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Pesticides-Environmental-fate-human-health-impacts-and-analytical-techniques-from-extraction-to-removal_2024_University-Mohammed-Premier-Oujda
Pesticides-Environmental-fate-human-health-impacts-and-analytical-techniques-from-extraction-to-removal_2024_University-Mohammed-Premier-Oujda
Abstract: Pesticides are a catchall term. It includes a wide range of chemicals used to
Received 07May2023, destroy several types of harmful pests (weeds, insects, etc.). They are used in large
Revised 02 Nov 2023, quantities due to their effectiveness. Although it is intended to eliminate the target pest, it
Accepted 03 Nov 2023 bypasses that and reaches the environment via various sources, thus causing soil and water
contamination. Also, pesticide exposure increases the possibility of human infection with
poisoning and serious illness. It is impossible to know all of the pesticides' detrimental
Citation: Taidi Y., El
effects on their users, but many of these concerns are well-known, have manifested in the
laghdach A. (2024)
past, and have been documented in different researches, such as poisoning occurrences,
Pesticides: Environmental
fate, human health impacts, malignancies, etc. This review manuscript highlights the sources and fate of pesticides in
and analytical techniques different environmental compartments, their health impacts, and the analytical techniques
from extraction to removal, deployed for their analysis. In addition, the review considered different remediation
Mor. J. Chem., 12(1), 89-129 techniques employed in reducing their footprint within the various environmental
compartments.
1. Introduction
Pesticides are a mixture of substances used to prevent, control, or destroy organisms that are
considered unwanted (plants, insects, fungi), regardless of how they are used (agriculture, industries,
urban areas (eg: gardens, roadways, etc.). A total of 80% of pesticides are used to eradicate insects,
15% is herbicides, 1.46% is for fungal plant diseases, and 3% for the rest of the types of pesticides
(Rajmohan et al., 2020). Fungi and weeds pose a major threat to a variety of agricultural crops
(Khammassi et al., 2023; Bazzi et al. 2013). Most arable crop production procedures include the use
of pesticides. Pests and diseases are estimated to be responsible for one-third of crop losses. When
conducting intensive agriculture in order to produce food and resources for a growing global
population, the use of pesticides is the primary means of reducing crop losses and increasing
agricultural yields (Carvalho, 2006; Rowell, 2014). Their widespread application in modern agriculture
contributes significantly to environmental pollution (Adeniyi et al., 2021). Pesticides are large gamuts
3.2.2. Leaching
There are several pesticides that are registered and utilized on a global scale, with some of them
having a high likelihood of polluting groundwater due to their leaching (Fontana et al., 2010,
Singh,2012). A number of factors have an impact on leaching (Connell, 2005, Han et al., 2013, Singh,
2012). Pesticides that are dissolved in water can migrate with the water in the soil, making solubility a
significant component for leaching. A further important element influencing pesticide leaching is soil
permeability (Fontana et al., 2010). The likelihood of pesticides leaching into the soil is also increased
by soil permeability. The half-life in aerobic soil and the adsorption coefficient (Koc) both have an
3.2.4. Volatilization
The process of a solid or liquid becoming a gas is known as volatilization. After being volatilized,
pesticides can be removed from the treated surface by air currents (Singh, 2012). The vapor pressure,
temperature, humidity, air movement, and soil characteristics like texture, organic matter content, and
wetness are some significant elements that affect the pesticide's rate of volatilization (Alamdar et al.,
2014, Connell, 2005, Zhu et al., 2017). The volatility of the pesticide will increase with the vapor
pressure (Tudi et al., 2021). Also tending to increase volatilization include high temperatures, low
relative humidity, and air movement (Connell, 2005). Organochlorine pesticides, for instance, are more
likely to be dispersed in the atmosphere in tropical regions than do temperate regions (Chakraborty et
al., 2015; Lamhadi et al. 2014; Garoiz et al., 2011). Moreover, the likelihood of a pesticide
volatilization is decreased when it is strongly adsorbed to soil particles (Wong et al., 2008). According
to Lisouza et al., 2020, the primary method through which humans are exposed to organochlorine
pesticides by volatilization is via contaminated surface waters.
Acute Chronic
-Burning
-Irritation (eyes, nose, and -Cancer
throat) -Defect from birth
- Itch -Disrupts infant growth
- Rash -Memory disorders
-Ulcers of the skin -Neurological disorders (e.g.
-Cough Parkinson's disease)
-Abdominal pain -Reduce attention span
-Dizziness -Reproductive problems
-Malaise -Immunotoxicity
-Diarrhea -Behavioral impairment
-Headaches -Endocrine disruption
-Nausea -Developmental disabilities
-Reduced vision -Skin conditions
-Salivation -Respiratory diseases (e.g.
-Vomiting Asthma)
-Wheezing
-Coma
-Death
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 100
a)
b)
Carbamates
Organochlorines Pyrethroids
Organophosphates
Figure 3. Potential effects of pesticides on human health (a) and examples of some effects by type of
pesticide (b)
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 101
et al., 2021). There are several extraction methods, the oldest of which is liquid-liquid extraction.
Figure 4 below illustrates a series of pesticides extraction techniques for environmental samples. The
studies of Hassaan and El Nemr, 2020 and Samsidar et al., 2018 summarized the advantages and
disadvantages of each of these technologies separately.
Extraction Techniques
Dispersive liquid-liquid
microextraction Liquid-Liquid Solid-Phase
(DLLME) Extraction (LLE) Extraction (SPE)
Hollow fiber-liquid
phase microextraction Combination SPE and Stir bar sorptive
(HF-LPME) DLLME extraction (SBSE)
Following extraction, the analyte components are detected in environmental matrices at the lowest
thresholds using conventional or advanced techniques. Conventional detection techniques include
well-known techniques based on chromatography, which is a method of separating the various
constituents present in a blend with the aim of purifying, identifying, and quantifying the substances
in analysis specimens. It allows a solution of the substance being studied to percolate in a column of
adsorbents where the existing components each progress at different speeds and are distributed in
distinct zones, causing their fracture in order to be analyzed easily. The most types commonly used are
gas chromatography (GC) and liquid chromatography (LC), which employ various detectors with
varying degrees of specificity. Hassaan and El Nemr, 2020 reported in their study the different
detection methods from the oldest to the most recent and tied them to the different forms of detectors
used as well as the advantages and disadvantages of each technique. Many detectors showed good
performance with various pesticides, but until now the mass spectrometry (MS) detector is considered
the best (Jianget al., 2014). It exhibits large advantages (no derivatization, higher sensitivity,
selectivity, and precision, good reproducibility, and a better anti-interference effect). It is also gaining
distinguished importance in organic environmental analysis (Samsidar et al., 2018). The combination
of these two techniques (MS-chromatography) achieves integration in the qualitative and quantitative
performance of the individual techniques by combining high discrimination power and high separating
power (Barceló and Hennion, 1997). For the vast majority of pesticides and for their dependability,
sensitivity, and selectivity, LC-MS or GC-MS are widely used in laboratories; they are critical for the
structurally sensitive and positive identification of particular types of pesticides as well as other
environmental contaminants (Stan et al., 1995; Tran et al., 2012). GC-MS has been widely used in
pesticide analysis. However, due to its success in the analysis of various pesticides, LC-MS has recently
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 102
become the most widely accepted and applied methodology (Liu et al., 2017; Martínez Vidal et al.,
2009; Montory et al., 2017; Shamsipur et al., 2016), due to the lipophilic nature of pollutants being
manufactured and frequently used.
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 103
vulnerability to enzymatic inhibitors are two stability/storage constraints of enzyme-based
electrochemical sensors (Bucur et al., 2018). For determining pesticide residues in diverse matrices,
electrochemical enzymatic biosensors based on various nanomaterials dropped on the surface of
electrodes have been created. In order to alleviate the stability problems of enzymatic sensors,
nanomaterials are being employed to immobilize enzymes, which helps them get beyond these
limitations. Because of the surface features that the nanomaterials' surface afforded, the inclusion of
nanomaterials to the enzyme-based sensors further enhanced their selectivity and electrochemical
performance (Aragay et al., 2012; Periasamy et al., 2009). For the electrochemical detection of
pesticides in solid samples, nanomaterials have recently been used to create paintable inks that can be
used to manufacture on-site painted electrodes (Bakytkarim et al., 2019). Using silicon carbide and
multiwalled carbon nanotubes (MWCNTs) as a nanomaterial ink and chitosan as a stabilizer,
Bakytkarim et al., 2019 created an easy and environmentally benign approach to change electrodes.
Low temperatures were used in the electrode modification method, and the modified electrode had a
considerable increase in parathion residue sensitivity. The quick and nondestructive detection of
pesticides on plant surfaces has also attracted interest in smart plant wearing biosensors (Giraldo et al.,
2019). In addition, to track the presence of pesticide residues, various types of sensors have been used,
such as voltammetric, amperometric and potentiometric biosensors.
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 104
with a limit of detection of 15 ppm, these techniques have been proven to be superior. By creating a
nanozyme (nanoceria) assisted technique for a dual-mode (smartphone-based colorimetric method and
spectroscopic method) detection of organophosphorus pesticide,(Wei et al., 2019) have combined
smartphone-assisted analytical technology. This method has been shown to be very effective at
detecting pesticides on-site, but requires sample pre-treatment by hydrolyzing the pesticide into para-
nitrophenol. In real environmental samples, and using (+) AuNPs, Qi et al., 2020 suggested an aptamer-
based colorimetric approach for the detection of ultra-low concentrations of acetamiprid. The aptamer's
conformational changes in the absence and presence of acetamiprid could be sensitively distinguished
by (+) AuNPs, which turned from red to blue in the absence of acetamiprid. Figure 5 briefly shows
the colorimetric detection mechanism, and Figure 6 provides a set of advanced detection techniques
of pesticides.
Advanced
Electrochemical detection Optical Biosensor
biosensor techniques
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 105
Table 2. Chemical techniques used for decontaminate water polluted by pesticides and their percentage of
pesticide removal efficiency
% of pesticide
S.N° Technique Pesticides References
removal efficiency
a- Adsorption
1 Chlorpyrifos (CP)
3 Malathion (ML)
Thiame-thoxam
5 55%
(TMX)
9 Atrazine
10 Prometon
84%–96.4% (Wu et al., 2012)
11 Graphene Family Ametryn
Materials
12 Prometryn
13 Phonamiphos
<85%
14 Dimethoate
15 Parathion-methyl
16 Pirimiphos-methyl
17 Malathion
(Liu et al., 2013)
18 Fenthion
>85%
19 Isocarbophos
20 Chlorfenvinphos
21 Profenofos
22 Methidathion
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 106
23 Phorate
24 Simeton 85%
25 Simazine 82%
26 Atrazine 98%
(Zhang et al., 2015)
27 Ametryn 95%
28 Prometryn 72%
29 Cyprazine 90%
Cellulose/graphene
30 triazine pesticides 95% (Zhang et al., 2015)
composite
Ferrite
31 Glyphosate >89% (Yamaguchi et al., 2017)
manganese/graphene
32 98%
(treated water)
Banana peel Atrazine (Silva et al., 2013)
33 39–57%
(river water)
34 AC-based adsorbent Triazole 99% (Crini et al., 2017)
35 carbamates 76.4% - 84.3% (Ćwieląg-Piasecka et al.,
Biochar
36 Metolachlor 70.2% 2018)
40 sulfosulfuron 99%
42 chlorotoluron 95%
43 acetochlor 90%
b- AOPs
iron-catalyzed
45 photo-activation of atrazine 90% (Popova et al., 2019)
the persulfate system
46 methyl parathion 72%
MnO2-HSO3 (Wang et al., 2019)
47 methylparaoxon. 86%
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 107
Peroxymonosulfate
48 2,4-D 92% (Golshan et al., 2018)
(PMS)
nanocomposite
photocatalyst
containing
MoS2/ZnS
49 dicofol 85% (Ahamad et al., 2020)
nanoparticles
embedded in N/S
doped
graphite carbon
c- Ozonation
50 isoproturon 70%
51 diurin 75%
-
52 parathion methyl 75%
(Ormad et al., 2008)
53 atrazine 50%
ozonation treatment
was
54 atrazine 90%
combined with
activated carbon
100% between
60
nZnO-catalytic 0.5 and 5 mg/L,
atrazine
ozonation 90.2%
61 (Pérez-Lucas et al., 2020)
increased to mg/L
ozonation combined
62 fluroxypyr 92%
with UV light
d- Fenton
63 - fenitrothion 98.5% to 100%
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 108
graphene-iron based
electro-catalyst that
was used as a
heterogeneous
67 Mecoprop
electro-Fenton (EF)
catalyst in a three-
dimensional Fenton
system.
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 109
Pesticide accumulation on the soil surface is required for plant transformation and phytovolitisation.
Soil properties, plant properties, and possibly indoor plants are needed to increase ideal plant treatment
potential. Effective phyto-treatment not only aims to achieve phytoaccumulation, but it can also be
accomplished without the use of endogenous phytobacterials. To maintain soil fertility, however, the
metabolic dissociation of pollutants within soil levels is also required (Alekhya et al., 2013; Vila et al.,
2007).
Also, contamination can be reduced or avoided through the utilization of the biobed(Dias et al.,
2020). They are bioreactors designed to treat pesticide residues leftover from farming activities
(Castillo et al., 2008; Diez, 2010), and are a system for protecting water resources, environmentally
friendly and effective (Dias et al., 2020). It's a hole in the ground filled with a biomix of 25 percent
peat, 50 percent of wheat straw, and 25 percent of agricultural soil, and covered with turf. It's developed
to dispose of pesticide residues from accidental spills so that the pesticides are degraded by the
microorganisms established in the substrate, at the same time, the uptake of pesticide residues also
takes place in the bio-mix, reducing their chemical availability (Castillo et al., 2008; Cooper etal.,
2016). The biobeds are distinguished by their cheapness, ease of construction, and scientifically proven
efficiency of over 20 years. Optimal temperature, humidity, microbial communities, and bioreactor
efficiency assessment methods, are variables that affect the efficiency of bioreactors (Dias et al., 2020).
A study by Diez et al., 2013 stated that in Chile each bio cell can be used for up to 5 years. It should
be noted that this period is not fixed but depends on the climatic features of each country, and it can be
monitored through modifications in the depth of the substrate. As a result, it is critical to understand
and determine the time required for each country before implementing this technology as an
environmentally safe system in the field.
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 110
of treating water with high COD in big quantities due to the restricted amount of dissolved oxygen
under atmospheric pressure is one of the limits of activated sludge; the aeration process raises the
technology expense. By increasing total air pressure in the pressured activated sludge, the amount of
soluble O2 increases. Increases in operating pressure, aeration time, and sludge concentration resulted
in more COD removal, with an ideal level of 85.0 percent to 92.5 percent COD elimination (Jin et al.,
2010).
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 111
and investigated the effect of triethylamine (TEA) as an accelerator on the membrane. The results
showed that adding TEA to the membrane improved water rejection and flux when compared to other
membranes, with diazinon rejection and water permeability increasing by 95.2 percent and 22 L/m 2/h
for the roughly 98.8% unmodified membrane and 41.56 L/m2/h for the TEA modified membrane,
respectively. Poly (piperazine amide) TFC nanofiltration membranes for pesticide removal have shown
considerable improvement (Karimi et al., 2016). Another study investigated the elimination of atrazine,
simazine, and diuron in the presence of humic acid using two flat sheets negatively charged organic
nanofiltration membranes (polypiperazine amide nanofiltration (NF) and OPMN-K membrane). The
results revealed that the NF membrane absorbed more pesticides than the OPMN-K membrane because
of its smaller molecular cut-off. In compared to the NF membrane, OPMN-K has a lower solute
retention and a higher permeate flux. Furthermore, raising the applied transmembrane pressure resulted
in a significant drop in the OPMN-K membrane's solute rejection and a little rise in the NF membrane's
solute retention (Pinto et al., 2018; Musbah et al., 2018; Vieira et al., 2020). Furthermore, the effect of
humic acid on pesticide residues varies depending on how the solute is formed and how membrane
molecules are retained. Diuron was the lowest absorbed by both membranes of all the pesticides
studied, owing to its high molecular mass, higher dipole moment, and linear shape, although this is
especially visible in the presence of humic acid. Importantly, polypiperazine amide nanofiltration and
OPMN-K membrane demonstrated a high ability to remove chemicals (Power et al., 2018; Wang et
al., 2017). Diuron and isoproturon (phenyl urea insecticides) were eliminated from agricultural field
water at a concentration of 2 mg/L in another study, using a thin-film composite polyamide reverse
osmosis membrane, the pesticides were eliminated at a rate of more than 95%. The results demonstrated
that the isoproturon filtration membrane caused more fouling than the diuron filtration membrane;
nevertheless, diuron's membrane rejection was consistently lower than isoproturon's(Mehta et al.,
2015).
6.3.3.2. Zeolites
Zeolites are a family of crystalline aluminosilicate materials with interconnected micropores that
demonstrate an extremely tight distribution of pore-size (Pham et al., 2016; Yang et al., 2016). Due to
its unique physicochemical characteristics, accessibility, and low price, zeolite has drawn considerable
attention in the scientific community. It is employed widely to remove pesticides and heavy metals in
agriculture, industry, and pollution management (Huong et al., 2016; Wen et al., 2016). De Smedt et
al., 2015 showed that zeolite can be used as an adsorbent to treat water contaminated with pesticides
like imidacloprid, isoproturon, bentazon, and metalaxyl-m, but the rate of adsorption is reliant on two
main factors, namely the polarity and mobility of the pesticides. Immobile pesticides like imidacloprid,
isoproturon, and metalaxyl-m tend to be bound to zeolites, whereas more mobile pesticides like
bentazon partitioned in water. Isoproturon and metalaxyl-m (non-ionic pesticides) have a greater
affinity for zeolites owing to their polarity. Valičková et al., 2013 assess the effectiveness of the zeolite
in removing chlorinated pesticides (hexachlorobenzene, heptachlor, hexachlorobutadiene,
pentachlorobenzene and lindane). The highest removal efficiency observed during the contact time was
93.8% for hexachlorobenzene. The second highest removal efficiency of 92.1% was achieved for
heptachlor, trailed by hexachlorobutadiene (83.7%), pentachlorobenzene (72.9%) and lindane (25.8%).
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 112
effluent may still have a total pesticide content that exceeds the requirements set by the Environmental
Protection Agency in the Water Framework Directive (WFD) on environmental quality standards
(EQS). Hence, there is a need to establish wastewater treatment plants that combine multiple techniques
like physical, biological, and/or chemical treatment procedures to ensure that heat-tolerant pollutants
such as pesticides are reduced to the required level before being released into the environment
(Goodwin et al., 2018).
Some hybrid technologies have proven to be successful, such as: Based on chemical oxygen
demand, the efficiency of pesticide removal when activated carbons were combined with ultrafiltration
and coagulation treatments was around 84 and 88 percent (Acero et al., 2012). The use of magnetic
activated carbon (MAC) and powder activated carbon (PAC) in combination with an ultrafiltration
(UF) membrane as a pretreatment for paraquat and linuron removal from water was examined by
Zahoor, 2013a. Due to its large surface area, PAC showed a high percent retention of paraquat and
linuron. The production of cake on the membrane surface, as well as the blackening of pipes and flow
meters, resulted in long backwash periods and a decrease in permeate fluxes for PAC. The MAC hybrid
approach, on the other hand, uses a magnet to remove MAC from a slurry, resulting in no cake
formation and minimal backwash delays. A study used a granular activated carbon (GAC)/UF hybrid
system to remove 2,4-D from water and found that 2,4-D had a high retention percentage and low
permeate flux, with the hybrid system achieving 100% retention of 2,4-D (Zahoor, 2013b). In addition,
Zahoor and Mahramanlioglu, 2011 evaluated the removal of 2,4-D from water utilizing MAC as a
pretreatment in combination with the UF membrane vs PAC as a pretreatment. The results showed that
the MAC impregnation procedure blocked the micropores in the activated carbon, resulting in a
reduction in the adsorbent's surface area, and hence a decreased pollutant adsorption capability.
Furthermore, when the MAC was utilized as a pretreatment and was removed from the slurry via the
magnetic process before entering the membrane system, no cake formed on the membrane surface. In
comparison to the PAC, where some pieces of the PAC were carried into the membrane, creating extra
washing time, the MAC required less backwashing time, making it more cost-effective. Finally,
because of its high adsorption capacity, cost efficiency, and simplicity of removal from the medium,
MAC was regarded a good pretreatment in UF systems (Saleh et al.,2020).
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 113
well as ozonation/H2O2 and nano-filtration, were the most effective atrazine removal techniques.
According to the same study, the ozonation technique combined to activated carbon shows a high
performance of removing (remove 100%) for 4 pesticides such as isoproturon, diuron, methyl parathion
and 2,4-D. Chlorination techniques shows also high rates of removal (100%) for isoproturon, diuron,
methyl parathion. While adsorption using wood charcoal, iron-catalyzed photo-activation and
ozonation, appears lower removal performance for 2,4-D, methyl parathion, and isoproturon and
diuron, respectively.
Conclusion
Pesticide contamination is one of the most significant worldwide challenges, posing a serious threat to
human health and the natural balance of the ecosystem. Pesticides do have a number of advantages,
the most notable of which is that they assist farmers to boost yields in the face of increasing population
expansion. Pesticides, on the other hand, are a lethal weapon with difficult-to-control effects due to
their vast range and misuse. Most, if not all, pesticides are harmful, albeit to varying degrees.
This review contained sources of environmental pollution, and disorders linked to pesticide exposure
were also addressed, as multiple studies have found a correlation between pesticide exposure and
infection with various cancers and other diseases. Lastly, this research summarized the various
pesticide analytical techniques: extraction, detection and removal techniques, as well as a presentation
of some of the techniques and pesticides that can be eliminated, as well as the percentage of removal,
which are reached according to well-determined conditions. Where adsorption by the graphene family
materials and Ozonation using an experimental reactor, Fenton, are considered examples of
technologies that have been able to remove 100% of some pesticides.
The treatment of pesticides requires a comprehensive scientific analysis in order to select appropriate
treatment techniques to avoid further toxic by-products. It is also necessary to choose the treatment
technologies best suited to the environmental conditions of each country, which will help increase the
treatment plant profitability.
Funding
The authors declare that no funds, grants, or other support were received during the preparation of this
manuscript.
Taidi & El laghdach, Mor. J. Chem., 2024, 12(1), pp. 89-129 114
Competing Interests
The authors have no relevant financial or non-financial interests to disclose.
Availability of data and materials
‘Not applicable’ for that specific section
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