Phenoxy Acid Herbicides Research Articles

Removal of phenoxy acid herbicide from water by magnetic mesoporous silicate

Superparamagnetic iron (II,III) oxide (Fe3O4)–MCM-41 was successfully synthesised using a direct hydrothermal route and was utilised as an excellent adsorbent for the removal of the herbicide 2,4-dichlorophenoxyacetic acid from aqueous solution. The superparamagnetic mesoporous adsorbent was fully characterised using X-ray diffraction, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, nitrogen (N2) sorption and vibrating-sample magnetometry (VSM). The synthesised adsorbent exhibited a high specific surface area of 444 m2/g, making it a suitable candidate for adsorption, where it provided a higher adsorption capacity. Based on the VSM study, the recorded saturated magnetisation was 15.9 emu/g, which confirmed the viability of easily separating the adsorbent from an aqueous medium using a magnet. The ability of iron (II,III) oxide–MCM-41 to adsorb the herbicide 2,4-dichlorophenoxyacetic acid from water was tested considering various parameters, such as pH, adsorbent dosage, contact time and pollutant concentration. The effectiveness of iron (II,III) oxide–MCM-41 in removing the herbicide reached its highest peak at pH = 5, 0.05 g adsorbent, 60 min contact time and 10 mg/l 2,4-dichlorophenoxyacetic acid. The maximum removal efficiency under optimum conditions was 94.8%. Based on the experimental data and kinetic studies, the adsorption process followed a pseudo-second-order kinetic and Langmuir isotherm model.

Occurrence, multiphase partitioning, drivers, and ecological risks of current-use herbicides in a river basin dominated by rice–vegetable rotations in tropical China

Rice–vegetable rotation practices prevail in subtropical and tropical agriculture worldwide, with applications of current-use herbicides (CUHs) vital for nontarget plant control. After application, CUHs migrate to environmental compartments, where the occurrence, fate, and ecological risks have not been well characterized. To further understand the occurrence and multiphase partitioning, as well as to evaluate potential drivers and mixture risks in environmental compartments, we analyzed 11 CUHs in 576 samples from 36 rice–vegetable rotations in Nandu River basin, Hainan, China. Samples included soil, water, suspended particulate matter, and sediment collected during both rice and vegetable planting periods. The CUH concentrations varied across environmental compartments, but with high levels of glyphosate and aminomethylphosphonic acid organophosphorus herbicides (OPHs) frequently detected, accounting for 82.3 % to 99.0 % in environmental compartments. Phenoxy acid (PAA) and chloroacetanilide (ANH) herbicides were detected at lower frequencies. Spatiotemporal variation was significantly different among OPHs, ANHs, and PAAs, with geographic and crop-related patterns most evident for CUHs rather than OPHs. Structural equation model, redundancy, and boosted regression tree analyses indicated environmental compartment properties (pH, organic matter, and Fe/Al oxides), crop type, and wet/dry climate were important drivers of spatiotemporal patterns. Fugacity ratios indicated multiphase partitioning and transport of CUHs differed in rice and vegetable planting periods. A new assessment framework based on species-sensitive distributions and environmental compartment weight index indicated unacceptable risks of CUHs (risk quotient >1 in >50 % of sites), with most risks from OPHs (10.5 % to 98.0 %) and butachlor, acetochlor, and 2,4-dichlorophenoxyacetic acid. Risk hot spots were identified as the soil, the central region, and the vegetable planting period, potentially threatening nontarget organisms (e.g., Lemna minor, Glomus intraradices, and Apis mellifera). This study provides a new risk assessment framework and demonstrates the domination of OPHs in CUH contamination and risks in the tropics, thus helping guide policymakers and stakeholders on herbicide management.

Poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith with bonded Tris ligands for use in hydrophilic interaction capillary electrochromatography

The facile preparation of a monolithic capillary column with surface bound polar ligands for use in hydrophilic interaction capillary electrochromatography is described. It involved the conversion of poly(carboxyethyl acrylate[CEA]-co-ethylene glycol dimethacrylate[EDMA]) precursor monolith (the so-called carboxy monolith) into a Tris bonded monolith by a post-polymerization functionalization process in the presence of a water soluble carbodiimide, namely N-(3-dimethylaminopropyl)-N´-ethylcarbodiimidehydrochloride. The carbodiimide assisted conversion, allowed the covalent attachment of the carboxyl group of the precursor monolith to the amino group of the Tris ligand via a stable amide linkage. This resulted in the formation of Tris poly(CEA-co-EDMA) monolith, which exhibited the typical retention behavior of hydrophilic interaction stationary phase when analyzing polar and slightly polar neutral or charged compounds. In fact, neutral polar species such as dimethylformamide, formamide and thiourea were retained in the order of increased polarity with acetonitrile rich mobile phase. Also, neutral p-nitrophenyl maltooligosaccharides (PNP-maltooligosaccharides) served as a polar homologous series for gauging the hydrophilicity of the Tris poly(CEA-co-EDMA) monolith, thus forming a versatile testing homologous series for other hydrophilic columns. Other polar anionic species (e.g., hydroxy benzoic acids and nucleotides) and weakly polar anionic compounds (e.g., dansyl amino acids and phenoxy acid herbicides) as well as polar weak bases namely nucleobases and nucleosides were used to probe the hydrophilic characters of the Tris poly(CEA-co-EDMA) monolith. The various polar and weakly polar compounds just mentioned revealed the wide potentiality of the hydrophilic interaction column under investigation.

Bisthiourea immobilized UiO-66-NH2 supported Fe2O3 nanoparticles to accelerate dual centers Fenton-like reaction

In this paper, an efficient catalyst UiO-66-BTU/Fe2O3 was synthesized by using bisthiourea modified zirconium-based metal organic framework (Zr-MOF). The UiO-66-BTU/Fe2O3 system features outstanding Fenton-like activity that is 22.84 times and 12.91 times larger than Fe2O3 and conventional UiO-66-NH2/Fe2O3 system. It also exhibits good stability, broad pH range and recycle ability. Through comprehensive mechanistic investigations, we have ascribed the excellent catalytic performance of the UiO-66-BTU/Fe2O3 system to 1O2 and HO as the reactive intermediates, cause Zr centers can make complexation with Fe to form dual centers. Meanwhile, the CS on the bisthiourea can form Fe-S-C bonds with Fe2O3, reducing the redox potential of Fe(III)/Fe(II) and influencing the decomposing of H2O2, which indirectly regulate the interaction between Fe and Zr to accelerate electron transfer during the reaction. This work exhibits the design and understanding of the iron oxides incorporated in modified MOFs with excellent Fenton-like catalytic performance to remove phenoxy acid herbicides.

Characterization of Urinary Pesticide Metabolite Concentrations of Pregnant Women in Suriname.

Prenatal exposure to pesticides and the association with adverse health outcomes have been examined in several studies. However, the characterization of pesticide exposure among Surinamese women during pregnancy has not been assessed. As part of the Caribbean Consortium of Research in Environmental and Occupational Health research program, 214 urine samples were collected from pregnant women living in three regions in Suriname with different agricultural practices: capital Paramaribo, the rice producing district Nickerie, and the tropical rainforest, the Interior. We used isotope dilution tandem mass spectrometry to quantify urinary concentrations of biomarkers of three pesticide classes, including phenoxy acid herbicides and organophosphate and pyrethroid insecticides, all of which are commonly used in agricultural and residential settings in Suriname. We observed that participants residing in Nickerie had the highest urinary metabolite concentrations of 2,4-dichlorophenoxyacetic acid and pyrethroids compared to those from Paramaribo or the Interior. Paramaribo had the highest concentrations of organophosphate metabolites, specifically dialkyl phosphate metabolites. Para-nitrophenol was detected in samples from Paramaribo and the Interior. Samples from Nickerie had higher median urinary pesticide concentrations of 2,4-dichlorophenoxyacetic acid (1.06 μg/L), and the following metabolites, 3,5,6-trichloro-2-pyridinol (1.26 μg/L), 2-isopropyl-4-methyl-6-hydroxypyrimidine (0.60 μg/L), and 3-phenoxybenzoic acid (1.34 μg/L), possibly due to residential use and heavy rice production.

Recent advances in the use of graphene for sample preparation

Sample preparation is playing an increasingly important role in sample analysis. The enrichment efficiency of the target and the removal effect of the sample matrix are strongly dependent on the extraction material. Therefore, the development of efficient extraction materials is an important research focus in the field of sample preparation. Various advanced materials such as nanomaterials, mesoporous materials, ionic liquids, aerogels, carbon materials, metal-organic frameworks, and covalent organic frameworks have been introduced to produce a diverse range of extraction materials for sample preparation. Owing to its unique physical and chemical properties, graphene, an excellent carbon nanomaterial, has attracted significant attention in different areas. Due to their unique advantages of large surface area, large π-electrons, excellent adsorption properties, abundant functional groups, and facile chemical modification, graphene-based materials have displayed excellent extraction performance for diverse analytes. Furthermore, graphene-based extraction materials have been applied to pretreat real samples from different fields. This paper provides an overview of the recent advances in graphene sample preparation from 2020 to date. The manuscript covers the use of graphene, graphene oxide, and the related functionalized materials as sorbents, as well as their specific applications in cartridge solid-phase extraction, dispersive solid-phase extraction, magnetic solid-phase extraction, stir bar sorptive extraction, fiber solid-phase microextraction, and in-tube solid-phase microextraction. To prevent the aggregation of graphene, three-dimensional graphene, porous graphene aerogels, graphene-modified silica, and stainless-steel mesh were developed for cartridge solid-phase extraction. Furthermore, some graphene-based extraction materials were used to develop online solid-phase extraction, which allowed for automatic and high-throughput tests. Graphene nanosheets and their hybrid materials with molybdenum disulfide or zinc oxide nanoparticles have been applied to dispersive solid-phase extraction, and several types of contaminants, including metal ions, bisphenol endocrine disruptors, paraben preservatives, and phthalates, could be captured. By combination with magnetic materials using the coprecipitation method or via chemical post-modification, many magnetic graphene extraction materials have been produced for magnetic solid-phase extraction. The introduction of magnetic graphene not only enhanced the extraction efficiency but also simplified the test process, making it highly suitable for complex samples such as food and biological samples. Similar to magnetic solid-phase extraction, stir bar sorptive extraction is a very simple and efficient extraction method that shows good extraction performance for metal ions and organic pollutants from environmental water, medicines in urine, and organic pollutants in cosmetics. In addition to its excellent applicability to solid-phase extraction, graphene delivered satisfactory performance for solid-phase microextraction. Graphene has been used as an extraction coating for the extraction of fibers or tubes by coupling solid-phase microextraction with chromatographic detection, and many kinds of organic pollutants, including polychlorinated biphenyls, phthalates, polycyclic aromatic hydrocarbons, toluene, xylenes, organophosphorus pesticides, phenoxy acid herbicides, and antibiotics, in environmental or biological samples have been successfully determined. The extraction mechanism, including π-π, electrostatic, hydrophobic, hydrophilic, and hydrogen-bonding interactions, is also discussed. Because of the mixed-mode interactions and rich functionalization, graphene-based extraction materials could effectively capture and selectively enrich different types of species. These extraction or microextraction techniques have been coupled with detection methods such as chromatography, mass spectrometry, and atomic absorption spectroscopy and widely used in environmental monitoring, food safety, and biochemical analysis. The future development of graphene in the field of sample pretreatment focuses on the following aspects: 1) functionalization of graphene with specific groups such as affinity groups, chelating groups, and molecularly imprinted sites to achieve unique extraction selectivity; 2) combination of graphene with the advanced materials, including covalent organic frameworks, metal organic frameworks, aerogels, and nanomaterials, thus realizing the complementary advantages between materials, so that the hybrid graphene materials find broad application prospects in sample preparation; 3) combination of electromagnetic materials with graphene to form electromagnetic composites, as well as the use of electromagnetic fields to improve extraction selectivity and efficiency; 4) exploiting the good performance of graphene-based materials to overcome the difficulty encountered in the pretreatment of complex samples; 5) development of more green methods to prepare graphene-based extraction materials or functionalize graphene, in line with the trends in green chemistry; 6) application of more graphene-based materials to online sample preparation for meeting the development trends in the field of analytical chemistry.

Magnetic molecularly imprinted polymer for the simultaneous selective extraction of phenoxy acid herbicides from environmental water samples

A selective magnetic molecularly imprinted polymer (MMIP) was synthetized with 4-chloro-2-methylphenoxyacetic acid as template and 4-vinylpiridine as monomer in presence of vinylized magnetite nanoparticles. Scanning electron microscopy, nitrogen adsorption-desorption isotherms, Fourier transform infrared spectrometry and vibrating sample magnetometry were applied to characterize the resulting material. The synthesized MMIP was applied as sorbent in magnetic molecularly imprinted solid-phase extraction (MMISPE) for selective extraction of a mixture of the five herbicides 4-chloro-2-methylphenoxyacetic acid (MCPA), 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB), mecoprop (MCPP), fenoxaprop (FEN) and haloxyfop (HAL). Several parameters affecting the extraction conditions were optimized to achieve the best extraction performance. The best MMISPE combined with HPLC-DAD gave detection and quantification limits between 0.33 and 0.71 μg L−1 and 1.1–2.4 μg L−1, respectively, were obtained. The precision of the whole method provided RSD values below 7.3%, and the accuracy was demonstrated by the analysis of several water samples of different origins, with recoveries ranged from 77 to 98%. Moreover, a remarkable re-usability of the MMIP sorbent, more than 65 uses without losses in extraction capacity, was obtained.

Determination of seven phenoxy acid herbicides in water by dispersive solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on cationic metal-organic framework mixed matrix membrane

离子型金属有机骨架材料(iMOFs)对离子型化合物具有良好的选择吸附性,利用水热法合成了一种金属有机骨架材料MIL-101-NH2,以聚偏二氟乙烯(PVDF)为交联剂将其制备成混合基质膜(MMM),然后用三氟甲烷磺酸甲酯进行季胺基功能化改性,最终得到阳离子型金属有机骨架膜材料MIL-101-$NMe_{3}^{+}$-PVDF MMM,采用分散固相萃取方式富集水中的苯氧羧酸类除草剂,建立了一种基于阳离子型MOF混合基质膜的分散固相萃取-超高效液相色谱-串联质谱(UPLC-MS/MS)测定水体中7种苯氧羧酸类除草剂的分析方法。通过傅里叶变换红外光谱和扫描电子显微镜对制备的混合基质膜进行表征,结果表明季胺基功能化改性是成功的,得到了阳离子型MOF膜。对影响萃取效果的主要因素(吸附剂用量、水样pH值、萃取时间、洗脱剂种类、洗脱剂体积及洗脱时间)进行了优化,确定了最佳萃取条件。以0.01%(v/v)甲酸水溶液和乙腈作为流动相进行梯度洗脱,目标化合物在ACQUITY UPLC BEH C18色谱柱(100 mm×2.1 mm, 1.7 μm)上分离,在电喷雾电离源、负离子模式下进行多反应监测(MRM),外标法定量。结果表明,7种苯氧羧酸类除草剂在各自范围内线性关系良好,线性相关系数均大于0.997,方法的检出限(LOD)和定量限(LOQ)分别为0.00010~0.00090 μg/L和0.00033~0.00300 μg/L。在0.005、0.05和0.2 μg/L 3个加标水平下进行加标回收率试验,7种待测物的平均回收率为80%~102%,日内、日间相对标准偏差分别为1.4%~9.4%和4.2%~12.6%。该方法操作简单、快速,灵敏度高,适用于环境水体中7种苯氧羧酸类除草剂的检测。

Bioaccumulation of current-use herbicides in fish from a global biodiversity hotspot: Lake St Lucia, South Africa

Agricultural pesticides threaten aquatic systems and biodiversity at a global scale, but limited information is available on the accumulation of current-use herbicides in tissues of aquatic organisms. Here, we examine the potential exposure and accumulation of currently used herbicides in two species of fish from Lake St Lucia, a global biodiversity hotspot located in South Africa. Muscle tissue samples were analysed for 11 widely used multi-residue and phenoxy-acid herbicides. Herbicide residues were detected in all samples analysed, with total concentrations ranging from 44.3 to 238 ng g−1 (Clarias gariepinus) and 72.2–291 ng g−1 dw (Oreochromis mossambicus). The most prominent herbicides detected included the two phenoxy-acid herbicides, MCPA (17.6 ± 12 ng g−1) and 2,4-D (28.9 ± 16 ng g−1), along with acetochlor (15.4 ± 5.8 ng g−1), atrazine (12.7 ± 7.1 ng g−1) and terbuthylazine (12.4 ± 12 ng g−1). Results indicate that fish at Lake St Lucia accumulate a complex mixture of herbicides, some previously unreported in tissue, highlighting the potential threat that agricultural runoff may pose to conservation areas. However, assessing the impact of herbicide accumulation on wild fish populations is difficult at present and urgent toxicological data are needed to better understand chronic exposure effects on aquatic organisms. A preliminary human health risk assessment indicated minimal risk associated with the consumption of local fish, but potential additive and synergistic effects of contaminant mixtures remain unknown.

Deep eutectic solvent-based emulsification liquid-liquid microextraction for the analysis of phenoxy acid herbicides in paddy field water samples.

An emulsification liquid–liquid microextraction (ELLME) method was successfully developed using phenolic-based deep eutectic solvent (DES) as an extraction solvent for the determination of phenoxy acid herbicides, 3,6-dichloro-2-methoxybenzoic acid (dicamba) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in environmental water samples. Five different phenolics-based DESs were successfully synthesized by using phenol (DES 1), 2-chlorophenol (DES 2), 3-chlorophenol (DES 3), 4-chlorophenol (DES 4) and 3,4-dichlorophenol (DES 6) as the hydrogen-bond donor (HBD) and choline chloride as the hydrogen-bond acceptor (HBA). The DESs were mixed at 1 : 2 ratio. A homogeneous solution (clear solution) was observed upon the completion of successful synthesis. The synthesized DESs were characterized by using Fourier transform infrared and nuclear magnetic resonance (NMR). Under optimum ELLME conditions (50 µl of DES 2 as extraction solvent; 100 µl of THF as emulsifier solvent; pH 2; extraction time 5 min), enrichment factor obtained for dicamba and MCPA were 43.1 and 59.7, respectively. The limit of detection and limit of quantification obtained for dicamba were 1.66 and 5.03 µg l−1, respectively, meanwhile for MCPA were 1.69 and 5.12 µg l−1, respectively. The developed ELLME-DES method was applied on paddy field water samples, with extraction recoveries in the range of 79–91% for dicamba and 82–96% for MCPA.

Serum concentrations of pesticides including organophosphates, pyrethroids and neonicotinoids in a population with osteoarthritis in Saudi Arabia

Human exposure to pesticides is widespread and has received much attention in recent years because of its link to adverse health outcomes. Measurement of urinary concentrations of pesticides and their metabolites is often used in the assessment of body burdens of these chemicals. However, pesticides and their metabolites can be present in blood circulatory system, although little is known on serum levels of pesticides. In this study, we aimed to examine the occurrence and profile of four organophosphate (OP), five pyrethroid (PYR) insecticides, two phenoxy acid (PA) herbicides, 14 neonicotinoid (neonic) insecticides and six dialkylphosphate metabolites in serum from 25 individuals diagnosed with osteoarthritis in Jeddah, Saudi Arabia. 2-Isopropyl-4-methyl-6-hydroxypyrimidine (IMPY), 3,5,6-trichloro-2-pyridinol (TCPY), 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 3-phenoxybenzoic acid, N-desmethyl acetamiprid, dimethylphosphate (DMP) and dimethylthiophosphate (DMTP) were detected in ≥80% of the serum samples analyzed. Metabolites of OPs, DMTP (median concentration: 2.14 ng/mL), DMP (1.04 ng/mL) and TCPY (0.84 ng/mL), collectively accounted for 67–83% of the total serum pesticide concentrations. Serum concentrations of pesticides were similar to or lower than those reported in urine. Our preliminary evidence suggests that serum can be used as a matrix for the assessment of exposure to OPs, PYRs, PAs and neonics.

Retention Modelling of Phenoxy Acid Herbicides in Reversed-Phase HPLC under Gradient Elution.

Phenoxy acid herbicides are used worldwide and are potential contaminants of drinking water. Reversed phase high-performance liquid chromatography (RP-HPLC) is commonly used to monitor phenoxy acid herbicides in water samples. RP-HPLC retention of phenoxy acids is affected by both mobile phase composition and pH, but the synergic effect of these two factors, which is also dependent on the structure and pKa of solutes, cannot be easily predicted. In this paper, to support the setup of RP-HPLC analysis of phenoxy acids under application of linear mobile phase gradients we modelled the simultaneous effect of the molecular structure and the elution conditions (pH, initial acetonitrile content in the eluent and gradient slope) on the retention of the solutes. In particular, the chromatographic conditions and the molecular descriptors collected on the analyzed compounds were used to estimate the retention factor k by Partial Least Squares (PLS) regression. Eventually, a variable selection approach, Genetic Algorithms, was used to reduce the model complexity and allow an easier interpretation. The PLS model calibrated on the retention data of 15 solutes and successively tested on three external analytes provided satisfying and reliable results.

Moving from lab to pilot scale in forward osmosis for pesticides rejection using aquaporin membranes

Often FO experiments are carried out with the prevalent FO lab-scale setup using a moderate-sized flat sheet membrane. This necessitates spending funds on providing FO apparatuses and using higher area of FO membranes associated with a larger amount of chemicals to evaluate the performance of the FO process in rejection of compounds of interest. In this paper, we used two different FO setups, a typical lab-scale system using flat sheet aquaporin membrane as well as a small pilot-scale setup using hollow fiber aquaporin membrane, to remove three pesticides from water: 2–6 Dichloro-benzamide (BAM), 2-methyl-4-chlorophenoxyaceticacid (MCPA), and 2-(4-Chloro-2-methylphenoxy)propionic acid (MCPP). The obtained rejection data of BAM was compared to our previous study on aquaporin FO membrane using a tiny FO system to investigate the effect of going from a tiny lab-scale to a pilot-scale setup. The diffusion-controlled rejection of BAM was found to be 93–94% using the standard lab-scale flat sheet membrane system while that was 98.7% using the pilot-scale hollow fiber membrane which is in accordance to our preliminary result of >97% with the tiny system. This study confirms the hypothesis that we can employ a very small piece of membrane and accurately use it to estimate the rejection performance of a pilot-scale FO membrane system. This finding allows for a cost-effective and quick test of a large number of molecules by most importantly, the use of a tiny piece of FO membrane. Moreover, both systems, in particular, the hollow fiber setup demonstrated an excellent rejection capability for the charged phenoxy acid herbicides by having rejection values of 99.2% for both MCPA and MCPP.

Three-dimensional chitosan/graphene oxide aerogel for high-efficiency solid-phase extraction of acidic herbicides in vegetables

A simple, facile method was adopted to synthesize three-dimensional chitosan grafted graphene oxide aerogel modified silica (3D CS/GOA@Sil) as an eco-friendly, sustainable extraction material for the preconcentration of phenoxy acid herbicides.

Biodegradation Potential and Ecotoxicity Assessment in Soil Extracts Amended with Phenoxy Acid Herbicide (2,4-D) and a Structurally-Similar Plant Secondary Metabolite (Ferulic Acid).

Phenoxy acid 2,4-D (2,4-dichlorophenoxy acid) is one of the most commonly-used herbicide in agriculture. Biodegradation of 2,4-D can be stimulated by structurally-related plant secondary metabolites such as ferulic acid (FA). The aim of this study is to: (1) assess the potential of indigenous soil bacteria to degrade 2,4-D in the presence of FA by PCR analysis of functional tfdA genes, (2) to determine the influence of 2,4-D and FA on samples ecotoxicity using Phytotoxkit® and Microtox® biotests. The detection of tfdA genes varied depending on the enrichment of samples with FA. FA suppressed detection of the tfdA genes, 100 µM 2,4-D induced higher detection of studied amplicons, while 500 µM 2,4-D delayed their detection. The ecotoxicity response was specific and differed between plants (PE% Lepidium sativum > Sinapis alba > Sorghum saccharatum) and bacteria (PE% up to 99% for Vibrio fischeri). Our findings confirm that 2,4-D and FA had a toxic influence on the used organisms.

Development of dispersive solid phase extraction based on dissolvable Fe3O4-layered double hydroxide for high-performance liquid chromatographic determination of phenoxy acid herbicides in water samples

Herein, magnetic nanoparticle coated with zinc-aluminum layered double hydroxide was successfully synthesized and characterized. The nanocomposite was used as an effective adsorbent to extract three phenoxy acid herbicides in water samples prior to high performance liquid chromatography-ultraviolet detection. An interesting characteristic of this sorbent is that it dissolves under acidic solution (pH < 4). As a result, the elution step was unnecessary, and no organic solvent was used in whole extraction process. Influential extraction factors such as pH of solution, amount of sorbent, type and volume of acidic solution and vortex time were optimized. The method displays low limits of detection (0.1−0.2 ng mL−1), good linearity (0.5−200 ng mL−1), acceptable precision (relative standard deviations were less than 9.3%) and accuracy (98.9–106.1%). Therefore, the method is sensitive, fast, eco-friendly, and suitable for determination of phenoxy acid herbicides in water samples.

A new environment-friendly supramolecular solvent-based liquid phase microextraction coupled to high performance liquid chromatography for simultaneous determination of six phenoxy acid herbicides in water and rice samples

A green supramolecular solvent (SUPRAS) has been ex situ synthesized and used as the extraction solvent for liquid phase microextraction (LPME) for six phenoxy acid herbicides including 2,4-dichlorophenoxyacetic acid (2,4-D), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2-(2,4-dichlorophenoxy)propanoic acid (Dichloprop), 2-(4-Chloro-2-methylphenoxy) propanoic acid (Mecoprop), 4-(2,4-dichlorophenoxy)butanoic acid (2,4-DB) and 4-(4-Chloro-2-methylphenoxy) butanoic acid (MCPB) before their analysis by HPLC. The SUPRAS was generated from the aggregation of sodium dodecyl sulfate (SDS) and tetrabutylammonium bromide (TBABr) at the molar ratio of 1:4, in the presence of AlCl3 at ambient temperature. The synthesized SUPRAS was found to be stable for at least one month and a single prepared batch can be used for extraction of 12 samples. The optimum conditions for the extraction were 20 µL of SUPRAS, 3.5% (w/v) of AlCl3, vortex for 20 s and centrifugation at 6000 rpm for 1 min. The micro-volume extraction phase was settled at the narrow bottom of the centrifugation tube allowing easy collection without any special equipment required, providing high efficiency and reproducibility for HPLC analysis. Under the optimum conditions, the method provided the enhancement factor of 37–149 with the limits of detection in the range of 1–2 µg L − 1. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) was used for rice sample preparation before extraction and analysis by HPLC. The proposed method was successfully applied for the analysis of the studied herbicides in water and rice samples with the good percentage recovery ranged from 81–110 and 81–108, respectively.

Modeling-based optimization of the simultaneous enantiomeric separation of multicomponent mixtures of phenoxy acid herbicides using dual cyclodextrin systems by Capillary Electrophoresis

In this work, the Dubsky's model proposed for Capillary Electrophoresis (CE) enantioseparation systems with a mixture of chiral selectors was applied to the rapid optimization of the simultaneous enantiomeric separation of a multicomponent mixture of six phenoxy acid herbicides using a dual system of two cyclodextrins (CDs), (2-hydroxypropyl)-β-CD (HP-β-CD) and heptakis(2,3,6-tri-O-methyl)-β-CD (TM-β-CD). Simply by carrying out a small number of individual experiments separately with each CD, the Dubsky's model enabled to foresee the results that could be obtained for any possible combination of concentrations and relative proportion of both CDs in the mixture. Results obtained in this work demonstrated that the model was successful by improving the previous results experimentally obtained by the trial and error method for the simultaneous enantiomeric separation of the six phenoxy acid herbicides studied in this work. In fact, the separation was improved in terms of enantiomeric resolutions obtained (from 1.2 to 4.2 for concentrations of CDs of 4 mM HP-β-CD and 16 mM TM-β-CD) and by considerably reducing the time to optimize the separation conditions enabling to find, in a faster and efficient way, the most adequate proportion of both CDs and the concentration of each CD in the mixture to obtain baseline separation of the twelve enantiomers. Additionally, the apparent complexation constants between enantiomers and each CD were calculated. This is the first time that the above-mentioned model was applied to a multicomponent mixture of chiral compounds.

Real-Time Measurement of Herbicides in the Atmosphere: A Case Study of MCPA and 2,4-D during Field Application.

Atmospheric sources of herbicides enable short- and long-range transport of these compounds to off-target areas but the concentrations and mechanisms are poorly understood due, in part, to the challenge of detecting these compounds in the atmosphere. We present chemical ionization time-of-flight mass spectrometry as a sensitive, real-time technique to detect chlorinated phenoxy acid herbicides in the atmosphere, using measurements during and after application over a field at Colorado State University as a case study. Gas-phase 2,4-dichlorophenoxyacetic acid (2,4-D) mixing ratios were greatest during application (up to 20 pptv), consistent with rapid volatilization from spray droplets. In contrast, atmospheric concentrations of 2-methyl-4-chlorophenoxyacetic acid (MCPA) increased for several hours after the initial application, indicative of a slower source than 2,4-D. The maximum observed gas-phase MCPA was 60 pptv, consistent with a post-application volatilization source to the atmosphere. Exposure to applied pesticides in the gas-phase can thus occur both during and at least several hours after application. Spray droplet volatilization and direct volatilization from surfaces may both contribute pesticides to the atmosphere, enabling pesticide transport to off-target and remote regions.

Determination of Phenoxy Acid Herbicides in Cereals Using High-Performance Liquid Chromatography–Tandem Mass Spectrometry

Phenoxy acid herbicide residues were found in cereals. A QuEChERS HPLC-MS/MS method was used for analysis of these herbicide residues. This technique could be used effectively for monitoring the safety of cereals.