons for photocatalysis make this process more controllable, and it is a
better alternative for fine photochemistry. The development of semiconductors for being irradiated by
UV LED is a trending research topic and a promising source of photons. LED lamps have been replacing
traditional incandescent halide and fluorescent mercury lamps for a wide variety of applications.
The advantages of LEDs are not only the small geometry, versatility, and robustness but also a more
prolonged time life, a high electrical efficiency (more than 60%) and a capability for generating radiation
at a particular wavelength [109–111]. This type of artificial light has been used for water purification,
sterilization, protective coatings and photo sensors from the near visible, UV to the IR spectrum
range [112,113]. Table 5 shows the application of this type of diodes for photocatalytic processes as an
alternative to the treatment of other organic matrices. There is only a study that reported a successful
application for removal of free cyanide [21]; therefore, it can be an emerging solution for the issue of
availability of UV radiation from the sun by coupling with another renewable source of energy instead
using direct sunlight or traditional incandescent lamps.

19
 Table 5. LED emerging photoreactors.

Year Description Main Findings

It is reported that UV LEDs at 800 mW are 100 times more efficient in comparison with 12 and 16
2013 Phenol photodegradation using batch UV LED at 375 nm.
W fluorescent UV Lamps [114].
Natural organic matter and emerging pollutants were removed from drinking water. It is
Processes 2019, 7, 225

2013 Drinking water potabilization using UV LED at 365 nm concluded that the photoreactor design with this type of light is more critical than the catalyst
load [111].
Used in the dyes photodegradation, organic matter of air and Proved the capability of organic matter using this type of light, which is better in term of the
2014
water. photoreactor size, energy consumption [110].
Oxytetracycline and 17-α-etinil estradiol as agriculture Reached a 100% degradation of total organic carbon with cumulative energy of about 12.5 kJ/L
2014
antibiotic degradation using UV LED light. [115].
Acetonitrile degradation in Green blue and red LED
2014 Degradation of about 100% was achieved in 2 h using low power (3 W) LEDs [116].
photoreactor with C-N TiO2 .
Chromium photoreduction using CdS and TiO2 with white
2014 The removal of chromium was about 93% in 240 min of reaction [117].
LED photoreactor.
It was found that Langmuir-Hinshelwood kinetics do not describe well the photoreactor
Methyl orange degradation modeling applying Controlled
2014 operating at Controlled Periodic Illumination. Novel mathematic modeling is required for
Periodic Illumination in a UV LED photoreactor.
pulsed photoreactors [118].

20
Selective photocatalytic reduction of nitrobenzene carried out The transformation of nitrobenzene to aniline was achieved using ethanol as the electron donor
2014
by UV LED light. with 100% of conversion [119].
The photoreactor uses a visible LED to enhance photoreduction of amines using methanol and
Evaluation of nitro-aromatic compounds using CdS as the
2014 isopropanol as electron donors (hole scavenger). The conversion was about 90% with a
catalyst.
selectivity of about 71% [120].
A CFD simulation experimental and validation of a UV LED The CFD established the best amount of irradiation, flowrate and photoreactor dimension in
2014
photoreactor for Escherichia coli disinfection. which best photo absorption is achieved for E. coli disinfection [121].
The Controlled Periodic Illumination demonstrated being more critical in the photonic efficiency
Methyl orange degradation under Controlled Periodic
2014 when the ON-OFF period is closer to the characteristic time of the reaction. Also proposes
Illumination with a UV LED.
photo-reductive degradation instead of a photooxidation mechanism [122].
Methyl ketone degradation using UV-vis LED with supported
2014 The removal was 100% of methyl ketone in 600 min of reaction using 56 LEDs [123].
TiO2 in alveolar foam.
 Table 5. Cont.

Year Description Main Findings

Photoreactor using graphene oxide ZnO for methylene blue Degradation of 100% of Methylene blue is achieved in 150 min using UV-A LEDs. Graphene
2014
degradation. oxide resulted in photocatalytic degradation enhancement than Degussa P25 [124].
Processes 2019, 7, 225

Evaluation of FeFNS-TiO2 activated by LED in pesticides

2014 Degradation of 90% achieved in 100 min of reaction [125]
mineralization.
Bacteria deactivation achieved in 120 min using TiO2 in an annular LED UV-A photoreactor
2015 E. coli disinfection modeling in a LED photoreactor
[126].
Direct Red 23 degradation in a continuous UV LED Complete oxidation of Direct Red 23 is done in homogeneous photocatalysis and 72 UV-LED
2015
photoreactor assisted with S2 O8 2− units [127].
Uses a photoreactor with UV-A LED for phenol and plywood Demonstrated a photocatalytic degradation of phenol about >90% in 13 min and total removal
2015
mill wastewater treatment. of tannic acid in plywood mill wastewater in 43 min [128].
Free cyanide degradation by the oxidative pathway in Demonstrated the free cyanide degradation in more than 10 h, using LEDs at UVA, UVB, and
2015
synthetic wastewater. UVC. The last one was the most effective in photooxidation [21].
Evaluated two systems in a coupled mini CPC and a traditional beaker with external UV-A LED
2017 Methylene blue degradation in a mini-CPC photoreactor. illumination. Demonstrated the capability of the mini CPC in harvesting LED Light in the
degradation [129].

21
CFD simulation to enhance LED light utilization and Demonstrated the utilization of a baffled plat plate photoreactor is useful for UV-LED light
2018
evaluation in iron cyano-metalic complexes. harvesting [89].
Iron cyanocomplexes degraded in anoxic conditions using a Achieved the photoreduction of iron and free cyanide liberation as a strategy of recovery
2018
mini-CPC UV LED photoreactor instead remediation for this iron cyanocomplex [88].
Processes 2019, 7, 225

5. Conclusions
In this review, the state-of-the-art in the application of photocatalytic processes for the
decontamination of synthetic and real cyanide wastewaters was presented. Photocatalytic processes
can be effective for removing free cyanide content via oxidative pathways. Complexed cyano-metallic
compounds are less studied in photoreactors, and usually, it requires the modification of selectivity by
applying electron donors as scavengers of unwanted radicals in order to enhance charge transfer to the
cyano-complex. The metal removal from inorganic cyanide matrices using photocatalytic processes
has been explored, and the direct metal reduction on the conduction band appears to be the main
mechanism as an electron acceptor at the conduction band. The use of unconventional UV LED lamps
represents a growing area for development of photoreactors. Likewise, little evidence has been found
of the treatment of metallic cyano-complexes from mining activities by using this type of UV source,
and the existing applications are not aimed at improving the use of photons in the illuminated area.
Although the evidence shows UV-vis LED application for other types of organic compounds, the
knowledge about its use for the elimination or treatment of inorganic substances is still scarce. As far
as it is known, none of the studies has compared the performance of the processes between different
types of radiation sources at different wavelengths for cyanide wastewater treatment using UV LED.

Author Contributions: L.A.B.-B. compiled the literature references for photocatalytic treatments of gold mining
cyanide wastewater. F.M.-M., A.H.-R., J.A.C.-M., C.F.B.-L. and L.R. restructured the information and contributed
to the design, analysis and edition of the manuscript. All authors discussed the results and commented on
the manuscript.
Funding: This research was funded by Colciencias (GRANT No. 1106-669-45250).
Acknowledgments: The authors are grateful to Universidad del Valle and Colciencias for the financial support to
produce this work (GRANT 1106-669-45250. Recuperación de oro y tratamiento de aguas residuales cianuradas en
la industria aurífera de la región pacífico Colombiana).
Conflicts of Interest: The authors declare no conflict of interest.

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 processes
Review
Characteristics and Treatment of Wastewater from
the Mercaptan Oxidation Process:
A Comprehensive Review
Ernesto Pino-Cortés 1, *, Silvio Montalvo 2 , César Huiliñir 2 , Francisco Cubillos 2
and Juan Gacitúa 2
1 Escuela de Ingeniería Química, Pontificia Universidad Católica de Valparaíso, Av. Brasil 2162, Valparaíso
2362854, Chile
2 Departamento de Ingeniería Química, Universidad de Santiago de Chile, Av. Libertador Bernardo O’Higgins
3363, Estación Central 9170022, Chile; [email protected] (S.M.); [email protected] (C.H.);
[email protected] (F.C.); [email protected] (J.G.)
* Correspondence: [email protected]; Tel.: +56-322372609

Received: 12 March 2020; Accepted: 31 March 2020; Published: 3 April 2020

Abstract: Sulfur compounds are removed from petroleum by the addition of sodium hydroxide at
a very high concentration. As a result, a residue called spent soda or spent caustic is generated,
being extremely aggressive to the environment. In this work, the chemical properties of this residue
are described in detail. The sodium hydroxide remains that have not reacted, sulfur compounds,
and organic matter are the primary pollutants reported. Additionally, the main characteristics of the
methods of treatment used to reduce them are described. This review comes from comprehensive
and updated research and bibliographic analysis about the investigation on the topic. The advantages
and disadvantages of the different treatment methods are highlighted. We established some criteria
to set out when assessing the application of each one of these treatments is considered.

Keywords: biological processes; electrochemical processes; oxidation processes; petroleum; phenols;

sulfides

1. Introduction
Petroleum is around 85% carbon and 12% hydrogen, while in the remaining 3%, we find several
elements that consist mainly of oxygen, nitrogen, and sulfur. The sulfur compounds limit the direct
use of petroleum in any of its forms, such as liquefied petroleum gas (LPG), due to its odorous,
corrosive, and environmentally harmful characteristics. Different techniques or methods are necessary
for the reduction of these compounds in petroleum. Among these sulfur compounds are mercaptans
and sulfides. Mercaptans are thiols containing the functional group formed by a sulfur atom and a
hydrogen atom (-SH). This functional group is called the thiol or sulfhydryl group. Examples of these
compounds present in LPG are methylmercaptan (H3 C-SH) and ethylmercaptan (H5 C2 -SH).
The technology used globally for mercaptan removal content in the oil industry is the mercaptan
oxidation (MEROX) process [1,2]. It is a catalytic conversion process in which mercaptans react to
produce disulfides. It is promoted by a catalyst which activates the oxidation at room temperature,
using atmospheric oxygen according to the following reactions:
Mercaptan + NaOH to form sodium mercaptan:

RSH + NaOH → RSNa + H2 O (1)

Processes 2020, 8, 425; doi:10.3390/pr8040425 29 www.mdpi.com/journal/processes

Processes 2020, 8, 425

Mercaptan oxidation to form disulfides + NaOH:

1 1
RSNa + O2 + H2 O → RSSR + NaOH (2)
4 2
As sodium hydroxide depletes as it reacts, its ability to remove sulfides and mercaptans also
decreases. When the disulfides accumulate to a few milligrams per liter, the OH− content falls below 5%,
whereby this depleted soda solution is purged. Other causes of sodas depletion are the accumulation
of mercaptans, Na2 S, phenolic compounds, emulsified naphthalenes, thiosulfates, carbonates, and Fe+2
precipitates [2]. The H2 S and CO2 that are also present in the medium to be oxidized react with the
caustic soda according to the following competitive reactions [3]:

H2 S + 2NaOH → Na2 S + 2H2 O (3)

CO2 + 2NaOH → Na2 CO3 + H2 O (4)

These side effects can cause several problems, such as the irreversible consumption of caustic
soda, low absorbing mercaptans by the presence of sodium salts, and the precipitation of solid due
to the accumulation of salt in the caustic solution. That is why a caustic solution purge and a fresh
soda replenishment are provided to prevent salt accumulation (Na2 S/Na2 CO3 ) from restoring the
appropriate NaOH concentration. Spent caustic (SC) is the name of the solution obtained once the
mercaptans react with NaOH. Without adequate treatment, SC can cause environmental problems.
The main focus of this comprehensive review is to expose different techniques released and
mentioned in the literature, to process the SC. The first approach is a brief description of its characteristics
that explain the environmental problems caused by SC. Following, the main body of this paper has a
series of processes that help neutralize sodas and allow their subsequent biological treatment. There is
no review published before or paper that reports this relevant information that could help engineers to
make better decisions in the petroleum industry. The analysis included information and results from
reports, theses, and research articles published recently.

2. SC Characteristics
SC is classified into three types [4]: sulfidic (SSC), cresylic (SCC), and naphthenic (SNC).
The composition of this type of waste is highly variable as can be seen in Table 1. SC solutions
are characterized by high pH (pH > 12) [5] and high sodium concentrations up to 2%–15% (w/w).
Conner et al. [6] also found that spent sulfidic caustics contained hydrosulfides (HS− ) and sulfides2−
greater than 2%–3% (w/w).

Table 1. Main chemical components present in spent sodas.

Parameters SMC Sulfidic Cresylic Naphtenic Reference

- 11–12.5 - - [7]
- 12–13.5 - - [8]
- 13.1–13.5 - - [9]
7.5–13 - - - [10]
pH - 11.2 -13 - - [5]
- 12–14 12–14 12–14 [11]
- 13.1–13.5 - - [12]
- 13–14 12–14 12–14 [13]
- 13–14 12–14 12–14 [14]
- 11.6–12.5 - - [15]

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Processes 2020, 8, 425

Table 1. Cont.

Parameters SMC Sulfidic Cresylic Naphtenic Reference

- 7.5–60 - - [7]
60.3–68.1 - - [16]
100–200 - - [8]
20–60 - - [17]
13.1–98.8 - - - [10]
COD - 62.7 - - [18]
(g O2 /L) 49.3 1 - - - [18]
74 - - - [18]
261 - - - [19]
- 5–90 50–100 150–240 [20]
- 66.7–156.5 - - [15]
114 - - - [21]
- 6–20 - - [17]
1.6–23.6 - - - [10]
TOC 92 - - - [19]
(g C/L) - 7.6 - - [18]
- 1–1.6 - - [12]
- 2–3 24–60 10–24 [20]
- 5000–10,000 - - [17]
BOD5
- 18,100 - - [18]
(mg O2 /L)
20,100 1 - - - [18]
- 5000–20,000 - - [7]
- 80–90 - - [8]
34,500 - - [17]
6500–22,500 - - - [10]
- 5100–7700 - - [7]
Sulfides - 17,800 - - [18]
(mg/L) 8040 - - - [18]
- 15,200–17,600 - - [12]
- 2000–52,000 0–63 <1 [20]
- 0–1 0.1 [14]
30,600–66,800 - - [15]
24,000 - - - [21]
- 1–4 - - [17]
- 0.5–4 0–1 0–0.1 [11]
1.4 - - - [19]
- 0.5–4 0–4 0–0.1 [4]
Sulfides
- 0.5–4 - - [14]
(% w/w)
- 0–5 - - [7]
- 2–300 - - [8]
- 0–2000 - - [17]
1.6–20 - - - [10]
1990 1 - - - [18]
6110 - - - [18]
Phenols
- 1.8–33.8 - - [12]
(mg/L)
540 - - - [21]
- 0–30,000 - - [8]
- 0.1–4 a - - [17]
Mercaptans
- 9800 - - [18]
(mg/L)
1800 - - - [18]
(% w/w) a
- 0–30,000 0–5400 <30 [20]

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Processes 2020, 8, 425

Table 1. Cont.

Parameters SMC Sulfidic Cresylic Naphtenic Reference

- 47–780 - - [7]
Benzene (mg/L) - 7.8–63.1 - - [12]
- 600 - - [15]
Toluene - 0.2–7.8 - - [12]
(mg/L) - 360 - - [15]
- - 10–25 0–3 [11]
Cresylic acids
- 0–4 2–25 0–3 [4]
(% w/w)
- - 2–25 0–3 [14]
Napthenic - - - 2–15 [11]
acids 19,700 1,b - - - [18]
(% w/w) - - - 2–15 [4]
(mg/L) b - - - 2–15 [14]
- 4–5 - - [8]
- 7.5 - - [17]
2–2.9 - - - [10]
NaOH
- 11.1 - - [3]
(% w/w)
- 2–10 10–15 1–4 [11]
- 2–10 1–15 1–4 [4]
- 2–10 1–15 1–4 [14]
2–2.9 - - - [10]
Carbonates - 0–4 0–0.5 - [11]
(% w/w) - - 0–0.5 - [4]
- 0–4 0–0.5 - [14]
1 napthenic + cresylic; a % w/w; b mg/L.

Often plants do not have the facilities to segregate the soda solutions used in these three types of
classifications. Therefore, a spent mixed caustic (SMC) is usually produced. The latter is considered
the fourth type of depleted or spent soda.
Processes of fuel gas, liquefied petroleum gas, and gasoline treatment generate sulfidic soda [13].
This depleted soda has a high concentration of sulfide and also a terrible smell. This type of waste can
not only be treated but could also be a reactant for the cellulose pulping process. Nevertheless, the cost
of transport generally discards this possibility [13].
The washing of the diesel and the fractions of jet fuels generate the exhausted naphthenic soda.
It contains very few sulfides, being mainly naphthenic acids. Naphthenes generally do not impart
unpleasant odors or toxicity to the caustic sodas, being partially soluble in sodas by increasing the
total organic carbon considerably in SC. Naphtenes is a general term used for cyclic alkanes or
non-aromatic hydrocarbons called cycloalkanes. Refinery naphthenes typically include cyclopentanes
and cyclohexanes as compounds of this group. This type of waste can also be sold if it is kept
insufficiently in pure form. However, processing at the same plant is most often the best option.
The exhausted cresylated soda (often called phenolic) is generated from the washing of gasoline
fractions and is composed mainly of aromatic, acid oils, cresols, and other organic acids. Cresylates
are a form of phenols containing a methyl group (CH3 ), often called phenolics as a family or group
of compounds. In their three forms, ortho, meta, and para cresol, they are not as toxic as phenols.
However, the cresylates have relatively high concentrations, between 1% and 35%. Cresylates or
cresylic acids, often referred to as acid oils, are solubilized at high pH, but readily separated at low pH.
It is not a question of eliminating these compounds from petroleum since they increase the amount
of octane in the final fuel; however, these are present in different concentrations in the depleted
sodas. The number of phenols in spent soda is the factor to consider it as a reagent for the production
of phenolic compounds. Otherwise, the low amount of oily acids drastically increases the costs of
transportation and its treatment in the plant is the best option.

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Due to the high content of organic matter, in addition to sulfur compounds, phenols, and
mercaptans, the depleted sodas are a liquid residue tough to treat [2,17], with a series of related
problems with their treatment of depleted among those highlights [2]:
• Strong odors of sulfides and mercaptans: the odor traces of these compounds are in the order of
parts per billion. As is known, these compounds are highly toxic even at minimal concentrations.
• High phenol concentrations: phenol is a highly inhibiting compound of biological activity.
Deficient concentrations of phenol have been shown to inhibit the biological removal of
organic matter.
• High concentrations of bio-refractory material: the presence of cresylic and naphthenic acids,
which are difficult to biodegrade, is another problem associated with SC. Naphthenic acids
facilitate foaming formation.
Shailja Singh and Shikha [22] mentioned the primary pollutants found in the effluent from various
processes in refineries. The liquid effluents generated in the oil refineries differ from one industrial
plant to another due to the variation in the configuration of the plant and in particular, to the type of
petroleum processed. For example, ammonia and hydrogen sulfide are the main substances present
in the wastewater from the isomerization process; meanwhile, the alkylation produces hydrofluoric
acid. Other processes in this industry such as fluid catalytic cracking, crude desalting, catalytic
hydrocracking, coking, distillation, catalytic hydrotreating, lubricating oil manufacture, sulfur removal,
catalytic reforming, and thermal cracking are summarized in the same publication.
In general, liquid petrochemical residues contain significant concentrations of suspended solids
(SS), chemical oxygen demand (COD), biochemical oxygen demand (BOD), oils and fats, sulfides,
ammonium, phenols, hydrocarbons, benzene, toluene, ethylbenzene, xylene, polycyclic aromatic
hydrocarbons, and heavy metals [23–26].
In order to avoid or reduce the environmental problems caused by SC, a series of processes have
been proposed that help neutralize sodas and allow their subsequent biological treatment.

3. Treatment Methods of SC

3.1. Initial Considerations

In general terms, the treatment of spent sodas is carried out in two types of processes in series;
the first one considers the removal of sulfides, phenols, and other compounds that can inhibit the
biological processes. These are later applied in order to remove the organic matter present in this
residue. The spent sodas cannot be directly biotreated for different reasons:
• The presence of phenols inhibits, at a specific concentration, the healthy metabolism of the
microorganisms that operate in the biological process.
• Spent sodas contain some low biodegradable compounds, such as naphthenic acids.
• The presence of naphthenic acids may result in operational issues in aerobic processes through
foam formation.
• The high COD concentration in SC makes impossible their direct treatment.
• They have a high pH, which is not adequate for the development of microorganisms.

3.2. Wet Air Oxidation (WAO)

In practice, this is the most widely used chemical treatment applied to spent sodas. This process
has been executed on several occasions as a pilot [27] at a plant [21,28–32] and laboratory level [33,34],
in addition to the diverse industrial plants [35] that have implemented the WAO system. It is basically
the oxidation of the soluble and suspended compounds that are present in this residue using oxygen
or air as an oxidant [21]. The oxidation is carried out at very high temperatures and pressures,
which depend on the strength of the material to be oxidized in the process and the quality required
from the final effluent.

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In the WAO process, several chemical reactions take place, such as:

Organics + O2 → CO2 + H2 O + RCOOH (5)

Sulphur species + O2 → SO2−

4 (6)
−
Organochlorides + O2 → Cl + CO2 + RCOOH (7)

Organic nitrogen + O2 → NH3 + CO2 + RCOOH (8)

Phosphorus + O2 → PO3−
4 (9)

Three ranges divide the operational conditions: low, medium, and high-temperature systems [36].
Oxidation takes place at temperatures of 200 ◦ C and 27.5 bars in low-temperature systems. This system
partially oxidizes sulfides into sulfates and thiosulfates [37]. In medium temperature systems, oxidation
takes place in the range of 200 ◦ C and 27.5 bars to 260 ◦ C and 86 bars. The ideal supply for this system
is naphthenic caustics sodas. Sulfides react to sulfates, and the mercaptans are also destroyed [38].
The high-temperature systems oxidize the cresylic caustics at a range from 240 ◦ C and 55 bars to 260
◦ C and 85 bars. Complete oxidation of sulfides, mercaptans, and other organic compounds can be

carried out, such as cresylic acids [39]. The typical industrial WAO systems can work with spent sodas
flows between 1 and 50 m3 /h and with a COD between 10,000 and 100,000 mg/L. However, for COD
levels above 50,000 mg/L, dilutions with water or fresh caustic solution are required. Diluted caustic
solutions help to reach different goals, among them, avoiding diluted salts concentrations below the
solubility levels in order to prevent incrustations. The other reason is to guarantee that alkalinity is not
consumed by oxidation when acid effluents could damage the construction materials of the system.
Finally, the addition of the caustic solution can help the oxidation of contaminants according to the
reactions that are described below [36].
Sulfide.
NaSH + 2 O2 + NaOH → Na2 SO4 + H2 O (10)
1 1
NaSH + O2 → Na2 S2 O3 + H2 O (11)
2 2
Thiosulfate.
Na2 S2 O3 + 2 O2 + NaOH → 2 Na2 SO4 + H2 O (12)

Mercaptan.
3
NaSR + O2 → RSO3 − Na (13)
2
Cresylic acid.

C6 H5 O − Na + 7 O2 + 11 NaOH → 6 Na2 CO3 + 8 H2 O (14)

C6 H5 O − Na + 5 O2 + 8 NaOH → 4 Na2 CO3 + CH3 COO − Na + 8 H2 O (15)

Naphthenic acid.

67 45
Na − C12 H22 O2 + O2 + 23 NaOH → 2 Na2 CO3 + H2 O (16)
7 2
59 39
Na − C12 H22 O2 + O2 + 20 NaOH → 10 Na2 CO3 + CH3 COO − Na + H2 O (17)
4 2
The WAO process can treat liquid currents containing cyanide, several heterocyclic compounds,
industrial sludge, and spent coal from adsorption processes [40]. Several industrial residues apply
this process, such as paper manufacture, textile sludge, among others. Figure 1 shows an outline of a
typical WAO process.

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Processes 2020, 8, 425

Figure 1. Typical outline of a wet air oxidation (WAO) system.

As can be seen in Figure 1, fresh soda or freshwater dilute the spent soda. The dilution ratio
depends on the strength of the spent soda. Then, the diluted spent soda is pumped at 27.5–85 bars
through a high-pressure pump. The addition of compressed air to the diluted spent soda is required in
order to supply the needed oxygen for the oxidation reaction. A heat exchanger preheated the mixture
at 200–260 ◦ C. The reactor must operate for a sufficient residence time that allows high oxidation of
the organic matter contained in the spent sodas (COD disposal). Since the reaction is exothermic,
the reactor’s effluent has a high temperature, so it can be used to preheat the diluted spent sodas
before entering the reactor [21]. Subsequently, the effluent coming out of the heat exchanger is cooled
and depressurized before being sent to a gas–liquid separator. Then, the separated liquid goes to
biological treatment. The effluent gas has 5%–21% of oxygen and some volatile organic compounds.
In Table 2, the values of a sample of the operational conditions of a WAO system from the Oil Refinery
of Manguinhos, S. A. in Rio de Janeiro, Brazil, are presented.

Table 2. Operational conditions of the WAO system in Manguinhos, Brazil [21].

Parameters Supply Effluent

Residence time (h) - 1
Oxidation temperature (K) - 533
COD (g/L) 114 ≈23
Sulfides (g/L) ≈24 <0.001
Total phenols (g/L) ≈0.45 <0.002

As can be observed, despite obtaining a removal percentage of 80% of COD, measured from
organic matter, it is still very high. This concentration is required to be reduced until reaching the
possible values to discharge it into a receiving current or another place for its final disposal. It could be
carried out through a biological process that can be done in this case, provided the low levels of sulfides
and phenols in the WAO effluent since the two chemical species were reduced in the process by almost
100%. Additionally, most of the remaining COD in the treated effluent comes from aliphatic acids
of low molecular weight, which can be biologically oxidized [37]. The oxidation pressure is directly
related to the oxidation temperature. The oxidation pressure is responsible for keeping the reaction in
the liquid phase. In this way, as the pressure increases, the oxidation pressure rises to keep the reaction
in the liquid phase. The WAO processes typically operate with hydraulic residence times of 45–120
min, the oxidation degree that takes place within the reactor affecting this parameter. Each WAO
system uses different hydraulic residence times to reach the degree of COD reduction required. The
selection of the construction material is critical in the WAO system, considering that the operation
takes place at a high temperature and pressure. Thus, the materials used must be appropriate for these
conditions. The WAO system presents some disadvantages and difficulties, among which the initial
investment cost stands out. This cost depends mainly on the operating conditions, which, at the same

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time, are related to the strength of the residue to be treated. As this strength increases, more severe
operating conditions are required, which increases the cost of the plant.
Tests and research are still carried out in order to improve this system, as well as combining this
process with others. A way of reducing the severe operating conditions is the use of solid catalysts in
the WAO to accelerate the reactions, and there are reports of cases where catalysts have been used
in this process [8,41]. This innovative technique is referred to as catalytic wet air oxidation (CWAO).
In recent years it has been studied in order to increase the efficiency to treat pollutants in industrial
effluents [42]. The studies have been developed to remove individual toxic substances and to expose
the best selection of metal catalyst-based support at lab scale. In general, the catalytic activity of
transition metal such as Vanadium, Ferrum, Nickel, Copper and others have been chosen as the most
common option.
Otherwise, researchers are still looking for better conditions of the process to treat most pollutants
in spent caustic using this technology.
Nunez et al. [43] added silver to Al2 O3 -ZrO2 mixed oxide to reduce p-cresol at 160 ◦ C and 15 bar
of O2 pressure, showing faster oxidation associated with more selectivity of this metal compared to the
test without it. Additionally, it reported that the highest concentration (20%) of ZrO2 in the catalyst
removed 50% and 96% for TOC and p-cresol, respectively.
Jagushte and Mahajani [34] studied the effect of the heterogeneous copper catalyst in the kinetics
of Equation (12) mentioned above at the lab-scale. As a result, the catalyst reduced the temperature
and time process to 30 ◦ C from 150 ◦ C and 4 min from 12 min, respectively, in a conversion of 99% of
the pollutant in alkaline conditions. It is remarkable to say that the batch experiments were carried
out at low temperatures and 0.69 MPa of oxygen partial pressure, showing first and 0.5 kinetic order
concerning thiosulfate and oxygen, respectively. Additionally, this study explained a strategy to
treat spent caustic under its results associated with the enhanced effect of phenols in the oxidation
of thiosulfate.
A similar study was reported by Zermeño-Montante et al. [44]. In this case, copper catalyst
in a silica support material achieved the complete sulfide oxidation at 70 ◦ C in 20 min. It showed
better results than a similar experiment with Vanadium/Clinoptilolite just for 6 min latter. Both cases
enhanced the WAO process for this pollutant. This report explained some of its results from Jagushte
and Mahajani [34],
Recently, Barge and Vaidya [45] experimented with ferrous sulfate to eliminate sodium sulfide.
That study innovated using a cheap and abundant catalyst, destroying 94% of COD at 100 ◦ C and
0.69 MPa of oxygen partial pressure within 1 h. It is remarkable to say those authors exposed the
Langmuir–Hinshelwood as the kinetic model to oxidize the reactant. These same authors, Barge and
Vaidya [46] used Graphene oxide (GO) and Ruthenium (Ru) as a catalyst in WAO for the treatment of the
cresylic spent caustic, obtaining the best results at 175 ◦ C and 0.60 MPa of O2 pressure, with removals
of 54.9%, 48.9%, and 61.2% as TOC, for 0-cresol, m-cresol, and p-cresol, respectively, in the typical
WAO. Meanwhile, when the Ru/GO catalyst was used for the same operating conditions, the removals
obtained were 66.4%, 53.4%, and 73.9%, as TOC, for 0-cresol, m-cresol, and p-cresol, respectively.

3.3. Acid Neutralization

In this type of process, alkaline caustic solution traps the acid components released from
acidified spent sodas [36]. This action results in sulfides and mercaptans being released as acid gases,
and naphthenic acids come to form some oil layer. One of the most significant differences between acid
neutralization and the WAO process is that the acid components of spent sodas are removed but not
destroyed, for example, phenols. In some cases, this entails the requirement of additional treatments
for the acidification effluents, for example, gas ignition or methods for sulfur recovery. In other cases,
this allows for any component present in spent sodas to be captured and reused.
As phenols are highly soluble in water, they are complicated to acidify. However, acidification
eliminates the trend of the formation of foam, similar to the one obtained in the WAO process at high

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temperatures. The cause of this is mainly the fact that the naphthenic compounds that tend to form
foam move to an insoluble phase and, even though they are not eliminated, they reduce their trend
to form foam. Additionally, some alkaline compounds that could form foam are acidified, reducing
this trend.
In some cases, acidification as a pretreatment for oxidation processes has been studied. Sheu and
Weng [47] treated the spent sodas from olefin plants containing a considerable amount of H2 S and
some mercaptans, phenols, and crude oils undergo a process of acid neutralization before a process
with Fenton reagent. Using sulfuric acid with a pH of up to 5, and 70 ◦ C, a little more than 90% of the
dissolved H2 S changes to the gas phase. From this pH, the conversion to dissolved sulfide (S2− ) is
minimal [48]. These authors were the first to report this pretreatment process.
Nuñez et al. [49] showed a reduction of 71% and 82% of COD in two batch experiments using
this procedure, under conditions of pH below 4. In this context, only the sulfide content was reduced
by pH reduction, the phenol concentration not being affected. The removal percentages were lower,
considering the analysis made by Sheu and Weng [47] and it was attributed to the use of synthetic and
real samples used. The last type has other substances that could inhibit the pH reduction to oxidize
the reactants.
In summary, acid neutralization or acidification reduces most of the COD and the trend to form
foam removing the naphthenic acids. Sulfuric acid is the chemical agent used in most cases in these
processes, due to its strength and lower price in comparison with other acids [50].

3.4. Advanced Oxidation Process (AOP)

These processes are defined as the processes that involve the formation of radical hydroxyls
(OH) that oxidize both organic and inorganic contaminants present in water and wastewater [51].
These radicals are the second most potent oxidants after fluorides [52]. Unlike the physical process
such as adsorption, filtration, and air stripping, the AOPs can destroy the contaminants rather than
transferring them from one medium into another [53]. The AOPs can be used to treat wastewater with
high COD and low biodegradability [54]. With these processes, complete oxidation of residues can be
reached, converting contaminants into water, CO2 , and innocuous inorganic products. However, it is
expensive and impractical to use these processes for the complete mineralization of compounds since
there are intermediate products that are resistant to chemical oxidation. A practical solution is to
use these processes as a pretreatment for biological treatments. The partial mineralization produced
by the AOPs generates intermediates with higher biodegradability and lower toxicity, which makes
them available for biological oxidation. It is very important to determine the quality of the residue
before selecting any AOP process, since this factor will affect the efficiency of the process, for example,
residues with high alkalinity have an excess of carbonate and bicarbonate compounds, which may
interfere with the oxidation reactions of hydroxyl radicals. These radicals react with those compounds
forming weaker radicals resulting in lower efficiencies of the minor oxidation processes [55]. This issue
can be solved by reducing the alkalinity to make sure there is no excess of these compounds in the
residues, which can be achieved in a relatively simple way by lowering the pH. Nitrates and nitrites can
also affect the efficiency of the AOP processes, which use UV light to generate hydroxyl radicals. These
compounds can absorb UV light and, thus, reduce the generation rate of free OH radicals. The turbidity
has the same effect over the efficiency of the AOP processes as nitrates and nitrites. Turbidity reduces
the production of hydroxyl radicals, since it acts as a barrier against UV light, which cannot penetrate
through the residue to be treated.
The AOP reaction systems consist of a catalyst and an oxidant. The catalyst task is to form hydroxyl
radicals from oxidants. There are several means to form these radicals, which can be photochemical,
photo-catalyzed, ultrasonic, and chemical oxidations.
The photochemical processes include UV radiation. Some studies mention the use of this
technology individually. Gurol and Vatistas [56] irradiated by UV a mixture of various phenolic
compounds, using 16 low-pressure mercury lamps, each of which emitted 2.2 Watts of radiation at

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254 nm. The results showed a faster initial rate remotion of phenol at pH 2.5 than p-cresol and xylenol
at the same condition. The duration of the experiments was 100 min, starting in 50 mg/L of the three
substances and achieving remotions in the range of 20%–30%. Neutral and basic (pH 9) conditions did
not exhibit significant changes in the initial rate remotion, observing the same removal efficiency for
those compounds at the same time. The authors concluded that the understanding of the reaction
mechanism at low-pH irradiation requires further research.
Spent caustic from the ethene plant were irradiated with UV by Yu et al. [57]. The results showed
low-efficiency COD removal (under 10%) in 180 min using an ultraviolet light source of 254 nm
wavelength. The high content of several persistent pollutants in spent caustic is not affected when this
technology is used by itself. That is why the UV radiation has not attracted industrial applications and
also lab-scale studies, and this is the evidence of a few reports about it.
Other photochemical technologies like ozone systems (UV/O3 ) and (UV/O2 ) systems have been
reported. Photo-catalysis includes photo-Fenton, while chemical oxidation includes O3 /H2 O2 and
H2 O2 /Fe3+ .

3.4.1. Ozone and UV Radiation (O3 /UV)

Ozone in water is an unstable compound, dissociating in alkaline water and forming free radicals
according to the following mechanism [58]:

O3 + OH− → O−
3 + OH
−
(18)

O−
3 → O2 + O
−
(19)
− +
O + H → OH (20)

The pH increase promotes the formation of hydroxyl radicals. The main disadvantage of using
only ozone is that the number of radicals produced is low, so in order to increase the efficiency of
the ozone, it is combined with other physical methods, such as UV rays, ultrasound or chemicals,
like hydrogen peroxide and Fenton reagent.
The photolysis of O3 starts the advanced oxidation processes with O3 and UV according to the
following reaction:
hν
O3 + H2 O → H2 O2 + O2 (21)

The hydrogen peroxide formed reacts then with the ozone to produce the free radical according to:

O3 + H2 O2 → 2 OH· + 3 O2 . (22)

Ozone photolysis occurs when UV radiation (wavelength of 254 nm) is applied to ozone-saturated
water [59]. According to Equations (21) and (22), in order to produce 1 mol of hydroxyl radical,
the consumption of 1 mol of ozone and half a mol of hydrogen peroxide is required. In this system,
contaminant degradation can occur due to the chemical oxidation of hydroxyl radical, the direct
oxidation of ozone, as well as the photolysis caused by the UV.
Two essential parameters considered those systems: the UV dose and the ozone concentration.
The UV dose required per ozone is responsible for the formation of radicals and it depends on the
strength of the water to be treated. Other important parameters to be considered in order to guarantee
efficient operations of these systems are the pH and the cleaning system of the radiation lamp [60].
The pH can influence the hydrogen peroxide generation. For a pH of less than 1.8, the photolysis
requires 1 mol of ozone to react with 1 mol of hydrogen peroxide. However, as the pH increases,
this ratio decreases. Cleaning the lamps is very important in order to avoid their siltation. The cleaning
frequency depends on the concentration of the compounds that can produce siltation, such as iron,
calcium, and magnesium.

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Gurol and Vatistas [56] also studied this technology. At lower pH 2.5, selective removal of phenols,
p-cresol, and xylenol were shown compared to neutral and alkaline conditions using ozone doses of
3.8 mg/L. Otherwise, a direct relation between pH and pollutant removal was reported. These three
substances were completely reduced at 100 min and pH 9. Therefore, this research exposed an additive
effect of the O3/UV system compared to its use individually.
Results for spent caustic from the ethene plant also were reported by Yu et al. [57]. They showed
COD removal and BOD/COD ratio improvement with the increase of ozone dosage in this technology.
An optimum of 3.3 g of COD removal per gram of O3 at a low dosage (0.6 g O3 /L) was found.
The advantages of these systems are the high removal that ozone and UV radiations produce since
more free radicals are produced than with other AOP systems. The main disadvantage of this system
is that ozone has to be disseminated through the liquid, which may be limited by the mass transfer in
the medium. The low stability of ozone in water can result in a higher energy demand, which increases
the capital and operational costs of the system. The last statement is part of the conclusions in the
paper mentioned before.

3.4.2. Hydrogen Peroxide and UV Radiation (H2 O2 /UV)

In this system, hydroxyl radicals are formed through two mechanisms: hydrogen peroxide
photolysis and hydrogen peroxide decomposition [61]. The formation of hydroxyl radicals from
hydrogen peroxide photolysis is shown in the following reaction:

hν
H2 O2 → 2 HO· (23)

The wavelength for this reaction is 250 nm. This reaction depends on the pH and, as it increases,
the number of hydroxyls also raises, and so does the number of hydroxyl radicals. The propagation
reactions of hydrogen peroxide are the following:

H2 O2 + HO· → HO2 · + H2 O (24)

H2 O2 + HO2 · → HO· + O2 + H2 O (25)

2 HO2 · → H2 O2 + O2 (26)

Finally, the chain reaction finishes:

2 HO· → H2 O2 (27)

Hydrogen peroxide follows two paths: the path of radiation and the path of decomposition.
However, the path of radiation is more efficient as more free radicals are formed, consuming fewer
peroxides. It is vital to keep the amount of peroxide as low as possible since this is an expensive material.
Some of the critical parameters of this system are the intensity of the UV lamp, the contact time within
the reactor, the operating pressure and temperature, and the dose of hydrogen peroxide. The intensity
of the lamp is necessary to form hydroxyl radicals and is, mainly, a residue strength function.
The main advantage of this AOP system is that it reaches a higher removal of contaminants than
the UV or H2 O2 systems individually. However, as previously mentioned, the presence of a certain
degree of turbidity harms the efficiency of the process. The non-contaminant compounds present in
the treated medium can also absorb UV, reducing the efficiency of the process.
The use of hydrogen peroxide and UV radiation to treat ethene spent caustic also has been reported
by Yu et al. [57]. The experiments showed almost 70% of COD removal efficiency when the ratio of
0.8 by H2 O2 /COD was used. This article mentioned a direct relation of H2 O2 dosage with removal
efficiencies of COD, but it reported the ratio amount mentioned before as the optimum condition.
While the hydroxyl radicals from the photolysis of H2 O2 reacts with COD, a higher amount of H2 O2

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inhibits this system. Additionally, it mentioned that the combination of H2 O2 and UV showed better
results than the use of these individual technologies.
In summary, this technology has not been widely studied and reported to treat spent caustic,
even when it is cheaper than the O3 /UV system when it was compared in textile effluent [62].

3.4.3. Ozone with Hydrogen Peroxide

The addition of H2 O2 to the system improves the production rate of hydroxyl radicals, as shown
in Section 3.4.1, according to Equation (22). This system is similar to the UV–hydrogen peroxide system.
However, the residue characteristics, such as the turbidity, influence the ozone–hydrogen peroxide
system less [62]. No information reported means that further research using this technology must be
studied to treat spent caustic.

3.4.4. Ozone, Hydrogen Peroxide and UV Radiation (O3 /H2 O2 /UV)

This system uses two oxidants, O3 and H2 O2 , in order to increase the formation of hydroxyl
radicals. At lab-scale Yu et al. [57] reported the optimum loaded of H2 O2 and O3 as 0.8 and 0.6
g/L, respectively, to reach 76% COD removal in the treatment of spent caustic from the ethene plant.
This research mentioned the improvement in the BOD/COD ratio from 0.22 to 0.52 when this technology
is used, compared to the H2 O2 /UV system. Even though the removal of the contaminants is increased
in the same way, the treatment costs also rise rapidly due to the use of two oxidants [62].

3.4.5. Ozonation and Ultrasound

Ultrasound is used to form hydroxyl radicals [63]. Ultrasound waves are transmitted and
introduced into the wastewater in alternate cycles of compression and expansion. This process
creates microbubbles when the amplitude of the expansion cycle is big enough to increase the
molecular distance to a distance higher than the required to remain in the liquid phase. The following
compression cycle makes the microbubbles collapse, producing extremely high temperatures and
pressures, which causes the breakdown of molecular water producing hydroxyl radicals. Several factors
influence the ultrasound systems, among which are the ultrasound frequency and the temperature
and pressure of the dissolved gas. The intensity of the ultrasound is related to the formation rate of
hydroxyl radicals. Higher ultrasound frequencies reduce the microbubbles’ collapse time resulting in a
very low possibility of recombination of hydroxyl radicals, which entails a higher generation rate of
hydroxyl radicals.
Occasionally, ozone is used along with an ultrasound to promote the formation of hydroxyl
radicals and improve the removal of contaminants [51].
The reaction produced between ozone and ultrasound in order to generate hydroxyl radicals is as
follows:
ultrasound
H2 O → H· + OH· (28)
ultrasound
O3 → O2 + O(3 P) (29)

O( P) + H2 O → 2 OH·
3
(30)

O2 + H· → HO2 · (31)

O3 + HO2 · → 2 O2 + OH· (32)

O3 + HO2 · → 2 O2 + OH· (33)

OH· + OH· → H2 O2 (34)

HO2 · + OH· → H2 O + O2 (35)

The main advantage of this system is that the energy required to form the hydroxyl radicals
is lower than the other AOPs, especially the ones that use UV, reducing the operational costs. The

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main disadvantage is that the amount of oxidant required, either ozone or hydrogen peroxide, is high,
which raises the operational costs [63]. There is no information reported about this system, meaning
that further research using this technology must be studied to treat spent caustic.

3.4.6. Fenton Reagent

The AOP system uses hydrogen peroxide as an oxidant agent and mixes it with a catalyst, which
is ferrous ion [64]. The reaction of hydrogen peroxide and ferrous ion is called Fenton chemistry. Its
practical application was carried out until the 60s [65], and it was used for the treatment of textile liquid
residues, liquid effluents, pulp and paper liquid effluents, and acid waters of petroleum refineries [66].
The main advantages of this AOP system are its high efficiency and capacity to treat several
contaminants. Some organics of low molecular weight, such as paraffin, chlorinated alkanes, and some
short-chain carboxylic acids, are resistant to Fenton’s oxidation.
The reactions involved in this system for the formation of hydroxyl radicals are the following:

Fe2+ + H2 O2 → Fe3+ + 3 OH· + OH− (36)

This is the initial reaction of the Fenton reaction. The formation of hydroxyl radicals is developed
through a complex chain reaction. Once the ferrous ion is formed, it can react with the hydrogen
peroxide according to:
Fe3+ + H2 O2 ↔ Fe − OOH2+ + H+ (37)

Fe-OOH2+ is an intermediate that is decomposed to form HO2 radicals according to the

following reaction:
Fe − OOH2+ → HO2 · + Fe2+ (38)

HO2 can oxidize contaminants, however, its oxidation power is much lower than other radicals.
Other chain reactions that occur in this system are the following:

Fe2+ + HO2 · → Fe3+ + HO2− + OH− (39)

Fe2+ + HO2 · → Fe2+ + O2 + H+ (40)

OH· + H2 O2 → H2 O + HO2 · (41)

Finally, the last step is carried out through the following reaction:

OH· + Fe2+ → OH− + Fe3+ (42)

The global reaction can thus be formulated as:

2Fe2+ + H2 O2 + 2H+ → 2 Fe3+ + 2 H2 O (43)

As it can be observed, the Fenton reaction requires an acid medium for it to occur. Once the
hydroxyl radicals are formed, the oxidation of contaminants takes place. If the oxidation is complete,
the contaminants can decompose in water, CO2 , and some innocuous inorganic salts [67].
The hydroxyl radicals can oxidize organic radicals (RH) through the removal of the organic radical
protons that form organic radicals, for example, according to:

RH + OH· → H2 O + R· (44)

This reaction is a chain propagation reaction. Once the organic hydroxyls are formed, the
subsequent oxidation can occur [68].

R· + H2 O2 → ROH + OH· (45)

41
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Ridge, as though the soil was not wet with the blood of brothers.
There, lying close to the rebel parapet, was the young and brave
captain, James H. Frost, of Company I, his calm face bathed by the
soft moonlight and looking as peaceful as though an angel guarded
his slumbers.
Further down the bloody track of the 124th lay twenty-two of its
braves, "sleeping the sleep that knows not breaking."
"The tempest may roar,
And the loud cannon rattle,
They hear not, they heed not,
They're free from all pain.
They sleep their last sleep,
They have fought their last battle,
No sound can awake them to glory again."

More than twenty-seven years have passed since that heroic

struggle on the steep mountain side of Missionary Ridge. The blue
and the gray sleep side by side in the National Cemetery at its base.
Chattanooga, then a small war-battered village, has grown, by
northern capital and northern industry, to be an important iron
manufacturing city. The Tennessee runs its bright and winding way
around the proud Lookout, but no rebel yell pollutes the air, and no
rebel rag defies the national authority, but all is peace and order,
industry and law. And so we bid farewell to the contemplation of one
of those great sacrifices that "saved us a nation."
 THE EAST TENNESSEE CAMPAIGN, AND THE
MARCH
FROM CHATTANOOGA TO KNOXVILLE.

Hooker's victorious legions had descended from Lookout. The battle

of Missionary Ridge had been fought and won. General Geary's
division of the 20th Corps had followed the beaten and disheartened
Bragg to Ringgold, and there attacking the enemy in his entrenched
position on the White Oak mountains, had suffered a repulse in
which the gallant 7th and 8th Ohio lost severely. It was there that
the idols of the 7th, Colonels Crane and Creighton, fell. But our
portion of the army advanced no further south at that time, and the
20th Corps went into winter quarters. But no such needed rest and
recuperation, after the long time of siege and starvation at
Chattanooga, seemed to fall to the lot of the 4th Corps of the Army
of the Cumberland.
The twenty-sixth day of November, 1863, the day after the battle of
Missionary Ridge, we spent in gathering up our beloved dead from
off the mountainside where they had charged so gallantly the day
before. We brought each regiment's sleeping braves and composed
them in long lines, each company's by itself. I wish those that love
war, that are filled with martial ardor, that are hoping that some
complication will involve us in a war with Great Britain, could have
walked with me along those lines of noble dead. There lay in
peaceful slumber all ages, all sizes and forms of men, from the
heavy, tall and bearded man of fifty to the smooth-faced lad of
fifteen.
O, could we feel the breaking hearts of wife, mother, father, sister,
brother, and affianced, when the shouting was over, when the
headlines of the great victory had become familiar, when the
congratulatory orders and proclamations had been issued and read,
and the cold, sad news had been conveyed to each home that
claimed a loved one lost in that great victory—then, and only then,
could we know and feel the real horrors of war. Then, I am sure, all
those that love war and delight in the clash of arms would lift their
voices for peace—lasting peace. We soldiers were not the real
sufferers—they were the sad, loving hearts at home. But then, as
now, duty was not to the dead, but to the living. Their manly forms
wrapped in their martial cloaks (the soldier's coarse blanket) were
tenderly buried on that beautiful elevation known as Orchard Knob,
which was the beginning of that National Cemetery where all the
wealth that a grateful nation and a loving people could lavish has
made it, in walks, drives, fountains, lawns, marbles, shrubbery and
flowers, one of the most beautiful places on earth. Here the name
and rank of each soldier is registered, when known, but alas, there
are thousands there that fill unknown and nameless graves.
But the news of the siege of Knoxville had come to us from the
hundreds of miles to the northward. Longstreet's Corps of the army
of northern Virginia had been detached from Bragg's army before
the battle of Missionary Ridge; Bragg, relying upon the strength of
the natural fortifications that he held, considered that it was only a
question of time when the battered remnants of Rosecrans' army,
that had been withdrawn from the lost field of Chickamauga, must
succumb to want and hunger; and the corps commanded by
Longstreet, and some other forces of the enemy in the north and
east parts of Tennessee, could soon render the situation of Burnside
at Knoxville as helpless as ours at Chattanooga. But the fortunes of
war, like all other things, change with time. Rosecrans had been
suspended and Hooker had been sent by Scranton to the Tennessee
in so short a space of time that the feat was the comment and
wonder of the watching world. Grant and Sherman had met.
The greatest living tactician and the most consummate handler of
men, were in counsel. Then, as I have stated, Bragg was beaten and
driven away, and Sherman marched to relieve Burnside. He was
given entire command, and within two days after the smoke of the
battle of Missionary Ridge had cleared away from the hilltops and
mountains around about Chattanooga, Sherman's army was on the
march up the Tennessee river for Knoxville, keeping on the east side
of the valley.
The first day our brigade only marched two miles, having to wait for
the other brigades and divisions to get out of the way.
We crossed the Chickamauga river a short distance above
Chattanooga on a pontoon bridge that had been put down by some
brigade of General Sherman's army. The next obstruction that we
encountered was a river that comes in from the east, the name of
which has slipped my memory. This had to be crossed by the aid of
a small river steamboat that had the capacity of taking over not
much more than a company at a trip, and we became very impatient
waiting this tedious process of transfer. It was a stern-wheel wheezy
affair, and I remember the boys rechristened it "The River Snail,"
and we put in our time making jokes at the expense of the boat and
crew, that acted as though the service they rendered was a matter
of force, and that they worked neither for love of country nor
compensation. At last we were safely across the river, and the old
stern-wheeler, years agone, marks some sand bar on the Tennessee
or some of its beautiful tributaries. Shortly after this steamboat ride
of almost one hundred feet we went into camp; the night was clear
and cold, and not being very well supplied with blankets, we had
difficulty in getting much sleep from Old Mr. Morpheus, the god that
the ancients supposed had charge of that soothing business.
November 29th we passed through the village of Georgetown, and
here we saw the stars and stripes first displayed by any citizens of
the south. The women came out and waived handkerchiefs and
almost anything else they could get hold of, while the "Old Blind
Mice"[3] made the air vocal with shouts and cheers for the first
people that seemed to love the old flag that we had seen since we
left Louisville, Ky. These poor people had had their homes desolated,
had been robbed of what few stores they had by the rebel army,
and, having the name of being union people, they had been
common plunder for every rebel trooper whose rough ride had taken
him into their village. No wonder they cheered and threw the old
flags they had kept during all those dark years of murder, pillage and
rapine to the breeze, when they saw "Uncle Billy" marching
northward with his army that would drive the hated rebel from their
own beautiful valley.

3. The pet name of the 124th.

December 6th found us in the valley of the Little Tennessee river, a
beautiful stream of water, clear as cut glass. This valley is one of the
most wealthy sections of east Tennessee. It may be rivaled by the
Sweetwater valley, perhaps. The inhabitants of these valleys being
rich before the war, and slaveholders, showed nothing but rebel
proclivities. We marched through what had been once a beautiful
village, called Marysville. It must have had at one time some two
thousand population, but it was sadly out of repair. There had been
a cavalry fight in its streets, and there was not a whole light of glass
remaining on the street that we marched through, and the houses
showed plainly the marks of the carbine and cannon shot.
It was at about this point that General Sherman issued his famous
order, to wit: "That any company, regiment or brigade, that struck
the enemy, should open the battle without regard to the position of
the balance of the army, and without awaiting further orders." This
was conclusive proof we were approaching Knoxville, and must be
within the vicinity of Longstreet's army, and we expected to hear the
battle open every minute. But the rebel general was, without doubt,
well versed in the literature of the nursery, and well remembered
"that he who fights and runs away, may live to fight another day.
While he who is in battle slain, can never rise to fight again."
General Longstreet, hearing of the near approach of Sherman's
army, attacked Fort Saunders, was dreadfully repulsed and then
abandoned the siege of Knoxville, without one of Sherman's army
having the chance to unload a musket at the boasting veterans of
the army of northern Virginia.
Monday, December 7th, we marched within two miles of Knoxville
and went into camp, having marched from Chattanooga in ten days,
over two hundred miles the way we came, having carried our rations
in our haversacks, and eighty rounds of cartridges to the man, never
having a wagon after we left Chattanooga. Here we met the 103d O.
V. I. The major of the 103d was a brother of our Lieutenant Colonel
Pickands, and we were well acquainted with many of the boys of
that regiment. The greetings that followed were not only cordial and
heartfelt, but enthusiastic, and the shouts that went forth when the
boys found that Burnside's army had been reinforced by the army
that marched fresh from one of the most important victories of the
war more than two hundred miles to relieve them, awoke the echoes
among the hills of the north.
We were tired and foot-sore and (to be candid about it), even at this
late day, I remember that we much preferred being cheered to
fighting Longstreet. Those gallant fellows offered us everything they
had in the world save something to eat and drink, which they had
not.
After a night of rest only known to tired, foot-sore soldiers, "free
from war's alarms," Lieutenant Stedman and myself procured passes
and went into the city of Knoxville. This was the largest city we had
seen since we left Nashville, and had a very neat and healthy
appearance, considering that it had been at times the headquarters
for both rebel and union armies. This city is situated at the
confluence of the French Broad river, that rises in the Blue Ridge
mountains of North Carolina, and the Holston, that comes down
from the Cumberland mountains of northeast Tennessee and
Virginia, forming the Tennessee river that flows past the city in a
deep rapid current. The Tennessee river at Knoxville is one of those
glorious streams that the lover of nature never views without
interest, and usually with delight.
Knoxville, with its beautiful streets, its bright and bounding river, its
mountains on the west and north, just near enough to be romantic,
with a naturally rich valley flanking it on all sides, must ever remain
one of the nicest, and one of the most delightful, towns in the world.
I have not been there since the war, but I am told by those that
have, that, with its unbounded wealth of iron, coal and marble, as
well as its splendid agricultural resources, added a climate that is
neither tropical nor northern, but the happy mean between the two,
its growth has been great and substantial. I suppose a member of
the Blind Mice, finding himself in the Knoxville of to-day, would
hardly know it from what he remembers of the Knoxville he marched
to relieve in the early winter of 1863-64.
This was the home of the celebrated Parson Brownlow, and I well
remember that on going down the main street of the city this day
that we first visited Knoxville, of seeing his brave and beautiful
daughter, Kate, standing under the flag, bowing and smiling to the
union soldiers as they raised their caps to her; all in very great
contrast to her demeanor when the rebels held the city and she kept
that same flag floating in defiance of the rebel crew that surrounded
her on every hand.
We promised her that the rebel foot should never again press the
streets of Knoxville save in captivity; a promise that we kept and
proved true, but how much our valor contributed to that result we
will see further on.
This same Parson Brownlow had two sons in the union army, James
and John, commanding at that time east Tennessee regiments.
We went down to the north end of the town and found a barber
shop in full blast, and concluded that we would indulge in the
benefits conferred by the tonsorial artist; so taking the chair without
inquiry as to terms, had our locks put in shape, and our faces made
more presentable; but when the time for the settlement came we
found the artist only charged fifty cents for hair cutting and thirty
cents for shaving, which caused us some surprise.
We next concluded to visit Fort Saunders, that General Longstreet
had made up his mind to take a few mornings before we arrived in
that vicinity. Of course we did not see the battle, and all I can give
you is what we saw after several days had passed. I am not certain,
but I should say that Fort Saunders stood northwesterly of the city,
and a full mile out from the same. I do not know whether the fort
was built by General Burnside or not, but I think it was built by him
after he was sent to that department, as the moats and parapets
seemed new. There must have been timber standing on the easterly
and northerly sides at no very great time before, as the ground was
covered with stumps, and they seemed new and strong, as though
the timber had been recently cut. General Burnside's men, expecting
the assault (as Fort Saunders seemed to be the key to General
Burnside's position), had contrived a very ingenious way of defense.
They procured a large quantity of telegraph wire, and stretched it
from one stump to another about knee high, winding it around each
stump a few times to make it secure. This they did with seemingly
very great industry, for nearly all the approaches to the fort were a
perfect network of wire. They also loaded a large number of shell
with fuzes cut at about five seconds, and had them placed handy
when the time came for the assault. This I have from one of the
defenders of the fort.
Just as the dawn was breaking in the east General Longstreet's
assaulting column drove in the pickets, and, with that yell that once
heard is never forgotten, came dashing on toward the fort; but when
they reached the wire they did some ground and lofty tumbling,
mostly ground, and the fort opened a most terrible fire of musketry,
shot and shell. But nothing daunted, though their formation was
badly broken up, they came on and soon filled the ditches around
the fort. Then the shells were lighted and thrown over the parapets
into the ditches, making fearful havoc as they exploded among the
swarming rebels. I suppose a more determined and bloody charge
was never made during the war. The rebels even climbed up the
embrasures of the fort, and the cannoneers cut them down with
axes.
But the short range shells and the heroic resistance made by the
defenders of the fort were too much for the unquestioned heroism
of the assailants, and what remained of them straggled back, as
best they could, to the main body of Longstreet's army.
I will not attempt to give a description of the scene in the ditches
and around the fort. It beggars all the horrors that language can
describe. When we visited the fort of course all the dead and
wounded had been removed; but when we came to walk along the
bottom of the moats that surrounded the fort, the evidences of the
sanguinary conflict still remained. Here lay a tongue, there, an ear,
and beyond, a jaw bone. I saw a hand lying opposite one of the
embrasures of the fort that was cut off as smoothly as though
severed with one blow from an ax; but though we rejoiced in a
defense that saved General Burnside's army, we were glad to leave
this scene of horror and return to camp where the Mice were resting
their weary limbs after the terrible march that we had endured.
December 29th, 1863, we moved our camp to the north into a fine
piece of woods, and remained there until the year 1863 had gone.
What a year of marchings, battles, and sorrow. How many of those
that left Camp Cleveland with us—just one year before—now "sleep
the sleep that knows not breaking." What a change in our regiment.
Our ranks have been thinned, but our effectiveness has been
increased. We have been tried in all the sad experiences of war.
Patriotism brought to our ranks very many never calculated, either
physically or mentally, to make soldiers. Their intentions were high
and noble, and they failed by no fault of theirs; their final discharge
was a mercy to them, and a blessing to us. Many came home and
abandoned army service forever. Many enlisted in other regiments,
for shorter terms and less arduous duties; but, as a rule, all did all
they could to maintain the integrity of the Union.
January 1st, 1864, opened the most eventful year of the war. Each
army had come to its full strength and vigor. "The summer soldier
and the sunshine patriot" had long since retired, and we had a man
as commander in chief of all the armies that had the correct notion
of the way of putting down the rebellion. A man that realized that
the theory of conquering rebel territory while the rebel armies
remained intact was worse than useless. That if armies are to be
destroyed, the quicker it can be accomplished, the more precious
lives saved. Great and decisive battles, with all their untold horrors,
are angels of mercy compared to the small battle, the skirmish,
where a few are lost and nothing accomplished.
But I find myself digressing, by the thoughts that come crowding up,
as I contemplate the value(?) of our east Tennessee campaign of
1864.
January 14th we struck tents, and crossing the river marched
twenty-two miles to a position known as Strawberry Plains. I never
knew why they called it by that name unless it was because it had
no appearance of ever having grown any strawberries, or because
the foothills of the Clinch mountains were too rough and irregular to
be called plains. I guess the fellow that furnished the name had
never been away from home.
On this march we saw the gallows where four citizens of east
Tennessee were executed. The gallows stood hard by the side of the
railroad track. These men were executed for a very heinous crime. It
may be briefly stated: They loved their country and their country's
flag too well to swear allegiance to the southern confederacy, and so
they were put to death.
The next day we marched to Dandridge, a small village situated on
the French Broad river, and camped in a beautiful pine woods.
Here we had orders from Colonel Pickands to fix up winter quarters,
as we would probably stay right here until the spring campaign
opened, and the pine poles were just the material from which to
construct winter quarters of the most commodious kind. For the
benefit of the Sons of Veterans I will describe the process. You must
remember at this time we were soldiers, and soldiers of the Uncle
Billy pattern and kind. If we had any shelter, save the starry
heavens, we had to carry that shelter on our backs, as well as our
camp equipage. Now, at this time, you must also remember that our
regiment was divided into messes, and that by the process of natural
selection four men would come together and call each other Pard.
What there was that kept these messes together I never knew. I
said they came together by natural selection for the reason that
when we find anything that we cannot explain we call it natural and
let it go. These messes of four would sing, quarrel, fight, make-up
and divide all they had with each other inside of twenty minutes.
Each member of each mess would swear that there were not three
as good foragers in the regiment as his three messmates. Somehow
or other, a good forager was always held up as a patron saint in the
124th Regiment. Chaplain Hubbard, of the 103d O. V. I., was the
"bright and morning star" in this business of all the members of the
army of occupation of east Tennessee. I call it the army of
occupation because, before I am done, you will see that is all we
did. Well, to resume, each one of these four messmates would carry
one piece, at least, of shelter tent. Sometimes more could be found,
but usually, where more were found, some others had less. This
more or less business was a common thing in the army.
Now in the first place the streets were laid out, which streets were
the parade grounds of the several companies, where they were
formed and marched to the regimental parade ground. The stumps,
when we camped in the woods, were carefully dug out of these
streets, and the same nicely graded and ditched. Then at the left-
hand side looking toward the regimental parade ground the quarters
of the messes were erected. This I know will seem very
commonplace to the old comrade, but you will bear with me, as I am
speaking to-day to many Sons of Veterans and others, that were too
young to be with us in this experience. The poles were then cut long
enough to cover with two pieces of shelter tent, then laid up,
notched at the corners to bring them down quite close, laid up high
enough so the soldier could stand upright comfortably. The ends or
gables were cobbed up to the peak, or fixed up with the extra tents,
poles were fastened on with bark or withes, and the tents make the
roof. Then the cracks were stopped with mud. A stick or stone
chimney is built in the back end. Two bunks are made, one on either
side, with crotches driven into the ground, and small poles laid
lengthwise and covered with pine boughs and the U. S. army blanket
make the bed. Gun-racks are made above each bunk for two
muskets and two sets of accouterments. An extra blanket is hung up
for a door, and the house is furnished by the inventive genius of the
mess. The bunks during the daytime furnish upholstered seats. This
house answers for kitchen, dining room, and dormitory, and a
healthier home does not stand in the city of Cleveland. One of the
best features of the whole business is, they were not liable to sale
under execution, or foreclosure, neither for delinquent taxes. This
house I have described was one of a large city our division built at
Dandridge. Please note how long they were suffered to enjoy the
fruits of their ingenuity and industry.
If I were called upon to organize an army that should accomplish the
greatest warlike good (if the word good can be used in connection
with the word war), I would start, in our experience as soldiers,
where we left off. The government should never build quarters for
soldiers, they should build their own. The government should never
furnish any transportation for well soldiers, and instead of staying in
camp, I would have them move from place to place, thereby
avoiding the disease that camps breed. The sooner the soldier
becomes self-sustaining, within a certain limit, the better for
themselves and the service.
January 16th Colonel Pickands came to my quarters and said he had
a soft snap for me; said that I had never had a detail, that I had
stayed right with the regiment since we took the field, and he was
only too glad to confer this favor. I thanked the genial commander,
though I had no desire to leave the Mice in that way; and had but
very little confidence in what he said he heard from headquarters,
"that we would probably stay where we were for three months."
About ten o'clock a. m. the detail was ready, consisting of 149 men.
The order was to march to New Market and guard the division
stores. We went through a fairly good country, and along in the
afternoon we met General Sheridan and staff. He was riding that
same black horse that afterward "carried him into the fray from
Winchester, twenty miles away." He asked a number of questions.
The first was, if I had heard any firing in the direction of Dandridge?
This question showed the true instinct of the great general; that he
was always looking out for a battle, and had he been in command of
the union forces in east Tennessee, the country would have been
electrified by the news of a signal victory won, instead of a
disastrous retreat from Dandridge, whereby so many of our poor
boys were captured, and carried to Andersonville and death. Soon
after we bade good-bye to Sheridan and staff one of the Mice, and
he must have been one of the kind known as ground mice, found an
apple-hole, and before I was aware of what was going on, the Mice
were all busy digging out apples. The owner came out and
protested; said he was a union man, had been from the start, and
his property should be protected. I agreed in all he said, and by the
time his protest was fully entered his apples had been transferred to
the capacious haversacks of the Mice. Of course I was to blame. I
should not have suffered the Mice to gnaw and destroy this good
man's apples; but what, I ask you, could I do with 149 men that had
not seen or tasted an apple since the fall of 1862? I offered to give
him a voucher for the apples, and told him if he was as good a union
man as he claimed to be the commissary department at Knoxville
would pay him. But he seemed to know what the voucher was worth
better than I and declined the same; we marched on to New Market,
arriving there after dark, having marched twenty-three miles since
ten o'clock.
I soon found nice quarters for my men in the abandoned houses of
the village, and my mess arrangements having been broken up, I
engaged boarding with an old lady that had two sons in the union
army. This was one of the worst battered towns I had seen in the
south. The sentiment was about equally divided between union and
rebel, and the town had been badly plundered by both sides. The
stores were at the station on the railroad, and after relieving the
men on duty with a detail of my men, had supper, and being very
tired, the old lady showed me a room, and I went to bed between
nice white sheets, the first time in more than twelve months. Visions
of feather beds, soft bread, pies and cakes, no marching, no picket
guard, haunted me until 3 o'clock the next morning, when I was
awakened by a loud rapping at my door; on getting out I saw the
yellow stripes of a cavalry orderly. He very politely handed me an
order directing me to march my detail back to Strawberry Plains, as
the army was falling back from Dandridge. I got out to the quarters
of the men as soon as I could, aroused the orderly sergeant and the
men, called in the guards at the station, and started back on the
railway track for the point to which we had been ordered. And that
ended the "soft snap."
The winter quarters the Mice had built, the city one day old, was
abandoned, and the brigade, wearied out by marching in the
deepest mud I ever saw, slept that night under the stars at
Strawberry Plains. What became of the stores at New Market I never
knew, and why we were ordered back I never knew. All I know
about the matter is that Uncle Billy had gone north to meet Grant at
Cincinnati, and General Sheridan was not in command.
We lost more men on the retreat from Dandridge than would have
been lost in a battle with Longstreet, and we had men enough to
have whipped him and driven him out of the state. But "the grand
army of occupation" was permitted to do no fighting, and so we
wallowed around in the mud of east Tennessee.
In a few days we marched down to Knoxville and below to a place
named in honor of one of America's greatest poets, I guess; in any
event, it had the poetical name of Lenore, and if not loved, it
certainly seemed lost. It may have been found since the war, but it
was certainly lost Lenore when we were there.
I suppose no part of the south suffered so much in the way of
partisan warfare as east Tennessee. This part of the state owned
very few slaves, and the inhabitants were largely true to the union
cause. Of course, the wealthy portion of the people were
slaveholders, and they were rebels to a man, and middle Tennessee,
Georgia, Virginia, and some portions of North Carolina were
intensely rebel, and thus you will understand that east Tennessee
was surrounded by a disloyal population. Then, again, the Tennessee
valley was the principal gateway from Richmond to the southwest
and, until the occupation of Knoxville by General Burnside, this valley
was continually being overrun by rebel troops of all sorts, from
infantry to mounted bushwhackers. The disloyal, when the rebel
army was present, informed on their loyal neighbors, and the old
men, the women, and the children had to seek safety in the woods,
ravines, and caves of the mountains, only to see their dear old
homes in flames behind them. Even the learned and respected
Judge Baxter, afterwards appointed judge of the United States circuit
court, who, before the war, had a fine residence and lucrative
practice in the city of Knoxville, was compelled to "lie out in the
bush," as they call it, for three months at one time, to save his life;
and yet with most remarkable magnanimity, through Judge Baxter's
influence, not an acre of rebel land or a rebel home was confiscated
in the whole of east Tennessee. While we were in one of the many
camps about Knoxville, the two regiments commanded by the
Brownlow brothers, James and John, veteranized, and under the
order of the government were granted thirty days' leave of absence.
I happened to be present at the time they disbanded. One of these
brothers made a speech to the two regiments. I don't remember
which one, but I never can forget one thing he said: "Take your
arms with you; you will not be wanted here for thirty days. Go home
and avenge the death of your fathers and brothers." This speech
was received by these hardy mountaineers as a license, as it was
intended to be, for murder and the desolating torch. Not a night
from that time on for thirty days but the heavens were aglare with
the flames of rebel homes, and the number of murders committed
will never be known "until the sea gives up its dead." But never did
the horrors of Indian massacre compare with east Tennessee for
deeds of murder and fiendish, remorseless cruelty from 1861 to
1865.
Then on the 17th moved back in the rain and mud, and went into
camp; and then on the 23d moved forward again, found no enemy
and then back to camp, having marched that day in the rain and
mud twenty-eight miles. Then on the 24th we struck tents and
marched twelve miles beyond Knoxville to Strawberry Plains again.
Then we were up and off to New Market. Then the next day
marched to Morristown, eighteen miles from New Market, and
occupied the abandoned quarters built by Longstreet's men. Stayed
in this camp until March 2d, 1864, and then marched back to New
Market. This marching and counter marching is of no particular
interest of itself, but I give it to you to show how we put in the time.
Of all the campaigning we ever did this of east Tennessee was the
most purposeless, seemingly profitless, and dismal. The most of the
time we were hard up for rations, and were compelled to forage on
a people as friendly as any in Ohio, and that had been robbed by
both armies. I never can forget the time we lay at Clinch Mountain
Gap, when it was so cold that we had to build log-heaps in front of
our tents to keep from freezing, that Colonel Pickands sent
Lieutenant Stedman with a file of men and a wagon to try and find
something to eat. I was at headquarters when he returned at night.
The colonel, with that usual smile, said: "Lieutenant, what success
to-day?" Stedman answered: "Nothing." "Why?" remarked the
colonel. Stedman replied, with an oath so terrific that I am sure it
was heard in Heaven (and which I hope the recording angel has
blotted out, and I know he has if he has attended strictly to
business), "that he would be —— —— before he would rob women
and children." When the recording angel became acquainted with
the noble Stedman, fresh from the bloody field of New Hope Church,
I am sure the accounts were properly adjusted.
Well, this must end my recollections of the very celebrated march
from Chattanooga to Knoxville and the winter campaign of east
Tennessee.
General Longstreet finally went back to the army of northern
Virginia, not that he was in any danger from us, but simply because
he became tired of the scenery and wanted a change, I suppose.
Nothing in history is grander than the relief of Knoxville; nothing
tamer and more devoid of sense than the balance of the campaign.
Yet we can draw from it all this useful lesson, that those brave
spirits, the noble men that endured the march and campaign, had a
patriotism and endurance that nothing of storm, of cold, of hunger,
of sickness, of bad management could dampen. And though many of
that band sleep in southern graves, yet many lived to bring back the
stars and stripes in triumph from the greatest conflict of modern
times and to see the rebellious states restored to a peaceful and
happy union.
 LIEUTENANT CHARLES M. STEADMAN.

Killed at Pickett's Mills, Georgia. May 27th,

1864.
 THE ATLANTA CAMPAIGN.

The spring of 1864 opened with millions of anxious patriots looking

in the direction of our armies.
General Grant had virtually been made commander in chief of all the
union forces, with personal direction of the Army of the Potomac.
Every lover of his country had come to understand that the policy of
conquering rebel territory and guarding rebel property would never
crush out rebellion.
The military policy of General Grant, of making the objective point of
campaigns the rebel armies, met the good sense and received the
hearty approval of the patriotic people of the United States.
Some raised the cry of "butcher," but every thoughtful man that
knew the desperate intentions, the bravery, the skill, and the strong
defensive positions occupied by the rebel armies, knew that their
destruction meant severe marches, terribly destructive battles,
thousands of brave men killed, and vastly more wounded and
maimed for life; but in the face of all these mighty sacrifices, that
the poverty of language will not enable us to describe, the patriotic
people of the north said, "We will sustain the army at all hazards,"
and the armies responded, "Let us set forward."
It is a well-known fact that in the winter of 1864, at the Burnett
House in the city of Cincinnati, Ohio, the two greatest generals
developed by the war, Grant and Sherman, met in counsel. Sherman,
while a line officer in the regular army, had become most thoroughly
acquainted with the topography of the state of Georgia, and it was
at this consultation that the campaign from Chattanooga to Atlanta
and the grand march "from Atlanta to the sea" were developed and
determined upon. It was at this consultation that Sherman said,
"The confederacy is a shell and I can march an army through it." It
was at this consultation that Grant said, "If you undertake it, I will
hold Lee and his armies, that they give you no trouble." At the end
of this meeting each of the great commanders repaired to his
respective scene of action to carry forward the purposes determined
on thereat.
The first of May, 1864, found assembled in the vicinity of
Chattanooga, and as far south as Ringgold, Ga., the forces with
which General Sherman proposed to crush the shell of the rebellion.
It consisted of the Army of the Cumberland, General George H.
Thomas in command; the Army of the Tennessee, under the especial
command of General McPherson; the 23d Corps, commanded by
General Schofield; the 20th Army Corps, still in command of the hero
of Lookout mountain, "Fighting Joe Hooker," as he was often called
in army circles, and also a brigade of regulars. Then as able
lieutenants in command of corps and divisions, Sherman had Logan,
Blair, Sickels, Stanley, Wood, Slocum, Osterhaus, and many others,
all fighting officers. Sheridan, at that time, had been transferred to
the Army of the Potomac by the especial order of General Grant,
who witnessed General Sheridan's heroic conduct at Missionary
Ridge.
I suppose very few of the people of the north ever had anything like
a correct idea of the magnitude of the work undertaken by General
Sherman in the campaign of Atlanta. The distance from Louisville to
Nashville is stated to be one hundred and eighty-five miles, and from
Nashville to Chattanooga it is said to be one hundred and fifty-one
miles, and from Nashville to Bridgeport on the Tennessee river, two
hundred and eleven miles. This long line of railway from Louisville to
Chattanooga, and from Nashville to Bridgeport, Ala., five hundred
and forty-seven miles, had to be guarded by military force every
mile. For it must be remembered that while the state of Kentucky
never went out of the Union and was ostensibly a loyal state,
nevertheless, it required more soldiers to look after its disloyal
citizens than she furnished to the cause of the Union, not for one
moment forgetting that the state of Kentucky furnished some as
brave and loyal soldiers as ever sprung a rammer and some as
valiant officers as ever drew a saber. Notwithstanding, she had a
large population in the aggregate that engaged in that disreputable
kind of warfare known as bushwhacking, and very many that did not
were ever ready to furnish aid and comfort to our enemy. Again, no
portion of Tennessee, save east Tennessee, laid any claim to
anything but intense love of the southern confederacy. Blockhouses
had to be constructed every few miles of this route and a vast
number of soldiers employed in keeping open this line of
communications. Nashville was the grand base of supplies, where
had been accumulated for many months all kinds of army stores,
and from this base General Sherman had to draw supplies of rations,
ammunition, and clothing for his campaign in Georgia; while the
route from Nashville to Louisville must be kept open to renew the
supplies at the base, as well as to send the sick and wounded to the
northern hospitals.
It is almost needless for me to state before this intelligent audience
that the genius of General Sherman was entirely equal to the
emergency. And while the oddities and comical features of great
men will usually be better remembered than any others, those of us
that participated in that memorable campaign will remember well
that no precautionary matter was overlooked by the ever watchful
general. If what he really meant by "light marching order" was so
difficult to understand that a cavalryman construed it to mean
"necktie and a pair of spurs," he was no less exacting of himself and
staff and many a night on this campaign he bivouacked as would a
picket on an outpost. The thoroughness of his preparation was the
sequel of his success. Knowing very well that overrunning rebel
territory did not make loyal citizens of its inhabitants, he took the
precaution to have his engineers make drawings of every wooden
bridge between Louisville and Chattanooga, and between Nashville
and Bridgeport. Nor was this all. He had his corps of mechanics
construct duplicate bridges for the entire line south of Nashville. He
was not satisfied only with his precautions to guard and care for his
line of communications to his base of supplies, but he in some
manner procured plans of the bridges from Chattanooga to Atlanta,
and had bridges constructed and loaded on flat cars ready for use at
any time when wanted. It was perfectly astounding the perfect order
and dispatch with which he reconstructed the railroads as his
campaign progressed, and with such celerity did his engineer corps
perform its duty that after the bridge was burned by the rebel rear
guards the same would be rebuilt, and the screams of the
locomotive would mingle with the rattle of the musketry of the
skirmishers just across the river, always reminding us that Uncle
Billy's railroad was in good working order and that our "cracker line"
was secure. But the vigilance of his preparation was not satisfied
with being able to keep up his railroad lines—he had the finest
pontoon corps that was ever organized.
Each man was drilled in the movements necessary to put down a
pontoon bridge or remove one from the water and replace the same
on the wagons as efficiently as an infantryman in the manual of
arms or a cannoneer in the handling of a fieldpiece. It was a sight
that seemed the perfection of celerity to witness his pontoon corps
put down a bridge, and every line of march was thoroughly
equipped in this particular.
But what I have heretofore described were not all the obstacles in
the way of the making of the Atlanta campaign a success. While we
were beyond the Tennessee mountains, while we had crossed the
Tennessee river, the country from Ringgold to the south bank of the
Chattahoochee river was naturally most admirable defensive ground.
Every few miles were high ridges and small mountain ranges
remarkably well adapted for defensive military positions; added to
this the enemy had no rear that required guarding, had no hostile
population to watch and distrust, had the most accurate information
as to streams and roads, had swarms of volunteer spies to inform
him of our every movement, and finally, had an army of slaves to do
his intrenching ready to his hand and use when he was ready to fall
back to a new position. This, all this, and more than I have time to
describe, must be considered if we would thoroughly comprehend
the military magnitude of the Atlanta campaign.
When General Sherman was ready to commence the forward
movement, there must have been assembled from Chattanooga to
Ringgold between eighty and one hundred thousand men, and on
the third day of May, 1864, just as the magnolias were beginning to
open their fragrant blossoms to the south wind, and the mocking
birds were beginning to make the woods vocal with their songs, our
division struck tents and commenced the march southward, and the
evening of the fourth found us two and one-half miles from Ringgold
confronting the enemy's pickets. From this time until the ninth we
made short marches southward, skirmishing with the rebels each
day. On the ninth our brigade was composed of the 124th O. V. I.,
the 41st O. V. I. the 93d O. V. I., the 9th I. V. I., and the 6th Ky. V. I.
The brigade was commanded by General William B. Hazen and we
had moved as far toward Dalton as a position known locally as
Buzzard's Roost, a pass in the White Oak mountains. Here we found
the rebels in position, the pass strongly fortified and commanded by
a number of heavy guns.
At this position our brigade had an order to charge the mountain at
the left of the pass, which order was executed, and we came within
two hundred yards of the top of the mountain, where we found it
broken off into palisades thirty feet in height. These palisades we
had no means of ascending and so the charge ended. Our regiment
lost three men killed and ten wounded. This movement was
afterwards explained as a demonstration to deceive the enemy, but
some of us will always think that we were the ones that were
deceived. There was heavy firing on the right of the pass and in the
direction of Snake Creek Gap, where a portion of Hooker's Corps
fought a severe battle, the 29th O. V. I. losing very heavily. While in
this position (Buzzard's Roost) we were terribly annoyed by
sharpshooters posted above the palisades, the bugler of the 93d
being killed.
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