\r\n\tMain emphasis should be on its applications. In every field MOFs can be used due to its greater stability and high surface area, but the focus should be on applications.
",isbn:null,printIsbn:null,pdfIsbn:null,doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"507abe0040ce1d146a7ed603648a1bb6",bookSignature:"Dr. Shobha Waghmode",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/7388.jpg",keywords:"MOFs, COFs, Nanomaterials, PANI, Agnps",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"July 11th 2018",dateEndSecondStepPublish:"October 1st 2018",dateEndThirdStepPublish:"November 30th 2018",dateEndFourthStepPublish:"February 18th 2019",dateEndFifthStepPublish:"April 19th 2019",remainingDaysToSecondStep:"2 years",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"197394",title:"Dr.",name:"Shobha",middleName:null,surname:"Waghmode",slug:"shobha-waghmode",fullName:"Shobha Waghmode",profilePictureURL:"https://mts.intechopen.com/storage/users/197394/images/13227_n.jpg",biography:"Savitribai Phule Pune University",institutionString:"Savitribai Phule Pune University",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"University of Pune",institutionURL:null,country:{name:"India"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"8",title:"Chemistry",slug:"chemistry"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"270935",firstName:"Rozmari",lastName:"Marijan",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/270935/images/7974_n.png",email:"rozmari@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. 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\n
1. Introduction
\n
In past decades, polymeric materials have been extensively used in construction, transportation, and electronic devices due to the high performance and cost-effectiveness [1]. However, most of the polymeric materials were intrinsically combustible, which caused the fire hazard. The necessity to improve the flame retardancy of polymeric materials was urgent, so that people started to incorporate flame retardants into polymers to produce flame retardant polymer composites. The commercial used flame retardants mainly included endothermic additives, halogenated additives, phosphorus additives, expandable graphite and melamine derivatives. However, using a single component flame retardant to make the polymer reach the desired flame retardant performance required high loading of additives, which can cause the deterioration of the mechanical properties of the polymer matrix. In order to enhance the flame retardant efficiency of additives, synergistic flame retardant systems were developed [2, 3, 4, 5, 6]. These systems contained two or more additives. Some additives were not flame retardant themselves, but can effectively synergize the performance with other flame retardants, thereby minimizing the total loading of the additives within the polymer matrices. The most common combinations, such as antimony oxides [7]/halogens [8], metal hydroxides [9, 10, 11]/zinc borate [12], and intumescent phosphates [13, 14] have already been widely used in various polymers and successfully commercialized. Recently, people started to use nano-scale additives to make polymer nanocomposites and expect further enhancement of the flame retardant performance. The practice of mixing nanoparticles with polymers to make polymer nanocomposites can be traced back to nineteenth century [15, 16]. Those composite materials inherited the properties of the nanoparticles and showed significant enhancement in performance compared to their polymeric matrices. However, the mechanisms for the reinforcement of the polymeric matrices by nanoparticles were not adequately understood until 1990s. This rise of polymer nanocomposites research benefitted from the growing availability of nanoparticles and the emergence of instrumentation to probe the nano-scale structure of materials [17]. Furthermore, powerful computers allowed for the development of theoretical models which together with experiments were used to develop the guiding principles for engineering new nanocomposites with desirable properties. These models highlighted the critical role of surface and interfacial energies between the fillers and the polymer matrix and as well as the role particle morphology. Consequently, research of flame retardant polymer nanocomposites has been widely reported from both academic and industrial laboratories [18, 19].
\n
In this review, we will mainly focus on the thermoplastic polymer based nanocomposites. Comparing to the thermoset polymer nanocomposites, thermoplastic polymer nanocomposites are easy to process and formulate in manufacturing, which makes them a very diverse and manageable composite system. This review describes the mechanisms of interaction between singular or binary thermoplastic polymer matrices with the commonly used nanoparticles: montmorillonite clay, graphene, nature nanotubes and fibers. The effect of nanoparticles influence on flame retardant efficiency was discussed, as well as the change in physical properties, such as impact resistance, ductility, gas permeability and rheology performance.
\n
\n
\n
2. Singular polymer matrix
\n
\n
2.1. Montmorillonite clays
\n
Montmorillonite is one of the most commonly used fillers in materials application. It could be dispersed in a polymer matrix to form polymer-clay nanocomposite. Okamoto et al. have shown that the organically modified montmorillonite clay could improve the thermal mechanical and gas barrier effect of poly (lactic acid) (PLA) [20]. By using wide-angle X-ray diffraction and transmission electron microscopy, they found that with the differences in clay modification, four different types of clay-polymer morphology were formed: intercalated, intercalated-and-flocculated, exfoliated and coexistence of intercalated and exfoliated. The intercalated structure achieved great mechanical property improvement, and the near exfoliated composite has the highest gas barrier effect. However, the mechanism of the surface interaction was not well developed. Also, to improve the degree of exfoliation of clay platelets, cation exchange with quaternary ammonium chloride salts was commonly used for clay modification. The development of this method was held back due to the toxicity of these salts [21].
\n
Recently, Guo et al. developed a much efficient way to determine the affinity between large aspect ratio nanoparticles and the polymer matrix by simply measuring the Young’s contact angle [22]. The relative affinity between PLA and Closite Na+ clay/Closite 30B (C-30B) clay were studied. They also used resorcinol di(phenyl phosphate) (RDP) adsorption to modify the Closite Na+ clay (C-Na+), which has been proven to perform better than using organoclays alone in conventional polymer systems [23]. The chemical formula of RDP is shown in Figure 1. With the nonpolar moieties of phenol groups and polar moieties of phosphoric acids groups, RDP could be used as a surfactant [24]. It has also been proven to react with polymers at high temperatures to form chars, which renders its ability to work as a flame retardant additive [25, 26]. In this research, a monolayer of these clay particles were formed on Si wafer using Langmuir–Blodgett (LB) technique. A 5 mg PLA pellet was melted on top of each clay monolayer and the Young’s contact angles at the polymer/clay surface/air interface were measured. The procedure is illustrated in Figure 2. Then with the combination of the interfacial energy equation and the equation for work of adhesion (Wa), the relationship between Wa and Young’s contact angle (A) was developed as below:
where\n\n\nγ\nl\n\n\n is the surface tension of liquid phase, which is PLA in this case. By substituting the measured contact angle and calculate the individual Wa between PLA and each clay (listed in Figure 2), they found that comparing to the original MMT clay C-Na+, the synthesized C-30B clay and the C-RDP clay were more compatible to the PLA matrix. Further small angle scattering (SAXS) and TEM results, shown in Figure 3, confirmed that there is no change on the interlayer spacing of C-Na+ clay and they formed tactoids inside the polymer matrix. The interlayer spacing for C-RDP increased from 2.04 to 3.65 nm, which indicates the polymer chains intercalated with the clay platelets. In the case for C-30B, the SAXS pattern only showed a weak secondary (002) peak which proved that the C-30B platelets were exfoliated. These results are in good agreement with the previous Wa measurement, which concludes that the work of adhesion between the clay platelets and polymer needs to increase to achieve particle exfoliation inside polymer matrix.
\n
Figure 1.
The chemical formula of RDP.
\n
Figure 2.
An illustration of creating monolayer of nanoparticle by LB technique, and a list of measure contact angle of PLA on each type of clay with calculated work of adhesion. Adapted from Ref. [22]. Copyright (2018) with permission from Elsevier.
\n
Figure 3.
TEM imaging and X-ray pattern of PLA/clay composites: (a) TEM images of PLA/C-Na+ blend (PCNa5), PLA/C-RDP blend (PCRDP5) and PLA/C-30B blend (PC30B5); (b) small angle X-ray scattering patterns of pure PLA and composites with clays. Adapted from Ref. [22]. Copyright (2018) with permission from Elsevier.
\n
Since C-30B are mostly exfoliated in the PLA matrix, Guo et al. continued to study its possible effect on improving the performance of flame retardant agent [4]. As a biodegradable polymeric material with good mechanical and processing properties, PLA has been extensively studied over recent years and has been used as a substitution for conventional polymers [27, 28]. In order to expand its usage into electron devices and automobile industry, the high flammability of PLA must be resolved. Melamine polyphosphate (MPP) was used in this study, which is a halogen-free flame retardant agent [29]. When used alone, 28 wt.% of MPP is needed to achieve the V0 grade in UL-94 vertical burning test. TEM images in Figure 4(a) showed that the MPP formed droplet shaped domains with a diameter around 500 nm. According to Araki et al., when large aspect ratio particles were used to compatible a binary system, the domain size is controlled by balancing between the reduction of system enthalpy and the increase of bending energy due to particle curvature [30], and the minimum domain size should be similar to the radius of particle platelets. When 1 wt.% of C-30B is added to the system, the MPP were better dispersed and the domain size were reduced to around 150 nm, which is similar to the radius of C-30B platelets. And only 17 wt.% of MPP is needed to obtain the V0 grade, as oppose to the previous 28%. However, further increase C-30B concentration to 2% resulted in enlarged and elongated MPP domain, which is to reduce the energy penalty brought by bending clay particles. And C-30B starts to form aggregates on the elongated MPP domain surface, which blocked the contact of polyphosphate to the PLA molecules. In the cone calorimetry test (listed in Table 1), the better dispersed MPP/1%C-30B system has lower average heat release rate (aHRR), peak heat release rate (pHRR) and total heat release (THR) than MPP with 2% C-30B. Examination of char residue also agree with this result. Intumescent char layers were found for both samples with only MPP and MPP/1% C-30B. As shown in Figure 4(b), the char layer of sample with only MPP is continuous and has a winkled structure due to the gas inflating during heating and releasing after cooling. Similar winkled structure was found on the char layer of sample containing MPP/1% C-30B, where the winkle was formed by dense polymer/clay aggregates. In contrast, the char layer of sample with MPP/2% C-30B was loose and powdery, which is composed of large polymer/clay agglomerates and has numerous micro-cracks. This result confirmed their theory that when clay platelets were exfoliated and act as a dispersant, the MPP is better dispersed which could increase the flame retardant efficiency. The exfoliated clay platelets also provide large surface area to interact with both polymer chain and MPP, improving the formation of the intumescent char. Yet the window of improvement is limited because further increasing clay content would result in clay aggregating on the polymer/FR interface and harming the FR performance.
\n
Figure 4.
TEM and SEM images of PLA/MPP/C-30B blends: (a) TEM images taken on cross-sections of PLA composites; (b) SEM images on the char residue after cone calorimetry test. Adapted from Ref. [4]. Copyright (2018) with permission from Elsevier.
\n
\n
\n
\n
\n
\n\n
\n
Sample
\n
Avg. heat release rate (kW/m2)
\n
Peak heat release rate (kW/m2)
\n
Total heat release (MJ/m2)
\n
\n\n\n
\n
100PLA
\n
6–1120
\n
1.1–29.0
\n
80–920
\n
\n
\n
PLA/MPP
\n
117.5
\n
12.6
\n
359
\n
\n
\n
PLA/MPP/1C-30B
\n
239.7
\n
17.3
\n
441
\n
\n
\n
PLA/MPP/2C-30B
\n
133.3
\n
13.4
\n
348
\n
\n\n
Table 1.
Cone calorimetry results of PLA/MPP/C-30B blends. Adapted from Ref. [4]. Copyright (2018) with permission from Elsevier.
\n
\n
\n
2.2. Graphene
\n
Having a similar platelet structure to clay, graphene is also a large aspect ratio nanoparticle and has gained great attention in many research areas due to its superior thermal conductivity, heat sink effect and great mechanical performance [31, 32, 33]. Given the large surface area and heat adsorption of graphene, Xue et al. developed a three component flame retardant ethylene vinyl acetate (EVA) composite as a replacement of polyvinyl chloride (PVC) for cable sheathing [6]. The three component FR system consists of aluminum hydroxide (ATH), molybdenum disulfide (MoS2) and graphene nanoplatelets (GNPs). When ATH was used alone, it could absorb heat and release water vapor during combustion, which could dilute the oxygen surround the sample surface. However, due to the poor compatibility between ATH and EVA, ATH would form large aggregates in the polymer matrix, which decreased the interfacial area for ATH to react and therefore decreasing its efficiency, as shown in the TEM images in Figure 5(a). As a result, 50–60 wt.% of ATH is needed to achieve the V0 grade in UL-94 test, which will greatly decrease the ductility of EVA. When substituting 2 wt.% of ATH to MoS2, the PHRR was reduced but a sharp peak is still observed on the heat release curve, as seen in Figure 6. This is because MoS2 have formed tactoids in EVA matrix, which decreased their surface area and reducing its ability to form protective char layer. On the other hand, when further substituting 2 wt.% of ATH to GNPs, a better dispersion was observed for both ATH and MoS2 and the heat release curve was flattened. TEM images showed that the domain size of ATH is greatly reduced and EDS mapping (Figure 5(b)) showed that MoS2 was partially exfoliated. This is contributed to the large surface area of graphene platelets, which could react at the polymer/filler interface and reducing the interfacial tension. Thus, as shown in Scheme 1, when the EVA composite with the three-component FR system was subject to high heat flux or flame, the ATH has a higher efficiency on absorbing heat and releasing water vapor due to the improved dispersion. The exfoliated MoS2 and GNPs will form protective char layer on the sample surface, which could reduce the peak heat release rate and flatten the heat release curve. The GNPs will start to decompose at around 635°C, but the MoS2 layer will continue to control the heat release. As a result, this EVA-ATH-MoS2-GNPs composite has a PHRR of 377 kW/m2, which is a huge reduction comparing to that of pure EVA, which is 1815 kW/m2.
\n
Figure 5.
(a) TEM images taken on cross-sections of EVA based composites; (b) SEM and EDS mapping of EVA based composites. Annotations of abbreviations used: A—ATH, M—MoS2, G—GNPs and numbers stands for weight ratio. Adapted from Ref. [6]. Copyright (2018) with permission from Elsevier.
\n
Figure 6.
Cone calorimetry results of EVA composites. Reproduced from Ref. [6]. Copyright (2018) with permission from Elsevier.
\n
Scheme 1.
The decomposition process of EVA/ATH/MoS2/GNPs composite. Adapted from Ref. [6]. Copyright (2018) with permission from Elsevier.
\n
\n
\n
2.3. Natural nanotubes and fibers
\n
Nanotubes such as carbon nanotube, Halloysite nanotube (HNTs), and cellulose fibers have gained increasing attentions in recent years to replace filler that have high environmental persistence [34, 35, 36]. They could also render the polymer composite to have increased mechanical properties [37]. When applied in the flame retardant composites, surface modification is commonly used to increase the flame retardancy. As previous mentioned, resorcinol bis (diphenyl phosphate) (RDP) is a liquid form flame retardant, which could be adsorbed on to fillers with hydroxyl groups. In the previously mentioned study [22], Guo et al. have also compared the change of work of adhesion between PLA and HNTs, with and without the RDP coating. They found that RDP coated HNTs had a higher work of adhesion to PLA than pure HNTs, which indicated that PLA wetted the RDP coating, and RDP could successfully improve the dispersion of HNTs. Thus, they used the same methodology to develop a new flame retardant PLA composite using RDP coated cellulose [5]. When subjected to flame, pure PLA burns easily with heavy dripping that could ignite the cotton on the bottom in a UL-94 test. An illustration of the burning proves is shown in Scheme 2. When 2 wt.% of RDP is added to the polymer, the sample could self-extinguish in 2 s, but it also induced heavy dripping due to the fact that RDP is also a liquid plasticizer. When 6 wt.% cellulose was used alone, the dripping was greatly reduced but the sample kept on burning for more than 30 s. Although neither RDP nor cellulose could make the composite pass the V0 criteria, they could significantly improve one of the factors that would lead to V0 grade. Naturally, the idea of combining the two occurred and the addition of only 8 wt.% RDP coated cellulose (CF-RDP) is needed for the PLA composite to self-extinguish in 2 s and only slight dripping was observed, which is also relatively cold and did not ignite the cotton on the bottom. Further SEM imaging and FTIR tests showed that RDP completely wets the cellulose surface though the hydrogen bond between RDP and cellulose, as shown in Figure 7. Cellulose also immobilized RDP which help retained its ability of plasticizing and surface blooming. When PLA/CF-RDP decomposes during combustion, CF-RDP will dehydrate, where it releases water vapor and lower the temperature by absorbing heat. The dehydration of CF-RDP is confirmed by the intensity reduction of the H-bonding on the FTIR spectra.
\n
Scheme 2.
An illustration of the UL-94 test process of PLA based composites. CF stands for cellulose fiber. Adapted from Ref. [5]. Copyright (2018) with permission from Elsevier.
\n
Figure 7.
SEM image and FTIR spectra of cellulose fibers: (a) SEM images taken on neat cellulose fiber with and without RDP coating; (b) FTIR spectra of neat cellulose fiber and RDP-cellulose before and after 10s burning. Adapted from Ref. [5]. Copyright (2018) with permission from Elsevier.
\n
\n
\n
\n
3. Binary polymer system
\n
Melt blending two different polymers together is one of the simplest way to produce a new material with combined properties. Yet most polymers tend to phase separate due to the large unfavorable enthalpy [38, 39, 40]. Although the block or graft copolymers could easily solve the problem, the synthesizing procedure is often system specific and expensive for industrial applications [41]. Thus, research on numerous possible compatibilizers have been done over several decades [42, 43, 44, 45]. As briefly mentioned before, Araki et al. have developed a theory for explaining the effect of clay in compatibilizing polymer blends [30]. Two types of polymer blends were studied: polystyrene/poly(methyl methacrylate) (PS/PMMA) blend stands for when only one polymer has a favorable interaction with clay; polycarbonate/poly(styrene-co-acrylonitrile) (PC/SAN) blend stands for when both polymers have similar affinity to clay platelets. In both situations, the organoclays have successfully reduced the domain size and phase separation, and the clay platelets appeared to be adsorbed onto the polymer interface and aligned following the contour of the domain. The compatibilizing effect would generally increase with increasing clay concentration. When the domain size is reduced with better compatibility, more interface area is created to contain the increased clay content. However, the clay platelets would start to bend when the domain size is smaller than the clay radius. This would result in increasing the bending energy, as opposed to reducing the system free energy. Thus, the compatibilizing effect of clay could only work to the extend where the minimum domain size is reached. And the minimum domain size is approximately equal to the linear dimension of the filler.
\n
Based on this theory, Park et al. studied the effect of clay’s effect on improving flame retardant efficiency in binary polymer systems [2]. For the PS/PMMA/Microfine AO3 (AO)/decabromodiphenyl ether (DB) blend, addition of Cloisite 20A clay (C-20A) could significantly improve the dispersion of DB and AO, shown in Figure 8, which result in passing the UL-94 V0 grade. C-20A clay was exfoliated in the polymer blend, and the FR agents were attached to the clay surface. Hence, the dispersion of FR agent was also improved and resulted in higher FR efficiency. However, for PC/SAN/DB/AO blend, adding C-20A did not enhance the flame retardant performance. They argue that for this blend, the attraction between clay and FR agent is larger than that between clay and the polymer blend. Thus clay has a lower degree of exfoliation and did not enhance the FR agent’s dispersion. Later on, they have also discussed the effect of RDP coating [23]. RDP coated clay was added to both PS/PMMA blend and PC/SAN24 blend and two different morphologies were observed. The RDP coated clay would segregate in the PMMA domain in PS/PMMA blend, whereas it was segregated on the polymer interface in PC/SAC24 blend. This difference is attributed to the interfacial tension difference between RDP with each polymer component, and the interfacial tension of the polymer interface. In PS/PMMA blend, the interfacial tensile of RDP/PS and RDP/PMMA were both larger than that of PS/PMMA interface. In this case, the addition of RDP-clay could not reduce the overall interfacial energy. As a contrast, the interfacial energy of PC/SAN24 interface is higher than that of PC/RDP-clay. Hence, the system interfacial energy would decrease with RDP-clay segregated on the PC/SAN24 interface. Further examination on the flammability of PC/SAN24 blend with RDP-clay also showed that during combustion, the RDP-clay worked against the phase separation and stabilized the polymer blend. RDP helped reducing the brittleness of the protective char layer, which in turn reduced the heat release rate and mass loss rate.
\n
Figure 8.
TEM images taken on cross-sections of PS/PMMA composites. Adapted from Ref. [2]. Copyright (2018) with permission from Elsevier.
\n
\n
\n
4. Physical properties
\n
\n
4.1. Impact resistance
\n
It was well known that for singular polymer matrix, the particle size and particle/polymer surface interaction have a great influence on the composite’s mechanical properties [46]. By comparing between C-Na+, C-RDP clay and C-30B clay, Guo et al. [22] concludes that the mechanical properties, such as impact strength and tensile strength, will decrease with increasing degree of exfoliation of the clay particles. This is due to the fact that the magnitude of the internal stress, which generated at the tip of the particle and could form micro-cracks, is in direct proportion to the particle aspect ratio. Given that the aspect ratio of exfoliated clay platelets could be several magnitudes larger than that of clay tactoids, it is easier for the micro-cracks to enlarge and propagate under external stress in the exfoliated polymer/clay blend. Moreover, a similar result was also found in binary polymer blends with clay [47]. When C-Na+, C-RDP clay and C-30B clay were added to a biodegradable PLA/poly(butylene adipate-co-butylene terephthalate) (PBAT) blend, C-30B performs best in reducing the domain size and increasing compatibility between two polymers, as can be seen in Figure 9. However, the PLA/PBAT blend with clays showed a rapid and huge reduction on the impact strength even with low clay concentration, as seen in Figure 10. This phenomenon is explained by the theory that the clay platelets formed a strong barrier at the polymer interface, which blocked inter-diffusion between two polymers, and as a consequence, the two polymer phases were easily separated under stress.
\n
Figure 9.
TEM images taken on cross-sections of PLA/PBAT based composites: (Blend) PLA/PBAT; (BCNa5) PLA/PBAT/5 wt.% of C-Na2; (BCRDP5) PLA/PBAT/5 wt.% of C-RDP; (BH5) PLA/PBAT/5 wt.% of HNTs; (BHRDP5) PLA/PBAT/5 wt.% of H-RDP; (BHRDP15) PLA/PBAT/15 wt.% of H-RDP. Adapted with permission from Ref. [47]. Copyright (2018) American Chemical Society.
\n
Figure 10.
Impact strength of PLA/PBAT based blends. Adapted with permission from Ref. [47]. Copyright (2018) American Chemical Society.
\n
To resolve the problem of the mechanical properties reduction, they discovered that tubular nanoparticles, such as Hollysite nanotubes, would lie perpendicular to the PLA/PBAT polymer interface instead of parallel as the clay, shown in Figure 9. Moreover, with this vertical orientation of HNTs particle, a “stitching” effect was observed where the impact strength first increase with the increasing HNTs concentration. The difference of particle orientation between nanotubes and clays is due to the fact that nanotubes are longer and more rigid than clay platelets. Hence, a much larger bending energy is required for nanotubes to lie along the domain curvature. As a result, the system energy is lower when nanotubes lie vertical to the polymer interface. In this way, nanotubes could enhance the interfacial diffusion and reinforce the binary polymer blend.
\n
\n
\n
4.2. Ductility
\n
For polymers that are highly flammable, high loading of flame retardant filler is generally need to render self-extinguish of the composite [48, 49, 50], which will significantly reduce the ductility of the material, making the composite hard to process. In the previous discussed three component flame retardant EVA composite [6], EVA/ATH/MoS2/graphene, the total FR filler loading was reduced from 60 to 40 wt.%, which maintained the elasticity of pure EVA and increased the tensile modulus and tensile strength to equivalent with that of PVC, as summarized in Table 2. With careful examination of the individual effect of each component, they discovered that addition of MoS2 to the EVA/ATH blend decreased the tensile modulus, strength and elongation, while addition of graphene significantly increased these mechanical properties. In the V0 blend containing all three components, the ultimate tensile strength is even higher than the EVA/ATH/graphene blend, which has the highest tensile modulus and elongation at break. This is achieved through the second quasi-elastic response, which is an indication of nanoparticles reinforcing the matrix against scission and polymer chain disentanglement. Thus, the addition of graphene platelets improved the overall FR particle dispersion which provide a larger surface area for polymer chain absorption, while MoS2 did not have the dispersant effect which lead to reduction of its specific surface area.
\n
\n
\n
\n
\n
\n
\n
\n\n
\n
Sample
\n
Young’s modulus (MPa)
\n
Tensile strength (MPa)
\n
Elongation at break (%)
\n
Impact toughness (J/cm3)
\n
UL-94 grade
\n
\n\n\n
\n
PVC
\n
6–1120 (avg. 38.8)
\n
1.1–29.0 (avg. 15.6)
\n
80–920 (avg. 308)
\n
N.A.
\n
V-0
\n
\n
\n
EVA/ATH
\n
117.5 ± 8.6
\n
12.6 ± 1.1
\n
359 ± 28
\n
39.3
\n
V-2
\n
\n
\n
EVA/ATH/MoS2
\n
163.5 ± 9.3
\n
14.1 ± 1.0
\n
306 ± 26
\n
35.0
\n
V-2
\n
\n
\n
EVA/ATH/GNPs
\n
261.6 ± 15.5
\n
19.7 ± 1.6
\n
455 ± 51
\n
72.9
\n
NG
\n
\n
\n
EVA/ATH/MoS2/GNPs
\n
258.4 ± 12.2
\n
21.5 ± 1.5
\n
448 ± 43
\n
70.7
\n
V-0
\n
\n\n
Table 2.
Tensile properties and impact toughness of EVA based blends. Reproduced from Ref. [6]. Copyright (2018) with permission from Elsevier.
\n
Ductility is also an important property which determines the extruding conditions when the polymers are processed. In particular, the recent popularity of FDM printing requires that the ductility of the blends needs to be preserved and allow them to be drawn into uniform filaments and withstand further drawing through the printer nozzles [51]. As mentioned in previous section [4], the addition of C-30B to PLA/MPP successfully improved the dispersion of MPP which provides a higher flame retardant efficiency. Through comparing the impact strength, the addition of MPP embrittles the PLA composite, while adding C-30B and MPP together restored the impact strength to the same level of pure PLA and even slight higher. Examination of the fracture surface showed that the MPP tactoids would delaminate from the PLA matrix under impact stress. With C-30B localized at the PLA/MMP interface, the micro-cracks brought by MPP tactoids were restricted by the rigid C-30B platelets. Therefore, the impact energy dissipation was improved and the PLA/MPP/C-30B blend was successfully drawn into filaments. The printed PLA/MPP/C-30B sample also achieved V0 grade in the UL-94 test. Figure 11 summarized the comparison of cone calorimetry test result and mechanical properties between molded and printed PLA/MPP/C-30B sample. The cone calorimetry data of printed sample was similar to the molded one. The impact strength, Young’s modulus, tensile strength and elongation of the printed sample was slightly lower than the molded sample, but the difference was within one statistical deviation. This is due to the incomplete fusion between the filaments during printing. Never the less, the printing process does not have a significant influence on the composite performance.
\n
Figure 11.
Comparison between molded and 3D printed PLA/MPP/C-30B blend: (a) UL-94 test results; (b) mechanical properties; (c) cone calorimetry test result. Adapted from Ref. [4]. Copyright (2018) with permission from Elsevier.
\n
\n
\n
4.3. Gas permeability
\n
Gas permeability is a very important factor for polymer materials used in packaging. Many studies have been established that layered particles have a great effect in enhancing the gas barrier effect [52, 53]. As part of their study on comparing between clay platelets and nanotubes, Guo et al. [22] derived individual equations to calculate the oxygen permeability for blends containing clay or nanotubes:
where, \n\nP\n\n is gas permeability of polymer with particle, and \n\n\nP\no\n\n\n is gas permeability of polymer without particle. \n\n∅\n\n is the volume fraction of nanoparticles.\n\nα\n\n is the aspect ratio of clay platelets. From the equations we could see that the aspect ratio of platelets particle could directly influence the gas permeability, whereas for tubular particles the gas permeability is independent on its dimension. Figure 12 shows the comparison between the measured gas permeability and the calculated value, and a scheme of the possible pathway in PLA blends with clay or nanotubes. For clay particles, when calculating the gas permeability with the dimension of single clay platelets, the calculated result is higher than the measured result. By back calculating the \n\nα\n\n value from the measured gas permeability, the values are equivalent to the aspect ratio of the tactoids, instead of dimension of the clay platelets. Therefore, the gas permeability of polymer/clay blend is directly affected by the work of adhesion (Wa) between the polymer and the clay surface. When Wa increases, the clay platelets have a higher degree of exfoliation in the polymer matrix, which result in a smaller tactoid aspect ratio and produces low gas permeability result. On the other hand, the measured gas permeability data for polymer/HNTs blend and polymer/H-RDP blend showed only slight decreasing with increasing nanotubes concentration. This result is in good agreement with the previous equation. Moreover, there is not much difference between the gas permeability data of polymer/HNTs and polymer/H-RDP, which is in agreement with the slight difference on their Wa. In conclusion, clay platelets have a higher barrier effect than nanotubes due to their structure difference, and the barrier effect will increase with increasing degree of exfoliation.
\n
Figure 12.
Gas permeability results of PLA based blends: (a) an illustration of oxygen pathway in PLA blends with clay or nanotubes; (b) comparison between calculated (dotted line) and measured values of gas permeability of PLA/clay blends; (c) comparison between calculated (dotted line) and measured values of gas permeability of PLA/nanotubes blends. Adapted from Ref. [22]. Copyright (2018) with permission from Elsevier.
\n
\n
\n
4.4. Thermal conductivity
\n
In addition to its compatibilizing effect and char promotion effect, the high thermal conductivity of graphene has drawn a great attention as well. Kai et al. melt blended graphene with polypropylene (PP) [54]. PP blends with carbon black and Cu microparticles, which also have high thermal conductivity, were also prepared. They found that at the same filler loading, the thermal conductivity of PP/graphene blend is two times higher than that of pure PP, as seen in Table 3, whereas the addition of carbon black or Cu only slightly increased the thermal conductivity. This effect is contributed to the large aspect ratio of graphene. The large surface area of graphene provides a better coupling between polymer chains and graphene. Comparing to the spherical structure of carbon black and Cu, it is easier for graphene platelets to form an efficient heat transfer path inside the polymer matrix. They also measured the thermal conductivity of PP/graphene at different graphene loading, and found that the thermal conductivity increased linearly with graphene concentration up to 50% graphene loading. Zhang et al. have stated that up to approximately 30 vol.% of filler, the thermal conductivity will first increase linearly with filler loading due to the increase in the contact area between filler and the polymer matrix [55]. Then the slop of this linear relationship will decrease because the filler starts to agglomerate within the polymer matrix and the conductive pathway was destructed. Thus, the linear relationship found by Kai et al. indicated that graphene platelets were uniformly distributed in the PP matrix. At 40% graphene loading, the thermal conductivity of PP/graphene blend is 2.0 W/mK, which is the same with flue gas in a metal heat exchanger. This result opens up the possibility of PP/graphene blends used in the application of heat exchanger which is also corrosion resistance and easy to process.
\n
\n
\n
\n
\n\n
\n
Sample
\n
Particle concentration (wt.%)
\n
Thermal conductivity (W/mK)
\n
\n\n\n
\n
PP
\n
100/0
\n
0.23
\n
\n
\n
PP/Cu
\n
80/20
\n
0.29
\n
\n
\n
PP/carbon black
\n
80/20
\n
0.36
\n
\n
\n
PP/GNPs
\n
80/20
\n
0.57
\n
\n
\n
70/30
\n
1.12
\n
\n
\n
60/40
\n
2.02
\n
\n
\n
50/50
\n
2.31
\n
\n\n
Table 3.
Thermal conductivity of PP based composites. Reproduced from Ref. [55] with open access.
\n
\n
\n
4.5. Rheology
\n
In general, since the addition of fillers will restrict polymer chain movement, they will reinforce the polymer matrix in the rheological response. The efficiency of the reinforcement is related to the interaction between the filler and the polymer matrix. Through the comparison between the G’ dependency on frequency of PLA blend with C-Na+, C-RDP and C-30B, Guo et al. [22] discovered that PLA/C-30B has the lowest slop at low frequency, and it is related to the fact that C-30B has the highest degree of exfoliation comparing to C-Na+ and C-RDP, shown in Figure 13. PLA blends with HNTs and H-RDP have the similar result to PLA/C-30B, which indicates the nanotubes are very effective in restrict the polymer chain motion. Moreover, the PLA/H-RDP blend have a better performance than PLA/HNTs blend, which is due to the higher affinity (Wa) between the PLA and particles induced by RDP coating. When utilized in flame retardant composites, using RDP alone will decrease the G’, which results in swelling the polymer chain and reducing the strength, and also caused heavily dripping during UL-94 test [5]. By adding cellulose to the PLA matrix, the G’ was increased at low frequency, which resulted in prevent deformation and reduce dripping during combustion. Replacing cellulose by RDP coated cellulose, the G’ further increased slightly showing that the RDP coating would increase the interaction between the polymer and the cellulose fiber. Hence, the RDP coated cellulose has a higher efficiency in prevent deformation upon heating and prevent dripping during combustion.
\n
Figure 13.
Rheology performance of PLA based composites. Adapted from Ref. [22]. Copyright (2018) with permission from Elsevier.
\n
For binary polymer systems, the morphology of the polymer phase separation and filler location play a significant role in the rheological response. In previous section, Guo, et al. [47, 56] showed that the addition of C-30B and C-RDP could effectively increase the compatibility between PLA and PBAT, while reducing the impact strength due to the strong barrier effect at the polymer interface. HNTs and H-RDP were not as effective at reducing the domain size and increasing the polymer compatibility, but the impact strength was enhanced with the “stitching” effect of nanotubes. The rheological response of PLA/PBAT blends were plotted in Figure 14, they found that the G’ of PLA/PBAT/C-30B and PLA/PBAT/C-RDP were both three magnitudes higher than PLA/PBAT control blend. This is attributed to the strong interaction between clay platelets and the polymers. However, at higher strain amplitude, both PLA/PBAT/C-30B and PLA/PBAT/C-RDP sample showed a G’ peak. This is identified as a stick slip motion caused by polymer chain confinement due to clay platelets blocking the polymer chain entanglement. On the G’ curve of PLA/PBAT/H-RDP blend, no peak was observed. This is also attributed to the nanotubes stay perpendicular to the polymer interface, and therefore the entanglement between two polymers was not affected.
\n
Figure 14.
Rheology response of PLA/PBAT blends with clays or nanotubes. Adapted with permission from Ref. [47]. Copyright (2018) American Chemical Society.
\n
\n
\n
\n
5. Conclusion
\n
We first reviewed the interaction between three widely used nanoparticles and singular polymer matrix. As being reported, the affinity between the nanoparticle and polymer could be determined by measuring the Young’s contact angle and calculating the work of adhesion (Wa). With a higher Wa, the nanoparticle will generally achieve a higher degree of exfoliation inside the polymer matrix. In a polymer composite where flame retardant particles tend to form agglomerates, the high exfoliated nanoparticle could act as a dispersant. They will segregate at the polymer/FR particle interface and increase the interaction between these two. As a result, the dispersion of the flame retardant particle is improved, as well as a higher flame retardant efficiency, which will render the polymer composite pass the V0 rating in UL-94 test at a lower filler content. We also looked at the surface interaction of nanoparticles in binary polymer systems, they perform in a similar mechanism as in the singular polymer system, where the dispersion of the flame retardant additive is improved and the phase separation is reduced. Moreover, the addition of the nanoparticles has a significant influence on the mechanical properties of the polymer composite. In a singular polymer matrix, when clay platelets were added, the impact strength will decrease with increasing degree of clay exfoliation, due to the high magnitude of internal stress created at the tip of exfoliated clay platelets. In binary polymer blends, the addition of clay will also decrease the impact resistance by localizing at the polymer interface and blocking the polymer chain entanglement across the interface. Tubular nanoparticle, on the other hand, will lie perpendicular to the polymer interface, which will enhance the impact and tensile properties by a “stitching” effect. Rheology performance was affected in the similar way as the impact and tensile properties. Clay has also been proved to have a higher improvement on the gas barrier effect than tubular particles. Large aspect ratio particles with high thermal conductivity, such as graphene, could also be used in applications for developing corrosion-resistant polymer composites for heat exchangers. In sum, the usage of nanoparticles could greatly increase the flame retardant efficiency by improving the filler dispersion in the polymer matrix, as well as other physical properties.
\n
\n\n',keywords:"polymer nanocomposites, filler dispersion, interfacial compatibility, flame retardancy, mechanical properties",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/64525.pdf",chapterXML:"https://mts.intechopen.com/source/xml/64525.xml",downloadPdfUrl:"/chapter/pdf-download/64525",previewPdfUrl:"/chapter/pdf-preview/64525",totalDownloads:789,totalViews:61,totalCrossrefCites:1,totalDimensionsCites:2,hasAltmetrics:0,dateSubmitted:"February 1st 2018",dateReviewed:"June 15th 2018",datePrePublished:"February 14th 2019",datePublished:"July 24th 2019",dateFinished:null,readingETA:"0",abstract:"The flame retardant efficiency of polymer nanocomposites is highly dependent on the dispersion of the nano-fillers within the polymer matrix. In order to control the filler dispersion, it is very essential to explore the interfacial compatibility between fillers and matrices, which provides a guide for the flame retardant nanocomposites compounding. In this short review, we mainly focus on the thermoplastic polymers and their interactions with the surfaces of the flame retardant fillers. Other physical properties of those nanocomposites such as mechanical properties, gas permeability, rheological performance and thermal conductivity are also briefly reviewed along with the flame retardancy, since they are all dispersion related.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/64525",risUrl:"/chapter/ris/64525",book:{slug:"flame-retardants"},signatures:"Yuan Xue, Yichen Guo and Miriam H. Rafailovich",authors:[{id:"176796",title:"Prof.",name:"Miriam",middleName:null,surname:"Rafailovich",fullName:"Miriam Rafailovich",slug:"miriam-rafailovich",email:"miriam.rafailovich@stonybrook.edu",position:null,institution:null},{id:"243777",title:"Dr.",name:"Yichen",middleName:null,surname:"Guo",fullName:"Yichen Guo",slug:"yichen-guo",email:"guoichen@gmail.com",position:null,institution:null},{id:"256679",title:"Ms.",name:"Yuan",middleName:null,surname:"Xue",fullName:"Yuan Xue",slug:"yuan-xue",email:"yuan.xue@stonybrook.edu",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Singular polymer matrix",level:"1"},{id:"sec_2_2",title:"2.1. Montmorillonite clays",level:"2"},{id:"sec_3_2",title:"2.2. Graphene",level:"2"},{id:"sec_4_2",title:"2.3. Natural nanotubes and fibers",level:"2"},{id:"sec_6",title:"3. Binary polymer system",level:"1"},{id:"sec_7",title:"4. Physical properties",level:"1"},{id:"sec_7_2",title:"4.1. Impact resistance",level:"2"},{id:"sec_8_2",title:"4.2. Ductility",level:"2"},{id:"sec_9_2",title:"4.3. Gas permeability",level:"2"},{id:"sec_10_2",title:"4.4. Thermal conductivity",level:"2"},{id:"sec_11_2",title:"4.5. Rheology",level:"2"},{id:"sec_13",title:"5. Conclusion",level:"1"}],chapterReferences:[{id:"B1",body:'Lubin G. Handbook of Composites. Springer Science & Business Media; 2013\n'},{id:"B2",body:'Pack S et al. Mode-of-action of self-extinguishing polymer blends containing organoclays. Polymer Degradation and Stability. 2009;94(3):306-326\n'},{id:"B3",body:'Si M et al. Self-extinguishing polymer/organoclay nanocomposites. Polymer Degradation and Stability. 2007;92(1):86-93\n'},{id:"B4",body:'Guo Y et al. Engineering flame retardant biodegradable polymer nanocomposites and their application in 3D printing. Polymer Degradation and Stability. 2017;137:205-215\n'},{id:"B5",body:'Guo Y et al. 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Effect of nanoclay hydration on barrier properties of PLA/montmorillonite based nanocomposites. The Journal of Physical Chemistry C. 2013;117(23):12117-12135\n'},{id:"B54",body:'Yang K et al. The thermo-mechanical response of PP nanocomposites at high graphene loading. Nano. 2015;1(3):126-137\n'},{id:"B55",body:'Zhang S et al. The effects of particle size and content on the thermal conductivity and mechanical properties of Al2O3/high density polyethylene (HDPE) composites. Express Polymer Letters. 2011;5(7):581-590\n'},{id:"B56",body:'Guo Y et al. Enhancing impact resistance of polymer blends via self-assembled nanoscale interfacial structures. Macromolecules. 2018;51(11):3897-3910\n'}],footnotes:[],contributors:[{corresp:null,contributorFullName:"Yuan Xue",address:null,affiliation:'
Department of Materials Science and Engineering, Stony Brook University, USA
Department of Materials Science and Engineering, Stony Brook University, USA
'},{corresp:null,contributorFullName:"Miriam H. Rafailovich",address:null,affiliation:'
Department of Materials Science and Engineering, Stony Brook University, USA
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1. Introduction
A pesticide is any substance which is used to prevent, destroy or repel any pest from causing any damage. The term pest represents any living organism that may cause harm to human in respect to food competition, destruction of property and spread of disease. Pests include insects, rodents, microbes, fungi and weeds (unwanted plants), etc. of agricultural, medical and veterinary importance, and therefore, a pesticide can be an insecticide, an insect and plant growth regulator, a fungicide, an herbicide, a molluscicide, and an algaecide, etc. based on the target pest organism.
The major site of action for most pesticides are the nervous and endocrine systems and, therefore, are also potentially toxic to human with serious direct or indirect adverse health effects. Human beings are exposed to pesticides directly or indirectly. Direct exposure occurs during pesticide application process in agriculture, public health and livestock, and fumigation while indirect exposure involves ingestion of contaminated food and water, and inhalation of pesticides droplets from the drift. Children are more susceptible to pesticides than adults due to their physical makeup, behavior and physiology, and exposure to very low levels at early developmental stages can cause adverse health effects. Codex Alimentarius committee and the Pesticide Data Program of the United States Department of Agriculture have established pesticide maximum residue limits in edible food which must be followed to avoid any health risks.
Pesticide exposures have been linked to the elevated incidence of human diseases such as cancers, Alzheimer, Parkinson, amyotrophic lateral sclerosis, asthma, bronchitis, infertility, birth defects, attention deficit hyperactivity disorder, autism, diabetes, and obesity, respiratory diseases, organ diseases and system failures. People who are exposed to pesticides are at a greater risk to develop various cancers including non-Hodgkin lymphoma (NHL), leukemia, brain tumors, and cancers of the breast, prostate, lung, stomach, colorectal, liver, and the urinary bladder.
Pesticides cause genetic and epigenetic changes by involving various processes at cellular levels. Pesticides may be involved in endocrine disruption and induction of inflammatory signals which result in production of reactive oxygen species (ROS) causing oxidative stress. ROS disrupt the cellular functions of mitochondria and endoplasmic reticulum.
This chapter covers different types, importance and modes of action of pesticides. Human exposure to pesticides and pesticide residues in food are also discussed. Finally, the impacts of pesticide exposure on human health with focus on the major chronic health effects (neurotoxic, genotoxic and carcinogenic, and reproductive effects) and recent findings regarding health effects associated with exposure to common types of pesticides, i.e., organochlorines, organophosphates, carbamates, pyrethroids and neonicotinoids insecticides, fungicides and herbicides are discussed.
2. Types of pesticides and pesticide formulations
2.1 Types of pesticides
Pesticides can be classified based on chemical classes, functional groups, mode of action, and toxicity. The active ingredients of most pesticides are either organic (contain carbon) or inorganic (minerals e.g. copper sulfate, ferrous sulfate, copper, lime, sulfur, etc.). Organic pesticides are hydrophobic and more complex than those of inorganic pesticides. Organic pesticides can be natural (produced from naturally available sources) or synthetic (artificially produced by chemical synthesis in factories). The major types of pesticides used in agriculture, forestry, landscape, medical and veterinary sectors are listed in Table 1.
Type of pesticide
Active ingredient
Target pests
Insecticides
Natural and synthetic
Insect (6-legged) pests of agricultural, forestry, landscape, medical and veterinary importance
Miticides/acaricides
Natural and synthetic
Mites (8-legged) pests of agricultural, forest, landscape, medical and veterinary importance
Fungicides
Natural and synthetic
Fungal diseases (molds, mildews, rust) of agricultural, forestry and landscape importance
Herbicides
Natural and synthetic
Unwanted plants (weeds) of agricultural and landscape importance
Insect growth regulators
Synthetic
Disrupt the growth and reproduction of insect pests. IGR are species or genus specific.
Pheromones
Natural and synthetic
Attract and trap male insects and are often species-specific.
Plant growth regulators
Synthetic
Alter plants growth, e.g., induce or delay flowering
Algaecides
Natural and synthetic
Algae growing on different surfaces, e.g., patios
Molluscicides
Natural and synthetic
Slugs and snails of agricultural, forestry and landscape importance
Biopesticides
Natural
Can be insecticides, fungicides or herbicides
Antimicrobials
Synthetic
Microbes (mostly bacteria) of medical and veterinary importance
Rodenticides
Natural and synthetic
Rodents (mice, rats) in agriculture, landscape, building, storages and hospitals
Treated seeds
Synthetic
Seeds coated with an insecticide or fungicide or both to prevent damage from soil insect pests and fungus diseases
Wood preservatives
Synthetic
Pesticides to protect wood from insect pests, fungus and other diseases
Minimum risk pesticides
Natural and synthetic
Any pesticides which have been proven safe for human and are exempt from registration by any regulatory authorities
Table 1.
Major types of pesticides used in agriculture, forestry, landscape, medical and veterinary sectors. (adopted from: National Pesticides Information Center at http://npic.orst.edu/ingred/ptype/index.html).
2.2 Pesticide formulations
Pesticides are sold as formulated products. Pesticide formulations are a combination of one or more active ingredients (a.i.) and several inert ingredients. Active ingredients control the pests. The inert ingredients help in solubility and stability of the product. A ULV (Ultra Low Volume) formulation need specialized spray equipment and the Ready-to-Use formulations are already diluted and are appropriate for indoor or small areas, for example, aerosols (A), granules (G), and most baits (B) [1].
Most liquid formulations are diluted with water according to the label directions. The three main types of liquid formulations are solutions, suspensions, and emulsions. A true solution is a mixture that cannot be separated by a filter or other mechanical means while a suspension is an even mixture of very small solid particles throughout a liquid and an emulsion is a mixture of droplets of one liquid in another liquid. Common Liquid Formulations are Emulsifiable Concentrate (E or EC), Solutions (S, CS), Emulsions in Water (EW), Flowables (F, L, or SC), Microencapsulated Pesticides (M or ME) and Aerosol (A).
In dry formulations the active ingredient is on the surface of a solid carrier, such as talc, clay, or ground corncobs. Common solid formulations include Granules (G), Wettable Powders (WP or W), Soluble Powder (SP or S), Water-Dispersible Granules (WDG) or Dry Flowables (DF Water-Soluble Bags/Packages (WSB) and Baits (B).
3. Importance of pesticides
The United Nations population division estimates 9.7 billion people by the year 2050 and to feed them, the Food and Agriculture Organization (FAO) of the United Nations estimates that an 80% increase in food production is necessary. This increase in production will come from an increase in yields of crops as well as a decrease of damage to crops due to pests. There are approximately 9000 species of insects/mites (14% loss), 50,000 species of plant pathogens (13% loss) and 8000 weeds species (13% loss) worldwide [2]. Without pesticide application the pest losses to fruits, vegetables and cereals would reach 78%, 54% and 32%, respectively. Pesticides are, therefore, indispensable in agricultural production and there will be a need for pesticide based pest control and food security in the future. Pesticides are also used to control vector-born infectious diseases such as Zika virus, Lyme disease, and rabies, household pests like cockroaches, bed bugs, and as repellents etc. More than 1000 active ingredients are used in pesticides around the world to ensure food safety and prevention from pests and the highest amount (~45%) is spent on herbicides followed by insecticides, fungicides, and other types of pesticides.
4. Human exposure to pesticides and exposure risks
4.1 Human exposure to pesticides
Human beings get exposed to pesticides either actively through occupational exposure or passively through non-occupational exposure. Pesticides occupational exposure may occur during manufacturing, transportation, sale, and application process including exterminators. For example, in an incident of occupational exposure, 2800 workers were poisoned during malathion spray for malaria vector control in Pakistan [3]. Parents working in agriculture industry usually take pesticide contaminated clothing, equipment home, which has been associated with the development of cancers in their children.
Non-occupational exposure may include pesticides residues ingestion with contaminated food and water and inhalation of pesticides droplets from the air through drift from point of release or fumigation. Human beings are also exposed to residual indoor sprays and outdoor fogging of insecticides applied against insect pests of public health importance and homeowners exposed to structural pest control pesticides. Additionally, treatment of ectoparasites in pets, e.g. fleas, is also a source of exposure, especially for children.
Exposure through the intact skin (dermal exposure) is the most common route and may occur as a result of a splash, spill, or spray drift, during mixing, loading, disposing, and/or cleaning of application equipment especially when proper protective equipment are not used. Dermal absorption can be influenced by the amount/concentration, duration of exposure and temperature/humidity. Absorption is high through groin areas, the eyes and ear canal. Liquid formulations (e.g., emulsifiable concentrates) are readily absorbed through the skin compared to the solid formulations (e.g., powders, dusts, and granules).
Accidental ingestion of pesticides (oral exposure) occurs by drinking from unlabeled containers when pesticides are stored in food/drink container, water stored in pesticide-contaminated bottles, eating or smoking while, or after handling pesticides or through application equipment or pesticide residues in food and water. Inhalation of pesticides (respiratory exposure) may occur due to application of fumigants (which change into toxic gas after coming in contact with moisture in air) or presence of fine droplets in air (particle or vapor drift) after application of pesticides. Pesticides can enter blood stream after absorption through lungs.
Pesticides are distributed throughout the human body through the bloodstream and are excreted through urine, skin, and exhaled into air after metabolism. These pathways also determine the toxicity of any pesticide. Pesticides recognized as persistent organic pollutant (POP) are fat soluble and are easily accumulated within the human fat-tissues, breast milk, and maternal blood placenta.
4.2 Pesticides exposure risks
The amount of risk from pesticide exposure depends on the toxicity and the exposure to the pesticide. Toxicity is a measure of how harmful or poisonous a pesticide is (causing sickness or other unwanted effects), while exposure is a measure of the contact (duration) with a pesticide. Toxicity of a pesticide is measured as lethal dose (LD50). The LD50 value is the statistical estimate of a pesticide (mg/kg of body weight) which will kill 50% of the test animals within a stated period of time (24 hours to 7 days). The LD50 value also depends on the route of entry of a pesticide; oral LD50 for oral ingestion, dermal LD50 for skin contact exposure and Lethal Concentration (LC50) for inhalation of fumigants and pesticide vapors.
A short term exposure or exposure to a single dose will cause acute toxicity with its health effects. Chronic toxicity results from repeated exposure to a pesticide over a longer period of time from several months to years. Hazard symbols, signal words and color on the primary display panel of a pesticide label are based on their dermal toxicity.
5. Pesticides modes of action
5.1 Insecticides
Insecticides Resistance Action Committee (IRAC) has classified insecticides into 32 groups based on their mode/site of action, in addition, there are 5 other types of insecticides with unknown modes of action. Most commonly used insecticides work at different sites in the nervous system of insects. Insecticides target the same sites of action in human nervous system and cause toxicity with adverse health effects. Carbamate (group 1A) and Organophosphate (OP) (group 1B) insecticides inhibit the enzyme Acetyl Choline Esterase (AChE) and cause hyper-excitation. AChE terminates the action of the excitatory neurotransmitter acetylcholine at the nerve synapses. Examples of pesticides inhibiting AChE include dichlorvos, malathion, phorate, carbaryl, carbofuran, etc. Cyclodiene organochlorine insecticides (OC) (group 2A) and phenylpyrazoles (group 2B) block the gamma amino butyric acid (GABA)-activated chloride channel causing hyper-excitation and convulsions. GABA is the major inhibitory neurotransmitter in insects. Examples of insecticides inhibiting GABA include endosulfan and fipronil. Synthetic pyrethroids and natural pyrethrins (group 3A) and DDT (group 3B) keep sodium channels open causing hyper-excitation and, in some cases, nerve blockage. Sodium channels are involved in the propagation of action potentials along nerve axons. Examples include deltamethrin and permethrin. Neonicotinoid insecticides (group 4A) bind to the acetylcholine site on nicotinic acetylcholine receptor (nAChRs) causing a range of symptoms from hyper-excitation to lethargy and paralysis. Examples include acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam. Other groups of insecticides that work on nervous system includes those which allosterically activate nAChRs (e.g. spinetoram, spinosad) or glutamate-gated chloride channels (GluCls) (e.g. abamectin, emamectin benzoate), or allosterically inhibit the GABA-activated chloride channel and cause paralysis (e.g. broflanilide and fluxametamide). Glutamate is an important inhibitory neurotransmitter in insects. Other insecticides will block the nAChR ion channel or sodium channels, e.g. indoxacarb, cause nervous system shutdown and paralysis.
5.2 Fungicides
Fungicides inhibit fungal growth by interfering with critical cellular processes. Fungicide resistance action committee (FRAC) classify fungicides and bactericides into 50 groups based on the site of action. Within each group, there are target sites, which are the specific enzymes to which the fungicides bind. The different known target sites include nucleic acids metabolism, cytoskeleton and motor protein, respiration, amino acids and protein synthesis, signal transduction, lipid synthesis or transport/membrane integrity or function, sterol biosynthesis in membranes, cell wall biosynthesis, melanin synthesis in cell wall and host plant defense induction. Some fungicides and herbicides are considered endocrine disrupting pesticides.
5.3 Herbicides
Herbicides are pesticides that inhibit or interrupt normal plant growth and development. Herbicides are widely used in agriculture, landscape industry, and non-crop areas for weed management. Herbicides resistance action committee (HRAC) has classified herbicides into 27 groups. These include: growth regulators (synthetic auxins; auxin transport inhibitors), seedling growth inhibitors, photosynthetic inhibitors, amino acid synthesis inhibitors, lipid synthesis inhibitors, cell membrane disrupters, pigment inhibitors.
Growth regulator herbicides consist of the synthetic auxin and auxin transport inhibitory compounds and the most commonly used synthetic auxins include 2,4-Dichlorophenoxyacetic acid (2,4-D), fluroxypyr, dicamba, quinclorac, dichlorprop, MCPA (2-methyl-4-chlorophenoxyacetic acid), mecoprop and picloram. These are commonly used systemic herbicides which mimic the plant growth hormone auxin (indole acetic acid) [4]. Some of these synthetic auxin herbicides disrupt human hormonal system. Atrazine is also a commonly used photosynthetic inhibitor herbicide. Glyphosate (Roundup) is an amino acid derivative and inhibits synthase of EPSPS enzyme, which is involved in the synthesis of the aromatic amino acids (tyrosine, tryptophan, and phenylalanine). Paraquat (gramoxone) is an electron diverter, and as a respiratory inhibitor can be a significant risk to humans if inhaled or ingested.
6. Pesticide residues in food, water and air
6.1 Pesticide residues
‘Pesticide residue’ means any specified substance in food, agricultural commodities, or animal feed resulting from the use of pesticides. The term also includes any derivatives of a pesticide, such as conversion products, metabolites, reaction products, and impurities considered to be toxic. Application of pesticides during the production or storage of agricultural commodities result in pesticide residues in food (fruits, vegetables, grain, meat, etc). Pesticide residues are also found in the drinking water. Pesticide residues can build up to harmful levels through bio-accumulation and bio-magnification within the food chain.
WHO, in collaboration with FAO performs pesticide risk assessment to humans, both through direct exposure and through residues in food. The WHO core assessment group on pesticide residues review toxicological data and establish the acceptable daily intakes (ADIs) and acute reference doses (ARfDs) of pesticide residues for different commodities through a lifetime of food consumption. The ADIs are amount of pesticide residues which will not result in adverse health effects. Codex Alimentarius Commission (the intergovernmental standards-setting body for food) establishes maximum residue limits (MRLs) for pesticides in food based on ADIs.
The MRL depends on the crop it is used on, and the same pesticide active ingredient may have different MRL values when used on different crops. Extraneous maximum residue limit (EMRL) refers to the maximum permitted limit of residues of mostly POP pesticides, which were previously used as pesticides but not registered any more, and residues arising from environmental contamination (including previous agricultural use) or residues from uses of these pesticides other than for agricultural purpose, e.g. DDT, Aldrin, etc.
6.2 Pesticide residues in food, water and air
There are several reports of pesticide residues detected on food exceeding the MRL values. For example, in India, vegetable samples were tested for the presence of OC, OP and pyrethroid insecticides, and 15.3% samples exceeded the MRL. In two Brazilian pesticide residue monitoring programs less than 3% of the samples had residue levels above the MRL. Pesticide residues were detected in 34% of samples of cereal grains collected throughout Poland and 3% samples contained residues over the maximum limit. A study from Maule Region (Talca, Chile) found pesticide residues on the fruits and vegetables schoolchildren brought as snack [5].
The pesticide residues detected in fruits and vegetables from Lithuania had multiple pesticides; 9 residues in grapes and tea, 5-9 residues in orange, mandarins, lemons, peaches, pears and 3-5 residues in pomegranates, plums, cucumbers, tomatoes and strawberries, and found that 2.6% samples exceeded the MRL values [6]. In a European Union study 14–23% of the samples had detectable residues of more than one active ingredient where 3.0–5.5% samples had residues levels above the MRL [7]. Exposure to multiple pesticide residues could be due to intake from a single food item containing multiple residues or from several food items each containing one or more residues. The combined toxic effects of two or more compounds can be independent, additive or synergistic.
Both recreational and medicinal cannabis samples contained high levels of residual pesticides and pesticides not legally allowed to be used on cannabis products in Oregon. Medicinal cannabis products were found to have mean levels of residual pesticides that were 3-12 times higher than recreational products, and 9 of the 50 pesticides identified were classified highly or extremely hazardous by the WHO [8].
Pesticide residues have been found in surface, groundwater and potable water samples from India [9]. Pesticide residues levels in river water and in drinking water samples in Turkey were significantly high compared with guideline values set by Turkey, EU and WHO as hazardous to human health [10]. Higher concentrations of pesticides in ambient air were recorded from potato farm sites in Prince Edward Island, Canada, Taihu Lake region of China and Kaweah Reservoir, CA, USA. A total of 87 pesticides were identified in the household dust samples from the rural Yakima Valley of Washington state, 47 of these have evidence of neurotoxicity included in the EPA list [11].
7. Impacts of pesticide use on human health
7.1 Acute health effects of pesticide exposure
The short-term acute adverse effects pesticide exposure on human health are stinging eyes, rashes, blisters, skin irritations, blindness, nausea, dizziness, diarrhea and death. Exposure to pesticides in agricultural work can cause serious risks to the respiratory system causing chronic cough, dyspnea, wheezing and expectoration, decreased lung capacity, asthma, and bronchitis. These respiratory problems were found in workers in flower crops in Ethiopia, coffee plantations in Brazil and banana plantations in Costa Rica. In banana farming in Rio Grande do Norte (Brazil), the use of pesticides was related to the symptoms of burning in the throat and lungs, airway congestion, cramps, skin peeling, diarrhea, headache, chest pain, weakness, cough and skin irritation.
In banana production region of the Ribeira Valley (Brazil), workers (majority males, low schooling, mean age 39.6 years and 13.8 years of working time) had moderate obstructive disorder (10.0%) and mild obstructive disorder (13.3%) with decreased FEV1 (forced expiratory volume in 1 second) and FEV1/FVC (the ratio between forced expiratory volume in the first second and forced vital capacity and is very important for the detection of obstructive disorders). Similarly, exposures to mixtures (pollutants and pesticides) in children with asthma in California were also associated with reduced lung function measures FEV1 and FVC [12].
Many studies have found positive associations with pesticide exposure and children’s respiratory and allergic effects such as asthma, wheezing, coughs, acute respiratory infections, hay fever, rhinitis, eczema, chronic phlegm, and lung function impairments. A study of school-age children with asthma in the agricultural community of Yakima Valley (Washington State) found that increase in exposures to OP insecticides was related with increase in LTE4 levels which was associated with a higher risk of asthma morbidity [13]. The neonicotinoid insecticides (e.g. imidacloprid, nitenpyram) are nicotinic receptors agonists and their exposure cause nausea, vomiting, muscle weakness, respiratory effects, headache, lethargy, and tachycardia.
7.2 Chronic effects of pesticide exposure
The long-term chronic adverse effects of pesticides exposure are cancers, birth defects, reproductive harm, neurological and developmental toxicity, immunotoxicity, and disruption of the endocrine system. The chronic effects of pesticides on human can be categorized into three major groups; neurotoxic effects, genotoxic and carcinogenic effects, and reproductive effects.
7.2.1 Neurotoxic effects
Neurotoxicity can be defined as any adverse effect on the central or peripheral nervous system caused by chemical, biological or physical agents. A developing nervous system in children (during replication, migration, differentiation, myelination of neurons, and synapse formation) is more susceptible to neurotoxic chemicals including pesticides. Chemicals (pesticides) can cause neuronal cell death by disruption of the cytoskeleton, induction of oxidative stress, calcium overload, or by damaging mitochondria. Most of the synthetic insecticides, some fungicides and herbicides, currently in use are neurotoxicants.
Pesticide molecules are small and lipophilic in nature, and can enter from blood to brain and then in neurons, glial cells and brain micro vessels. Pesticides can disrupt blood-brain barrier receptors in the central nervous system which enhance chronic toxicity and affect the receptor-mediated transcytosis. Neuronal cells are more susceptible to oxidative stress due to their high polyunsaturated fat content in the myelin sheaths, low anti-oxidative capabilities, enzymatic systems with transient metals that aid in the production of free radicals, and demand for high oxygen and glucose metabolism rate.
OPs and carbamates bind to and phosphorylate/carbamalate the AChE which causes accumulation of acetylcholine at cholinergic synapses causing overstimulation of muscarinic and nicotinic cholinergic receptors. Neuropsychiatric disorders, such as anxiety and depression, are observed in patients with acute and long-term poisoning from OPs. OPs may also cause an intermediate syndrome and OP-induced delayed polyneuropathy (OPIDP) 1-3 weeks after a single exposure. In carbamates, the AChE inhibition is reversible and acute intoxication is generally resolved within a few hours.
The OP insecticides can disturb the function of mitochondria by inducing oxidative stress in central nervous system through critical depletion of mitochondrial energy, the activation of proteolytic enzymes, and DNA fragmentation leading to apoptosis. The dysfunction of mitochondria and oxidative stress is responsible for several neurological diseases, including Parkinson’s disease, seizure, cognitive dysfunction, attention and memory deficits, dementia, depression, and Alzheimer’s disease. OP triggered induction of a xanthine oxidase may play a role in cognitive impairment.
In a study, increased inhibition of cholinesterase enzyme with increased exposure to OP insecticides was confirmed in both occupationally exposed (OE) and environmentally exposed (EE) groups of people. The OP exposure, mainly in the EE group, was associated with a diminished neuropsychological performance; general mental status, language, memory, attention, executive function, praxis and psychomotricity.
Acute poisoning due to exposure to OP (particularly chlorpyrifos) was reported with higher prevalence of peripheral polyneuropathy, and deterioration of cognitive functions (verbal fluency, and visual and auditory memory) was observed in agricultural workers and in inhabitants of rural agricultural areas. Exposure to OP insecticides in rural schoolchildren was associated with a lower processing speed in children and an IQ lower than expected for their age.
Exposure to type I pyrethroids cause tremor syndrome (behavioral arousal, aggressive sparring, increased startle response, and fine body tremor progressing to whole-body tremor, and prostration) while type II pyrethroids exposure cause salivation syndrome (profuse salivation, coarse tremor progressing to choreoatetosis, and clonic seizure). The poisoned cerebral cortex affect learning, memory, emotions, and movement. Pyrethroids exposure has been positively associated with hearing loss in U.S. adolescents. Pyrethroids exposure induced Tau protein malfunction which may be the mechanism underlying cognitive impairment. Paraquat, triazine and pyrazole (herbicides) through oxidative stress, raised influx of calcium and the stimulation of nitrogen oxide species, and aggravated Aβ amyloidogenesis cause cognitive impairment.
Exposure to endocrine disrupting chemicals (EDCs) including many pesticides can disrupt maternal thyroid imbalance which can result in permanent and lifelong neurodevelopmental consequences for their children, including attention-deficit disorder, autism spectrum disorder, and cognitive and behavioral dysfunction. Workers of fruit and seed export companies in a rural area of Santiago exposed to methyl bromide (CH3Br, a fumigant) had increased concentration of CH3Br in blood after application which resulted in a higher frequency of insomnia, headaches, paresthesias, mood swings, memory loss, and decreased concentration [14].
Parkinson’s disease (PD) is characterized by progressive degeneration of dopaminergic neurons of the nigrostriatal pathway and the formation of alpha-synuclein (α-syn)-containing Lewy bodies. Dieldrin (OC) is selectively toxic to dopaminergic cells, disrupts striatal dopamine activity, and may promote α-syn aggregation while ziram (dithiocarbamate fungicide) increases the probability of synaptic vesicle release by dysregulation of the ubiquitin signaling system and increases excitability in both aminergic and glutamatergic neurons leading to PD.
7.2.2 Genotoxic and carcinogenic effects
A genotoxic agent can be a physical, chemical or biological agent that can interact with the genetic material (DNA) causing alterations, damage or ruptures, and those that interfere with enzymatic processes of repair, genesis or polymerization of proteins involved in chromosome segregation. These alterations could lead to impaired embryonic development or be the initial steps in the development of cancer. Pesticides exposure can cause genomic damage. Genetic damage caused by pesticides is broadly classified into three classes; (i) Pre-mutagenic damage like DNA strand breaks and DNA adducts (ii) gene mutations like insertion, deletion, inversion and translocation (iii) chromosomal aberrations, including loss or gain of whole chromosome (aneuploidy), deletion or breaks (clastogenicity), and chromosomal rearrangements.
Farmers exposed to pesticide mixtures in Greece had possible clastogenic (chromosome breakage cause mutation) and aneugenic (abnormal number of chromosomes) effect of pesticides on the genetic material. DNA methylation changes in the placenta were significantly associated with the maternal plasma concentrations of OCs in early pregnancy causing prenatal toxicity. OPs affect DNA methylation, induce the AChE gene expression and activate the NMDA glutamate receptors resulting in calcium influx in the post-synaptic neurons leading to degeneration.
Genetic damage has been reported from exposure to malathion (OP), carbofuran (carbamate), triflumuron (Insect growth regulator), imidacloprid, acetamiprid and thiamethoxam (neonicotinoid insecticides), pentachlorophenol (OC), Emamectin benzoate (used in agriculture, household, and veterinary medicine), and tembotrione (novel post-emergence herbicide) (Table 2).
WHO Hazard Class
Band color
Signal word
Dermal LD50 (mg/Kg)
Solid formulation
Liquid formulation
Class Ia Extremely Hazardous
Red
VERY TOXIC
<10
<40
Class Ib Highly Hazardous
Red
TOXIC
10–100
40–400
Class II Moderately Hazardous
Yellow
HARMFUL
100-1000
400-4000
Class III Slightly Hazardous
Blue
CAUTION
>1000
>4000
Class U Products unlikely to present a hazard
Green
Table 2.
Pesticides hazard classification by FAO.
Cancer is characterized by an uncontrolled cell growth with limitless replication, resistance to apoptosis, alteration of growth factors (GFs), resistance to chemotherapy, metastasis and angiogenesis. Cancer develops as a result of multi-factorial complex interactions of genetic and lifestyle factors including, diet, stress, physical and biological agents, infections, and exposure to the hazardous chemical substances. Pesticides exposure acts as a stimulant to cancer and chronic low-dose is considered one of the important risk factors for the increasing cancer incidence. Table 3 presents a list of pesticides suggesting carcinogenicity in different types of studies.
Non-Hodgkin lymphoma (NHL) is a diverse group malignancies and its incidence has increased worldwide. Patients with immune dysfunction are at a high risk to develop NHL. Studies have reported an elevated risk of NHL with exposure to several classes of pesticides. Terbufos (OP nematicide), dimethoate, malathion and chlorpyrifos (OP insecticide), and 2,4-D and dichlorprop (chlorophenoxy herbicides) have been associated with significant risk of developing HL.
7.2.2.2 Leukemia
Leukemia has been associated with occupational exposure with a higher risk in livestock farmers and golf course superintendents. The risk of chronic myelocytic leukemia (CML) and acute myeloblastic leukemia (AML) was found to be higher in women. Children whose parents used garden and indoor insecticides, or whose mothers had been exposed while pregnant had increased rates of all types of leukemia. Children living on farms and those exposed to household pesticides have increased risk of leukemia. Association between occupational exposure to pesticides and chronic lymphocytic leukemia (CLL) has been reported from Spain. A nationwide study in France showed a moderate increase in incidence of childhood AL in municipalities where viticulture is common.
7.2.2.3 Brain cancer
Brain tumors are the most common solid tumors in children and the leading cause of cancer-related mortality during childhood. A positive association has been reported between parental occupational, prenatal or residential exposure, living on a farm, mothers living on farms, rural activity and childhood brain tumors. Increased risk for primitive neuroectodermal tumors (PNETs) was associated with maternal exposure living on pig or poultry farms. Exposure to pyrethroid formulations used to control mosquitoes and cockroaches at home also increase the risk of brain tumors.
7.2.2.4 Breast cancer
Breast cancer is the leading cause of cancer-related deaths among women. About 650 pesticides out of the 800 used worldwide can affect the functioning of the endocrine system and are called endocrine disrupting pesticides (EDPs). EDPs have the potential ability to act as tumor promoters and increasing risk of breast cancer. All women diagnosed with breast cancer between 1995 and 2005 in the city of Arica (geographic area that received massive aerial applications of malathion in 1980) were 5.7 times more likely to suffer from breast cancer compared to women diagnosed during the same period in the city of Iquique, Chile [14]. Several chemical classes of insecticides, fungicides and herbicides have been associated with breast cancer in women (Table 3).
7.2.2.5 Prostate cancer
Prostate cancer is the second most common cancer in men globally, and accounts for 7% of all cancers. More than 95% of cases of prostate cancer are androgen-dependent. The higher incidence of prostate cancer, at least in part, has been associated with the hormone disrupting pesticides and consistent positive associations between prostate cancer and pesticide exposure have been reported.
7.2.2.6 Hepatocellular carcinoma
Hepatocellular carcinoma (HCC) is the 6th most common cancer, and the 4th most common cause of cancer-related mortality. The major risk factors include hepatitis B virus (HBV), hepatitis C virus (HCV), alcohol, aflatoxin contaminated foods, obesity, smoking and type 2 diabetes besides pesticides. Pesticides exposure has been associated with increased risk of developing HCC.
7.2.3 Reproductive effects
EDCs are emerging as one of the leading risks and are recognized as serious and urgent threats to public health. In laboratory studies, EDCs are reported to shorten gestation, alter intrauterine growth, and disrupt metabolic programming. Prenatal exposure to EDCs can affect fetal neurodevelopment through disruption of peroxisome proliferator activated receptors, mainly estrogen receptors, and thyroid hormone receptors.
Failure of testosterone production in Leydig cells leads to failure of testosterone-bound androgen receptor-mediated gene transcription necessary for spermatogenesis. Many studies have shown that various pesticides decrease testosterone levels. Testosterone is required for the final stages of sperm maturation, so a decrease in intra-testicular testosterone is likely to impair fertility. Vinclozolin (fungicide) and chlorpyrifos (OP) can reduce testosterone production. Exposure to higher concentrations of OP and dialkyl phosphates (metabolites of OPs), p,p’-DDE, fenvalerate and atrazine (chlorotriazine herbicide) have been consistently associated with lower semen quality (sperm concentration, motility, and morphology).
A study of male children from a village of cashew plantations, where endosulfan (OC, EDC) had been aerially sprayed for more than 20 years, showed a delay in sexual maturity and an alteration in sex hormone synthesis. Endosulfan, in exposed mothers, can move via trans-placental route and breast feeding to children. Exposure during critical periods of development might contribute to decline conception rates and increased incidence of female reproductive disorders, such as altered cyclicity, endometriosis, fetal growth retardation, and pregnancy loss [60].
A high incidence of spontaneous abortions 81.02 / 1000 live newborns was reported in Valparaíso Region (agricultural area) compared to 9.5 /1000 live newborns in the rest of Chile. A 28% incidence of congenital malformations in live newborns was reported in the O’Higgins Region (agricultural area) compared to only 15% of cases in non-agricultural in Chile [14].
8. Conclusion
Pesticides are used in managing pests of agricultural and public health importance, and their use will continue in future because of food security and vector control. Additionally, pesticides are used at home in fumigation for structural pests and to mitigate household pest using aerosols or sprays. It is difficult to eliminate pesticides in the near future, but they should be used with care and caution. Most pesticides are potentially toxic to human beings resulting in severe health consequences including cancers.
Epidemiological evidence suggests that there is an increased incidence of different diseases including leukemia, lymphoma, and several other types of cancers in farmers, and those who are associated with application of pesticides. There is also evidence that parental exposure, as well as, exposure in early life or adolescence could increase the longer-term risks.
Since animal studies are problematic, expensive and often generate ethical problems, cell cultures are increasingly used as a model of research. Correctly conducted and properly selected, the cell culture is an excellent experimental model reflecting human exposure to different xenobiotics through all relevant routes. The cell cultures are also becoming more widely used to study the effect of pesticides on the human body at a molecular level, which is necessary to understand the hazards and determine the level of exposure.
Some pesticides (OCs) are no longer used worldwide due to their persistence and toxicity. However, their residues or metabolites are still found in food and water samples. The use of OPs and carbamate insecticides has been reduced since the arrival of newer chemistries in different parts of the world but most of them are still use around the world.
The workplace safety standards and proper pesticide management and storage must be implemented to reduce the risks posed to human health. Pesticide users should be aware of their risks and proper handling, as well as must use personal protective equipment which are effective in reducing damage to human health. To ensure healthy childhood growth, efforts should be made to develop comprehensive pesticides risk mitigation strategies and interventions to reduce children’s exposure.
It is critical to achieve sustainable development in agricultural systems. Newer approaches in pest management have been developed which should be encouraged. For example, RNA interference- (RNAi-) based pesticides are emerging as a promising new biorational control strategy [61] and steam treatment at temperature of 150.56°C can kill 93.99% of nematode 97.49% of bacteria [62].
Future research need in the context of minimizing the impact on human health due to exposure to pesticides include an urgent need to eliminate the use of carcinogenic pesticides and to develop environmentally sound integrated pest management (IPM) strategies that use the minimum amount of pesticides. Such IPM strategies should aim at reducing the pesticides residues on food products and pesticides-free water and air.
Acknowledgments
The author acknowledges the financial support by the Sultan Qaboos University, Muscat, Oman. This work was funded through an Internal Grant # IG/AGR/CROP/18/02.
\n',keywords:"pesticides, cancer, endocrine disruption, pesticide residues, toxicity",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/73921.pdf",chapterXML:"https://mts.intechopen.com/source/xml/73921.xml",downloadPdfUrl:"/chapter/pdf-download/73921",previewPdfUrl:"/chapter/pdf-preview/73921",totalDownloads:133,totalViews:0,totalCrossrefCites:0,dateSubmitted:"June 30th 2020",dateReviewed:"August 31st 2020",datePrePublished:"November 4th 2020",datePublished:null,dateFinished:null,readingETA:"0",abstract:"Pesticides are used in managing pests and their use will continue in future because of food security and vector control. Most pesticides are potentially toxic to human beings resulting in severe health consequences. There is also evidence that parental exposure, as well as, exposure in early life or adolescence could increase the longer-term risks. Pesticide exposures have been linked to many human diseases such as Alzheimer, Parkinson, amyotrophic lateral sclerosis, asthma, bronchitis, infertility, birth defects, attention deficit hyperactivity disorder, autism, diabetes, and obesity, respiratory diseases, organ diseases and system failures. People who are exposed to pesticides are at a greater risk to develop various cancers including non-Hodgkin lymphoma (NHL), leukemia, brain tumors, and cancers of the breast, prostate, lung, stomach, colorectal, liver, and the urinary bladder. The cell culture is an excellent experimental model reflecting human exposure to pesticides at a molecular level which is necessary to understand the hazards. Pesticide users should be aware of their risks and proper handling, as well as must use personal protective equipment which is effective in reducing damage to human health. Carcinogenic pesticides must be eliminated and sustainable and new approaches in pest management should be encouraged.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/73921",risUrl:"/chapter/ris/73921",signatures:"Riaz Shah",book:{id:"10030",title:"Emerging Contaminants",subtitle:null,fullTitle:"Emerging Contaminants",slug:null,publishedDate:null,bookSignature:"Dr. Aurel Nuro",coverURL:"https://cdn.intechopen.com/books/images_new/10030.jpg",licenceType:"CC BY 3.0",editedByType:null,editors:[{id:"14427",title:"Dr.",name:"Aurel",middleName:null,surname:"Nuro",slug:"aurel-nuro",fullName:"Aurel Nuro"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:null,sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Types of pesticides and pesticide formulations",level:"1"},{id:"sec_2_2",title:"2.1 Types of pesticides",level:"2"},{id:"sec_3_2",title:"2.2 Pesticide formulations",level:"2"},{id:"sec_5",title:"3. Importance of pesticides",level:"1"},{id:"sec_6",title:"4. Human exposure to pesticides and exposure risks",level:"1"},{id:"sec_6_2",title:"4.1 Human exposure to pesticides",level:"2"},{id:"sec_7_2",title:"4.2 Pesticides exposure risks",level:"2"},{id:"sec_9",title:"5. Pesticides modes of action",level:"1"},{id:"sec_9_2",title:"5.1 Insecticides",level:"2"},{id:"sec_10_2",title:"5.2 Fungicides",level:"2"},{id:"sec_11_2",title:"5.3 Herbicides",level:"2"},{id:"sec_13",title:"6. Pesticide residues in food, water and air",level:"1"},{id:"sec_13_2",title:"6.1 Pesticide residues",level:"2"},{id:"sec_14_2",title:"6.2 Pesticide residues in food, water and air",level:"2"},{id:"sec_16",title:"7. Impacts of pesticide use on human health",level:"1"},{id:"sec_16_2",title:"7.1 Acute health effects of pesticide exposure",level:"2"},{id:"sec_17_2",title:"7.2 Chronic effects of pesticide exposure",level:"2"},{id:"sec_17_3",title:"7.2.1 Neurotoxic effects",level:"3"},{id:"sec_18_3",title:"Table 2.",level:"3"},{id:"sec_18_4",title:"7.2.2.1 Non-Hodgkin lymphoma and Hodgkin lymphoma",level:"4"},{id:"sec_19_4",title:"7.2.2.2 Leukemia",level:"4"},{id:"sec_20_4",title:"7.2.2.3 Brain cancer",level:"4"},{id:"sec_21_4",title:"7.2.2.4 Breast cancer",level:"4"},{id:"sec_22_4",title:"7.2.2.5 Prostate cancer",level:"4"},{id:"sec_23_4",title:"7.2.2.6 Hepatocellular carcinoma",level:"4"},{id:"sec_25_3",title:"7.2.3 Reproductive effects",level:"3"},{id:"sec_28",title:"8. Conclusion",level:"1"},{id:"sec_29",title:"Acknowledgments",level:"1"}],chapterReferences:[{id:"B1",body:'University of Kentucky. PESTICIDE FORMULATIONS; Kentucky Pesticide Safety Education Program [Internet]. 2020. 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