Pesticide Pollution in Agricultural Soils and ...

Current Pollution Reports https://doi.org/10.1007/s40726-018-0092-x

LAND POLLUTION (GM HETTIARACHCHI, SECTION EDITOR)

Pesticide Pollution in Agricultural Soils and Sustainable Remediation Methods: a Review Shixian Sun 1 & Virinder Sidhu 2 & Yuhong Rong 3 & Yi Zheng 1,4

# Springer International Publishing AG, part of Springer Nature 2018

Abstract An increasing number of pesticides have been used in agriculture for protecting the crops from pests, weeds, and diseases but as much as 80 to 90% of applied pesticides hit non-target vegetation and stay as pesticide residue in the environment which is potentially a grave risk to the agricultural ecosystem. This review gives an overview of the pollution in agricultural soils by pesticides, and the remediation techniques for pesticide-contaminated soils. Currently, the remediation techniques involve physical, chemical, and biological remediation as well as combined ways for the removal of contaminants. The microbial functions in rhizosphere including gene analysis tools are fields in remediation of pesticide-contaminated soil which has generated a lot of interest lately. However, most of those studies were done in greenhouses; more research work should be done in the field conditions for proper evaluation of the efficiency of the proposed techniques. Long-term monitoring and evaluation of in situ remediation techniques should also be done in order to assess their long-term sustainability and practical applications in the field. Keywords Pesticides . Agricultural soil . Pollution . Sustainable remediation

Introduction Pesticides have been present as an essential part of agriculture and have played a decisive role in protecting crops and livestock from yield reductions for many decades. Pesticide application is still considered the most effective and accepted means for plant crop protection from pests [79]. However, as little as 1% of an applied pesticide reaches the target pest and the remainder ends up in soil, water, and air, ultimately entering our food chain and affecting non-target species including humans [63, 86], flora and fauna, and soil enzyme activity [21, This article is part of the Topical Collection on Land Pollution * Yi Zheng zhengyi–[email protected] 1

Faculty of Landscape Architecture, Southwest Forestry University, Kunming 650224, People’s Republic of China

2

Department of Civil, Environmental and Ocean Engineering, Stevens Institute of Technology, Hoboken, NJ 07030, USA

3

Landscape Architecture College, Southwest Forestry University, Kunming 650224, People’s Republic of China

4

Yunnan Provincial Department of Education, Kunming 650223, People’s Republic of China

28]. As much as 80 to 90% of pesticides that are applied to crops hit non-target vegetation directly, or can drift or volatilize from the treated area off-site and contaminate air, soil, and non-target plants. About 80% of all applied pesticides could be detected, with half of these residues found as transformation products (TPs) with a persistence of more than a decade. Forty-seven percent of the TPs were detected in the top soils of Switzerland where Bparent compound^ was applied [25]. Groundwater may be polluted by pesticides via leaching [93]. Pesticides pose a huge risk to human beings indirectly, via food chain and contamination of natural resources. For example, pesticide pollution has been implicated in the rise of Bcancer villages^ which stem from the mortality rate of cancer being significantly higher than average because of widespread pesticide use [64]. Migrant workers and their offspring have exhibited negative and latent health effects stemming from chronic exposure to pesticides and their lingering persistence in the environment, especially the endocrine disruptor compounds (EDC) often leading to an increased risk of obesity and neurological issues [82, 96]. Chlorpyrifos, an organophosphate neurotoxic insecticide, poses a significant risk to children’s intelligent quotients (IQs) via contamination of food crops [31]. Benfuracarb is cytotoxic to human cells [24]. Anticholinesterase pesticide poisoning is associated with an increased risk of hypothyroidism [38, 39].

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Soil, a major natural resource underpinning the survival and development of human beings, is a vital resource for plant life in the environment. Soil is the biggest sink of organic pollutants, and farmland soil is the key part of the agricultural ecosystem. Therefore, the quality of crops and food safety is closely linked to the quality of farm soils, which is thereby related to human health. Soils, the most essential part of ecosystems, may be contaminated by organic and inorganic pollutants including pesticides [72, 97]. Soil contamination with pesticides influences agricultural ecosystems by affecting soil microbial populations, bacterial diversity, nitrogen transformations [28], soil animals [118], and soil enzymes [110]. The fungicide azoxystrobin negatively affects soil microbial biodiversity [6, 28]. Pesticides can reach underground aquifers in crop fields [3]. An increasing proportion of arable soils has been reported to be contaminated with pesticides to varying degrees, especially in developing countries such as China. A report by the Ministry of Environmental Protection of Land and Resources of China in 2014 stated that 16% of cultivated area was contaminated with heavy metals and pesticides of all the surveyed cultivated soils [17]. The recently used pesticides were found to persist at relatively high concentrations in soil and were also present in vegetables and fish in the two communes of Northern Vietnam, posing threats to human health directly and via food chain through bioaccumulation [35]. The urban environment surrounded by agricultural areas can potentially be affected by pesticides through bulk deposition; for example, 98.5% of soil samples tested in Winnipeg, a city in the Canadian Prairies in Manitoba Province, contained herbicides, insecticides, fungicides, and their metabolites [27]. Glyphosate is the most widely used pesticide in prairie agriculture and accounted for 65% of total pesticide deposition over 2 years [27]. The pollution resulted in the deterioration of quality of arable soils making sustainable remediation of soils contaminated by pesticides a desirable goal [16, 85].

Aims and Scope The aim of this review is to highlight pesticide pollution of arable soils, appraise the techniques used to clean the pesticide pollutants from farmland soils, and evaluate the mechanisms underpinning the remediation of contaminated farmland soils. Knowledge of the effects of soil pollutants will enhance an understanding of the increased threat by agro-chemicals, especially by pesticides, which can probably be used as a reference by practitioners who will work on the restoration of contaminated farmland soils. This review summarizes and evaluates (1) the recent research on pesticide residue in farmland soils and (2) established remediation strategies and mechanisms, especially regarding pesticide contaminants. Other

contaminants and media other than farmland soils (e.g., groundwater) are outside the scope of this review.

Agricultural Soils Polluted by Pesticides Agricultural chemicals consist of pesticides and fertilizers. In modern agricultural systems, pesticides are defined as special bioactivators, also known early on as economic poisons in the USA [122, 123]. Pesticides are mostly organic chemicals used in agricultural systems. Pesticides are comprised of insecticides, bactericides, and herbicides according to their functions. Based on the chemical structure, they include organo-phosphorus, organo-chlorines, nitrogen-benzenes, phenols, metallo-organics, and other compounds. The increasing use of pesticides has been one of the major non-point sources of pollution in agriculture [66]. Seventy percent of pesticides used in agriculture enter the soils leading to farmland soil pollution by the pesticide residues [108]. In recent years, herbicides represented 30–40% of all pesticides used in agriculture, and in the last 10 years, the area of chemical weed control has increased to 31 million ha−2 in China [106]. In the global pesticide market, insecticides and bactericides make up 30 and 26%, respectively, of the pesticide usage in agriculture in 2014 [128]. The adverse effects of pesticides have been increasing due to the improper use of pesticides induced by a lack of awareness and pesticide overuse which has been reported in rice, cotton, maize, and wheat production [45]. Pesticides affect soil quality and agricultural production in various ways. An increase in the concentration of herbicides above their recommended field application rates could change the growth and activities of microorganisms, influencing nutrient cycling in soil [20]. It has been reported that prodiamine, indaziflam, and isoxaben reduced root mass of hybrid Bermuda grass relative to non-treated plants and these pre-emergent herbicides reduced the accumulation of macro- and micro-nutrients such as phosphorus (P), sulfur (S), potassium (K), magnesium (Mg), and manganese (Mn) in the foliar tissues of the affected plants [11]. The use of insecticides (acetamiprid and carbofuran) at field application rates in the groundnut fields stimulated the activities of enzymes (arylamidase and myrosinase); however, higher concentrations of these pesticides were toxic to the enzyme activities in black and red clay soils [71]. Sulfur is an essential nutrient for agricultural crop production; pesticides influence agricultural production by changing the availability of specific nutrients [105]. The application of monocrotophos significantly changed the rate of sulfur oxidation in black and red soils in India with enhancing sulfur oxidation after 7 and 14 days of pesticide application alone or in combination with mancozeb in the black soil [105].

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Different Types of Pesticides in the Environment Organophosphorus pesticides (OPs) are an increasing concern due to a potential risk to wildlife and human health, and they are among the most frequently detected pesticides in contaminated soils [8]. In the agricultural soils of the Yangtze River Delta of China, 93% of soil samples contained OPs, with total concentrations of nine OPs ranging from < 3 to 521 ng g−1 dry weight, with a mean of 65 ng g−1 [80]. The organochlorine pesticides (OCs), many of them listed as persistent organic pollutants (POPs) and prohibited for use, were still detected in soils and air because of their persistence in the environment [33]. In the testing of soil samples, 14 OCs with an average of 57 ng g−1 were found in the soils of Wangyanggou River in Shijiazhuang City, China and 2,2-bis(4-chlorophenyl)-1,1,1-trichloroethane pesticides (DDTs) were the dominant compounds in surface water, sediments, soils, and maize seeds [120]. All 45 soil samples from the vegetable fields in Wuhan, Yichang, and Xiangyang (Hubei Province) contained P,P′-DDT and P,P′DDE as the main contaminants [121]. Three types of OCs were detected in all soil samples from the upper reaches of Haihe River with a total concentration of OCs as 139 ng g−1 and average of 40 ng g−1 DDTs and their metabolites 1-chloro2,2-bis(4′-chlorophenyl)ethylene (DDMU), dodecyl-beta-Dmaltoside (DDM), benzene-1,2-dicarboxylicaciddibutylester (DBP) and hexachlorocyclohexane pesticides (HCHs) were the main pollutants in the soil as a combination of their early usage and new input in some areas [83]. Anti-cholinestearase pesticides, including organophosphates and carbamates are the most common cause of pesticide poisoning in the world [37, 57]. Some POP pesticides, such as endosulfan, pose an environmental risk in agricultural soils through the practice of straw incorporation and sedimentation, even though the main risk in the Breceiving-retentionrelease^ route is the atmosphere [74]. The fungicide cyazofamid has a short life in differently textured agricultural soils and therefore has little chance of contaminating groundwater [102]. OCs and their metabolites pose a grave risk in agricultural soils as OCs were detected in 27 of 29 soil samples tested in Turkey and ranged from 6 to 1090 μg kg−1 dry soil in areas where OCs were heavily used between the 1940s and 1980s in Turkey [2]. 4,4′-DDE was present above the acceptable risk levels in the agricultural soils of Mersin District in Turkey [2]. Sometimes, obsolete pesticides pollute the agricultural and surrounding soil because of improper disposal and persistence in the environment. Some banned chlorinated pesticides have been quantified in surface soils and raw foods (meat, dairy, and plants) from four rural areas of Tajikistan from 2011 to 2014. DDT was consistently measured as the highest individual pesticide at each of the four sampling areas, along with gluconodeltalactone (BHC) isomers and endosulfan [9]. Some disposed POPs including 4500 dumps of obsolete pesticides

decreased to 1033 with huge efforts in Ukraine by the end of 2014 [51]. However, the Polygon site remains contaminated and requires further assessment and remediation because of hexachlorobenzene (HCB) waste [51]. In the last two decades, pesticides have posed a threat to the inhabitants and livestock of the White Nile and Gezira states because of unprotected stocking and agricultural systems [76]. In China (Inner Mongolia), 21 OCPs were detected in agricultural soils (102 ng g−1) and pastoral areas (0.2–24 ng g−1) with HCHs and DDTs being the main contaminants [127]. In the soils supporting different types of vegetation, the largest residues of OCPs, HCHs, and DDTs were present in vegetables, watermelon patches, and soybean fields [127]. The OC residues were higher in agricultural soils as compared to pastoral areas [127]. Therefore, barring conventional detection, genomic tools were used for assessing the effects of pesticides on agro-ecosystems [43]

Remediation of Pesticide-Contaminated Agricultural Soils General Remediation Techniques for Organic Chemicals Remediation methods include (1) ex situ method, in which contaminated soil is excavated and transported to another location for treatment, (2) on-site, in which contaminated soil is excavated and treated on-site before returning to the original state, and (3) in situ, in which the contamination is treated onsite without excavating and removing the contaminated soil [88]. The selection of remediation method is dependent upon whether the pesticide contamination is localized or diffused in the agricultural soils [73]. Ex situ method was commonly used as the soil remediation method earlier, but it has several drawbacks including the high cost of soil excavation and transport in addition to destroying the ecosystem. Therefore, in situ restoration has become the key focus recently [116]. Polluted soil can be remediated using physical, chemical, and biological techniques [26, 44]. These relevant techniques are (1) bioremediation, (2) phytoremediation, (3) chemical oxidation, (4) surfactant extraction, (5) electrokinetic remediation, and (6) thermal desorption. Although, the physical and chemical techniques are suitable for the remediation of pesticide-contaminated agricultural soil. However, those technologies are mainly used for industry-impacted soil, seldom recommended for remediation of the extensive areas of agricultural soil that are contaminated by organic chemicals, because physical and chemical techniques require high equipment and treatment costs and may lead to damage of the biological and chemical qualities of soil [58, 107]. Compared with physical and chemical remediation, bioremediation, phytoextraction and phytovolatilization are biological

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approaches used to remove and detoxify organic contaminants in agricultural soils [59, 78, 124]. Bioremediation alone was usually unable to remove persistent and highly toxic contaminants from agricultural soil within a shorter time [38, 39]. However, bioremediation enhanced by surfactants is a promising technology for improving the bioavailability and removal efficiency of organic pollutants in agricultural soil [46, 77, 109, 117, 125, 126]. This list does not include all remediation strategies, but rather, it focuses on some established approaches that have accompanying literature assessing the soil properties. Even though these techniques are used for pesticide remediation, the primary application may be for other types of contaminants such as electrokinetic remediation, which is primarily applied to remediate heavy metal contamination of soils. Thus, information provided in this review may be applicable beyond pesticide contamination of agricultural soils.

Remediation Technologies for Pesticides Bioremediation reduces pesticide contamination of agricultural soils by improving natural biodegradation processes via metabolic activities of microorganisms, and it is becoming popular for being an efficient, cost-effective, and environment-friendly in situ treatment [88, 92]. Pesticide contamination of agricultural soils represents non-point source contaminants and ex situ chemical remediation technologies have been used earlier [73]. However, chemical remediation methods are unrealistic for diffused pollution of agricultural soils by pesticides. Instead, in situ bioremediation can be a better treatment [118]. Bioremediation involves phytoremediation and microbial remediation. Phytoremediation of pesticides from soil is based upon plant uptake, vegetation degradation, volatilization, and combined degradation by root exudates and rhizosphere microorganisms [62]. The degradation rate of deltamethrin in soil had a direct relationship with microbial activity in soil [42]. Bacterial populations with P450 cytochrome genes positively influenced the aerobic bioremediation of pesticides [22]. Vetiver (Chrysopogon zizanoides) is suitable for phytostabilization of moderately dioxin-contaminated sites [71]. Electrokinetic soil flushing (EKSF) is used for the remediation of soils polluted with different contaminants [111]. When the polluted soil is subjected to an electric field between anodes and cathodes, the contaminants in the soil can be removed or transferred into the flushing fluid that can then be treated or mobilized via electro-osmosis, electromigration, and electrophoresis. The EKSF process used for the removal of pesticides from contaminated soils has become a hot topic of discussion in the remediation community [115] and has recently been combined with other remediation technologies such as bioremediation and permeable reactive barriers [89, 111]. Several studies have described the rhizoremediation of polychlorinated biphenyls (PCBs), dioxins, decabromodiphenyls, phenanthrene, pyrene, and heavy metals [31, 34, 98, 114]. The use of a

combination of plant species and microbial strains has brought the spotlight on remediation [114].

Sustainable Remediation Methods for Agricultural Soils For agricultural soils polluted by pesticides, most in situ sustainable remediation technologies can be used. There is a considerable impetus to develop bioremediation technologies as well as combined technologies for use such as rhizosphere remediation, fertilized-assisted remediation, and rhizoremediation combined with microbial remediation. The key enzymes and fungi which are helpful in pesticide removal along with potential interactions with other soil microorganisms should be researched further in the future of rhizosphere remediation technology [68]. An increasing research focus is on the combined techniques for remediation such as electrokinetic remediation with biological permeable reactive barriers for the remediation of soil polluted by insoluble organics [69]. Ultrasound-assisted soil washing has been combined with bioaugmentation for the remediation of soil polluted by polycyclic aromatic hydrocarbons (PAHs) and heavy metals [14]. Tourmaline catalyzed Fenton-like reaction (TCFR) combined with Phanerochaete chrysosporium (TCFR + P) was used for the removal of polybrominated diphenyl ethers (PBDEs) in field soil microcosms [52]. Nanoremediation [zero valent iron nanoparticles (nZVI)] combined with electrokinetics was used for the removal of PCBs from soil, with the removal rate increasing from 20% to > 75% in contaminated soils [29]. Fenton-like oxidation combined with soil washing can potentially be an approach for the remediation of soil contaminated by PCBs [65]. Anaerobic or facultative anaerobic microflora and phytoremediation have been combined for treating the soil contaminated by POPs (DDTs and trifluralin) [41]. Gene tools were used for biomineralization of soil contaminated with pesticides [23]. Microbes and transgenic plants can also be used for the remediation of pesticide-contaminated soils [40].

Discussion As Table 1 shows, some physical remediation technologies were used for the removal of pesticide-contaminated soil, such as electrokinetic soil fences (EKF) [89], electrokinetic soil flushing [89, 90, 101], soil washing, and solar-powered electrokinetic remediation [104]. The major mechanism of those technologies was that the pesticide was removed from the contaminated soil to the flushing fluids through adsorption, desorption, and volatilization. Some chemical remediation technologies, such as enhanced electrokinetic-Fenton [10], advanced oxidation process [86], and photo-degradation [84] were used for pesticide-contaminated soil through special chemical reactions (abiotic degradation). Both physical and

Curr Pollution Rep Table 1

Current research work on the remediation and efficiency of treatment strategies of pesticide-polluted soils (2015–2017)

Remediation methods

Pesticide and efficiency of treatment

Reference

Advanced biodegradation

Biochar resulted in significant reduction in soil DDT levels and soil microbial activity after 60 days. 86–88% degradation efficiency was achieved in about 3.5 h under UV light or enhanced sunlight; 99.86% of degradation was achieved in UV/TiO2/K2S2O8 system in the same irradiation time. 95% of initial spiked terbuthylazine (TBA) was removed from soil microcosms upon bioaugmentation with ammonium-grown Arthrobacter aurescens TC1 inocula during the first 3 days. Around 70% on average of initial TBA remained in the non-bioaugmented control soil during the 14 days. An extra 26.8% of oxyfluorfen was removed with surfactant (calcium dodecyl benzene sulfonate). More than 80% of pesticide (30 mg/kg) was eliminated, 2, 4-D was removed by 95% after 15 days of treatment. 50% of the initial 2, 4-D from the soil was eliminated; 25% remained in the soil, and the remaining 25% was volatilized after 40 days treated by the electrolyte wells. More than 22% of the spiked (20 mg kg−1) 2, 4-D transported to the flushing fluids, 57% of removal of 2, 4-D by volatilization. The main mechanism for the 2, 4-D’s removal was volatilization. A maximum of 67% of the triazoles from a real vineyard soil (north-west of Spain) was degraded by enhanced electrokinetic-Fenton treatment after 27 days. Mixed pesticide/chlorpyrifos, fluazifop-p-butyl, carbofuran, indoxacarb samples, glyphosate. The dissipation of tested pesticides in treatments fertilized by organic, compost and biofertilizer was faster than in both of chemical and non-fertilizer treatment. Rhizobacteria were isolated from Okra (Abelmoschus esculentus L.); S10 and S20 had the maximum pesticide tolerance for bifenthrin pesticide degradation. The prior application of imidazolinones did not stimulate microbial degradation of herbicides (imidazolinone /imazethapyr, imazapyr, imazapic, imazamethabenz, imazamox) from the same chemical group. Two new Citrobacter isolates, closely related to Citrobacter amalonaticus were isolated and completed the genomic sequences, which were confirmed that were capable of reproducing chlordecone transformation. Five different bacteria were isolated from cockroaches living in the endosulfan-contaminated soils: Pseudomonas aeruginosa G1, Stenotrophomonas maltophilia G2, Bacillus atrophaeus G3, Citrobacter amolonaticus G4, and Acinetobacter lwoffii G5. After 10 days of incubation, the biodegradation yields obtained from those bacteria ranged from 57 to 88%. The morphological, biochemical and 16S rRNA gene sequence analysis confirmed that the isolated bacterium for dichlorvos degradation is Pseudomonas stutzeri smk. Cyhalothrin and other pyrethroids could be degraded by Bacillus thuringiensis and some metabolites were identified and degradation pathway by cleavage of both the ester linkage and diary bond in a microorganism. Bacteria and putative genes confirmed pentachlorophenol (PCP) dechlorination and phenol degradation accomplished in segments 0–565 cm and 0–865 cm, respectively, contributing to a high PCP mineralization rate of 3.8665 μM d 611. Strain JPL-2 was isolated; the chain length of the alcohol moiety strongly affected the hydrolysis activity of the FeH (100 mg L−1) toward aryloxyphenoxy propanoate (AOPP) herbicides. Cypermethrin-degrading Bacillus strain SG2 was isolated which degraded the compound up to 81.6% within 15 days under standard growth conditions in minimal medium. Xanthomonas sp. 4R3-M1, Pseudomonas sp. 4H1-M3, and Rhizobium sp. 4H1-M1were isolated; all of these three bacterial strains almost completely metabolized CP (10 mg/L) and TCP. Xanthomonas sp. 4R3-M1 and Pseudomonas sp. 4H1-M3 could also degrade TCP (10 mg/L) as a sole carbon and nitrogen source. Rhizobium isolated (SR G, SR I, SR 01) from the root nodules of Sesbania rostrata SRG was efficient in removal of glyphosate about 44%, followed by SR I (40.8%) and SR 01 (38.7%), respectively. Also, removal of monocrotophos by SR G, SR 01 and SR I was among 27~34%. Environmental linuron mineralization depends on multispecies bacterial food webs and governed by currently unidentified enzymes. Organisms containing either libA or hylA contribute simultaneously to linuron biodegradation in the same environment.

[30]

Advanced oxidation process

Bioaugmentation

Electrokinetic soil fences (EKF) Electrokinetic soil flushing (EKSF) Electrokinetic soil flushing (EKSF) Electro-remediation

Enhanced electrokinetic-Fenton Fertilizer assisted dissipation

Microbial degradation Microbial degradation

Microbial degradation


Microbial degradation Microbial degradation





Microbial degradation/rhizobium

Microbial remediation

[86]

[101]

[89] [101] [89] [90]

[10] [99]

[75] [12]

[13]

[32]

[48] [54]

[55]

[61]

[81]

[87]

[100]

[36]

Curr Pollution Rep Table 1 (continued) Remediation methods

Pesticide and efficiency of treatment

Reference


94.6 and 87.3% carbaryl (150 mg/kg) were degraded by Bacillus and Morganella, respectively. Coryne bacterium showed only moderate carbaryl degradation at 48.8%. Carbaryl catabolic genes are organized into three putative operons, Bupper,^ Bmiddle,^ and Blower.^ The role of horizontal gene transfer event(s) in the acquisition and evolution of the carbaryl degradation pathway in Pseudomonas sp. strain C5pp. The dissipation rates of deltamethrin were 99.4% in 96 h at 10 ml L−1 initial concentration and 22.8% in 100 mg L−1 cultured with the degrading bacterium, only dissipated 74.9% in 25 days and was only 45.1% in 96 h without bacterium. Arbuscular mycorrhizal fungi (AMF) and/or PGPR could degrade methamidophos (50–100 mg/kg) residue in the plant. Glomus etunicatum + fluorescence (Pf) significantly reduced methamidophos concentration in the root zone soil, through mineralizing the substance by 52–60.6% within the range of 50–100 mg/kg. Three bacterial strains isolated from soil (Cepa1, Cepa2, and Cepa3) belong to Enterobacteriaceae family. Those bacteria could survive and degrade monocrotophos (200 mg/kg) in 30 days. Very rapid degradation of ethoprophos and carbofuran was observed in soil samples from Greece with no previous applications of carbofuran. Very slow degradation of both pesticides with a history of combined applications. Annual use of thiocarbamate herbicide (S-ethyl dipropylcarbamothioate (EPTC) may have resulted in cross-activation for rapid biodegradation of carbofuran. 2-year average half-lives of thifluzamide in paddy soil were 17.92 days in Nanjing, 20.71 days in Xiaoxian, and 13.92 days in Changsha. Photo-degradation of chlorpyrifos by UV light followed the first-order kinetics. The rate of chlorpyrifos photo-degradation increased in the presence of Cu2+ and Fe2+; microbial and abiotic degradation of chlorpyrifos was affected by Cu2+ and Fe2+. After 144 h of exposure to gaseous ozone, the concentration of simazine was reduced by over 80%. The degradation of pesticide was accompanied by changes in the physicochemical parameters of soil. The transgenic thaliana plants can be resistant to the harmful effects of simazine (SIM) and can be used as a phytoremediator of environmental SIM contaminants. After 21 days, most atrazine taken up by prairie grasses from sand culture was degraded to metabolites, 60–80% of 14C detected in leaves. Yellow Indian grass showed low resistance to atrazine toxicity and low uptake of 14C atrazine in liquid hydroponic cultures. 72% removal of endosulfan (8 mg/kg) from the bulk soil by alfalfa, which was more efficient than tomato, sunflower, and soybean. After 60 days of treatment, sunflower presented the highest endosulfan (8000 ng/g dry weight) levels in roots and leaves along with the highest phytoextraction capacity and accumulation. It evidenced to be the best phytoremediation candidate among tomato, sunflower, soybean, and alfalfa for endosulfan residues in soils. Ricinus communis L. could remove 25 to 70% contaminants (hexachlorocyclohexane (HCH), DDT, heptachlor, Aldrin) after 66 days. Ricinus communis L. can be used for phytoremediation of such compounds. Saccharum plant in combination with yeast (Candida VITJzN04) is an effective alternative for lindane removal. High atrazine, chlorpyrifos and isoproturon dissipation in the planted pots (biobed planted with Lolium perenne, Festuca arundinacea, and Trifolium repens) compared with the unplanted pots, the grass layer enhanced pesticide removal in biobed. The removal rate of atrazine (0.02 g/kg) in Pennisetum rhizosphere soil was improved by 15% after 28 days through changes in the bacteria, fungus, and actinomycetes in the soils. After 135 days of exposure, about 50–60% endosulfan (1500 μg/g) removed when it was inoculated with rhizospheric bacteria from Vetiveria zizanioides. 70–100% of pirimicarb and imidacloprid were removed from clayey, silty loamy, and sandy soils by adsorbents(watermelon peel and used tea leaves)after 360–480 min of treatment. 90 and 74% of 2, 4-D (500 mg dm−3) were removed after 15 days by electro-remediation powered by solar energy.

[67]



Microbial/rhizospheric remediation


Natural degradation

Natural degradation Photo-degradation

Physic-chemical

Phytoremediation Phytoremediation

Phytoremediation Phytoremediation

Phytoremediation

Phytoremediation and bioaugmentation Phytoremediation/rhizoremediation

Rhizoremediation

Rhizospheric and microbial degradation Soil washing

Solar-powered electrokinetic remediation

[112]

[125, 129]

[56]

[8]

[47]

[53] [84]

[7]

[4] [50]

[70] [70]

[91]

[94] [113]

[60]

[103] [104]

[104]

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chemical remediation technologies are suitable for the point sources of pesticide-polluted soils. For example, pesticide production and storage sites which were heavily contaminated with pesticides. The efficiencies of technologies varied from 20 to 100% and were influenced by many factors (Table 1). For example, around 100% of organophosphate pesticides were degraded in UV/TiO2/K2S2O8 system in 3.5 h [86]. Bioremediation consists of phytoremediation and microbial remediation. Among biological approaches, the use of microbes with degradation ability is considered the most efficient and cost-effective option to clean pesticide-contaminated sites. Also, as a sustainable technology, biodegradation has become the most important and dominant way for removing toxic pesticides from the environment [1, 15, 18, 19, 101]. For agricultural soils, most of the pesticide pollution was diffused in the field. Therefore, ex situ and on-site treatments are less practical for the non-point source of pesticide contamination, and physical and chemical remediation technologies have been used to a limited extent in the pesticide-contaminated agricultural soils. In situ biodegradation is increasingly utilized for the remediation of soils polluted by pesticides. As Table 1 shows, around 80% of current research on remediation of pesticide-polluted soils is related to biodegradation through microbes. Specific bacteria and/or fungi were isolated from the contaminated soils and then used for the degradation of pesticides in greenhouse studies [13, 32, 56, 75]. Advanced biodegradation with biochar or bioaugmentation was used for increasing the efficiency of biodegradation [18, 30, 101]. Phytoremediation was also an effective bioremediation technology for removal of pesticides from contaminated soil through plant uptake, phytoextraction, phytovolatilization, and rhizoremediation [4, 50, 70, 91, 113]. Combined remediation technology was used for removal of pesticide-polluted soil. Physicochemical techniques were combined for degradation of Simazine [7], phytoremediation combined with bioaugmentation was used for removal of Lindane from soil [94], and rhizospheric bacteria and microbial degradation were combined for increasing the efficiency of endosulfan removal [100, 103]. Other than the general mechanism of phytoremediation, remediation plants improved the rate of atrazine removal through bacteria, fungi, and actinomycetes in the rhizospheric soil [60]. Combined soil washing and CDEO was used for the removal of atrazine from soils [95]. Fertilizer (organic, compost, and biofertilizer) and cow-dung slurry were used to promote biodegradation or dissipation of pesticides from the contaminated soils [49, 99] because of long dissipation time in the natural conditions [47, 53]. Even so, the combined technology and research was less reported in the remediation of specific pesticide-polluted soils. Combined remediation technologies were increasingly being used in the remediation area. For example, strategies with biochar-microbe interactions were still used in the remediation area of organic pollution and heavy metals [129], nanoremediation coupled

with electrokinetics for PCB removal from soil [29], and composting and biochar was combined to enhance the adsorption ability of functional group for heavy metal or organic pollutant for improving the efficiency of remediation [119]. Therefore, bioaugmentation and combined remediation techniques are being increasingly used in remediation of pesticidecontaminated soils for achieving higher efficiency.

Conclusion Various kinds of pesticides have polluted agricultural soils because of non-point sources of pollution and different plant varieties which require intensive pesticide application to maintain their crop stands and yields. Agricultural soils polluted by pesticides have enticed remediation owing to the harmful effects of pesticides on the health of human beings, flora, fauna, and environment. This review provides an overview of the recent pollution in agricultural soils from pesticides and the remediation technologies used for pesticidecontaminated soils. The research on physical, chemical, and bioremediation technologies is also summarized. The efficiency of pesticide remediation techniques is influenced by various factors such as polluted soil type, physical and chemical properties of the pesticide, extent and concentration of the pesticide, climatic conditions, and presence of other mixed contaminants in the soil. The physical treatments combined with chemical treatments such as soil washing, EKSF, electro-remediation, TCFR, and advanced oxidation processes are effective technologies for removing pesticides from the polluted soils. However, the physical treatment techniques need equipment and treated soil would have to be collected at some site, as with ex situ procedures, but excavation and transport of agricultural soil is highly costly and not practical. The in situ treatment is suited for remediation of most agricultural soil pollution being spread in the farmland soils. Bioremediation has numerous advantages over physical and chemical treatments being non-destructive, in situ, less costly, environmentally friendly, easy to operate, and therefore broadly applied in agricultural soil remediation (as compared to physical and chemical remediation techniques) and has thereby become the sustainable technique and leading research area in remediation [5]. Phytoremediation and microbial remediation are the major bioremediation techniques being used these days. Plants remove pesticides from soil mainly through plant uptake, sequestration, metabolism, volatilization, releasing enzymes, and excretions for microbial metabolism of pesticides in the rhizosphere. In situ bioremediation is better for agricultural soils polluted by pesticides. Other than some pesticide-degrading microbes including bacteria, fungi, and actinomycetes, some biosurfactants and bioaugmentation techniques have been used for increasing the efficiency of

Curr Pollution Rep

bioremediation as well as combined remediation techniques being the focus of research in remediation techniques. Importantly, the remediation research of pesticidecontaminated agricultural soils on a field scale is lacking. More work should be done to evaluate the efficiency of proposed remediation techniques and the associated costs in real field scenarios. The contaminated soils frequently contain multiple contaminants that may interact with each other as well as with soil, plants, animals, and microbes in the agricultural system; hence, successful remediation is contingent on understanding these interactions and accounting for them in designing appropriate treatments.

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Acknowledgements The authors would like to thank Dr. Dibyendu Sarkar for his invitation in writing this review article. Thanks are also due to the Center of Postdoctoral Studies of Landscape Architecture, Southwest Forestry University, Kunming, the People’s Republic of China, for their support.

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Funding Information This work was supported by the National Natural Science Fund of China (No. NSFC41563014; NSFC31460551).

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Compliance with Ethical Standards Conflict of Interest Shixian Sun, Virinder Sidhu, Yuhong Rong, and Yi Zheng declare that they have no conflict of interest.

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