What are the Main Sensor Methods for Quantifying Pesticides in Agricultural Activities? A Review.

In recent years, there has been an increase in pesticide use to improve crop production due to the growth of agricultural activities. Consequently, various pesticides have been present in the environment for an extended period of time. This review presents a general description of recent advances in the development of methods for the quantification of pesticides used in agricultural activities. Current advances focus on improving sensitivity and selectivity through the use of nanomaterials in both sensor assemblies and new biosensors. In this study, we summarize the electrochemical, optical, nano-colorimetric, piezoelectric, chemo-luminescent and fluorescent techniques related to the determination of agricultural pesticides. A brief description of each method and its applications, detection limit, purpose-which is to efficiently determine pesticides-cost and precision are considered. The main crops that are assessed in this study are bananas, although other fruits and vegetables contaminated with pesticides are also mentioned. While many studies have assessed biosensors for the determination of pesticides, the research in this area needs to be expanded to allow for a balance between agricultural activities and environmental protection.

Efficiency of a low-cost pyramid-shaped solar still for pesticide removal from highly contaminated water.

Water pollution by pesticides and other chemical contaminants is a subject of major importance due to the risk for human health and the environment. The search for remediation processes able to withdraw chemical contaminants from water and to allows water reuse is an urgent need. Herein, a simple and cheap system for pesticides removal was constructed and evaluated using water samples contaminated with two widely used herbicides (imazapic and imazethapyr, at g L-1 level). Operation parameters and process efficiency, in terms of removal rate in the reclaimed water and degradation rate of pesticides in the dry residue, were quantitatively determined. The model was tested in real-world field experiments and was able to remove more than 99.95% of both contaminants from a 10 L solution containing 4.16 ±â€¯0.94 g of imazethapyr and 1.31 ±â€¯0.17 g of imazapic, generating reusable water with minimum volume loss (<2.5%). Liquid chromatography coupled to mass spectrometry was used to determine the herbicides content in all samples and to estimate the degree of degradation of the substances as well as the occurrence of transformation products of imazapic and imazethapyr. The system efficiency in removing contaminants of emerging concern from surface water was also evaluated. The process have generated output water with undetected levels for two fungicides present in a local river in Southern Brazil.

Development of magnetic dispersive solid phase extraction using toner powder as an efficient and economic sorbent in combination with dispersive liquid-liquid microextraction for extraction of some widely used pesticides in fruit juices.

In this study, for the first time, a magnetic dispersive solid phase extraction method using an easy-accessible, cheap, and efficient magnetic sorbent (toner powder) combined with dispersive liquid-liquid microextraction has been developed for the extraction and preconcentration of some widely used pesticides (diazinon, ametryn, chlorpyrifos, penconazole, oxadiazon, diniconazole, and fenazaquin) from fruit juices prior to their determination by gas chromatography-flame ionization detection. In this method, the magnetic sorbent is mixed with an appropriate dispersive solvent (methanol-water, 80:20, v/v) and then injected into an aqueous sample containing the analytes. By this action the analytes are rapidly adsorbed on the sorbent by binding to its carbon. The sorbent particles are isolated from the aqueous solution in the presence of an external magnetic field. Then an appropriate organic solvent (acetone) is used to desorb the analytes from the sorbent. Finally, the obtained supernatant is mixed with an extraction solvent and injected into deionized water in order to achieve high enrichment factors and sensitivity. Several significant factors affecting the performance of the introduced method were investigated and optimized. Under the optimum experimental conditions, the extraction recoveries of the proposed method for the selected analytes ranged from 49-75%. The relative standard deviations were ≤7% for intra- (n = 6) and inter-day (n = 4) precisions at a concentration of 10 µg L-1 of each analyte. The limits of detection were in the range of 0.15-0.36 µg L-1. Finally, the applicability of the proposed method was evaluated by analysis of the selected analytes in some fruit juices.

Characterization of pesticide sorption behaviour of slow pyrolysis biochars as low cost adsorbent for atrazine and imidacloprid removal.

Agri-wastes biochars viz. eucalyptus bark (EBBC), corn cob (CCBC), bamboo chips (BCBC), rice husk (RHBC) and rice straw (RSBC) and acid treated RSBC (T-RSBC), were characterized for their physico-chemical properties and sorption behaviour of atrazine and imidacloprid was studied. Kinetics study suggested that except atrazine adsorption on RSBC, which was best explained by the pseudo second order model, sorption of atrazine and imidacloprid on biochars was well explained by the modified Elovich model. Among the five normal biochars, the RSBC showed the maximum atrazine (37.5-70.7%) and imidacloprid (39.9-77.8%) sorption. The phosphoric acid treatment of RSBC further enhanced the sorption of both pesticides in T-RSBC. The Freundlich adsorption isotherms were highly nonlinear and percent adsorption decreased with increase in pesticide concentration in solution. Pesticide adsorption on biochars was affected by their aromaticity, polarity, pore diameter, pH and weak acid fraction. Thus, rice straw biochars have great potential for environmental implications and can be exploited as adsorbents for pesticide industry spewed waste water purification.

Glycolipid biosurfactants: main properties and potential applications in agriculture and food industry.

Glycolipids, consisting of a carbohydrate moiety linked to fatty acids, are microbial surface active compounds produced by various microorganisms. They are characterized by high structural diversity and have the ability to decrease the surface and interfacial tension at the surface and interface, respectively. Rhamnolipids, trehalolipids, mannosylerythritol lipids and cellobiose lipids are among the most popular glycolipids. They have received much practical attention as biopesticides for controlling plant diseases and protecting stored products. As a result of their antifungal activity towards phytopathogenic fungi and larvicidal and mosquitocidal potencies, glycolipid biosurfactants permit the preservation of plants and plant crops from pest invasion. Also, as a result of their emulsifying and antibacterial activities, glycolipids have great potential as food additives and food preservatives. Furthermore, the valorization of food byproducts via the production of glycolipid biosurfactant has received much attention because it permits the bioconversion of byproducts on valuable compounds and decreases the cost of production. Generally, the use of glycolipids in many fields requires their retention from fermentation media. Accordingly, different strategies have been developed to extract and purify glycolipids. © 2016 Society of Chemical Industry.

Challenging conventional risk assessment with respect to human exposure to multiple food contaminants in food: A case study using maize.

Mycotoxins and heavy metals are ubiquitous in the environment and contaminate many foods. The widespread use of pesticides in crop production to control disease contributes further to the chemical contamination of foods. Thus multiple chemical contaminants threaten the safety of many food commodities; hence the present study used maize as a model crop to identify the severity in terms of human exposure when multiple contaminants are present. High Content Analysis (HCA) measuring multiple endpoints was used to determine cytotoxicity of complex mixtures of mycotoxins, heavy metals and pesticides. Endpoints included nuclear intensity (NI), nuclear area (NA), plasma membrane permeability (PMP), mitochondrial membrane potential (MMP) and mitochondrial mass (MM). At concentrations representing legal limits of each individual contaminant in maize (3ng/ml ochratoxin A (OTA), 1µg/ml fumonisin B1 (FB1), 2ng/ml aflatoxin B1 (AFB1), 100ng/ml cadmium (Cd), 150ng/ml arsenic (As), 50ng/ml chlorpyrifos (CP) and 5µg/ml pirimiphos methyl (PM), the mixtures (tertiary mycotoxins plus Cd/As) and (tertiary mycotoxins plus Cd/As/CP/PM) were cytotoxic for NA and MM endpoints with a difference of up to 13.6% (p≤0.0001) and 12% (p≤0.0001) respectively from control values. The most cytotoxic mixture was (tertiary mycotoxins plus Cd/As/CP/PM) across all 4 endpoints (NA, NI, MM and MMP) with increases up to 61.3%, 23.0%, 61.4% and 36.3% (p≤0.0001) respectively. Synergy was evident for two endpoints (NI and MM) at concentrations contaminating maize above legal limits, with differences between expected and measured values of (6.2-12.4% (p≤0.05-p≤0.001) and 4.5-12.3% (p≤0.05-p≤0.001) for NI and MM, respectively. The study introduces for the first time, a holistic approach to identify the impact in terms of toxicity to humans when multiple chemical contaminants are present in foodstuffs. Governmental regulatory bodies must begin to contemplate how to safeguard the population when such mixtures of contaminants are found in foods and this study starts to address this critical issue.

Typical low cost biosorbents for adsorptive removal of specific organic pollutants from water.

Specific organic pollutants (SOPs) such as phenolic compounds, PAHs, organic pesticides, and organic herbicides cause health and environmental problems due to their excessive toxic properties and poor biodegradability. Low-cost biosorbents are considered as a promising alternative for conventional adsorbents to remove SOPs from water. These materials have several advantages such as high sorption capacities, good modifiability and recoverability, insensitivity to toxic substances, simple operation in the treatment processes. However, previous reports on various types of biosorbents for removing SOPs are still moderately fragmented. Hence, this paper provides a comprehensive review on using typical low-cost biosorbents obtained from lignocellulose and chitin/chitosan for SOPs adsorption. Especially, their characteristics, biosorption mechanism together with utilization for eliminating SOPs are presented and discussed. The paper also gives a critical view regarding future applications of low-cost biosorbents in SOPs-contaminated water treatment.

2,4-D adsorption to biochars: effect of preparation conditions on equilibrium adsorption capacity and comparison with commercial activated carbon literature data.

Batch isotherm experiments were conducted with chars to study adsorption of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Chars generated from corncobs, bamboo and wood chips in a laboratory pyrolyzer at 400-700 °C were compared with traditional kiln charcoals collected from villages in S/SE Asia and with activated carbons (ACs). 2,4-D uptake by laboratory chars obtained from bamboo and wood chips after 14 h of pyrolysis at 700 °C, from wood chips after 96 h of pyrolysis at 600 °C, and one of the field-collected chars (basudha) was comparable to ACs. H:C and O:C ratios declined with pyrolysis temperature and duration while surface area increased to >500 m(2)/g. Increasing pyrolysis intensity by increasing temperature and/or duration of heating was found to positively influence adsorption capacity yield (mg(2,4-D/g(feedstock))) over the range of conditions studied. Economic analysis showed that high temperature chars can be a cost-effective alternative to ACs for water treatment applications.

Stereoselective quantitation of mecoprop and dichlorprop in natural waters by supramolecular solvent-based microextraction, chiral liquid chromatography and tandem mass spectrometry.

Liquid chromatography (LC)/tandem mass spectrometry (MS/MS) after supramolecular solvent-based microextraction (SUSME) was firstly used in this work for the enantioselective determination of chiral pesticides in natural waters. The method developed for the quantitation of the R- and S-enantiomers of mecoprop (MCPP) and dichlorprop (DCPP) involved the extraction of the herbicides in a supramolecular solvent (SUPRAS) made up of reverse aggregates of dodecanoic acid (DoA), analyte re-extraction in acetate buffer (pH = 5.0), separation of the target enantiomers on a chiral column of permethylated α-cyclodextrin under isocratic conditions, and detection of the daughter ions (m/z = 140.9 and 160.6 for MCPP and DCPP, respectively) using a hybrid triple quadrupole mass spectrometer equipped with an electrospray source operating in the negative ion mode. Similar recoveries (ca. 75%) and actual concentration factors (ca. 94) were obtained for both phenoxypropanoic acids (PPAs). The quantitation limits were 1 ng L(-1) for R- and S-MCPP, and 4 ng L(-1) for R- and S-DCPP, and the precision, expressed as relative standard deviation (n = 6) was in the ranges 2.4-2.7% ([R-MCPP] = [S-MCPP] = 5 ng L(-1) and [R-DCPP] = [S-DCPP] = 15 ng L(-1)) and 1.6-1.8% (100 ng L(-1) of each enantiomer). The SUSME-LC-MS/MS method was successfully applied to the determination of the enantiomers of MCPP and DCPP in river and underground waters, fortified at concentrations between 15 and 180 ng L(-1) at variable enantiomeric ratios (ER = 1-9).

Rapid analysis of organochlorine and pyrethroid pesticides in tea samples by directly suspended droplet microextraction using a gas chromatography-electron capture detector.

A simple and efficient directly suspended droplet microextraction (DSDME) has been developed to extract and pre-concentrate organochlorine and pyrethrin pesticides from tea samples prior to analysis by a gas chromatography-electron capture detector (GC-ECD). The optimal experimental conditions of DSDME were: 100 µL isooctane exposed for 15 min to 5 mL of the tea aqueous sample stirred at 1100 rpm. For most of the target analytes, the optimal pretreatment of DSDME processes led to no significant interference of tea matrices. The approach was applied to the determination of organochlorine and pyrethroid pesticides in tea samples, with a linearity range of 0.0005-2 µg/mL. The relative recoveries of all the pesticides ranged between 80.0% and 120.8% with relative standard deviations (RSDs) in the range of 0.8-19.9% (n=5). The limits of detections (LODs) ranged between 0.04 and 1 µg/L for all the target pesticides.

The use of date palm as a potential adsorbent for wastewater treatment: a review.

BACKGROUND: In tropical countries, the palm tree is one of the most abundant and important trees. Date palm is a principal fruit grown in many regions of the world. It is abundant, locally available and effective material that could be used as an adsorbent for the removal of different pollutants from aqueous solution. REVIEW: This article presents a review on the role of date palm as adsorbents in the removal of unwanted materials such as acid and basic dyes, heavy metals, and phenolic compounds. Many studies on adsorption properties of various low cost adsorbent, such as agricultural waste and activated carbons based on agricultural waste have been reported in recent years. CONCLUSION: Studies have shown that date palm-based adsorbents are the most promising adsorbents for removing unwanted materials. No previous review is available where researchers can get an overview of the adsorption capacities of date palm-based adsorbent used for the adsorption of different pollutants. This review provides the recent literature demonstrating the usefulness of date palm biomass-based adsorbents in the adsorption of various pollutants.

Microwave-assisted extraction and large-volume injection gas chromatography tandem mass spectrometry determination of multiresidue pesticides in edible seaweed.

A microwave-assisted extraction method followed by clean-up with solid-phase extraction (SPE) combined with large-volume injection gas chromatography-tandem mass spectrometry (LVI-GC-MS/MS) for the analysis of 17 pesticides in wild and aquaculture edible seaweeds has been developed. An experimental central composite design was employed to evaluate the effects of the main variables potentially affecting the extraction (temperature, time, and solvent volume) and to optimize the process. The most effective microwave extraction conditions were achieved at 125 °C and 12 min with 24 mL of hexane/ethyl acetate (80:20). SPE clean-up of the extracts with graphitized carbon and Florisil, optimized by means of the experimental design, proved to be efficient in the removal of matrix interferences. The analytical recoveries were close to 100% for all the analytes, with relative standard deviations lower than 13%. The limits of detection ranged from 0.3 to 23.1 pg g(-1) and the limits of quantification were between 2.3 and 76.9 pg g(-1), far below the maximum residue levels established by the European Union for pesticides in seaweed. The results obtained prove the suitability of the microwave-assisted extraction for the routine analysis of pesticides in aquaculture and wild seaweed samples.

Design and study of a cost-effective solar photoreactor for pesticide removal from water.

In order to remove pesticides from water, a basic photoreactor has been built. We evaluated the performance of this photoreactor using two commercial photocatalytic materials from Ahlstrom group and from Saint-Gobain, with solar and artificial UV-lamps. We compared the kinetics of photocatalytic degradation and mineralization of Diuron in the same reactor with of both photocatalyst supports. We showed that Diuron is easily degraded under solar or artificial irradiation, while the kinetics of mineralization in the same condition are very slow. The behaviour of these commercial materials has been studied after several uses in the same conditions. We showed the effectiveness of this basic and cheap photoreactor for the elimination of pesticide in water.

Application of statistical design of experiment with desirability function for the removal of organophosphorus pesticide from aqueous solution by low-cost material.

This paper deals with the multiple response optimization for the removal of organophosphorus pesticide quinalphos [QP: O,O-diethyl O-2-quinoxalinyl phosphorothioate] from the aqueous solution onto low-cost material and tried to overcome the drawbacks of univariate optimization. Used tea leaves were used as low-cost adsorbent and batch equilibration method was followed for this study. A Box-Behnken design was used to develop response model and desirability function was then used for simultaneous optimization of all affecting parameters in order to achieve the highest removal% of quinalphos. The optimum conditions of factors predicted for quinalphos removal% were found to be: pH 8.83, concentration 7 mg L(-1) and dose 0.40 g. Under these conditions, maximum removal% of quinalphos was obtained 96.31%. Considering the above optimum conditions, the adsorption isotherms were developed and provided adsorption capacity of 196.07 microg g(-1) by using Langmuir equation, indicating that used tea leaves may be applied as a low-cost material for pesticides removal from aqueous matrices.

Simultaneous determination of pesticides at trace levels in water using multiwalled carbon nanotubes as solid-phase extractant and multivariate calibration.

The application of solid-phase extraction with multivariate calibration for simultaneous determination of three toxic pesticides in tap and reservoir waters was presented. The proposed analytical method was used for the determination of atrazine, methidathion, and propoxur in complex water samples without the need for chromatographic separation. Among the applied multivariate calibration methods, partial least squares (PLS-1) method was found the most effective for pesticides quantification. Multiwalled carbon nanotubes (MWCNTs) adsorbent showed a perfect extraction/preconcentration of pesticides present at trace levels. The experimental factors that affect pesticides extraction by MWCNTs adsorbent such as sample volume, eluent volume, solution pH, and extraction flow rate were studied and optimized. The figures of merit of the proposed method were: limits of detection 3, 2, and 3 microg l(-1) and linear ranges 5-30, 3-60, and 5-40 microg l(-1) for atrazine, methidathion, and propoxur, respectively. A good precision was reported for the method, R.S.D. values were always less than 5.0%. Satisfactory results were reported for simultaneous determination of trace levels of pesticides in complex matrices. In tap water, the percent recoveries for pesticides were extended from 95 to 104% and R.S.D. from 1 to 3%, while lower recoveries were observed in reservoir water: 84-93% (R.S.D.: 1-3). Although the pesticides can be accurately quantified by SPE and liquid chromatography, SPE-PLS-1 method was found simpler and operated at lower running costs.

Low cost sorbents for the removal of methyl parathion pesticide from aqueous solutions.

Sorptive potential of selected agricultural waste materials i.e. rice (Oryza sativa) bran (RB), bagasse fly ash (BFA) of sugarcane (Saccharum officinarum), Moringa oleifera pods (MOP) and rice husk (RH) for the removal of methyl parathion pesticide (MP) from surface and ground waters has been investigated. Optimization of operating parameters of sorption process, i.e. sorbent dose, agitation time, pH, initial concentration of sorbate, and temperature have been studied. The sorption data fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) sorption isotherms. The maximum capacities of RB, BFA, MOP and RH for MP were calculated to be 3.6+/-0.8, 5.3+/-1.4, 5.2+/-1.5 and 4.7+/-1.0 mmolg(-1) by Freundlich, 0.39+/-0.009, 0.39+/-0.005, 0.36+/-0.004 and 0.35+/-0.008 mmolg(-1) by Langmuir and 0.9+/-0.08, 1.0+/-0.10, 1.0+/-0.10 and 0.9+/-0.07 mmolg(-1) by D-R isotherms respectively, employing 0.1g of each sorbent, at pH 6, 90 min agitation time and at 303 K. Application of first order Lagergren and Morris-Weber equations to the kinetic data yielded correlation coefficients, close to unity. Thermodynamic parameters of sorption process, i.e. DeltaH, DeltaS and DeltaG were computed and their negative values indicated the exothermic and spontaneous nature of sorption process. The pesticide may be stripped by sonication with methanol, making the regeneration and reutilization of sorbents promising. The sorbents investigated exhibited their potential applications in water decontamination, treatment of industrial and agricultural waste waters.