**3. Loss of efficiency**

under field conditions show a lower efficiency of clothes washed in the laboratory past and not only passed with 10 and 20 wash cycles, although the values are higher than 98%. Under laboratory conditions, the 30 cycles of washes and hot ironing do not significantly reduce the efficiency of PPE [6]. This result is due to the washing procedure number 8 - called gentle,

**Figure 3.** (A) A closed chamber used for assessment of protective clothing against pesticide. (B) Spraying layout

**Figure 2.** Chemical structure of polytetrafluoroethylene polymer. C, carbon; F, fluor; and n, repeating units (polymer).

Espanhol-Soares et al. investigated the dermal exposure using a protective clothing applying the efficiency tests conforming to ASTM F 1359, under a spray bath using an exposure level greater than ISO 17491-4. The ISO 17491-4 procedure is required to evaluate complete protection sets in the standard ISO 27065. However, in this work, the ASTM standard was adapted to the flow similar to that of ISO 17491-4 for method A. Nevertheless, the total dermal exposure without the use of the protective clothing was 21426.5 mL L−1, according to ASTM 1359 (total volume sprayed 1.98 L). This value is higher than 2265.3 mL L−1, obtained for method B

established in ISO 6330: 2000 [6].

72 Insecticides - Agriculture and Toxicology

according to ASTM 1359. (C) Spray layout (ISO 17491-4) [43].

#### **3.1. Pesticides (types of formulations, active ingredient, viscosity, etc.)**

The penetration of the pesticides is defined by the passage of a chemical compound, which passes through openings, pores of the materials, seams, holes, or other imperfections of overlapping of the clothing [43]. The movement of the pesticide molecule occurs in three stages: adsorption, absorption, and desorption. The adsorption is controlled by the ratio of the tissue surface energy to the surface tension of the spray mixture. Absorption is the way the pesticide interacts within the tissue structure. This movement is determined by the tissue structure and the size of the pesticide molecule. Desorption is the ability of the pesticide to penetrate the tissue [44].

The pesticides used in the ISO 22608 test, which were diluted and undiluted, are glyphosate, chlorpyrifos, and copper hydroxide in a water-repellent material, being greater penetrations for diluted solutions, mainly for solutions of chlorpyrifos and copper hydroxide. For the insecticide chlorpyrifos, the material was rejected after five uses and washes with the value of penetration of 5.5% for the diluted solution. For the solution undiluted material, it was disregarded after 20 washes of the material used in the field, but the evaluation with the glyphosate solution used in certification tests of garments was only reproved after 30 uses and washes after use in the sugar cane culture. These results indicate that it is necessary to carry out the tests with insecticides also for the clothing certification [45].

The water repellency and the contact angle with the Teflon-treated polyester increase with the concentration of water-repellent substances applied to the fabric and decrease with the

Evaluation of Insecticides in Protective Clothing http://dx.doi.org/10.5772/intechopen.76075 75

Obendorf et al. evaluated the adsorption of ionic surfactants present in soaps after washing processes in cotton fabrics. They found that the change in pH in the wash solution affects the adsorption of surfactants in the tissues. Cationic surfactants are adsorbed on cotton fabrics because of the negative charges [53]. This mechanism of adsorption may explain why certain

For many times, the inefficiency of protective clothing is due to improper use or poorly constructed, and pesticides penetrate into clothing through openings, seams, zippers, folded sleeves, and poor overlaps of sleeves with gloves [54]. Such inefficiency of protection against

The resistance to penetration of protective material against pesticides depends on the methodology used and the type of tissue. In fabrics made of 100% cotton with a water-repellent treatment (Phobol oil), penetrations below 1.6% have been found when evaluated by the trough, pipette, and atomizer test method. However, in cotton/polyester composite fabrics, the penetration is 12.8% with the pipette method, 16.5% with the gutter method, and no pen-

Although water-repellent fabrics cause discomfort to workers, especially in the hottest agricultural regions, it is believed that with the proof of EPI efficiency, the applicator distribution on the regions of the body, and with the methodologies of evaluation of the exposures, the EPI should be recommended for the most exposed areas of the body and provide safety and lesser

Protective clothing has been studied through the ergonomic property testing in dummies in chambers with controlled environmental and exposure conditions [56]. In the dermal exposure, dummies can be used for assessment methods. Therefore, the penetration or retention of insecticides is evaluated, as in the evaluation of malathion spraying on protective clothing used to control dengue [22]. However, there are few studies in the literature that quantita-

Machera et al. used the procedure of ISO 22608 to evaluate the penetration of pesticides in protective clothing materials. For materials containing cotton/polyester (50/50%) with 215 g/m<sup>2</sup> treated with NanoTex® water repellent, the penetration was 2.4% after 15 washes. However,

was 18.7%, after five washes [29]. Therefore, it has been found that the cotton yarns in the

Shaw and Schiffelbein tested approximately 100 different fabrics used in the manufacture of pesticide applicator clothing and verified that the highest levels of protection were found on

, the penetration

in cotton-dressing materials without water-repellent treatment with 287 g/m<sup>2</sup>

**3.3. Design of the garments (type of material, presence of sewing, weight, etc.)**

increase in the number of AATCC washes of 22 [52].

pesticides may be absorbed by the skin of the worker [54].

tively evaluate the efficiency of closed-loop protection sets.

material provide the highest penetration of the test solution.

pesticides are more retained in the tissues.

etration with the atomizer method [42].

discomfort to the worker as well [55].

water-repellent garments [9].

The penetration and retention of pesticides depend on the type of material: cotton (100%) retains more atrazine than other materials, due to the strong attraction of the molecules in tissue [46]. Nelson et al. evaluated that the differences on the retention of pesticides in protective materials are attributed to the type of the fiber of the material, since the retention of pesticides in cotton materials (100%) occurs in a greater proportion than in cotton/polyester materials (50/50%). The retention of carbaryl, in the formulation-concentrated suspension, and atrazine (concentrated suspension and wettable powder) is higher in cotton material; the cypermethrin (wettable powder) and the trifluralin (emulsifiable concentrate) are higher in cotton/polyester material [47].

#### *3.1.1. Insecticides impregnated in protective clothing*

In addition to the evaluation of insecticides in protective clothing, the protective clothing has been impregnated by insecticides using the coating method [48]. Protective clothing used in areas with a higher incidence of diseases such as malaria, Chikungunya, dengue, Yellow fever, African tick-bite fever, *Aedes aegypti,* and Culex mosquitoes are generally impregnated with permethrin. The mixture of this insecticide with repellents may be 100%, depending on the applied dose and the type of coating applied on the clothes (as dip coating or spray). However, the use and wash decrease the efficiency, and it is suggested that after five uses, the insecticides must be reapplied in clothing [49].

The insecticide permethrin was impregnated in military uniform clothing (65% cotton and 35% polyester, weight of 220 g/m2 ) for prevention in malarious areas. After its use in the field, the residual concentration of permethrin is ≥200 mg permethrin/m<sup>2</sup> . The insecticide-coated clothing after 218 washes obtained the remaining permethrin at a concentration of 130 and 95 mg/m2 . The established value for *A. aegypti* mosquito mortality was 200 mg/m2 [50]. Clothing impregnated with a mix of repellent and organosorption inhibited 56.25% of bites. A group of the clothes were manually impregnated with the repellent KBR3023 (10 g/m<sup>2</sup> ) and another group were impregnated through the combination of pyrimiphos-methyl (150 mg/m2 ).

#### **3.2. Washing and permeation processes**

An important factor in the loss of repellency of the protective materials against pesticides is the water temperature and the movements during washing used in garments. These facts affect the efficiency of cleaning agents and affect the protection of cotton fabrics as well [51].

The water repellency and the contact angle with the Teflon-treated polyester increase with the concentration of water-repellent substances applied to the fabric and decrease with the increase in the number of AATCC washes of 22 [52].

Obendorf et al. evaluated the adsorption of ionic surfactants present in soaps after washing processes in cotton fabrics. They found that the change in pH in the wash solution affects the adsorption of surfactants in the tissues. Cationic surfactants are adsorbed on cotton fabrics because of the negative charges [53]. This mechanism of adsorption may explain why certain pesticides are more retained in the tissues.

#### **3.3. Design of the garments (type of material, presence of sewing, weight, etc.)**

The pesticides used in the ISO 22608 test, which were diluted and undiluted, are glyphosate, chlorpyrifos, and copper hydroxide in a water-repellent material, being greater penetrations for diluted solutions, mainly for solutions of chlorpyrifos and copper hydroxide. For the insecticide chlorpyrifos, the material was rejected after five uses and washes with the value of penetration of 5.5% for the diluted solution. For the solution undiluted material, it was disregarded after 20 washes of the material used in the field, but the evaluation with the glyphosate solution used in certification tests of garments was only reproved after 30 uses and washes after use in the sugar cane culture. These results indicate that it is necessary to carry

The penetration and retention of pesticides depend on the type of material: cotton (100%) retains more atrazine than other materials, due to the strong attraction of the molecules in tissue [46]. Nelson et al. evaluated that the differences on the retention of pesticides in protective materials are attributed to the type of the fiber of the material, since the retention of pesticides in cotton materials (100%) occurs in a greater proportion than in cotton/polyester materials (50/50%). The retention of carbaryl, in the formulation-concentrated suspension, and atrazine (concentrated suspension and wettable powder) is higher in cotton material; the cypermethrin (wettable powder) and the trifluralin (emulsifiable concentrate) are higher in

In addition to the evaluation of insecticides in protective clothing, the protective clothing has been impregnated by insecticides using the coating method [48]. Protective clothing used in areas with a higher incidence of diseases such as malaria, Chikungunya, dengue, Yellow fever, African tick-bite fever, *Aedes aegypti,* and Culex mosquitoes are generally impregnated with permethrin. The mixture of this insecticide with repellents may be 100%, depending on the applied dose and the type of coating applied on the clothes (as dip coating or spray). However, the use and wash decrease the efficiency, and it is suggested that after five uses, the

The insecticide permethrin was impregnated in military uniform clothing (65% cotton and 35%

after 218 washes obtained the remaining permethrin at a concentration of 130 and 95 mg/m2

nated with a mix of repellent and organosorption inhibited 56.25% of bites. A group of the

An important factor in the loss of repellency of the protective materials against pesticides is the water temperature and the movements during washing used in garments. These facts affect the efficiency of cleaning agents and affect the protection of cotton fabrics as well [51].

) for prevention in malarious areas. After its use in the field, the

. The insecticide-coated clothing

).

[50]. Clothing impreg-

) and another group

.

out the tests with insecticides also for the clothing certification [45].

cotton/polyester material [47].

74 Insecticides - Agriculture and Toxicology

polyester, weight of 220 g/m2

*3.1.1. Insecticides impregnated in protective clothing*

insecticides must be reapplied in clothing [49].

**3.2. Washing and permeation processes**

residual concentration of permethrin is ≥200 mg permethrin/m<sup>2</sup>

The established value for *A. aegypti* mosquito mortality was 200 mg/m2

clothes were manually impregnated with the repellent KBR3023 (10 g/m<sup>2</sup>

were impregnated through the combination of pyrimiphos-methyl (150 mg/m2

For many times, the inefficiency of protective clothing is due to improper use or poorly constructed, and pesticides penetrate into clothing through openings, seams, zippers, folded sleeves, and poor overlaps of sleeves with gloves [54]. Such inefficiency of protection against pesticides may be absorbed by the skin of the worker [54].

The resistance to penetration of protective material against pesticides depends on the methodology used and the type of tissue. In fabrics made of 100% cotton with a water-repellent treatment (Phobol oil), penetrations below 1.6% have been found when evaluated by the trough, pipette, and atomizer test method. However, in cotton/polyester composite fabrics, the penetration is 12.8% with the pipette method, 16.5% with the gutter method, and no penetration with the atomizer method [42].

Although water-repellent fabrics cause discomfort to workers, especially in the hottest agricultural regions, it is believed that with the proof of EPI efficiency, the applicator distribution on the regions of the body, and with the methodologies of evaluation of the exposures, the EPI should be recommended for the most exposed areas of the body and provide safety and lesser discomfort to the worker as well [55].

Protective clothing has been studied through the ergonomic property testing in dummies in chambers with controlled environmental and exposure conditions [56]. In the dermal exposure, dummies can be used for assessment methods. Therefore, the penetration or retention of insecticides is evaluated, as in the evaluation of malathion spraying on protective clothing used to control dengue [22]. However, there are few studies in the literature that quantitatively evaluate the efficiency of closed-loop protection sets.

Machera et al. used the procedure of ISO 22608 to evaluate the penetration of pesticides in protective clothing materials. For materials containing cotton/polyester (50/50%) with 215 g/m<sup>2</sup> treated with NanoTex® water repellent, the penetration was 2.4% after 15 washes. However, in cotton-dressing materials without water-repellent treatment with 287 g/m<sup>2</sup> , the penetration was 18.7%, after five washes [29]. Therefore, it has been found that the cotton yarns in the material provide the highest penetration of the test solution.

Shaw and Schiffelbein tested approximately 100 different fabrics used in the manufacture of pesticide applicator clothing and verified that the highest levels of protection were found on water-repellent garments [9].

Oliveira and Machado Neto evaluated the penetration of the insecticide methamidophos into two types of tissues: a cotton water repellent (153 g/m<sup>2</sup> to 0.25 mm) fabric and another jeans fabric (458.66 g/m2 to 0.75 mm). The authors noted that after 30 washes at manual washing with soap, more insecticides penetrated into lighter tissue (21.05%) than in the heavier tissue (0.12%) [57].

**References**

[1] Keifer MC, Firestone J. Neurotoxicity of pesticides. Journal of Agromedicine [Internet].

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[2] Nicolopoulou-Stamati P, Maipas S, Kotampasi C, Stamatis P, Hens L. Chemical pesticides and human health: The urgent need for a new concept in agriculture. Frontiers in Public Health. 2016;**4**:148-153. Available from: http://journal.frontiersin.org/Article/10.3389/

[3] Faria NMX, Fassa AG, Facchini LA. Pesticides poisoning in Brazil: the official notification system and challenges to conducting epidemiological studies. Ciência & Saúde Coletiva. 2007;**12**(1):25-38. Available from: http://www.scielo.br/scielo.

[4] Rosa BT, Borges LAC, Pereira SP, Antonialli LM, Chalfoun SM, Baliza DP. Estudo sobre boas praticas agricolas em uma associaçaoo de cafeicultores familiares por meio da

[5] BRAZIL. Ministério do Trabalho e Emprego. Portaria no 3.214, de 8 de junho de 1978, Ministério do Trabalho e Emprego. Aprova as Normas Regulamentadoras – NR – do Capitulo V, Titulo II, da Consolidação das Leis do Trabalho, relativas a Segurança e Medicina do Trabalho. Norma Regulamentadora Equipamento de Proteção Individual-NR 6. Disponível em: http://trabalho.gov.br/images/Documentos/SST/NR/NR6.pdf

[6] Machado AA. Efficiency of individual protection equipment with a certificate of approval. against aquosa and oleosa calle malathion used in nebulization [thesis].

[7] Marinho MO. Loss of effectiveness of hydro-repellent materials in the protection against pesticides by washing process [dissertacion]. Jaboticabal: São Paulo State University; 2013

[8] Espanhol-Soares M. Determination of efficiency and useful life of individual protection sets to pesticides according to the procedure for use and wash [thesis]. Jaboticabal: São

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[10] ISO. International Organization for Standardization. ISO 27065: Protective clothing— Performance requirements for protective clothing worn by operators applying pesti-

[11] ISO. International Organization for Standardization. ISO 22608: Protective clothing protection against liquid chemicals: Measurement of repellency, retention, and penetration of liquid pesticide formulations through protective clothing materials. Geneva; 2004. 11 p

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Marinho [7] evaluated the material of the protective clothing by ISO 22608 with seven types of washes with a machine programmed according to ISO 6330 and a manual washing as well. As a result, before the washing, all materials met the criterion of approval of the requirement rule ISO 27065 (ISO, 2011). After the 5, 10, 20, and 30 wash cycles, the penetrations of the test formulation (glyphosate) were higher than 5% for the materials without ironing process and no longer meeting the criteria of approval. All materials (cotton 100%, cotton 65% + polyester 35%), when ironing, had a penetration of <5%, in five uses and washes. However, the 50% cotton +50% polyester material had the same result in 20 uses and washes.
