clean

technologies

Review
Water Pollution and Agriculture Pesticide
Samira Mosalaei Rad, Ajay K. Ray and Shahzad Barghi *

Department of Chemical and Biochemical Engineering, Western University, London, ON N6A 5B9, Canada
* Correspondence: sbarghi2@uwo.ca; Tel.: +1-519-661-2111 (ext. 81275)

Abstract: The agricultural industry uses substantial amounts of water (the highest in the world)
mostly for irrigation purposes. Rapid population growth and, consequently, growing demand for
food have increased the use of pesticide to have higher yield for crops and other agricultural products.
Wastewater generated as a result of excessive use of pesticides/herbicides in agricultural industry
is becoming a global issue specifically in developing countries. Over 4,000,000 tons of pesticides
are currently used in the world annually and high concentrations above their threshold limits have
been detected in water bodies worldwide. The generated wastewater (contaminated with pesticides)
has negative impacts on human health, the ecosystem, and the aquatic environment. Recently,
biodegradable and biocompatible (including plant-based) pesticides have been introduced as green
and safe products to reduce/eliminate the negative impacts of synthetic pesticides. Despite positive
advantages of biopesticides, their use is limited due to cost and slow interaction with pests compared
to chemical pesticides. Pesticides may also react with water and constituents of soil resulting in for-
mation of intermediates having different physical and chemical properties. Diffusion, dispersion, and
permeation are main mechanisms for transfer of pesticides in soil and water. Pesticides may degrade
naturally in nature; however, the time requirement can be very long. Many mathematical models
have been developed to simulate and estimate the final fate of pesticides in water resources. Develop-
ment of new technologies and environmentally friendly pesticides to reduce water contamination is
becoming increasingly important.

Keywords: wastewater; agriculture; pesticides; treatment; modeling

Citation: Rad, S.M.; Ray, A.K.; Barghi,
S. Water Pollution and Agriculture
Pesticide. Clean Technol. 2022, 4,
1088–1102. https://doi.org/ 1. Introduction
10.3390/cleantechnol4040066
Pesticides/herbicides use in agriculture is very common to increase production and
Academic Editor: Patricia Luis ensure sufficient high quality affordable food for the growing population. These pesticides
Received: 15 September 2022
are mostly produced synthetically and like almost all chemicals pose a potential risk to
Accepted: 18 October 2022
human health and the environment. Pesticide use is inevitable in agricultural systems. New
Published: 20 October 2022
pesticides are being introduced continuously with enhanced properties for selective use
and less negative impacts. Spraying is a common way of introducing pesticides over large
Publisher’s Note: MDPI stays neutral
areas of land, most of which can be carried away by wind, water runoff, and atmospheric
with regard to jurisdictional claims in
weathering processes, and thus up to 95% of herbicides and over 98% of insecticides may
published maps and institutional affil-
not reach the targeted pests [1]. Physical and chemical interactions in the atmosphere can
iations.
lead to formation of intermediates with negative impacts. Nevertheless, these pesticides
eventually find their way to surface and ground water as well as lakes and oceans through
different mechanisms. Uncontrolled application of pesticides in agriculture may result
Copyright: © 2022 by the authors.
in alteration of products’ quality and changes in the level of different enzymes in human
Licensee MDPI, Basel, Switzerland. body, leading to various health problems [2]. Traditional pesticide formulations generally
This article is an open access article have a high concentration of organic solvents with low dispersion, remaining in soil for
distributed under the terms and a long time, and moving through the environment and putting biological systems at risk.
conditions of the Creative Commons Those who work in agricultural open fields and greenhouses and the pesticide industry are
Attribution (CC BY) license (https:// usually exposed to higher concentration of pesticides.
creativecommons.org/licenses/by/ The world population is estimated to be 9–10 billion by the year 2050 [3], increasing the
4.0/). need for more food. The agriculture industry is the highest user of clean water, mainly used for

Clean Technol. 2022, 4, 1088–1102. https://doi.org/10.3390/cleantechnol4040066 https://www.mdpi.com/journal/cleantechnol

Clean Technol. 2022, 4 1089

irrigation purposes, which can be easily contaminated by pesticides. More than 1200 pesticides
and herbicides, some of which are banned in Europe, are currently in use in the world [4].
Although some of these herbicides can be degraded naturally in the soil, many of them
are not easily degraded and remain in the environment for extended periods of time [5].
Municipal, industry, and agricultural wastes are discharged directly to various water
bodies in many countries. Drugs, dyes, herbicides, pesticides, and other products of daily
use have been detected in ground/underground water. Irrigation and rain also facilitate
transportation of pesticides into ground/underground water especially those which are
soluble in water [6]. Health issues such as hematologic and hormonal abnormalities,
infertility, fetal malformation, neurological diseases, and cancer are commonly observed
among those exposed to these pesticides. The underlying mechanisms of these effects are
genotoxic, neurotoxic, and endocrine-disrupting actions [7–9].
The maximum consumption per hectare of pesticides is about 25 kg and Asia is the
highest in the world. Global use of pesticides is comprised of 47.5% herbicides, 29.5%
insecticides, 17.5% fungicides, and others account for only 5.5% [10]. Pesticide use is crucial
in modern agriculture. Without proper use and management of pesticides, there would
be a substantial loss of agricultural products to pests (for example, about 40% in crops).
Exposure to pesticides used in agriculture has been related to autoimmune diseases such
as systemic lupus erythematosus [11]. It has also been linked to neurodegenerative and
respiratory diseases and various forms of cancer [12].
Skin and respiratory irritations as well as diseases such as Parkinson’s, leukaemia, and
autism were found to be higher in residential areas close to agricultural lands where pesticides
were used continuously [13]. Excessive use of synthetic pesticides may also result in high
concentrations of heavy metals (used in production of pesticides) in soil, which alters the
biochemistry and microbial activities in soil with a negative impact on plants [14,15].
Agricultural water pollution may be due to fertilizers as they have a high concentration
of nutrients (containing specifically nitrogen and phosphorus). When fertilizers are utilized
in crop production more then the required amount, the excess amounts will remain in soil
particles and finally be washed off the soil during irrigation or by rain, finding their way to
water resources. Phosphates, which are not as soluble as nitrates, may get adsorbed onto
soil particles and pollute the water thorough soil erosion.
Animal wastes are also rich source of nutrients and can be used as fertilizer. In
aquaculture industry, excess nutrients and animal wastes may pollute the water. Table 1
summarizes most common water contaminants in agriculture.

Table 1. Categories of major water pollutants in agriculture and the relative contributions of the three
main agricultural production systems [16].

Relative
Pollutant
Indicators/Examples’ Crops Contribution by: A
Category
Livestock
Primarily nitrogen and phosphorus present in chemical and organic
Nutrients fertilizers as well as animal excreta and normally found in water as *** *** *
nitrate, ammonia, or phosphate
Herbicides, insecticides, fungicides, and bactericides, including
organophosphates, carbamates, pyrethroids, organochlorine pesticides,
Pesticides *** _ _
and others (many, such as DDT, are banned in most countries but are still
being used illegally and persistently)
E.g., ions of sodium, chloride, potassium, magnesium, sulphate, calcium,
Salts and bicarbonate. Measured in water, either directly as total dissolved *** * *
solids or indirectly as electric conductivity
Measured in water as total suspended solids or nephelometric turbidity
Sediment *** *** *
units—especially from pond drainage during harvesting
Clean Technol. 2022, 4 1090

Table 1. Cont.

Relative
Pollutant
Indicators/Examples’ Crops Contribution by: A
Category
Livestock
Chemical or biochemical oxygendemanding substances (e.g., organic
Organic
materials such as plant matter and livestock excreta), which use up * *** **
matter
dissolved oxygen in water when they degrade
Bacteria and pathogen indicators., e.g., Escherichia coli, total coliforms,
Pathogens * *** *
faecal coliforms, and enterococci
Metals E.g., selenium, lead, copper, mercury, arsenic, and manganese * * *
Emerging
E.g., drug residues, hormones, and feed additives _ *** **
pollutants

Pesticides can have detrimental impacts on weeds and insects, which indirectly affect
the production yield. Therefore, new pesticides which are more selective and less toxic are
being produced and gradually replace the older ones.
Vaccines, antibiotics, growth hormones, and drug consumption have increased in
recent decades by humans or use in livestock, which can reach water resources in differ-
ent ways.
Heavy metals which exist in pesticides and animal feed are considered as emerging
pollutants and more than 700 of them and their metabolites have been detected in Euro-
pean aquatic environments [17]. Agricultural activities may reintroduce these pollutants
into aquatic environments through the generated wastewater. An estimated 35.9 Mha of
agricultural lands are subject to indirect use of the wastewater [18].
Generally, pests become resistant to pesticide when used for a long period of time,
and therefore new pesticides need to be developed continuously, requiring new treatment
methods and/or modification of existing ones. Pesticides have been classified based their
functionality, lethal dose (LD50), type of impact on health, mode of action, etc. Pesticides
have been classified in three categories as shown in Table 2 [19].

Table 2. Classification of Pesticides [19].

Pesticide Class: Substance

Organochlorine: Endosulfa
Organophosphate: Diazinon, Malathion, parathion, chloropyrifos
Carbamate: Aldicarb, carbofuran, carbary1
Insecticide
Pyrethroid: Deltamethrin, Fenpropathrin
Neonicotinoid: Acetamiprid, thiamethoxam
Phenylpyrazole degradate: Aldicarb sulfoxide, Endosulfan sulfate
Triazine: Atrazine, cyanazine
Herbiside
Cloroacetamide: alaclor, butachlor, dimethenamid, metolachlor
Benzamide: Fluopicolide, zoxamide
Carboxamide: Boscalid captofol
Fungiside Chlorinated hydrocarbon: Hexachlorbenzene
Organophosphate: Edifenphos, iprobenfos
Chlorophenyl: Dichloran, quintozene

These pesticides have different characteristics with specific impacts on human health [20].
Pesticide characteristics and their effects are shown in Table 3.
Clean Technol. 2022, 4 1091

Table 3. Type of pesticide pollutants in water [20].

Group Chemical Composition Characteristics Effects

Organochlorine (DDT, Non-polar and lipophilic Lipid soluble, toxic to variety Tend to accumulate in fatty tissue of
aldrin, lindane, atoms including carbon, of animals and long-term animals, biomagnification effect via
chlordane) chlorine, hydrogen atoms. persistence. food chain.
Soluble in organic solvent as
Organophosphate Aliphatic, cyclic, and Tend to infiltrate into aquifers and
well as water. Less persistence
(Malathion, diazinon, heterocyclic possess central reach groundwater. Affects central
than chlorinated
parathion) phosphorus atom in molecule. nervous system.
hydrocarbons.
Alkaloid obtained from petals Less persistent than other
Pyrethroids of plant species, namely pesticides, therefore safest to
Affects nervous system.
(pyrethrins) Chysanthemun be used as household
cinerariefolium. insecticides.
Chemical structure based on
Only killed limited spectrum
alkaloid of a plant species,
Carbamates (Carbaryl) Relatively low persistence. insects but highly toxic to
namely Physostigma
vertebrate species.
venenosum.
Biological (Becillus
Microorganism, viruses, and Applied against forest pests
thuringiensis, Bt and Affect other caterpillars.
their metabolic products. (butterflies) and crops.
its subspecies)

Insoluble chlorinated hydrocarbon pesticides have the potential to remain in soil for a
longer time. Therefore, organophosphorus compounds such as Diazinon and Malathion
were used instead. The main reason for their use is their rapid degradability so that they
do not pollute water. Carbamate pesticides are used as a replacement for chlorinated hy-
drocarbons. Their active ingredients are not easily adsorbed to soil particles, thus reaching
surface/subsurface waters. Pesticides undergo different processes in the environment, as
shown in Figure 1 [21].

Figure 1. Transformation process of pesticides and their effect [21].

Agriculture pesticides are generally complex molecules and undergo several different
reactions to become completely degraded. Pesticide transformation/conversion to other
Clean Technol. 2022, 4 1092

molecules starts when introduced at a site. Degradation is more complex for insoluble
pesticides as soluble pesticides are degraded much easier in the environment. The degradation
reactions may be fast or slow and the intermediate molecules formed during the degradation
may have different properties and follow different pathways to be mineralized, which depends
on the type, physical, and chemical properties of the pesticide. Heat and photodegradation
imposed by solar radiation play a major role in the breakdown of pesticide molecules.
A large number of mechanisms have been reported in the literature for degradation of
agriculture pesticides. Despite the large variety in proposed degradation mechanisms, the
main reactions are oxidation, reduction, and hydrolysis. Microorganisms play a key role in
the biodegradation of pesticides where complex biochemical reactions occur.

Biopesticides and Nanotechnology

Due to negative impacts of synthetic pesticide, there is an increasing interest in
biodegradable and biocompatible materials for the formulation of non-toxic, safe, en-
vironmentally friendly, and efficient pesticides. They have little negative impact on the
surrounding ecosystem and human health [22]. Biopesticides are generally derived from
natural resources such as animals, plants, bacteria, and certain minerals and can provide
an alternative to synthetic pesticides used to control pest populations in agriculture [23].
Biopesticides are more advantageous to traditional pesticides due to their low toxicity
and target specific nature, effectiveness in small doses, fast biodegradability, low exposition,
and negligible emission. Although biopesticides are an environmentally friendly alternative
to chemical pesticides, they are not as strong [24,25]. According to the FAO definition,
biopesticides include those biocontrol agents that actively and selectively invade target
pets [26]. Biopesticides fall into three main categories:
1. Microbial pesticides are microorganisms, such as viruses, bacteria, or fungi that prey
on the pests that cause harm to crops
2. Plant-incorporated pesticides are produced by plants that mostly have been geneti-
cally modified.
3. Biochemical pesticides are herbal pesticides that have naturally chemicals that possess
pest-repelling properties.
Similar to other pesticides, biopesticides may develop mutations and resistances in
the target pests in agriculture [26].
Development of nanotechnology in recent decades has provided solutions to many
problems in production materials with different applications including pest control.
Nanoscience and nanotechnology have facilitated formulation, design, and preparation
of environmentally friendly biopesticides (called nano-biopesticides) with controlled re-
lease. Embedding genetic materials in biopesticides have improved their effectiveness [27].
The use of nanomaterials in the development of new biopesticides/nano-pesticides with
unique features for specific targets have been increased significantly in recent years [28].
The extremely small size and large surface area of nanoparticles play a major role in their
applications in different areas of engineering and science, in the fields of pest control and
management in agriculture, medical, pharmaceuticals, etc. Although nanoparticles can be
produced synthetically using chemical, physical, and biological methods, they can also be
found in nature, in plants such as algae, in the form of superoxide nano-particles and insects.
High mobility and solubility as well as low toxicity, stability, and high efficiency are other
characteristics of nano-biopesticides with a promising future for their applications in the
agriculture industry. High selectivity of nano-biopesticides for targets of interest can reduce
the required dosage. Groups of biopesticides such as nano-herbicides, nano-fungicides,
nano-pesticides, and nano-insecticides (referred to as nano-agrochemicals) have great po-
tential to replace traditional synthetic pesticides. Several biopesticides have been approved
by the European body Ecocert and some by Organic Farmers & Growers (OF&G) [29].
Although the use of nanomaterials to enhance crop production can be a breakthrough for
sustainable agriculture and control of plant pathogens, their release into the environment
may have negative health issues.
Clean Technol. 2022, 4 1093

Plants, algae, bacteria, and fungi use their protein and metabolites to absorb inorganic
metals which can be further processed in biosynthesis of eco-friendly nanoparticles. For
example, the fungus Pleurotus cornucopiae var. citrinopileatus can produce silver NPs which
have antifungal activity. Biopesticides may undergo nano-coating for better delivery
methods for pest control in agriculture and crop production facilities [30].

2. Water Pollution by Pesticides

Water contamination is mostly the result of agricultural and urban runoff, where
herbicides/pesticides find their way through leaching in soil or by direct discharge of
contaminated wastewater [21].
Pesticides interact with water in different ways due to their physical and chemical prop-
erties. All pesticides have main ingredients that are mixed/dissolved in inert compounds (e.g.,
solvent) to adjust their concentration. Therefore, water pollution in agricultural systems may
be due to the presence of active ingredients as well as fillers and impurities or intermediates
during the degradation process. Diffusion, dispersion, and permeation are the main mecha-
nisms for transfer of pesticides in soil and water. At the same time, the natural degradation of
pesticides in soil or water may result in the formation of intermediates. Interaction between
pesticide and soil and/or water is a complex phenomenon with little information in the
literature. The stability of pesticides is generally related to their half-life. Persistent pesticides
have a long half-life and pose threats for a longer time.
Although municipal and industrial wastewater discharges substantial amount of
wastewater into water bodies, agriculture accounts for 70 percent of water abstractions
worldwide. Large amounts of agrochemicals (mostly pesticides/herbicides) are discharged
into the water, endangering human health, aquatic ecosystems, and plants [31]. According
to FAO, the agricultural land, which requires irrigation, has more than doubled (about
320 Mha in 2014) in recent decades [25], which has increased the use of pesticides and
eventually affected ground/underground water quality.
About 85–90% of all fresh water is used for irrigation of agricultural land in Africa
and Asia. Agriculture withdrew 67% of the world’s total freshwater in 2000 [31].
Based on the U.S. Geological Survey (USGS) carried out in mid 199s, 90% of major
rivers’ water and fish samples close to agricultural and urban land contained pesticides [32].
The herbicides 2,4-D, diuron, and prometon were among the 21 pesticides detected most of-
ten in surface and ground water across the nation with concentrations above the guidelines.
High concentrations of pesticides above their threshold limits were detected at 13–30% of
all surface and ground waters in Europe between 2013 and 2019, as shown in Figure 2 [33].

Figure 2. Pesticide concentrations in surface and ground water [34].

Clean Technol. 2022, 4 1094

Figure 2 shows one or more pesticides with concentrations above their threshold for all
surface water monitoring sites each year between 2013 and 2019. The number of pesticides
in surface water ranged from about 10 to over 100 with the lowest being in Austria [6] and
the highest in France [29].
Pesticide concentrations higher than the acceptable limit were also reported in surface
waters in Mexico (Cienega area of Jalisco). In a comprehensive study on the concentration
of pesticide in India, high concentrations were also observed in river water, surface water,
ground water and, interestingly, rainwater [35].
An analysis of samples from 1204 wells across the United States showed the presence
of 109 pesticides and 116 pesticide degradates. Among those, about two-thirds contained
pesticides and three-quarters contained degradiant. The most common detected pesti-
cides were Atrazine, Hexazinone, Prometon, Tebuthiuron, four Atrazine degradates, and
one metolachlor degradates, detected in >5% of the wells with 1.6% of the wells having
concentrations approaching levels of potential concern [6].
The annual use of conventional pesticides in the United States between 2005–2012 was
about 400–450 million kg, excluding biological and antimicrobial pesticides. Glyphosate,
atrazine, metolachlor-(S), 2,4-D, and acetochlor were the most commonly used herbicides
in United States between 1992–2017 [36].
Pesticides are being transported from land to ground water by rain fall and irrigation,
where permeable soil is more susceptible to the process. Pesticides with high persistence
and a low tendency to adsorb to soils and sediments are detected easily [37]. A higher
concentration of pesticides is generally observed in shallower groundwater than deeper,
and older groundwater, as drainage systems in agricultural areas can divert shallow
groundwater to surface water [38].
In five studies, when evaluating up to 80 pesticide compounds and 9 degradates,
Atrazine and its degradant deethylatrazine (DEA) were the most detected [33]. The eighth
most detected compound was Dieldrin, an insecticide (3.1%) while Propoxur concentration
was reported as 1.8%. The most detected fungicide was Metalaxyl (0.7%) [39,40].
The formulation of green, safe, and efficient pesticides is one of the ongoing challenges
in the pesticide industry. Design and production of targeted environmentally friendly
pesticides with controlled release through chemical modification offers great potential for
new formulations. One of the emerging technologies is production of pesticides using
genetically modified plants.

Wastewater Treatment
Removal of pesticides from water requires knowledge of physical and chemical prop-
erties of pesticides and their interactions with water (e.g., ionization, solubility, etc.). There-
fore, different design approaches and operating conditions are necessary for the treatment.
Due to the large amount of wastewater in agriculture, physical processes are generally
preferred to avoid using large volume of chemicals, which may generate new sources of
pollution to the environment. The concentration of pesticides in water is low even when
it is much higher than the threshold limits, therefore, adsorption is the preferred option
for the separation of pesticides from water. Different adsorbents are available for different
classes of pesticides in terms of hydrophobicity, molecular structure, and size, such as
activated charcoal, activated carbon, organoclays, inorganics, and plant-based adsorbents
(bio-adsorbents). A detailed review of different adsorbents and their selectivity for different
pesticides can be found elsewhere [41].
The large diversity n size and shape of pesticide molecules has been used to separate
them from water using membranes processes such as nanofiltration and ultrafiltration [42].
The combination of membrane separation and adsorption was proven to be more
effective for the removal of pesticides from water [43,44].
The complete removal of carbaryl and carbofuran (micropollutants) from public water
was reported using a combined technique of adsorption (fixed bed of granular activated
carbon) and microfiltration from public water [45].
Clean Technol. 2022, 4 1095

In recent decades, advanced oxidation processes (AOPs), which are based on forma-
tion of hydroxyl radicals (OH) to degrade pesticides in wastewater to nontoxic compounds,
have been studied extensively. Hydroxyl radical is a very powerful highly reactive nons-
elective oxidant that can be produced in an aqueous solution using certain chemicals or
photocatalysts such as titania to destruct organic molecules. Titania is the most commonly
used photocatalyst that can generate electron-hole pair when irradiated by ultraviolet
light to initiate reactions, leading to the formation of hydroxyl groups. Due to the large
band gap of titania, doping is applied to reduce the bandgap and thus facilitate using
visible light instead of UV light. AOPs have been successfully employed for decomposition
of pesticides [46,47].
To enhance pesticides’ degradation efficiency and selectivity, a combination of AOPs
have been successfully employed. Nearly complete mineralization of pesticides in water
can be achieved using H2 O2 , ozone, and metallic oxide [48].
Advanced oxidation processes can be also combined with physical processes such as
adsorption to degrade pesticides. AOPs such as chlorination and ozonation, followed by
adsorption using activated carbon removed over 90% of 44 pesticides from water [49].
Live microorganisms such as fungi and bacteria have been found to be effective
in the degradation of pesticides in water. The process is referred to as biodegrada-
tion. Jariyal et al. (2018) used three different microorganisms (Brevibacterium frigoritolerans,
Bacillus aerophilus, and Pseudomonas fulva) to remove organophosphate residues in water
achieving biodegradation efficiencies over 97.5 percent [50]. Complete degradation of
Carbaryl was reported using Rhodopseudomonas sphaeroides [51,52].
Recently, living plants have been used for the degradation of pesticides in water.
The process is known as phytoremediation and is used for decomposition of clomazone
with over 50% efficiency. Phytoremediation efficiency is challenging to determine due to
the exposure of plants to other microorganisms living in soil as well as other weathering
processes involved [53]. One of the most used plant-based pesticides (extensively used in
agriculture crops) is derived from neem, which is a tropical Asian tree (Azadirachta indica)
that has insecticidal and antiseptic properties. The potential benefits are that they are
economical, environmentally friendly, effective, and of low toxicity to non-target organisms,
including humans [53,54].
Genetically modified (GM) foods have been produced by introducing genetic material
(DNA) from other organisms to the plants by genetic engineering. GM foods have been
found to be more resistant to pests; for example, GM crops needed 40% less pesticide,
which has a huge impact on water contamination in crop agriculture. There are sporadic
reports about positive and negative impacts of GM foods but there is no solid scientific
proof for that; however, it seems that GM foods are becoming crucial in feeding the world’s
growing population, especially in harsh environments/climates [55].
Application of the treatment processes for a very large amount of agriculture wastew-
ater needs more research to optimize the process for an effective, feasible, and environmen-
tally friendly treatment.

3. Modeling and Simulation

Large quantities of wastewater are generated in agriculture, therefore experimentation,
management, and control at such levels are time consuming and costly. Models that are
simplified representations of real-world systems are used to simulate the fate of pollutants
and estimate the changes in water quality at different locations to an acceptable level.
Due to the complexity of real-world problems, simplifying assumptions are used and
therefore models cannot be completely accurate; however, they are reliable enough to help
in providing policies, strategies, and actions for mitigation purposes. Models with different
strengths and limitations are used in the field of water quality. These can be applied at
different scales to support planners and policymakers in designing cost-effective measures
for addressing water pollution in agriculture [56,57].
Clean Technol. 2022, 4 1096

The models are mainly related to the flux of polluted water and transformation processes.
Water transportation, quality, meteorology and hydrology, land characteristics and manage-
ment and transformation processes are of main concern. Irrigation and type of agriculture as
well as plants, soil, and the environment make such modeling activities a challenging task.
Leaching and water runoff are generally the first stages in pesticide transportation.
A mathematical model based on a system of ordinary differential equations was devel-
oped to provide farming alertness for pest administration in crops production, considering
plant biomass, type of pest, and control level. Using the local pest-free and coexistence
equilibria and applying the control theory, the criteria to decrease pest contamination in
crop fields were achieved [58].
To control the pest population in crop fields under different dynamic regimes, a mathe-
matical model based on Z-type control was applied. The pest population and its fluctuation
were successfully controlled and the results were verified by actual field data [59].
Despite the unique advantages of biopesticides, they suffer from time requirements as
well as cost. However, a combination of biopesticides with chemical/synthetic pesticides
has shown to reduce time and cost. A mathematical model was developed to show the
effectiveness of such an approach to pest control for Jatropha curcas plantation. The model
successfully predicted the optimum concentration profile for biopesticides and chemi-
cal pesticide using optimal control theory, minimizing negative impacts, and improving
feasibility. The numerical simulations justified the results [60].
Bacteria, algae, fungi, protozoa, and viruses have been used as microbial pest control
agents used for specific pests. Viruses such as Baculoviridae (nucleopolyhedroviruses)
[NPV] and granuloviruses are among very strong biopesicides. More than 400 insect
species have been reported as hosts for baculoviruses. A mathematical model was sta-
blished to study the interaction between a virus and a pest. The interaction follows the
Michaelis–Menten type and the virus attacks the pest population only with no recovery or
immunization of the pest. A good agreement was reported compared to available data in
the literature [61].
Jena and Kar proposed and analyzed an ecological system and studied the dynamics
of pest control systems using the prey–predator model. They developed a mathematical
model with three state variables, namely the susceptible pest, the infected pest, and the
biological predator to the pest. Additional food sources were considered in the model
to help the predator to survive when the prey concentration is negligible. The role of
additional food is very much important in relevance to pest control because it helps to
protect predator populations when the pest population is not sufficient. Considering the
cost and environmental impact and using Pontryagin’s maximum principle, the optimal
pest control strategy was obtained [62].
An ecophysiological model of plant–pest interaction and multi-criteria decision anal-
ysis was developed to optimize crop management when considering two contrasting
objectives: (1) maximizing crop production and (2) minimizing environmental impact
related to fertilization, irrigation, and pesticide deployment. A mechanistic plant growth
model and a pest population model were considered [63].
Pesticide dissipation is a complex phenomenon which depends on pesticide type,
environmental factors, transfer processes, degradation phase partitioning, etc. Prediction of
pesticide dissipation half-life in plants is important in estimating the fate of pesticides. Over
4500 data points on pesticides’ half-lives were used with four machine learning models
(i.e., gradient boosting regression tree [GBRT], random forest [RF], supporting vector
classifier [SVC], and logistic regression [LR]) to predict dissipation half-life intervals using
extended connectivity fingerprints (ECFP), temperature, plant type, and plant component
class as model inputs. Despite successful outcomes of the model, due to the large number
of variables and uncertainty involved in their prediction, more data is required to improve
the models’ performance [64].
Yadav and Kumar used mathematical modeling to study an ecosystem consisting of
two types of preys and their predators in agriculture. The two preys had a long time and
Clean Technol. 2022, 4 1097

short time to grow (sugarcane and vegetable, respectively) with predators that can attack
them both simultaneously. The various equilibria of the system were obtained, and the
stability conditions were analyzed [65].
The Environment Protection Agency (EPA) offers models for evaluation of pesticides
leaching. The Global Livestock Environmental Assessment Model (GLEAM) [66] and the
transformation process-based model (LEACHM) [67,68] are currently in use. The most
employed mathematical models have been listed in Table 4.

Table 4. List of mathematical models for pesticides fate in agriculture.

Description Model Reference

Based on IPM * technique Abraha et al., 2021 [69]
Optimum control approach Chowdhury et al., 2019 [61]
Crop Pest management and Prey–predator based Tang and Cheke, 2005 [70]
control pest-epidemic model Wang et al., 2011 [71]
microbial pesticide model Wang et al., 2017 [72]
Pest Population control by
Sun and Chen, 2009 [73]
infected pasts
Watershed model, single-event AGNPS Merritt et al., 2003 [74]
capabilities DWSM Borah et al., 2002 [75]
Long-term effects of AnnAGNPS Bingner and Theurer, 2001 [76]
hydrological changes and water HSPF Donigian et al., 1995 [77]
and soil management practices SWAT Neitsch et al., 2002 [78]
Study of hydrology and
non-point source pollution, MIKE SHE Borah and Bera, 2003 [79]
small watersheds
Loague and VanderKwaak,
Numerical models considering InHM
2002 [80]
surface and subsurface
Panday and Huyakorn, 2004
hydrologic MOD-HMS
[81]
HydroGeoSphere Colautti et al., 2005 [82]
EXAMS Burns, 2000 [83]
Concentration of pesticides and the Mackay Level III Model Mackay, 2001 [84]
their fate in rivers, steady state QUAL2E Brown and Barnwell, 1987 [85]
conditions principal component Gramatica and Di
analysis Guardo, 2002 [86]
MIKE11 DHI 1995 [87]
Dynamic in-stream water HR Wallingford and
ISIS
quality models HalcrowUK, 1998 [88]
RWQM1 Reichert et al., 2001 [89]
WASP Wool et al., 2001 [90]
Pesticide fate modeling in TOXSWA FOCUS, 2001 [91]
surface water PERPEST Van den Brink et al., 2006 [92]
* Integrated Pest Management.

In most cases, the predictions made through modeling and simulation efforts have
been supported by field and lab experiments in a relatively narrow range of parame-
ters. More comprehensive models are required to take into account different parameters
simultaneously.

4. Wastewater Treatment Cost

Similar to all industries, feasibility is one of the main concerns in wastewater treatment
industries. Access to affordable clean water has been and probably will be one of the
serious challenges worldwide. Population growth, industrialization, agriculture, energy
production, etc. have introduced new pollutants to water that require advanced treatment
processes, adding more to the cost of clean water production. Therefore, a detailed study of
water treatment processes and associated costs is vital to reduce/optimize the cost, making
clean water available, especially to developing countries with limited water resources. The
cost of wastewater treatment plants depends on the process, design configuration, as well
Clean Technol. 2022, 4 1098

as the quality of the treated water. Obviously, the cost per unit volume of the treated water
decreases by increasing capacity. The detailed cost and profitability analysis including the
capital cost and operating cost is out of the scope of this study. Due to the large variations
and conditions in different plants, it is quite challenging to compare the cost of different
wastewater treatment plants [93].
The capital cost for a 150,000 gallon per day of a typical wastewater treatment plant
(including design to start-up) is estimated to be between USD 500,000 to 1.5 million, while
operating costs vary considerably due to the cost of energy, labor, and local rules and
regulations. The cost of an industrial wastewater treatment plant strongly depends on the
type of industry and wastewater as well as the target quality [94]. Detailed information
about cost estimation can be found elsewhere [95].
Advanced oxidation processes have been employed as a tertiary water treatment
option. Despite variabilities of auxiliary processes (e.g., adsorption, filtration etc.) to
improve efficiency, cost estimation has been carried out for some plants. It was reported that
the capital cost in the range of 0.035–0.05 EUR/m3 and an operating cost of 0.04 EUR/m3
of treated wastewater for an ozonation process combined with adsorption (granular and
powder activated carbon). A cost analysis of wastewater treatment plants is a complex
process due to uncertainties involved, and, thus, the reported values are an approximation
for the initial assessment of wastewater treatment plants [96].

5. Conclusions
Water pollution by pesticides used in agriculture is increasing at an alarming rate
due to the need for more food by the growing population, requiring the use of many
pesticides in agriculture. It is a multidimensional challenging problem and requires com-
prehensive actions and cooperation from various sectors involved. Pesticides undergo
different processes in a complex fashion which makes it challenging to apply the existing
mitigation processes. A high concentration of pesticides has been detected worldwide and
the need for effective treatment processes is urgent. Biopesticides seems to be a promising
approach, however, the limitations such as their effectiveness and cost have made their
application challenging. The combination of biopesticide and chemical pesticides can
increase the effectiveness of pest control strategies with less impact on the environment.
Many mathematical models have been introduced for pest population control as well as
treatment of agriculture wastewater. These models are applicable to certain conditions and
are usually within a narrow range of variables. Physical treatment processes are preferred
over chemical processes for agriculture wastewater due to use of large amount of chemicals,
which may lead to generation of new pollutants. Research is needed to reduce source load
and minimize water pollution along flow paths and find a feasible effective method for
wastewater treatment.

Author Contributions: Original draft preparation, S.M.R., Review and editing, A.K.R. and S.B. All
authors have read and agreed to the published version of the manuscript.
Funding: This research received no funding.
Institutional Review Board Statement: Ethical approval not required.
Informed Consent Statement: The study did not involve humans.
Conflicts of Interest: The authors declare no conflict of interest.

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