Advanced Oxidation Processes for

Effluent Treatment Plants Maulin P.

Shah
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ADVANCED
OXIDATION
PROCESSES FOR
EFFLUENT
TREATMENT
PLANTS
ADVANCED
OXIDATION
PROCESSES FOR
EFFLUENT
TREATMENT
PLANTS
Edited by
MAULIN P. SHAH
Elsevier
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Editor’s biography

Maulin P. Shah is currently a research scientist at the Environ-

mental Biology Lab, India. Dr. Shah has served as an assistant pro-
fessor at Godhra, Gujarat University since 2001. He has more than
160 research publications in highly reputed national and interna-
tional journals. He is an active editorial board member in 75
highly reputed journals in the field of Environmental and Biolog-
ical Sciences. He has been appointed as an editor-in-chief of
two journals: the Research Journal of Microbiology and the Jour-
nal of Biotechnology and Biomaterials. His work has been focused
on assessing the impact of industrial pollution on the microbial
diversity of wastewater following cultivation-dependant and
cultivation-independent analysis. Maulin’s work involves isola-
tion, screening, identification, and genetic engineering of the high
impact of microbes for the degradation of hazardous materials.

xv
Contributors

Komal Agrawal Bioprocess and Bioenergy Laboratory, Department

of Microbiology, Central University of Rajasthan, Ajmer, Rajasthan, India
J. Anandkumar Department of Chemical Engineering, National Institute
of Technology Raipur, Raipur, Chhattisgarh, India
Aditi Banerjee Centre for Nanotechnology, Indian Institute of Technology
Guwahati, Guwahati, Assam, India
Jay Bergi Department of Biotechnology, Shree Ramkrishna Institute
of Computer Education and Applied Sciences, Surat, Gujarat, India
Navneeta Bharadvaja Plant Biotechnology Laboratory, Delhi Technological
University, Delhi, India
Q.Q. Cai Department of Civil & Environmental Engineering, Faculty
of Engineering, National University of Singapore, Singapore, Singapore
Jayashankar Das SOA Deemed to be University, Bhubaneswar, Odisha,
India
Shivika Datta Department of Zoology, Doaba College, Jalandhar, Punjab,
India
Sushma Dave Jodhpur Institute of Engineering and Technology, Jodhpur,
Rajasthan, India
S.H. Deng Department of Civil & Environmental Engineering, Faculty
of Engineering, National University of Singapore, Singapore, Singapore
Daljeet Singh Dhanjal Department of Biotechnology, Lovely Professional
University, Phagwara, Punjab, India
Anurag Garg Environmental Science and Engineering Department, Indian
Institute of Technology Bombay, Mumbai, India
Shashwati Ghosh Sachan Department of Bio-Engineering, Birla Institute
of Technology, Mesra, Ranchi, Jharkhand, India
J.Y. Hu Department of Civil & Environmental Engineering, Faculty of
Engineering, National University of Singapore, Singapore, Singapore
Pyla Jayasree Indian Institute of Technology Bhubaneswar, Argul, Odisha,
India
L. Jothinathan Department of Civil & Environmental Engineering, Faculty
of Engineering, National University of Singapore, Singapore, Singapore

xi
xii Contributors

Sukhmanpreet Kaur Department of Chemistry, Rayat Bahra Institute

of Engineering and Nano-Technology, Hoshiarpur, Punjab, India
Prateek Khare Department of Chemical Engineering, Madan Mohan
Malaviya University of Technology, Gorakhpur, Uttar Pradesh, India
Prashant Kumar Department of Bio-Engineering, Birla Institute of
Technology, Mesra, Ranchi, Jharkhand, India
Vijay Kumar Regional Ayurveda Research Institute for Drug Development,
Gwalior, Madhya Pradesh, India
Vineet Kumar Environmental Microbiology and Biotechnology Laboratory,
School of Environmental Sciences, Jawaharlal Nehru University,
New Delhi, Delhi; Department of Environmental Microbiology, Babasaheb
Bhimrao Ambedkar (Central) University, Lucknow, Uttar Pradesh, India
Lal Mohan Kundu Centre for the Environment; Department
of Chemistry, Indian Institute of Technology Guwahati, Guwahati,
Assam, India
Sandhya Mishra Applied Phycology and Biotechnology Division, CSIR—
Central Salt and Marine Chemicals Research Institute, Bhavnagar, India
H.Y. Ng Department of Civil & Environmental Engineering, Faculty
of Engineering, National University of Singapore, Singapore, Singapore
S.L. Ong Department of Civil & Environmental Engineering, Faculty
of Engineering, National University of Singapore, Singapore, Singapore
Lalit M. Pandey Centre for the Environment; Bio-Interface & Environmental
Engineering Lab, Department of Biosciences and Bioengineering, Indian
Institute of Technology Guwahati, Guwahati, Assam, India
Ratnesh Kumar Patel Department of Chemical Engineering, Madan
Mohan Malaviya University of Technology, Gorakhpur, Uttar Pradesh,
India
V. Prashanth Indian Institute of Technology Bhubaneswar, Argul, Odisha,
India
Parth Rajput Indian Institute of Technology Bhubaneswar, Argul, Odisha,
India
Shristi Ram Applied Phycology and Biotechnology Division, CSIR—Central
Salt and Marine Chemicals Research Institute, Bhavnagar; Academy of
Scientific and Innovative Research (AcSIR), Ghaziabad, India
Neelancherry Remya Indian Institute of Technology Bhubaneswar, Argul,
Odisha, India
Romina Romero Technological Development Unit (UDT), University
of Concepcion, Coronel, Chile
 Contributors xiii

Arpita Roy Plant Biotechnology Laboratory, Delhi Technological University,

Delhi, India
Biju Prava Sahariah University Teaching Department, Chhattisgarh Swami
Vivekanand Technical University, Bhilai, Chhattisgarh, India
Monalisa Satapathy Department of Chemical Engineering, National
Institute of Technology Raipur, Raipur, Chhattisgarh, India
Maulin P. Shah Research Scientist, Environmental Microbiology Lab,
Ankleshwar, Gujarat, India
Ravi Shankar Department of Chemical Engineering, Madan Mohan
Malaviya University of Technology, Gorakhpur, Uttar Pradesh, India
Shambhoo Sharan Department of Chemical Engineering, Madan
Mohan Malaviya University of Technology, Gorakhpur, Uttar Pradesh,
India
Joginder Singh Department of Biotechnology, Lovely Professional
University, Phagwara, Punjab, India
Simranjeet Singh Department of Biotechnology, Lovely Professional
University, Phagwara; Punjab Biotechnology Incubator (PBTI);
RAWTL, Department of Water Supply and Sanitation, SAS Nagar,
Punjab, India
Swati Singh Environmental Science and Engineering Department, Indian
Institute of Technology Bombay, Mumbai, India
Sushma Rani Tirkey Applied Phycology and Biotechnology Division,
CSIR—Central Salt and Marine Chemicals Research Institute,
Bhavnagar; Academy of Scientific and Innovative Research (AcSIR),
Ghaziabad, India
Ratna Trivedi Department of Environmental Science, Shree Ramkrishna
Institute of Computer Education and Applied Sciences, Surat, Gujarat,
India
Ayushi Verma Plant Biotechnology Laboratory, Delhi Technological
University, Delhi, India
Pradeep Verma Bioprocess and Bioenergy Laboratory, Department
of Microbiology, Central University of Rajasthan, Ajmer, Rajasthan, India
Rahul Verma Centre for the Environment, Indian Institute of Technology
Guwahati, Guwahati, Assam, India
Aparna Yadu Department of Chemical Engineering, National Institute
of Technology Raipur, Raipur, Chhattisgarh, India
Preface

Water treatment technologies such as adsorption or mem-

brane filtration, advanced oxidation processes offer the possibility
of the complete conversion of hazardous substances to carbon
dioxide, water, and salt-free producing residues. However, one
challenge is the combination of advanced oxidation processes
with other unit operations to enhance the overall process effi-
ciency. The most significant disadvantages of advanced oxidation
processes are the high energy consumption and the production of
critical intermediates. New knowledge of oxidant production with
higher yields, reactions paths, reactor design, a combination of
processes, the determination of dangerous intermediates such
as genetic test methods, and water applications has been reused.
All these parameters are considered keys to exploiting the poten-
tial of advanced oxidation processes for water treatment and
reuse. Advanced oxidation processes are purification technologies
aimed at degrading and mineralizing unsurpassed organic matter
from wastewater by reaction with hydroxyl radicals. Recently,
these technologies were proposed as a solution for the treatment
of emerging contaminants, in particular pharmaceuticals and
personal care products. The advanced oxidation process reactions
can further be supported by iron catalysts and UV radiation,
resulting in the formation of photopentone systems. The opti-
mum design, operation, and control of these processes can be
driven by sophisticated process system design tools that combine
advanced oxidation process science, photo-Fenton chemistry,
and cutting-edge technology with model-based optimization
strategies. However, the use of optimization tools requires the
availability of reliable models.
The following contents are discussed:
The basic principles of oxidation reactions are fundamental for
the successful application of advanced oxidation processes in
complex matrices such as water and wastewater. The investiga-
tions of reaction paths and modeling promote understanding
the basics. The Fenton reaction is one of the oldest induced iron
oxidation processes and is used worldwide in its entirety. How-
ever, there are some drawbacks such as high sludge production,
iron leaching, acidic pH, etc. We try to overcome these drawbacks
through a better understanding of the process, using reaction
promoters and heterogeneous catalysts. Photocatalysis was
xvii
xviii Preface

discovered more than 30 years ago by Japanese scientists.

Although a huge number of investigations have been carried
out to achieve a better understanding of the process and the reac-
tion pathways, no commercial application is available worldwide.
Other catalysts under development with an emphasis on higher
photonics efficiency, a shift of the absorption spectrum to the vis-
ible light range, and higher photoreactor efficiency could help
overcome constraints. Oxidation processes are used in many
plants around the world to remove inadequate substances. New
applications suggest opportunities for further development. Inte-
grating advanced oxidation processes into processes offers other
economic benefits. Combinations with biological processes and
in particular membrane bioreactors are continually investigated
and supported by toxicological tests.
This work is a useful reference for researchers and students
involved in wastewater technologies, including analytical and
environmental chemistry, chemical and environmental engineer-
ing, toxicology, biotechnology, biochemical engineering, liquid
waste management, and related fields. It is intended to encourage
industrial and public-health scientists as well as decision-makers
to accelerate the application of AOPs as technological alternatives
for the improvement of wastewater treatment plants.
Advanced oxidation processes
1
for complex wastewater
treatment
Vineet Kumara,b, Maulin P. Shahc
a
Environmental Microbiology and Biotechnology Laboratory, School of
Environmental Sciences, Jawaharlal Nehru University, New Delhi, Delhi, India.
b
Department of Environmental Microbiology, Babasaheb Bhimrao Ambedkar
(Central) University, Lucknow, Uttar Pradesh, India. cResearch Scientist,
Environmental Microbiology Lab, Ankleshwar, Gujarat, India

1 Introduction
Complex wastewater with high COD, BOD, and color is dis-
charged from various industries such as distilleries, breweries,
tanning, leather manufacturing, pulp-paper, etc. (Chandra and
Kumar, 2015, 2018). Among them, the alcohol distilleries are
one of the major sources generating high-strength complex
wastewater (Nataraj et al., 2006). A medium-scale distillery using
sugarcane molasses, a by-product of sugar production that is the
most commonly used raw material, can generate an average of
12–15 L of complex wastewater per liter of alcohol produced
(De Vrieze et al., 2014; Kumar and Chandra, 2020). This high-
strength complex wastewater is also known as spent wash,
stillage, raw effluent, or vinasses. Distillery spent wash is an
undesirable viscous, hydrophilic, and residual brown colored liq-
uid waste, which contains high levels of biological oxygen
demand (40,000–60,000 mg L
1), chemical oxygen demand
(90,000–190,000 mg L
1), and total dissolved solids (90,000–
150,000 mg L
1) with an acidic pH (3.0–4.07) (Acharya et al.,
2011; Singh and Dikshit, 2011; Chandra and Kumar, 2017a). Spent
wash also contains residual reducing sugars, phenolics, lipids,
proteins, amino acids, and volatile organic acids generated by

Advanced Oxidation Processes for Effluent Treatment Plants. https://doi.org/10.1016/B978-0-12-821011-6.00001-3

# 2021 Elsevier Inc. All rights reserved. 1
2 Chapter 1 Advanced oxidation processes for complex wastewater treatment

the yeasts during fermentation process. Besides

the organic con-
2

tent, a high mineral

load of sulfate SO 4 , potassium (K+), phos-
2
2+ +
phorous PO4 , calcium (Ca ), and sodium (Na ) has been
reported in generated spent wash ( Jain and Srivastava, 2012;
Chandra and Kumar, 2017a). Moreover, it also contains large con-
centrations of heavy metals viz. iron (Fe), zinc (Zn), nickel (Ni),
manganese (Mn), lead (Pb), mercury (Hg), copper (Cu), and chro-
mium (Cr) ( Jack et al., 2014; Mahar et al., 2013). Recently, spent
wash was reported to contain high amounts of butanedioic acid
bis(TMS)ester; 2-hydroxysocaproic acid; benzenepropanoic acid,
α-[(TMS)oxy], TMS ester; vanillylpropionic acid, bis(TMS), and
other recalcitrant organic pollutants such as 2-furancarboxylic
acid, 5-[[(TMS)oxy] methyl], TMS ester; benzoic acid
3-methoxy-4-[(TMS)oxy], TMS ester; and tricarballylic acid
3TMS (Chandra and Kumar, 2017a). According to the USEPA
(2012), most of these identified organic compounds are toxic, car-
cinogenic, mutagenic, and endocrine disruptors in nature while
some organic compounds in spent wash are recalcitrant to biodeg-
radation (Chowdhary et al., 2018). The pollutants present in gener-
ated spent wash are reacting to each other and make the
wastewater more toxic and complex (Arimi et al., 2014; Kumar
and Sharma, 2019). Depending on the sugarcane origin and opted
industrial process for alcohol production, the intrinsic composi-
tion of spent wash can vary significantly. The acidic pH (from 3.8
to 5) of spent wash is associated mainly with the presence of
organic acids produced by the yeasts during the alcoholic fermen-
tation process. The acidity of the spent wash causes the dissolution
of metals in water bodies. Moreover, the dark brown color of spent
wash is imparted by complex compounds such as melanoidin, car-
amel, hexose alkaline degradation products (HADP), furfurans
(from acid hydrolysis), lignin, and polyphenols as well as plant pig-
ments such as carotenoids, chlorophyll, anthocyanins, and tan-
nins, which make spent wash more complex (Hatano et al., 2008;
Dai and Mumper, 2010; Arimi et al., 2014; Zhang et al., 2017). These
colorants are concentrated in molasses after the crystallization of
sugar and are further transferred to the spent slurry during molas-
ses fermentation. Among the color-causing pigments, melanoidin
is the major dark brown color pigment of spent wash, and it is
produced through nonenzymatic browning reactions such as the
Maillard reaction, alkaline degradation reactions, or sugar degra-
dation occurred at medium temperature ( >50 °C) and in a basic
pH medium (Hodge, 1953; Coca et al., 2004; Kumar and
Chandra, 2018a). Melanoidin polymers are generally regarded to
be heterogeneous and acidic with a high molecular weight (5000
and 40,000 Da) along with similar chemical properties to humic
 Chapter 1 Advanced oxidation processes for complex wastewater treatment 3

substances (i.e., humic and fulvic acids) (Liang et al., 2009; Liu et al.,
2013; Kumar and Chandra, 2020). They are composed of highly dis-
persed colloids, which are negatively charged due to the dissocia-
tion of carboxylic acids and phenolic groups. Melanoidins are
difficult to characterize due to their varying sizes and the types
of reducing sugars and amino acids involved in their formation
(Chandra et al., 2008; Arimi et al., 2014; Hatano and Yamatsu,
2018). It has been reported that melanoidins have net negative
charges. Therefore, different heavy metals such as Cu, Cr, Cd, Fe,
Zn, Ni, and Pb strongly bind with melanoidins to form organo-
metallic complexes in distillery spent wash (Migo et al., 1997;
Hatano et al., 2013, 2016; Chandra et al., 2018a,b,c).
Over the last decades and due to its high inorganic loads, spent
wash has been widely used as a liquid fertilizer for sustainable
agriculture (Kumar and Chopra, 2012; Jain and Srivastava, 2012;
Kumari et al., 2015). However, regulations have made spreading
spent wash more difficult because of its low pH and high organic
and inorganic content, which may be responsible for groundwater
contamination and soil compaction (Ansari, 2014). Some studies
have indicated that spent wash negatively affects the physical
properties of soil, such as hydraulic conductivity and redox poten-
tial (Alves et al., 2015). Thus, the safe disposal of spent wash is
becoming a serious problem throughout the world (Chowdhary
et al., 2018). Different conventional processes such as anaerobic
digestion (biomethanation), anaerobic lagoons, and activated
sludge are available to treat spent wash (Kumar and Sharma,
2019; Kumar et al., 2020). Among them, biomethanation is a pop-
ular, cost-effective, first-step conventional biological treatment of
spent wash that produces methane to meet part of the power
requirement in distilleries (Khairnar et al., 2013; Sankaran et al.,
2017). This methane gas is mainly utilized for running steam
boilers to generate electricity. On average, 1 m3 of spent wash pro-
duces 38–40 m3 of biogas (Sankaran et al., 2014). Moreover, in
most instances during biomethanation, the melanoidin com-
pounds repolymerize, thereby intensifying the color of spent wash
and making the decolorization of wastewater even more difficult
(Zhang et al., 2017). The polymerization may also extend to differ-
ent levels, and it occurs in complex ways. After biomethanation,
the distillery wastewater still retains a high COD (40,000–
52,000 mg L
1), BOD (8000–12,000 mg L
1), and substantial color
(Saner et al., 2014; Naveen and Premalatha, 2016). Most of the dis-
tilleries employ a direct two-stage aerobic process for further
treatment of the biomethanated spent wash. Often, it becomes
recalcitrant [biodegradability index (BI) <0.2]) to further effective
treatment by biological aerobic processes. The antioxidizing
4 Chapter 1 Advanced oxidation processes for complex wastewater treatment

properties of melanoidins and plant phenolics make the wastewa-

ter toxic to living organisms. Therefore, the primary biological aer-
obic and anaerobic treatments were found to be ineffective to
degrade color compounds (Caderby et al., 2013; Moraes et al.,
2015; Kaushik et al., 2018). The major challenges of this partially
treated or untreated colored distillery wastewater before it can
be safely disposed into the environment are the removal and deg-
radation of color-contributing compounds such as malanoidins,
caramel, and phenolics and their metabolic products as well as
inorganic compounds (Ray and Ghangrekar, 2015). The conven-
tional wastewater treatment processes are designed to reduce
solids in suspension, biodegradable organic products, microor-
ganisms, and nutrients from wastewater, but not to reduce the
chemical pollutants and much less emerging chemical pollutants
(Shah et al., 1989; Ghosh et al., 2004; Chandra et al., 2018a). How-
ever, for the treatment of spent wash by conventional methods
such as aerobic and nonaerobic digestion, the ratio of BOD to
COD should be 40.6 (Chain and Dewalle, 1977). Distillery waste-
water after biomethanation has a high BOD/COD, which would
cause the destruction of microorganisms that are useful in
biodegradation processes. Conventional anaerobic-aerobic treat-
ment processes can remove a maximum of only 6%–7% of the ini-
tial concentration of melanoidins from spent wash (Blonskaja and
Zub, 2009). Hence, the biomethanated spent wash still has a high
organic and inorganic load, which requires further treatment
before its safe disposal into the environment (Chandra et al.,
2015, 2018b; Chandra and Kumar, 2017; Sanchez-Galvan and
Bolanos-Santiago, 2018). The shortfalls of existing treatment tech-
nologies include the huge fuel consumption for air diffusion for
the aerobic oxidation of organic matter, and the pollution of
groundwater and surrounding lands by the leaching of pollutants
from aerated lagoons (Padoley et al., 2012a,b; Moraes et al., 2015;
Chowdhary et al., 2018). Therefore, these methods are expensive
and not eco-friendly as they generate large amounts of sludge,
which also requires safe disposal and can cause secondary pollu-
tion (Liang et al., 2009; Liu and Zhang, 2014; Liakos and
Lazaridis, 2014).
When untreated or partially treated complex wastewater is dis-
charged into a water resource (rivers, lakes, and lagoons), mela-
noidins reduce sunlight penetration, which in turn decreases
both the dissolved oxygen concentration and the photosynthetic
activity of marine plants; this creates anaerobic conditions that
kill most of the aquatic life (Ramakritinan et al., 2005; Kumar
and Gopal, 2001). Additionally, the discharge of spent wash into
water bodies releases an unpleasant odor and also contributes
 Chapter 1 Advanced oxidation processes for complex wastewater treatment 5

to disseminating endemic diseases in the absence of natural pred-

ators. The disposal of spent wash on land is equally hazardous; it
inhibits seed germination and depletes vegetation by reducing the
soil alkalinity and manganese availability (Pandey et al., 2008;
Bharagava and Chandra, 2010). The dark brown colored wastewa-
ter after biomethanation and further dilution is used for irrigation,
causing gradual soil darkening that affects the physicochemical
properties of soil while also being harmful for beneficial soil
microorganisms (Chidankumar and Chandraju, 2008; Juwarkar
and Dutta, 1989). Sometimes, the leaching of spent wash into
the groundwater table results in severe groundwater contamina-
tion ( Jain et al., 2005; Chauhan and Rai, 2010). The direct dump-
ing of colored wastewater poses the risks of soil salinization
(Kaushik et al., 2005) and contamination of groundwater by heavy
metals (Mahar et al., 2013). Hence, untreated spent wash is an
ecotoxic effluent and is unsafe for use in any form for humans
and the environment such as agricultural and aquatic ecosystems
(Kaushik et al., 2005; Ayyasamy et al., 2008; Alves et al., 2015). The
wastewater discharge sites and their adverse effects on humans
and animals are shown in Fig. 1. There is an urgent need to treat

(A) (B)

(C) (D) (E)

Fig. 1 A view of complex colored wastewater discharged from alcohol distilleries and its impact in environment:
(A) spent wash, (B) biomethanated spent wash, (C) aquatic pollution, and (D, E) soil pollution.
6 Chapter 1 Advanced oxidation processes for complex wastewater treatment

these industrial effluents to remove contaminants prior to dis-

charge into the surrounding soil and water bodies (Kaushik
et al., 2018). Recent advances in newly developed processes to
treat distillery wastewater include different physical, chemical,
biological, and integrated techniques. Nowadays, “advanced oxi-
dation processes” (AOPs) have received great attention for the
removal of organic pollutants present in various industrial efflu-
ents (Wang and Xu, 2011; Deng and Zhao, 2015). AOPs have been
used as alternative and effective options for treating untreated or
partially treated DSW.
This chapter offers latest and advanced information about the
various AOPs and their degradation mechanisms of pollutants
that are being used for the treatment of complex distillery waste-
water. Further, the authors also discussed issues associated with
practical wastewater treatment and offered suggestions for the
direction of future research.

2 Advanced oxidation processes (AOPs)

AOPs are considered highly effective wastewater treatment
technologies for removing low biodegradability, refractory, inhib-
itory, or high chemical stability pollutants. The AOP mechanisms
rely on the in situ formation of highly reactive oxidant species,
mainly hydroxyl radicals (OH). The OH radicals are highly effec-
tive, powerful, ubiquitous in nature, and nonselective with
electrophilic behavior and a redox potential of 2.8 V, which accel-
erate the oxidation and degradation of a wide range of contami-
nants in wastewater by abstracting a hydrogen atom from
aliphatic carbon, or adding a hydrogen atom to the double bonds
and aromatic rings (Wang and Xu, 2011; Oturan and Aaron, 2014).
The OH is compounds to destroy and even mineralize them into
carbon dioxide (CO2), water (H2O), and inorganic salts to some
extent.
Organic species + HO ! CO2 + H2 O + inorganic ions (1)
The organic compounds containing carbon-carbon double bonds
in their structure are more reactive toward OH. However, the life-
time of OH is extremely short (t  10
3 s), and once the OH has
formed, it can give rise to several elementary reactions. The AOPs
are also operated at ambient temperature. Other radicals and
active oxygen species generated in AOPs are superoxide radicals
ðO2
Þ, hydroperoxyl radicals ðHO2
Þ, sulfate radicals (SO4
),
and organic peroxyl radicals (ROO) (Manickavachagam et al.,
2014; Oturan and Aaron, 2014). These radicals are formed from
 Chapter 1 Advanced oxidation processes for complex wastewater treatment 7

a less reactive primary oxidant such as hydrogen peroxide (H2O2)

or ozone (O3). The generation of these reactive agents can be
achieved by means of several processes, including sonolysis,
ozone-based processes (ozonation), ultraviolet (UV) irradiation,
Fenton oxidation, photo-Fenton oxidation, ultrasound, photoca-
talysis, and various combinations of these technologies such as
Fenton (H2O2/Fe2+), photo-Fenton (H2O2/UV/Fe2+), peroxidation
combined with ultraviolet light (H2O2/UV), peroxone (O3/H2O2),
peroxone combined with ultraviolet light (O3/H2O2/UV), the O3/
UV system, O3/TiO2/H2O2, and O3/TiO2/electron beam irradia-
tion (Fig. 2).

2.1 Fenton and photo-Fenton oxidation treatment

Fenton oxidation is a very effective and advanced technology
to treat complex distillery wastewater (Hadavifar et al., 2009). In
addition to improving the biodegradability of the effluent, the
Fenton process removes the remnant COD, toxicity, and color of
the wastewater (Bhoite and Vaidya, 2019). In the Fenton treatment
process, the Fenton reagent, a mixture of H2O2 and ferrous iron
salts (Fe2+), generates highly reactive radical (OH), which involves

Fig. 2 Different categories of

advanced oxidation processes
(AOPs) used for complex
wastewater treatment.
8 Chapter 1 Advanced oxidation processes for complex wastewater treatment

a complex reaction sequence and ultimately leads to organic

removal of the wastewater (Zhang et al., 2019). The Fe2+ initiates
and catalyzes the decomposition of H2O2 in acidic conditions,
resulting in the generation of OH. The Fenton process mecha-
nism is presented by the following reactions:
Fe2 + + H2 O2 ! Fe3 + + OH
+ OH (2)
Fe2 + + OH ! Fe3 + + OH
(3)
OH + RH ! H2 O + R (4)
R + Fe 3+
! R + Fe
+ 2+
(5)
The Fenton oxidation and adsorption pretreatment of biometha-
nated spent wash improves the biogas recovery (Bhoite and
Vaidya, 2019). Using a ferrous sulfate catalyst for diluted wastewa-
ter, a 54% reduction in COD was achieved within 1 h in acidic
medium (pH 3) at ambient temperature (30°C). After postoxida-
tion, the BI value was improved (0.33). After subsequent adsorp-
tion over activated carbon (loading 5%) for 1 h, the COD reduction
(70%), and BI value (0.43) improved further. Upon anaerobic treat-
ment with 1% acclimatized biomass, 1 Nm3 of biogas (47% CH4)
was additionally formed per m3 of treated wastewater; without
pretreatment, this value was 0.9 Nm3 (just 11% CH4). Lastly, aero-
bic treatment was performed and the results were encouraging:
the BI was improved to 0.51 and the COD reduction was activated
94%. Although the oxidation processes based on the Fenton reac-
tion are chemically very effective to treat a wide range of organic
pollutants in wastewater, they have several limitations that
include high sludge formation; operation at adverse pH values
(2–3); the addition of relatively large amounts of Fe2+; the concen-
tration of H2O2; slowing down of the Fenton reaction after the ini-
tial conversion of Fe2+ to ferric ions (Fe3+); the presence of other
ions such as phosphate, sulfate, fluoride, bromide, and chloride;
the inactivation of heavy metal ions in the sludge by the formation
of hydroxide complexes; and the need to separate the catalyst
after the process (Wang and Xu, 2011; Oturan and Aaron, 2014).
Moreover, another limiting feature of the Fenton reaction-based
oxidation process is the generation of recalcitrant intermediates,
which can constrain the complete mineralization of pollutants.
Even with the existence of these latent limitations, conventional
Fenton reaction processes have been extensively used in small-
scale industrial wastewater treatment or special pollutant
removal.
In pursuit of the limitations of the classical Fenton process,
several other processes have been developed from that process.
 Chapter 1 Advanced oxidation processes for complex wastewater treatment 9

The first process was to couple light energy from UV sources or

emissions from the sun in a process called photo-Fenton oxida-
tion. The photo-Fenton process (H2O2/Fe2+/UV) involves OH for-
mation through the photolysis of H2O2 in the presence of UV. In
the presence of UV irradiation, the Fe3+ produced in Eq. (3) is
photocatalytically converted to Fe2+, with the formation of an
additional equivalent of OH.
Fe3 + + H2 O ! Fe2 + + H + + OH (6)
The photo-Fenton reaction gives faster rates and higher degrees of
mineralization compared to the conventional Fenton process.
This reaction can be driven by low energy photons, and it can also
be achieved using solar irradiation. This fact can significantly
reduce the operational cost of the treatment (Ebrahiem et al.,
2017). Besides, this process has been instrumental in improving
the kinetics and the performance of the classical Fenton process,
including decreasing the demand for the catalyst and improving
color removal. However, the photo-Fenton process does not
address the other limitations, especially the low pH operation
and the problem of high heavy metal ions in the final wastewater
(Ahmed et al., 2011). There are also reports of enhanced perfor-
mance in COD removal, an increase in biodegradability, and the
detoxification of complex wastewater after treatment with
photo-Fenton oxidation (Derakhshan and Fazeli, 2018). The tox-
icity of H2O2 to several microorganisms and the use of excess
amounts of H2O2 could possibly deteriorate the overall degrada-
tion efficiency for cases where the Fenton process is followed by
biological oxidation. Additionally, the necessity of wastewater
acidification due to the optimum low pH range (pH 3) for the
photo-Fenton reaction occurrence, and the inevitable need for
catalyst removal at the end of the reaction are additional limita-
tions of these AOPs. Another key modification to the classic Fen-
ton process aims at eliminating the limitations of low pH
operation and the recovery of spent catalysts from wastewater
by the use of heterogeneous Fenton processes. It entails embed-
ding the ferrous catalyst and the acid group on a carrier material.
By limiting the catalyst supply in the effluent, the method ensures
that minimal sludge is formed by the coagulation process. In addi-
tion, the amount of heavy metal ions in the sludge and treated
effluent is minimized. The catalyst ions are supposed to be slowly
released from the embedment where they react with the H2O2 to
form the radicals. The use of modified natural zeolite as a hetero-
geneous Fenton catalyst in the treatment of recalcitrant industrial
wastewater was reported by Arimi (2017). In this study, the zeolite
pellets were modified by pretreatment with sulfuric acid (H2SO4),
10 Chapter 1 Advanced oxidation processes for complex wastewater treatment

nitric acid (HNO3), and hydrochloric acid (HCl), before embed-

ding on the Fe2+ ions. The H2SO4-Fe2+-modified catalysts showed
the highest activity, which achieved 90% color and 60% TOC (total
organic carbon) removal at 150 g/L pellet catalyst dosage, 2 g/L
H2O2 at 25°C. The heterogeneous Fenton with the same catalyst
improved the biodegradability of the anaerobic effluent from
0.07 to 0.55. In addition to posttreatment, the catalyst was also
applied to pretreat the raw molasses distillery wastewater and
increased its biodegradability by 4%. Subsequently, the color of
the resultant anaerobic effluent was also reduced. The author
recommended that the modified zeolite can be used as a hetero-
geneous Fenton catalyst in the pretreatment of the raw molasses
distillery wastewater before anaerobic digestion with minimal
COD loss. However, the UV and photocatalysis processes are also
costly because of the high energy requirements.

2.2 Ozone-based oxidation treatment

The ozonation/ozonolysis process seems to be a promising
oxidation treatment technology for the removal of colorant from
molasses-derived wastewater or synthetic distillery wastewater
(Otieno et al., 2019; Kim et al., 1985). O3 is usually generated in situ
by electric discharge in a stream of oxygen (O2) or air, leaving nei-
ther odors nor residual tastes. It is widely used for disinfection due
to its strong cell lytic activity that can kill the microorganisms
found in the wastewater (Martı́nez et al., 2011). In the ozonation
process, O3 is used as a powerful oxidizing agent (E0 ¼ 2.07 V) that
is able to transform the organic pollutants into smaller com-
pounds or CO2, H2O, and sulfate and nitrate anions when S and
N atoms are present (Wang and Xu, 2011; Deng and Zhao,
2015). Once O3 is dissolved in H2O, it reacts with a large number
of organic compounds in two possible ways: direct oxidation as
molecular O3, or an indirect reaction through the formation of
secondary oxidants such as free radicals, that is, OH. Both O3
and OH are strong oxidants and are capable of oxidizing a num-
ber of organic pollutants, finally reducing the value of COD in
wastewater (Gulyas et al., 1995; Rice, 1995). Different detailed
mechanisms have been proposed to explain the OH generation,
and the overall reaction involving OH generation is expressed as
follows (Wang and Xu, 2011; Deng and Zhao, 2015):
O3 + H2 O ! 2OH + 4O2 ðOzonationÞ (7)
In the presence of other oxidants or irradiation, the OH yield can
be significantly improved. For example, in the peroxone
(O3/H2O2) system, the O3 decomposition and OH production
 Chapter 1 Advanced oxidation processes for complex wastewater treatment 11

are enhanced by hydroperoxide ðHO2
Þ produced from H2O2

decomposition. H2O2 produces HO2
under basic conditions.
HO2
induced from H2O2 reacts with O3 and produces some free
radicals.
H2 O2 ! HO2
+ H + ðO3 =H2 O2 Þ (8)



HO2 + O3 ! OH + O2 + O2 ðO3 =H2 O2 Þ (9)
In O3/UV irradiation, H2O2 is generated as an additional primary
oxidant through photolysis of the O3, which produces the forma-
tion of OH. H2O2 further generates OH radicals, as shown in the
following reaction (Deng and Zhao, 2015):
O3 + H2 O + hv ! H2 O2 + O2 ðO3 =UV Þ (10)
H2 O2 + hv ! 2OH ðPhotolysis of H2 O2 Þ
(11)
H2 O2 + OH ! HO2
+ H2 O ðPhotolysis of H2 O2 Þ
The above optimizes the application of ozone, and the concentra-
tions of OH (E0 ¼ 2.80 V) that are produced by O3 decomposition
in aqueous solutions produce a significant increase in the decom-
position rate of pollutants (Gulyas et al., 1995). In addition, H2O2 is
a weak acid with a relatively high oxidant potential (E0 ¼ 1.77 V),
which alone does not lead to the generation of hydroxyl radicals.
The slow reactions rates make the process ineffective when oxi-
dizing more refractory and recalcitrant pollutants. Therefore,
the addition of H2O2 with O3 increases the rate of O3 oxidation
by allowing an enhancement in the quantum yield of the forma-
tion of the OH (Rice, 1995).
Ozone can selectively attack the double bonds (e.g., C]C,
N^C) and functional groups (e.g., dCH3, dOH, and dCH3) in
acid or neutral conditions with limited concentrations
(Mantzavinos and Psillakis, 2004). Melanoidins, polyphenols,
and other contaminants of distillery wastewater have double
bonds (C^N and C]C) and other functional groups in their
structure can be selectively broken down by O3 without the exten-
sive oxidation of the vast organic matter (OMs) (Naik et al., 2010).
In 1985, Kim and his colleagues investigated the decolorization
and degradation products of melanoidins prepared from a
glucose-glycine system with the use of O3. In this study, melanoi-
dins were decolorized to degrees of 84% and 97% after ozonolysis
at
1°C for 10 and 90 min, respectively; the mean molecular
weight of melanoidins decreased from 7000 to 3000 Da after ozo-
nolysis for 40 min. The selectivity of O3 was clearly demonstrated
in the study of Martin Santos et al. (2003), where 80% of phenolics
and 16% of the organic load were removed after the ozonation of
molasses-based distillery wastewater at an acid condition. Thus,
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 GENERAL CATARRHAL STOMATITIS.
BUCCAL INFLAMMATION.
Mature animals most subject: Causes in horse, mechanical, chemical, microbian
irritants—alkalies, acids, caustics, hot mashes, ferments, fungi, rank grasses,
excess of chlorophyll, clover, alfalfa, acrid vegetables, bacterial infection secondary,
acrid insects in food; symptomatic of gastritis, pharyngitis, diseased teeth, specific
fevers. Symptoms: Congestion and tumefaction of buccal mucosa, lips and salivary
glands; Epithelial desquamation; fœtor; salivation; froth; papules; vesicles.
Prognosis. Treatment: Cool soft food; antiseptics; wet applications to skin;
derivatives.
This is much more common in the adult than in suckling domestic
animals. None of the domestic mammals or birds can be considered
immune from it, but as its causes and manifestations differ
somewhat it seems well to consider it separately in the different
genera.
 GENERAL CATARRHAL STOMATITIS IN
SOLIPEDS.

Causes. These may be classed as mechanical, chemical, microbian

and other irritants. In the horse it is often due to the reckless
administration of irritant liquids as remedies. Owing to the length of
the soft palate the horse can refuse to swallow any liquid as long as
he chooses, and some of the worst cases of stomatitis I have seen
resulted from the retention in the mouth of caustic alkaline liquids
given under the name of “weak lye.” Strong acids and caustic salts
dissolved in too little water or other excipient, or suspended in
liquids in which they cannot dissolve, or made into boluses which are
crushed between the teeth are not infrequent conditions. Too hot
mashes given to a hungry horse is another cause of this trouble.
Fermented or decomposed food is often most irritating. Coachmen
will sometimes induce it by attaching to the bit bags of spicy or
irritant agents, to cause frothing and make the animal appear
spirited.
Fungi in fodders are among the common causes. The rust of wheat
(puccinia graminis), the caries of wheat (tilletia caries), the blight
(erysiphe communis), ergot (claviceps purpurea), the fungus of rape
(polydesmus excitiosus) and the moulds (penicillium and puccinia)
have all been noticed to coincide with stomatitis, and charged with
producing it. On the other hand, at given times, one or other of these
cryptogams has been present extensively in the fodder without any
visible resultant stomatitis. The apparent paradox may be explained
by the fact that these fungi vary greatly in the irritant or harmless
nature of their products according to the conditions under which
they have grown, and the stage of their development at which they
were secured and preserved. Ergot notoriously differs in strength in
different years, on different soils, under various degrees of sunshine,
shade, cloud, fog, etc. In different States in the Mississippi valley it is
not uncommon to find stomatitis in horses in winter, fed on ergoted
hay, while cattle devouring the same fodder have dry gangrene of
feet, tail and ears. Yet in other seasons the ergot fails to produce
these lesions. Rank grown, watery vegetation, especially if it contains
an excess of chlorophyll is liable to cause stomatitis. Red and white
clover, trefoil, hybrid and purple clover, and alfalfa have all acted
more or less in this way, though in many cases, the food has become
musty or attacked by bacterial ferments. Some of the strongly
aromatic plants, and those containing acrid principles (cicuta virosa,
œnanthe crocata, mustard, etc.) cause buccal inflammation and
salivation.
The irritation in many such cases is not due to one agent only, the
vegetable or other irritant may be the starting point, acting but as a
temporary irritant, the action of which is supplemented and
aggravated by the subsequent attacks of bacterial ferments on the
inflamed, weakened or abraded tissues. The bacteria present in the
mouth, food or water would have had no effect whatever upon the
healthy mucosa, while they make serious inroads on the diseased. On
the other hand the vegetable, mechanical or chemical irritant would
have had but a transient effect, but for the supplementary action of
the bacteria.
In horses that have the bad habit of retaining masses of half
masticated food in the cheeks the growth of cryptogams is greatly
enhanced and such food often becomes violently irritating.
Among other mechanical causes may be named pointed or barbed
hairs or spines (barley awns, spikes, thorns, etc.) which, lodging in a
gland orifice, or in a wound of the gum or mucosa, form a source of
irritation or a centre for bacterial growth and abscess.
Again, irritants of animal origin must be named. These are not
taken by choice, but when lodged in fodder, or in the pastures they
are taken in inadvertently with the food. In this way poisonous
insects, and especially hairy caterpillars, cantharides, potato bugs,
etc., gain access to the mouth.
It must not be overlooked that stomatitis occurs as an extension,
sympathetic affection or sequel of diseases of other organs. Gastritis
is usually attended by redness and congestive tenderness of the
tongue, especially of the tip and margins, and other parts of the
buccal mucosa, notably the palate just back of the incisors, are often
involved. In other cases it appears as a complication of pharyngitis,
laryngitis, of affections of the lower air passages, of the teeth and
periodontal membrane or of the salivary glands.
It appears also in a specific form in certain fevers, as in horsepox,
pustulous stomatitis, aphthous fever and even in strangles. Mercurial
stomatitis, rarely seen at the present time, is one of the worst forms
of the disease, and like the infectious forms will be treated
separately.
Lesions and Symptoms. At the outset and in the slighter forms of
congestion there is merely heat and dryness of the buccal mucosa.
Redness may show on the thinner and more delicate portions of the
membrane, as under the tongue, on the frænum, and on the
sublingual crest. But elsewhere it is hidden by the thickness of the
epithelium, and the manifestations are merely those of suppressed
secretion with local hyperthermia.
As the congestion is increased there is seen, even at this early
stage, a slight thickening or tumefaction of the mucosa, especially on
the gums, lips, the sublingual area, the orifices of the salivary glands,
and the palate back of the upper incisors. On the dorsum of the
tongue, the cheeks and lips, generally the lack of loose connective
tissue tends to prevent the swelling.
With the advance of the inflammation the redness of the mucosa
extends, at first in points and circumscribed patches, and later over
the entire surface. The epithelium drying and degenerating in its
surface layers forms with the mucus a sticky gummy film on the
surface, which, mingling with decomposing alimentary matters gives
out a heavy, offensive or even fœtid odor.
The different parts of the mouth are now tender to the touch, and
this, with the fœtor and even bitterness of the bacterial products
combine with the general systemic disturbance in impairing or
abolishing appetite. In any case mastication becomes slow and
infrequent, and morsels of food are the more likely to be retained, to
aggravate the local condition by their decomposition.
The dry stage is followed by the period of hypersecretion, and in
this the salivary glands take a prominent part, so that ptyalism
(slobbering) becomes the most marked feature of the disease. The
saliva mixed with the increasing secretion of mucus and the
abundance of proliferating and shedding epithelium, escapes from
the lips and falls in stringy masses in the manger and front of the
stall. When there is much motion of the jaws and tongue it
accumulates as a froth around the lips.
A careful examination of the mucosa will sometimes detect slight
conical elevations with red areolæ, representing the tumefied orifices
of the obstructed mucous follicles, and later these may show as
minute erosions. Even vesicles have been noticed (Weber,
Dieckerhoff, Kosters), but when these are present one should
carefully exclude the specific stomatites such as horsepox, contagious
pustular stomatitis, aphthous fever, etc.
Erosions of the mucosa and desquamation of the epithelium have
been noticed in horses fed on purple (hybrid) clover, buckwheat or
ergot, and in some of these cases the inflammation has extended (in
white faces especially) to the skin of the face, the mucosa of the nose,
and the adjacent glands, and as complications icterus, constipation,
colics, polyuria, albuminuria and paresis of the hind limbs have been
observed. These latter are common symptoms of cryptogamic
poisoning.
Prognosis. In uncomplicated cases the disease is not a grave one,
lasting only during the continued application of the local irritant, and
recovering more or less speedily when that has been removed.
Complications are dangerous only when due to some specific disease
poison (glanders, actinomycosis, strangles, etc.), and even poisoning
by the usual cryptogams of leafy or musty plants is rarely persistent
in its effects.
Treatment. This resolves itself into the removal of the irritant
cause and the soothing of the irritation. When the cause has been
definitely ascertained the first step is easy.
In the direction of soothing treatment, a careful selection of diet
stands first. Fibrous hay and even hard oats, barley or corn may have
to be withheld, and green food, or better still, bran mashes, gruels,
pulped roots or fruits allowed. Scalded hay or oats, ensilage, sliced
roots, or ground feed may often be taken readily when the same
aliments in their natural condition would be rejected or eaten
sparingly.
 Medicinal treatment may often be given in the drinking water
which should always be allowed in abundance, pure and clean. In the
way of medication chlorate of potash, not to exceed one-half to one
ounce per day according to the size of the animal, may be added,
together with an antiseptic (carbolic acid, borax, permanganate of
potash, common salt, naphthol, creolin, hyposulphite of soda). In
case of severe swelling, a cap made to fit the head with strips wet in
alum and vinegar or other astringent solution maintained against the
intermaxillary space may be desirable. Support for the tongue may
be necessary as mentioned under glossitis.
In case of complications on the side of the bowels, liver or kidneys,
laxatives, diuretics and antiseptic agents may be called for.
 GENERAL CATARRHAL STOMATITIS IN
CATTLE.
Dense resistant mucosa protective: Affection usually circumscribed. Action of
violent irritants, and toxins of specific fevers. Mechanical irritants. Symptoms:
Salivation; congestion; eruptions; erosions; ergot; acrid vegetables; caustics.
Treatment: Astringents; antiseptics; refrigerants; derivatives; tonics. Removal of
foreign bodies. Lesions and symptoms in sheep.
The mouth of the ox as Cadeae well says has a cuticular epithelium
too thick and resistant to be easily attacked by microbes. It follows
that infected inflammations are far more frequently circumscribed
than in the thinner and softer buccal mucosa of the horse. The more
general buccal inflammations come more particularly from the use of
food that is too hot or that contains strongly irritant agents. The
thickness of the buccal epithelium however, is no barrier to the local
action of poisons operating from within as in rinderpest, or aphthous
fever, or in malignant catarrh, nor is it an insuperable barrier to the
local planting of the germs of cow pox, anthrax, actinomycosis, or
cryptogamic aphtha (muguet). The wounds inflicted by fibrous food
make infection atria for such germs, hence the great liability to such
local inflammations, in winter when the animals are on dry feeding.
For the same reason, perhaps, the prominent portions of the buccal
mucosa,—the papillæ—are sometimes irritated themselves while
serving as protectors for the general mucous surface, and hence they
become specially involved in inflammation, which constituted the
“barbs” of the old farriers. Utz records a buccal inflammation
occurring in herds fed on green trefoil, first cutting, showing that
even in cattle this agent may determine a general stomatitis.
Symptoms. These do not differ from those of the horse, and
resemble, though often in a milder form, the buccal manifestations of
aphthous fever. There is the difficulty of mastication and
indisposition to take in fibrous aliment, the drivelling of saliva from
the mouth, or its accumulation in froth around the lips, the frequent
movement of the tongue and jaws, and the congestive redness,
papular eruption, vesication, or even erosion of the affected mucous
membrane. It is always necessary to guard against confounding the
simple stomatitis, and the slighter infected inflammations, from the
more violent infections above referred to. The special diagnostic
symptoms must be found under the respective headings. The
aphthous fever is not to be expected in American herds, but the
stomatitis which is associated with ergot in the food is met more
particularly in winter and spring, and must not be confounded with
the specific disease, on the one hand nor with the simpler forms of
buccal inflammation on the other. In the case of ergoted fodder the
signs of ergotism in other situations will be found, in the affected
animals, such for example as necrotic sloughs and sores around the
top of the hoof, sloughing of the hoof or of one or more digits, or of
the metatarsus, of the tip of the tail or ear; abortions, convulsions,
delirium, lethargy or paralysis. If not seen in the same animals some
of these forms may be observed in other members of the herd. Then
the buccal lesions are in themselves characteristic: soft, whitish,
raised patches of the epithelium (rarely blisters) are followed by
desquamation and exposure of the red, vascular surface beneath, and
this tends to persist if the ergoted fodder is persisted in.
Treatment. Simple stomatitis of the ox generally tends to
spontaneous and early recovery. The simplest astringent and
antiseptic treatment is usually sufficient to bring about a healthy
action. Borax given in the drinking water, not to exceed four ounces
per day, or the same amount mixed with syrup or honey and
smeared occasionally on the tongue, or hyposulphite or sulphite of
soda, or weak solutions of carbolic acid will usually suffice, after the
irritant cause has been removed. Vinegar, or highly diluted mineral
acids may be used but are somewhat hurtful to the teeth. Decoctions
of blackberry bark or solutions of other vegetable astringents may be
used as alternatives. When there is evidence of irritant matters in the
stomach or bowels, a saline laxative will be advisable to be followed
by vegetable bitters or other tonics. Thorns and other foreign bodies
imbedded in the tongue or other part of the mouth must be
discovered and removed.
 CATARRHAL STOMATITIS IN SHEEP.
The more delicate buccal mucosa in these animals would render
them more subject to inflammations, but this is more than
counterbalanced by the mode of prehension of aliments, not by the
tongue, but by the delicately sensitive lips, and further by the
daintiness and care with which these animals select their food. The
treatment would not differ materially from that prescribed for the
ox.
 GENERAL CATARRHAL STOMATITIS IN
DOGS.
Causes: burns; spiced food; bones; sepsis; ferments; pin caterpillar; dental and
gastric troubles. Symptoms: careful prehension and mastication; congestion;
swelling; eruption; erosion; furred tongue; stringy salivation; fœtor; swelling of
lips, cheeks, intermaxillary space, and pharynx. Treatment: demulcent foods;
antiseptics; derivatives; tonics; care of teeth and gums.
Causes. Hot food is a common cause in hungry dogs. Spiced food
in house dogs fed scraps from the table tend to congestion of mouth
and stomach alike. Irritation through wounds with bones, especially
in old dogs with failing teeth, and in exceptional cases the impaction
of a bone between the right and left upper molars are additional
causes. Putrid meat must also be recognized as a factor, the septic
microbes seizing upon the wounds and spreading from this as an
infecting centre. Lactic acid and other irritant products developed
through fermentation of particles of food retained about the gums
and cheeks soften the epithelium and irritate the sub-epithelial
tissue, causing congestion. Megnin draws attention to the fact that
the pin caterpillar (bombyx pinivora) found on the stalks of couch
grass (Triticum repeus) produces buccal irritation when chewed and
swallowed to induce vomiting. As in other animals more or less
buccal congestion attends on gastric congestion and inflammation.
Dental troubles are often sufficient causes.
Symptoms. The animal becomes dainty with regard to his food,
picking up the smaller or softer pieces and rejecting the larger or
harder. Mastication is painful and selection is made of moist or soft
articles which can be swallowed without chewing or insalivation. The
mouth is red and hot, and at times the mucous membrane eroded, or
blistered, the lesions concentrating especially on the gums and
around the borders of the tongue. The dorsum of the tongue is
furred, whitish, yellowish or brownish. Saliva collects in the mouth
and escapes in filmy strings from its commissures, and the odor of
the mouth becomes increasingly foul. Swelling of the lips, cheeks or
intermaxillary space marks the worst cases.
 Treatment. Withdraw all irritant and offensive aliments. Give
soups, mushes, scraped or pounded lean meat in small quantities,
washing out the mouth after each meal with a 20 per cent. solution of
permanganate of potash or borax or a two per cent. solution of
carbolic acid. Cadeac advises against chlorate of potash on account of
its known tendency to bring about hæmoglobinæmia in dogs. A
laxative and bitters may be called for in case of gastritis or
indigestion, and any morbid condition of the teeth must be attended
to. Decayed teeth may be removed. Tartar especially must be cleaned
off by the aid of a small wooden or even a steel spud and a hard
brush with chalk will be useful. A weak solution of hydrochloric acid
is usually employed to loosen the tartar, but this is injurious to the
structure of the teeth and had best be avoided if possible. Tincture of
myrrh is especially valuable both as a gum-tonic and as a deodorant
and antiseptic. This may be rubbed on the irritated gums as often as
the mouth is washed.
 GENERAL CATARRHAL STOMATITIS IN
SWINE.

Causes: Irritants; ferments; noose on jaw; specific poisons. Symptoms: Careful

feeding; thirst; frothy lips; champ jaws; redness; swelling; fœtor. Treatment:
Cooling, astringent, antiseptic lotions; mushy food; derivative; tonics.

Causes. Swine suffer from simple stomatitis when exposed to

thermal, mechanical or chemical irritants. Food that is too hot, or
that which is hard and fibrous, or that which contains spikes and
awns, capable of entering and irritating gland ducts or sores, or food
which is fermented or putrid, food or medicine of an irritant
character. The habit of catching and holding swine with a running
noose over the upper jaw, and the forcing of the jaws apart with a
piece of wood in search of the cysticercus cellulosa are further
causes. In several specific infectious diseases inflammation of the
mucous membrane with eruption or erosion is not uncommon. Thus
aphthous fever is marked by vesicular eruption, muguet by epithelial
proliferation and desquamation, hog cholera and swine plague by
circumscribed spots of necrosis and erosion. Patches of false
membrane are not unknown, and local anthrax, tubercle and
actinomycosis are to be met with. Inflammation may start from
decaying teeth.
Symptoms are like as in other animals, refusal of food, or a
disposition to eat sparingly, to select soft or liquid aliments, to
swallow hard materials half chewed or to drop them, to champ the
jaws, and to seek cold water. Accumulation of froth around the lips is
often seen, and the mouth is red, angry, dry, and hot, and exhales a
bad odor.
Treatment does not differ materially from that adopted in other
animals. Cooling, astringent, antiseptic lotions, honey and vinegar,
and in case of spongy or eroded mucosa, tincture of myrrh daily or
oftener. Soft feeding, gruels, pulped roots, or well kept ensilage may
be used, and clean, cool water should be constantly within reach. In
case of overloaded stomach or indigestion a laxative followed by
bitter tonics will be in order.
 CATARRHAL STOMATITIS OF BIRDS. PIP.

Causes: hurried breathing; local irritants; exposure; filthy roost. Symptoms:

gaping; roupy cry; epithelial pellicle on tongue, larnyx. or angle of the bill.
Treatment: pick off pellicle; smear it often with glycerized antiseptic. Remove
accessory and exciting causes.

This form of inflammation of the tongue of birds is characterized

by the increased production and desiccation of the epithelium so that
it takes on a horny appearance. According to Cadeac it may
accompany various inflammatory affections of the air passages,
which cause hurried breathing with persistently open bill, and thus
entail evaporation of the moisture. More commonly it has its primary
cause in local inflammation of the surface in connection with damp,
cold, draughty hen-roosts, and above all, the accumulation of
decomposing manure and the exhalation of impure gas. Even in such
cases the abnormal breathing with the bill open is an accessory cause
of the affection.
Symptoms. The breathing with open bill should lead to
examination of the tongue, but above all if at intervals the bird with a
sudden jerk of the head emits a loud shrill, raucous sound, which
reminds one of the cough of croup. The tip and sides of the tongue
are found to be the seat of a hard, dry, and closely adherent epithelial
pellicle, which suggests a false membrane.
Treatment. The common recourse is to pick or scrape off the
indurated epithelial mass, leaving a raw, bleeding surface exposed.
This is then treated with a solution of borax, or chlorate of potash.
Cadeac deprecates this treatment as useless and dangerous, and
advises the disintegration of the dry epithelial mass with a needle
taking care not to prick nor scratch the subjacent sensitive tissue,
and to wash with a 5 per cent. solution of chlorate of potash. A still
more humane and effective method is to make a solution of
hyposulphite of soda in glycerine and brush over the affected surface
at frequent intervals. This may be conveniently applied through the
drinking water.
In case of implication of the lower air passages or lungs, the
treatment must be directed to them, and soft, warm, sloppy food and
the inhalation of water vapor will prove of great advantage. Secure
clean, sweet, dry pens, pure air, and sunshine. (See pseudo
membranous enteritis.)
 LOCAL STOMATITIS.

Division of circumscribed buccal inflammations: palatitis; gnathitis gingivitis;

glossitis. Causes: injuries; acrid; venomous or caustic agents; diseased teeth;
foreign bodies in gland ducts; malformed jaws; infections, etc. Symptoms:
salivation; difficult prehension and mastication; dropping half masticated morsels;
distinctive indications of different caustics; abrasion; abscess; slough; infective
disease lesions. Treatment: for palatitis, massage by hard corn ears, scarification,
laxatives; for gnathitis, care for teeth and ducts, astringent washes, eliminate
mercury; for glossitis, remove cause, use antidote to venom, or to chemical irritant,
astringent, antiseptic lotions or electuaries, evacuate abscess, soft, cool diet,
elevate the head, suspend the tongue.

Localized inflammations in the buccal cavity are named according

to the portion of the lining membrane attacked;—palatitis if seated
in the roof of the mouth; gnathitis if restricted to the cheeks;
gingivitis if to the gums; and glossitis if to the tongue.
Palatitis. Lampas. Congestion of the hard palate behind
the upper front teeth. This is usually seen in young horses during
the period of shedding the teeth and is caused by the irritation and
vascularity consequent on teething. The red and tender membrane
projects beyond the level of the wearing surfaces of the upper
incisors, and may materially interfere with the taking in of food. A
common practice in such cases is to feed unshelled Indian corn, the
nibbling of which seems to improve the circulation in the periodontal
membrane and by sympathy in the adjacent palate. Superficial
incisions with the lancet or knife will usually relieve, and may be
followed by mild astringent lotions if necessary. If apparently
associated with costiveness or gastric or intestinal irritation a dose of
physic will be demanded. Nothing can excuse the inhuman and
useless practice of burning the parts with a hot iron.
 Gnathitis. Inflammation of the Cheeks. Usually resulting as
a distinct affection from irregular or overgrown teeth, or the entrance
of vegetable spikes into the gland ducts, these cause local swelling
and tenderness, slow imperfect mastication, dropping of food half
chewed, accumulation of food between the cheeks and teeth,
thickening, induration and sloughing of the mucous membrane with
excessive fœtor.
Treatment. Consists in correcting the state of the teeth and ducts
and using one of the washes recommended for glossitis.
Gingivitis. Inflammation of the gums. This is either
connected with the eruption of the teeth in young animals and to be
corrected by lancing the swollen gums and giving attention to the
diet and bowels; or it is due to scissor-teeth or to the wear of the
teeth down to the gums in old horses; or it is dependent on diseased
teeth, or mercurial poisoning, under which subjects it will be more
conveniently considered. Barley awns or other irritants must be
extracted.
Glossitis, Inflammation of the Tongue. Causes. Mostly the
result of violence with bits, ropes, etc., with the teeth, or with the
hand in giving medicine; of scalding food, of acrid plants in the food:
of irritant drugs (ammonia, turpentine, croton, lye, etc.), or of sharp,
pointed bodies (needles, pins, thorns, barley and other barbs, etc.)
which perforate the organ. In exceptional cases leech and snake bites
are met with especially in cattle, owing to the tongue being exposed
when taking in food. Local infections and those of the specific forms,
determine and maintain glossitis.
Symptoms: Free flow of saliva, difficulty in taking in food or
drinking, and red, swollen, tender state of the tongue, which in bad
cases hangs from between the lips. The mucous membrane may be
white, (from muriatic acid, alkalies, etc.), black, (from oil of vitriol,
lunar caustic, etc.), yellow, (from nitric acid, etc.), or of other colors
according to the nature of the irritant. It may be raised in blisters,
may present red, angry sores where the epithelium has dropped off;
may become firm and indurated from excessive exudation; may swell
and fluctuate at a given point from the formation of an abscess; or
may become gangrenous in part and drop off. Breathing is difficult
and noisy from pressure on the soft palate. There is usually little
fever and death is rare unless there is general septic infection.
 Treatment will depend on the cause of injury. In all cases seek for
foreign bodies imbedded in the organ and remove them. If snake
bites are observed use ammonia or potassium permanganate locally
and generally, or cholesterin as a local application. If the irritation
has resulted from mineral acids, wash out with calcined magnesia
lime water, or bicarbonate of soda or potash. If from alkalies (lye)
use weak vinegar. If from caustic salts employ white of egg,
vegetable-gluten, boiled linseed, slippery elm, or other compound of
albumen or sheathing agent. In ordinary cases use cold astringent
lotions, such as vinegar and water; vinegar and honey; borax, boric
or carbolic acid, chlorate of potash, alum or tannin and honey.
Poultices applied around the throat and beneath the lower jaw are
often of great value. The bowels may be relieved if necessary by
injections, as it is usually difficult to give anything by the mouth. If
ulcers form touch them daily with a stick of lunar caustic or with a
fine brush dipped in a solution of ten grains of that agent in an ounce
of distilled water. For sloughs use a lotion of permanganate of
potash, one drachm to one pint of water, or one of carbolic acid, one
part to fifty of water. If an abscess forms give a free exit to the pus
with the lancet, and afterward support the system by soft nourishing
diet, and use disinfectants locally. As in all cases of stomatitis, the
food must be cold gruels or mashes, or finely sliced roots will often
be relished.
The mechanical expedient of supporting the tongue in a bag is
essential in all bad cases, as if allowed to hang pendulous from the
mouth inflammation and swelling are dangerously aggravated.
 APHTHOUS STOMATITIS. FOLLICULAR
STOMATITIS.
Causes: in horse, ox, dog; rough, fibrous food, blistering ointments, bacteria.
Symptoms: general stomatitis, and special; papules with grayish centres and red
areolæ, vesiculation, ulceration. Treatment: Astringent, antiseptic, derivative,
tonic, stimulant.
This is a rare affection in ruminants where the thickness of the
epithelial covering appears to be a barrier to infection or injury,
while it is common in the more delicate and sensitive buccal mucosa
of the horse and dog. In the horse the ingestion of irritant plants with
the food and the penetration of vegetable barbs into the mucous
follicles may be charged with causing the disease, while in both horse
and dog the licking of blistering ointments and the local action of
fungi and bacteria are factors in different cases.
Symptoms. With the ordinary symptoms of stomatitis, there
appear minute firm, whitish, circular elevations representing the
openings of the inflamed mucous or salivary follicles, having a
reddish areola, and grayish white vesicular centre. They may amount
to a line or more in diameter, and on bursting leave red cores or
ulcers. The whole mouth may be affected or the disease may be
confined to the lips, gums or tongue.
Treatment. Beside the general astringent washes, this affection is
greatly benefited by the local use of antiseptics, as sulphite or
hyposulphite of soda, 2 drachms in a quart of water. Borax,
permanganate of potash, carbolic acid or other antiseptic in suitable
solution may be substituted. Saline laxatives are often useful to
remove sources of irritation in stomach and intestines, and iron salts
(chloride or nitrate) in full and frequently repeated doses may be
given internally. Ulcers may be cauterized and soft food and pure
water given from an elevated manger.
 ULCERATIVE STOMATITIS. GANGRENOUS
STOMATITIS.
Causes: specific disease poisons; debility; rachitis; cancer; chronic suppuration;
irritation—mechanical, chemical, thermic, venomous, etc. Symptoms: difficult,
imperfect prehension and mastication, salivation, bleeding, swollen, puffy
epithelium, blisters, extending erosions, deep or spreading. Duration. Treatment:
correct constitutional fault, tonics, soft, digestible food, antiseptics, mild caustics.
This is characterized by the formation of necrotic spots and
patches of the buccal epithelium, with desquamation, and the
formation of more or less rodent ulcers of the sub-epithelial mucosa.
Like other ulcerative processes it is usually due to microbic invasion,
and in this way it may supervene on other and simpler forms of
stomatitis. It also varies in its manifestations and nature according to
the genus of animal, and the specific microbe present.