The role of organic colloids in herbicide transfer to rivers: a quantitative study of triazine and phenylurea interactions with colloids

For moderately hydrophobic compounds such as most pesticides adsorption on colloids (<0.2 microm) may play a key role in pesticide mobility as well as in their degradation by chemical and microbiological processes. However, until now, pesticide-organic colloid interactions are poorly understood. Quantitative data for sorption equilibria on colloids of two series of herbicides including triazines (atrazine, simazine, terbutylazine, prometryne, desethylatrazine, and desisopropylatrazine) and phenylureas (isoproturon, linuron, neburon, and diuron) sampled in the Seine river (urban zone) and the Marne river (agricultural zone) are presented. Partition coefficient of herbicides on colloids (K(com)), were evaluated by solid-phase extraction coupled with high-performance liquid chromatography-UV diode-array detection (SPE-HPLC-UV/DAD). In the case of triazines a satisfactory log-log correlation was found between K(com) and octanol-water coefficient (K(ow)) values. Phenylureas did not obey this correlation, with K(com) values being about two times higher than those of triazines. The existence of two distinct types of adsorption behaviour on colloids partly explains the different occurrence of triazines and phenylureas in surface waters.     

Enantiomeric and isomeric separation of herbicides using cyclodextrin-modified capillary zone electrophoresis

Cyclodextrin-modified capillary zone electrophoresis (CD-CZE) was applied successfully to the enantiomeric and isomeric separation of three herbicides (imazaquin, diclofop and imazamethabenz). Commercially available cyclodextrins were evaluated for separation of the enantiomers and isomers of the three herbicides having varied molecular structures. The enantiomers of imazaquin and diclofop, and the isomers of imazamethabenz could be resolved with a resolution of ≥1.5. The resolution was found to depend on pH of the run buffer, cyclodextrin type and cyclodextrin concentration. By employing mixed cyclodextrins in the running buffer, the three herbicides were simultaneously separated in a single run. In addition, rapid (less than 3 min) enantiomeric separation is demonstrated using imazaquin as a model herbicide. The reported capillary electrophoresis (CE) methods are simple, rapid, efficient and reproducible and our results demonstrate that CE provides a powerful analytical tool for enantiomeric and isomeric separation of herbicides.     

Isotachophoretic determination of herbicides prometryne, desmetryne, terbutryne and hydroxy-derivatives of atrazine and simazine in extracts of milk

A method is described for the determination of the triazine herbicides prometryne, desmetryne, terbutryne, OH-atrazine and OH-simazine in purified extracts of milk using analytical capillary isotachophoresis. The reproducibility of isotachophoretic analyses was 3.5% and the detection sensitivity reached 2 ng. Recovery of triazines from fortified samples of homogenized full milk (0.05 mg/L) was about 65%.     

Imidazolinone and triazine herbicides in soils in relation to the complexes formed with Cu(II) ions

Imidazolinone and triazine herbicides are used in many countries and may have a great impact on metal biocycles in soil. This article deals with the dynamics of imidazolinone and triazine herbicides in soils related to the formation of complexes with Cu(II) ions, which can be very stable. The stability constants of the complexes formed by five imidazolinone herbicides and ten triazine herbicides with Cu(II) ions are determined by means of fast, easy, and inexpensive measurements performed by ultraviolet–visible spectroscopy, for imidazolinones, and voltammetry (cyclic and differential pulse), for triazines. Because of the occurrence of dissociation reactions, the determinations were performed at three pH values for imidazolinones and at one pH value for triazines. In aqueous solutions of 5 < pH < 10 (corresponding to the majority of soils of agricultural use), the herbicides form very stable complexes with the Cu(II) ions, the complexes being integrated by two ligands (herbicides) and one copper ion. In conclusion, crops treated with such herbicides in conjunction with Cu(II) salts experience a decrease in its persistence and effectiveness. In addition, the herbicides and the copper ions may pass to the phreatic layer of the soil, increasing the chance of pollution.     

Photodegradation study of some triazine-type herbicides

Triazines are amongst the most widely used herbicides. Since triazines can be found in many environmental compartments, their fate in ecosystems and the characterization of their degradation pathways in the environment are to be determined. In this paper we report on a study intended to investigate the photodegradation of some triazine-type herbicides: atrazine, cyanazine, terbuthylazine and terbutryn. The rate of photodegradation process was determined, and degradation schemes were outlined for the compounds studied. Moreover, experiments with different degrading energies were carried out in order to gain information about the effect of total degrading energy on the photodegradation process. The most significant processes of photodegradation of triazines are the partial or complete loss of side-chains, or rather the substitution of the heteroatom-containing side-chain to hydroxyl-group. Besides consecutive processes, loss of the different side-chains takes place parallely also, thus, different metabolites will be formed having mixed side-chains, until the cyanuric acid and 2-amino-4,6-dihydroxy-1,3,5-s-triazine are formed by losing all the side-chains. The presence of the dimer products could be detected during the degradation of all triazines. This proves the radical character of processes occurring during the photodegradation. Increasing the degradation energy (15 to 125 W) has raised the degradation rate by 2-5, and the chlorine containing metabolite—which was still present in the completely degraded mixture during the low-energy experiments—has completely disappeared from the mixture, thus, the increased degrading energy is favorable to the formation of less dangerous, nature identical metabolites.     

Analysis of agrochemicals by capillary electrophoresis

An increasing amount of articles using capillary electrophoresis as an investigation tool for pesticides and environmental pollutants were found over the last few years in analytical chemistry oriented journals. This review covers a wide literature range of the 1990s and concentrates on the analysis of organic agrochemicals (herbicides, fungicides, insecticides, acaricides, etc.) with capillary electrophoresis (capillary zone electrophoresis, micellar electrokinetic chromatography with CE-UV-visible or laser-induced fluorescence detection) as well as with the on-coming hyphenated techniques like capillary electrophoresis-electrospray ionization mass spectrometry. The principal preconcentration methods that allowed real sample analysis with CE are also briefly discussed. The pesticides, the separation methods, the used electrolytes, the detection types, the detection limits and the preconcentration methods were classified and presented in tabulated form as a rapid information tool.     

Comparative study of separation and determination of triazines by micellar electrokinetic capillary chromatography and nonaqueous capillary electrophoresis: application to residue analysis in natural waters

The separation and determination of a mixture of chloro- and methylthiotriazines in water samples by both micellar electrokinetic capillary chromatography (MEKC) and nonaqueous capillary zone electrophoresis (NA-CZE) were compared. The characteristics of both methods proved to be very similar in terms of separation efficiency and analysis times, but application of these methods for the analysis of triazines in natural waters, with a prior preconcentration step, revealed significant differences. A preconcentration step by solid-phase extraction (SPE) with Oasis HLB cartridges was accomplished for the determination of triazines at sub-ppb levels in drinking and river waters; when NA-CZE was used after this SPE step, electropherograms with fewer interferences and more stable baselines were obtained than when separation was carried out using MEKC. Another aspect related to the application to real samples was the lack of precision encountered upon evaluating the electrophoretic signals generated when using SPE coupled with NA-CZE. Here, we demonstrate the importance of choosing an appropriate internal standard for analyte quantification. It is recommended that a triazine belonging to the same family as that of the triazine to be determined should be used as internal standard.     

Determination of triazine herbicides in natural waters by solid-phase extraction and non-aqueous capillary zone electrophoresis

Capillary zone electrophoresis (CZE) in an organic medium was used to analyse triazines at sub-ppb concentration levels in natural waters after a preconcentration step using conventional C18 cartridges and new Oasis HLB devices. With both sorbents, satisfactory results were obtained on analysing deionized water. However, on analysing natural waters, both sorbents showed very different types of behaviour. The different variables affecting the elution of both sorbents were studied, resulting in the choice of Oasis HLB as the most suitable for later separation by CZE in non-aqueous medium. Combination of a preconcentration step with electrokinetic injection revealed that capillary electrophoresis with simple UV detection can also be used satisfactorily for the quantification of micropollutants in natural waters. The detection limits obtained varied between 0.01 and 0.05 microg l(-1), depending on the type of matrix analysed. The day-to-day precision varied between 0.9% and 2.3%, expressed as the relative standard deviation.     

Solid-phase extraction and sample stacking-capillary electrophoresis for the determination of quaternary ammonium herbicides in drinking water

Conditions for the simultaneous determination of paraquat, diquat and difenzoquat by capillary zone electrophoresis were established by combining two preconcentration procedures. Off-line solid-phase extraction was used for the isolation and preconcentration of quats in drinking water. Quats were then analysed by capillary electrophoresis using sample stacking with matrix removal as on-column preconcentration procedure. Two different porous graphitic carbon cartridges were compared. The breakthrough volumes of the three herbicides were calculated and the loading capacity of the sorbents was compared. Recoveries higher than 80% for difenzoquat and around 40% for paraquat and diquat were obtained when a sample volume of 250 ml was percolated. For the stacking-capillary electrophoresis analysis of quats, 50 mM acetic acid-ammonium acetate (pH 4.0), 0.8 mM cetyltrimethylammonium bromide with 5% (v/v) methanol as carrier electrolyte was used. Detection limits, based on a signal-to-noise ratio of 3:1, were lower than 0.3 microg l(-1) for standards in Milli-Q water, and lower than 2.2 microg l(-1) for drinking water samples. Run-to-run and day-to-day precision of the method were established. The two preconcentration procedures used together was successfully applied to the analysis of the three herbicides in spiked drinking water at concentrations below the maximum admissible US Environmental Protection Agency levels.     

悬浮固化分散液液微萃取-毛细管电泳法测定水中磺酰脲类除草剂

建立了悬浮固化分散液液微萃取-毛细管电泳法同时测定水中磺酰脲类除草剂残留的方法。以十二醇为萃取剂、甲醇为分散剂,采用悬浮固化分散液液微萃取技术对水样进行分离提取,并结合毛细管电泳法进行测定。该方法可以有效提取、分离、检测水中残留的微量苯磺隆、吡嘧磺隆、苄嘧磺隆等9种磺酰脲类除草剂,各待测物在10.0~1000 μg/L范围内线性关系良好,相关系数r≥0.992,方法检出限为2.40~7.50 μg/L,方法精密度为6.55%~13.9%。将该方法用于实际水样的测定,取得了较满意的结果,加标回收率为82.0%~104%。该方法简便快速,适合水中磺酰脲类除草剂的同时测定。     

Multiresidue methods using solid-phase extraction techniques for monitoring priority pesticides, including triazines and degradation products, in ground and surface waters

The review describes the use of solid-phase extraction (SPE) techniques for monitoring priority pesticides in ground and surface waters. The focus is on triazine herbicides and their degradation products. Data concerning the fate, occurrence, properties and extraction of triazines and their degradation products using different SPE techniques are tabulated and discussed.     

Microextraction by packed sorbent liquid chromatography with time‐of‐flight mass spectrometry of triazines employing a molecularly imprinted polymer†

Molecularly imprinted polymers for the determination of triazines were synthesized by precipitation using atrazine as template, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinker, and 2,2′‐azobisisobutrynitrile as initiator. The polymers were characterized by infrared spectroscopy and scanning electron microscopy and packed in a device for microextraction by packed sorbent aiming for the preconcentration/cleanup of herbicides, such as atrazine, simazine, simetryn, ametryn, and terbutryn in corn samples. Liquid chromatography coupled with time‐of‐flight mass spectrometry was used for the separation and determination of the herbicides. The selectivity coefficient of molecularly imprinted polymers was compared with that of nonimprinted polymer for the binary mixtures of atrazine/propanil and atrazine/picloram, and the values obtained were 15.6 and 2.96, respectively. The analytical curve ranged from 10 to 80 μg/kg (r = 0.989) and the limits of detection and quantification in the corn matrices were 3.3 and 10 μg/kg, respectively. Intra‐ and interday precisions were < 14.8% and accuracy was better than 90.9% for all herbicides. Polymer synthesis was successfully applied to the cleanup and preconcentration of triazines from fortified corn samples with 91.1–109.1% of recovery.     

Capillary electrophoresis applied for the determination of acidity constants and limiting electrophoretic mobilities of ionizable herbicides including glyphosate and its metabolites and for their simultaneous separation

Thermodynamic acidity constants and limiting ionic mobilities were determined for polyprotic non-chromophore analytes using capillary electrophoresis with capacitively coupled contactless conductivity detection. It was not necessary to work with buffers of identical ionic strength as ionic strength effects on effective electrophoretic mobilities were corrected by modeling during data evaluation (software AnglerFish). The mobility data from capillary electrophoresis coupled to conductivity detection were determined in the pH range from 1.25 to 12.02 with a high resolution (36 pH steps). With this strategy, thermodynamic acidity constants and limiting ionic mobilities for various acidic herbicides were determined, sometimes for the first time. The model analytes included glyphosate, its metabolites, and its acetylated derivates (aminomethyl phosphonic acid, glyoxylic acid, sarcosine, glycine, N-acetyl glyphosate, N-acetyl aminomethyl phosphonic acid, hydroxymethyl phosphonic acid). The obtained data were used in simulations to optimize separations by capillary electrophoresis. Simulations correlated very well to experimental results. With the new method, the separation of glyphosate from interfering components like phosphate in beer samples was possible.     

Graphene oxide based in‐tube solid‐phase microextraction combined with liquid chromatography tandem mass spectrometry for the determination of triazine herbicides in water

A novel in‐tube solid‐phase microextraction method based on a graphene oxide coated column was developed for the determination of triazines in waters. This column was prepared by the covalent modification of monolayer graphene oxide sheets onto the inner wall of a fused‐silica capillary. Scanning electron microscopy showed that the thickness of the graphene oxide coating was ～30 nm, with a porous, wrinkled membrane‐like structure. Its performance was evaluated through the extraction of triazines in water. Results showed that the coating was stable for at least 100 replicate extractions, and variety of multi‐columns was less than 10%. Flow rate, loading volume, pH, and ionic strength of samples played an important effect on the extraction. The high extraction efficiency was mainly attributed to π–π stacking and hydrogen bonding interactions. The in‐tube solid‐phase microextraction was used in the determination of triazines with liquid chromatography and tandem mass spectrometry, and the detection limits were 0.0005–0.005 μg/L for five triazine compounds. Further, the method was applied to the analysis of triazine herbicides in real samples including tap water, sea water, and river water, and the recoveries were 82.8–112.0, 85.4–110.5, and 81.6–105.9%, respectively, with RSDs of 2.7–7.1%.     

Determination of Maleic Hydrazide in Potato Samples Using Capillary Electrophoresis with Dual Detection (UV‐Electrochemical)

A new method for the separation of a mixture of different herbicides (propham, chlorpropham, asulam, metamitron, linuron, and maleic hydrazide) using MEKC is proposed. A base‐line separation for the mixture of herbicides is achieved in less than six minutes. The detection limits obtained for all the herbicides were lower than 1.0 μM using UV detection. This separation method was used for the determination of maleic hydrazide in potato samples. If a dual (UV‐electrochemical) detection system is employed, chlorpropham can be also detected. The results obtained showed that electrochemical detection was ten folds more sensitive than UV detection for maleic hydrazide. The detection limit of the proposed method for maleic hydrazide employing electrochemical detection was 1.3 μg g^?1, this value is lower than 50 μg g^?1, which is the maximum residue level permitted for this plant growth regulator in potato samples. The results obtained in the work clearly demonstrate the advantage of using electrochemical detection coupled to capillary electrophoresis, using this detection the concentration limits are not compromised by miniaturization and the components required are simple and inexpensive.     

Factors Responsible for the Electrophoretic Behavior of Carboxylic Acid and Triazine Derivatives under Conditions of Capillary Zone Electrophoresis and Micellar Electrokinetic Chromatography

The effects of the pH, nature, and ionic strength of the running buffer; temperature; and surfactants, organic solvents, and macrocyclic compounds added to the buffer solution on the electrophoretic separation parameters of anionic, cationic, and neutral components of complex mixtures of organic compounds under the conditions of capillary zone electrophoresis and micellar electrokinetic chromatography. Pesticides from the series of chlorophenoxycarboxylic acids and triazines, as well as amino acids and substituted benzoic acid derivatives, were used as model systems. The predominant role of the addition of macrocyclic reagents, in particular, -cyclodextrin, as buffer electrolyte components was noted.     

Determination of triazines and dinitroanilines in waters by high-performance liquid chromatography after solid-phase extraction

A rapid and selective method for the simultaneous determination of triazines and dinitroanilines in real water matrices is suggested based on a preliminary adsorption on an RP-18 cartridge, an elution step using acetonitrile and HPLC separation with a Lichrosorb RP- Select B column and UV detection. The washing step cartridge is critical for triazines: terbutryn is eluted with quantitative recovery only after washing with an NH₃ solution. The degree of enrichment of the compounds studied has been determined: triazine recoveries are quantitative, while dinitroaniline recoveries are between 66% and 78% at the lowest fortification level. The detection limits for the ten herbicides are in the range 0.03-0.1 μg/l. The analysis time is 2 h.     

Polypyrrole-Coated and Polysulfate-Modified CE Capillaries

Fused-silica capillaries covalently coated with polypyrrole offer some interesting properties for capillary electrophoresis. The polymeric, surface-bonded coating is chemically stable and reduces the adsorptive properties of the silica surface. At the same time, the weak positive surface charges offer the possibility of creating a strongly anionic surface when poly-sulfates are used as counter-ions. This affords an electroosmotic flow which is largely independent of pH. With sodium dodecyl sulfate in the background electrolyte, this effect is further enhanced. The potential of the approach is demonstrated with the separation of herbicides by micellar electrokinetic chromatography. Repeatability of electroosmotic mobility of less than 1% RSD is achieved.

     

Rapid target analysis for pesticides in water by online coated capillary microextraction combined with liquid chromatography and tandem mass spectrometry

The applicability of online trace enrichment with custom-made coated capillaries combined with tandem mass spectrometry was demonstrated for the target analysis of selected pesticides (mainly herbicides, e.g., triazines, phenylureas, and acetanilides) in water. The developed method allows rapid determination of several widely used plant protectants within a total analysis time of 11 min. Good linearity (r > or = 0.995) was obtained for the selected pesticides in the range of 0.050-50 microg/L. The relative standard deviations (RSDs) of the peak areas were < or = 3.8% for spiked Milli-Q water (5 microg/L). The RSDs obtained in analyses of spiked (1 microg/L) water samples (brook water, river water, sewage plant effluent) ranged from 2.9 to 6.8%, indicating low influence of the matrix on enrichment and detection. The detection limits, which ranged from 10 to 90 ng/L, fulfilled the requirements of the European regulations for drinking water. The polyacrylate coating of the extraction capillary showed good stability in the presence of water and acetonitrile and allowed > or = 100 extractions with 1 capillary.