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Recent Strategies for Environmental Remediation of Organochlorine Pesticides

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Recent Strategies for Environmental Remediation of Organochlorine Pesticides applied sciences Review Recent Strategies for Environmental Remediation of Organochlorine Pesticides Timothy O. Ajiboye 1,2 , Alex T. Kuvarega 3 and Damian C. Onwudiwe 1,2,* 1 Material Science Innovation and Modelling (MaSIM) Research Focus Area, Faculty of Natural and Agricultural Sciences, North-West University, Mafikeng Campus, Private Bag X2046, Mmabatho 2735, South Africa; [email protected] 2 Department of Chemistry, School of Physical and chemical Sciences, Faculty of Natural and Agricultural Sciences, North-West University, Mafikeng Campus, Private Bag X2046, Mmabatho 2735, South Africa 3 Nanotechnology and Water Sustainability Research Unit, College of Science, Engineering and Technology, University of South Africa, Florida 1709, South Africa; [email protected] * Correspondence: [email protected]; Tel.: +27-18-389-2545; Fax: +27-18-389-2420 Received: 29 June 2020; Accepted: 27 July 2020; Published: 10 September 2020 Abstract: The amount of organochlorine pesticides in soil and water continues to increase; their presence has surpassed maximum acceptable concentrations. Thus, the development of different removal strategies has stimulated a new research drive in environmental remediation. Different techniques such as adsorption, bioremediation, phytoremediation and ozonation have been explored. These techniques aim at either degrading or removal of the organochlorine pesticides from the environment but have different drawbacks. Heterogeneous photocatalysis is a relatively new technique that has become popular due to its ability to completely degrade different toxic pollutants—instead of transferring them from one medium to another. The process is driven by a renewable energy source, and semiconductor nanomaterials are used to construct the light energy harvesting assemblies due to their rich surface states, large surface areas and different morphologies compared to their corresponding bulk materials. These make it a green alternative that is cost-effective for organochlorine pesticides degradation. This has also opened up new ways to utilize semiconductors and solar energy for environmental remediation. Herein, the focus of this review is on environmental remediation of organochlorine pesticides, the different techniques of their removal from the environment, the advantages and disadvantages of the different techniques and the use of specific semiconductors as photocatalysts. Keywords: organochlorine; emerging contaminants; photocatalysis; pesticides; degradation 1. Introduction The conventional approach to the removal of pesticides from the environment are not effective for the complete removal of these pollutants. This is evident in the fact that despite their usage over the years, the negative impacts of pesticides on the environment and humans still remains a challenge. More than 17 million deaths has been reported to occur as a result of pesticide poisoning from 1960 till 2019 [1]. Despite the alarming statistics, this number is even assumed to be underestimated since majority of pesticide poisoning in the poor rural communities were not accounted for due to poor death registry [1]. Pesticides are used worldwide to prevent weeds, fungi and pests from attacking plants. Their wide usage has increased their enormous dispersal in soils, groundwater and drinking water [2]. The best way to identify them is through classification. The first method of classification is based on the use of the pest or organism they kill. For example, termites (termiticides), vegetation (silvicides), fishes (piscicides), birds (avicides) and nematode (nematicides). Others are Appl. Sci. 2020, 10, 6286; doi:10.3390/app10186286 www.mdpi.com/journal/applsci Appl. Sci. 2020, 10, 6286 2 of 24 Appl. Sci. 2020, 10, x FOR PEER REVIEW 2 of 23 snail and slugs (molluscides), viruses (virucides), mites (acaricides), insects and mites (ovicides), weed (ovicides),(herbicides), weed bacteria (herbicides), (bactericides), bacteria fungi (bactericides), (fungicides) fungi [3]. (fungicides) The second [3] classification. The second is classification based on the isactive based components on the active and components chemical composition and chemica of thel composition pesticides. Pesticidesof the pesticides. may be synthetic Pesticides pyrethroid, may be syntheticcarbamates, pyrethroid, organophosphorus carbamates, or organophosphorus organochlorine as or shown organochlorine in Figure1[ 4as]. shown in Figure 1 [4]. FFigureigure 1. 1. TypesTypes of of pesticides pesticides based based on on chemical chemical composition. composition. OneOne of thethe mostmost commonly commonly used used pesticides pesticides are organochlorine are organochlorine pesticides. pesticides. Organochlorine Organochlorine pesticides pesticidesare designed are to designed specifically to impedespecifically some impede particular some living particular organisms. living Just likeorganisms. other pesticides, Just like they other are pesticides,different from they other are chemicaldifferent pollutantsfrom other because chemical they pollutants are intentionally because released they are into intentionally the environment. released They intoare predictablythe environment. toxic and They disrupt are predictably the neural function toxic and of thedisrupt pests, the leading neural to function their death of [the5]. Organochlorinepests, leading tocompounds their death are [5]. part Organochlorine of persistence compounds organic pollutants are part (POPs)of persistence and they organic are characterized pollutants (POPs) by chlorine and theyattachments, are characterized possession by of chlorine functional attachments, groups that possession are polar, andof functional the presence groups of cyclic that structureare polar, which and themay presence be aromatic. of cyclic They structure generally which remain may in be an aromatic. undegraded The formy generally in the environment remain in an for undegraded a long time. formIn addition, in the environment they can travel for over a long distancetime. In becauseaddition of, theirthey semivolatilecan travel over property long anddistance they are because lipophilic of their(they semivolatile mount-up in tissuesproperty that and have they fats are like lipophilic nerves) in nature(they mount [6]. When-up humansin tissues or animalsthat have consume fats like fish nerves)that are contaminatedin nature [6] with. When organochlorine humans or pesticides, animals theconsume active componentsfish that are of thecontaminated pesticides could with be organochlorinereleased into the pe systemsticides, which the haveactive detrimental components effect. of the Due pesticides to their nature could and be properties,released into organochlorine the system whichpesticides have are detrimental found in every effect. part Due of the to ecology their nature including and desert, properties, snow, waterorganochlorine bodies, soil pesticides and air despite are foundthe fact in that every their part usage of the have ecology been banned including by several desert, countries. snow, water Examples bodies, of so organochlorineil and air despite pesticides the fact are thatfuran their (dibenzo-p-furans), usage have been dioxin banned (dibenzo-p-dioxins), by several countries. polychlorinated Examples of biphenyls, organochlorine chlordane, pesticides toxaphene, are furandichlorodiphenyltrichloroethane (dibenzo-p-furans), dioxin (DDT) (dibenzo and dieldrin.-p-dioxins Others), polychlorinated include aldrin, mirex,biphenyls, hexachlorobenzene, chlordane, toxaphene,heptachlor [dichlorodiphenyltrichloroet7,8]. New organochlorine pesticideshane (DDT) such asand imidacloprid dieldrin. Others have recently include being aldrin, reported mirex, [9]. hexachlorobenzene,The structures of some heptachlor of the organochlorine [7, 8]. New pesticidesorganochlorine are shown pesticides in Figure such2. as imidacloprid have recently being reported [9]. The structures of some of the organochlorine pesticides are shown in Figure 2. Appl. Sci. 2020, 10, 6286 3 of 24 Appl. Sci. 2020, 10, x FOR PEER REVIEW 3 of 23 Figure 2. Structures of some organochlorine pesticides. Reprinted from [10] [10].. Copyright (2017), with permission from Elsevier. Their persistence in the environment could be attributed to the difficulty in hydrolyzing the Their persistence in the environment could be attributed to the difficulty in hydrolyzing the carbon–chlorine bond of the aromatic compounds. This bond is strong due to the overlap of the carbon–chlorine bond of the aromatic compounds. This bond is strong due to the overlap of the p- p-orbital of chlorine and the pie bond of benzene. It has been reported that the more the number of orbital of chlorine and the pie bond of benzene. It has been reported that the more the number of chlorine attachments to the aromatic ring, the higher the stability of the organochlorine compounds chlorine attachments to the aromatic ring, the higher the stability of the organochlorine compounds to hydrolysis [11]. Other factors that affect their hydrolysis rate are catalysis by metal ions, ionic to hydrolysis [11]. Other factors that affect their hydrolysis rate are catalysis by metal ions, ionic strength, presence of sediments, pH and temperature. A very important point to note about these strength, presence of sediments, pH and temperature. A very important point to note about these organochlorine pesticides is that they are all toxic in nature and this makes their removal from the organochlorine pesticides is that they are all toxic in nature and this makes their removal
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