Dichlorprop Research Articles

Phytotoxicity of the chiral herbicide dichlorprop: Cross-talk between nitric oxide, reactive oxygen species and phytohormones

Nitric oxide (NO), reactive oxygen species (ROS), and phytohormones in plants often initiate responses to sources of abiotic stress. However, we have a poor understanding of the cross-talk between NO, ROS, and phytohormones during exogenous chiral auxin-induced phytotoxicity. In this study, the toxicity of the chiral synthetic auxin herbicide dichlorprop (DCPP) to Arabidopsis thaliana, as well as the mutual regulation of NO, hydrogen peroxide (H2O2), superoxide anion (O2.-), and phytohormones at the enantiomeric level was investigated. The ROS production exhibited an enantioselective manner, further, that was positively correlated with the change of the morphological indicators. This confirmed that ROS played an important role in the enantioselective effect of DCPP. The distribution of ROS and NO was partially overlapped, indicating that the production of NO may be affected by ROS, and also related to the degree of plant damage. In terms of phytohormones, the level of salicylic acid (SA), jasmonic acid (JA), and abscisic acid (ABA) in the whole plant increased as the (R)-DCPP concentration applied increased, however, the trend has changed, when the data of leaves and roots was discussed separately. The results revealed that the redistribution of phytohormones may exist between leaves and roots, caused by the joint action of ROS and NO. The differences in the biological activity identified between the two enantiomers in this study enhance our understanding of the toxicity mechanism of exogenous auxin via their effects on phytohormones.

Enantioselective biodegradation and enantiomerization of dichlorprop in soils

The dissipation of racemic, R-, and S- dichlorprop (DCPP) in four soils were studied in the laboratory. The half-lives of racemic DCPP were from 10.5 to 19.8 days. Preferential degradation of R- or S-DCPP was detected in all soils, even in one soil that the apparent enantiomeric fraction remained constant during incubation. The enantiomerization of DCPP was found to proceed in both directions, except in forest soil that no enantiomerization of S- to R-DCPP was observed. The isomerization equilibrium constant (K = kRS/kSR) in two vegetable soils were 0.54 and 0.53, respectively, favoring herbicidally active R enantiomer, while in paddy soil K was 1.60, favoring an inversion of R into S enantiomer. Real-time PCR showed that the rdpA gene was not detected in all indigenous and DCPP amended microcosms probably because of relative short incubation time and low amendment concentrations. In contrast, the sdpA gene was present in indigenous soils and significantly elevated after DCPP addition with the highest relative abundance around day 10 in all microcosms. Illumina sequencing of the 16S rRNA gene showed that the relative abundance of Proteobacteria significantly increased in all DCPP treated soils. DCPP-degrading related families, Sphingomonadaceae and Comamonadaceae, enhanced in all soils, while Burkholderiaceae elevated only in paddy soil with preferential degradation of S-DCPP and Pseudomonadaceae only in forest soil with R-enantiomer preference. The sdpA gene sequencing revealed that about 92%–99% of bacteria harboring sdpA genes in studied soils belong to Alphaproteobacteria.

Dichlorprop induced structural changes of LHCⅡ chiral macroaggregates associated with enantioselective toxicity to Scnedesmus obliquus

The enantioselective toxic mechanisms of chiral herbicides in photosynthetic organisms are closely related to the production of reactive oxygen species (ROS) production, however, there are few reports on how the enantioselective production of ROS can be triggered. In suboptimal conditions, photosynthesis is one of the most important processes in the production of ROS, especially in the process of light utilization and electron transfer. In this study, we investigated the interactions between chiral herbicide dichlorprop (DCPP) enantiomers and the chiral macroaggregates of the photosynthetic light-harvesting chlorophyll a/b pigment-protein complexes (LHCII) in Scenedesmus obliquus, which is of great significance in capturing and utilizing sun light, and also in dissipating the excess excitation energy. The results of the circular dichroism indicated that DCPP induced the structural changes of the LHCII chiral macroaggregates in an enantioselective manner and that the (R)-DCPP treated-group showed a bigger change accompanied by a changed enantioselective dissipation of the excitation energy. The excitation energy was excessed in DCPP treated-groups and the degree of excess was enantioselective and the detrimental non-chemical energy triggered the enantioselective production of ROS, that induced the enantioselective toxicity to green algae S. obliquus. Overall, this study has identified that how the enantioselective production of ROS can be triggered in chloroplasts; this can help to reveal the enantioselective mechanisms of chiral herbicides to photosynthetic organisms.

Enantioselective Phytotoxicity of Dichlorprop to Arabidopsis thaliana: The Effect of Cytochrome P450 Enzymes and the Role of Fe.

The ecotoxicology effects of chiral herbicides have long been recognized and have drawn increasing attention. The toxic mechanisms of herbicides in plants are involved in production of reactive oxygen species (ROS) and cause damage to target enzymes, but the relationship between these two factors in the enantioselectivity of chiral herbicides has rarely been investigated. Furthermore, even though cytochromes P450 enzymes (CYP450s) have been related to the phytotoxicity of herbicides, their roles in the enantioselectivity of chiral herbicides have yet to be explored. To solve this puzzle, the CYP450s suicide inhibitor 1-aminobenzotriazole (ABT) was added to an exposure system made from dichlorprop (DCPP) enantiomers in the model plant Arabidopsis thaliana. The results indicated that different phytotoxicities of DCPP enantiomers by causing oxidative stress and acetyl-CoA carboxylase (ACCase) damage were observed in the presence and the absence of ABT. The addition of ABT decreased the toxicity of (R)-DCPP but was not significantly affected that of (S)-DCPP, resulting in smaller differences between enantiomers. Furthermore, profound differences were also observed in Fe uptake and distribution, exhibiting different distribution patterns in A. thaliana leaves exposed to DCPP and ABT, which helped bridge the relationship between ROS production and target enzyme ACCase damage through the function of CYP450s. These results offer an opportunity for a more-comprehensive understanding of chiral herbicide action mechanism and provide basic evidence for risk assessments of chiral herbicides in the environment.

Enantioselective disturbance of chiral herbicide dichlorprop to nitrogen metabolism of Arabidopsis thaliana: Regular analysis and stable isotope attempt

As the most essential element, nitrogen play a pivotal role in plant physiological process, which is susceptible to contaminants. However, the enantioselective effects of chiral herbicides on nitrogen metabolism have not been comprehensively understood. In this study, effects of chiral herbicide dichlorprop (DCPP) on the nitrogen behaviors in Arabidopsis thaliana were investigated. The results revealed that the uptakes of inorganic nitrogen (NO3− and NH4+) were preferentially impacted by herbicidal active (R)-DCPP, where the transportation of beneficial NO3− was inhibited but the toxic NH4+ was accumulated. As for nitrogen assimilation, enantioselectivity was disappeared and reoccurred when NO3− was assimilated into NH4+. Furthermore, the pathways of NH4+ assimilation differed in Arabidopsis exposed to DCPP enantiomers, where (S)-DCPP remained almost the same to the control relying on GS-GOGAT cycle, but the dominant pathway in (R)-DCPP group was shifted to glutamate dehydrogenase route. Consequently, a profound enantioselectivity was also observed in the effects on amino acids synthesis. As for nitrogen stable isotope fractionation, (R)-DCPP led to more negative δ15N values than (S)-DCPP at 0.3μM, indicating the selective uptake of toxic NH4+ and different discrimination of δ15N was also observed between DCPP enantiomers. Moreover, stable isotopic evidence also revealed the disturbance caused by DCPP to the balance of nitrogen demand and consumption in A. thaliana. All these results may contribute to the final enantioselective toxicity, providing a new sight into the better understanding the action mechanism of chiral herbicides.

Joint interpretation of enantiomer and stable isotope fractionation for chiral pesticides degradation

Chiral pesticides are important contaminants affecting the health and functioning of aquatic systems. The combination of stable isotope and enantiomer analysis techniques has been recently proposed to better characterize the fate of these contaminants in natural and engineered settings. We introduce a modeling approach with the aim of unifying and integrating the interpretation of isotopic and enantiomeric fractionation. The model is based on the definition of enantiomer-specific isotopologues and jointly predicts the evolution of concentration, enantiomer fractionation, as well as changes in stable isotope ratios of different elements. The method allows evaluating different transformation pathways and was applied to investigate enzymatic degradation of dichlorprop (DCPP), enzymatic degradation of mecoprop methyl ester (MCPPM), and microbial degradation of α-hexachlorocyclohexane (α-HCH) by different bacterial strains and under different redox conditions. The model accurately reproduces the isotopic and enantiomeric data observed in previous experimental studies and precisely captures the dual-dimensional trends characterizing different reaction pathways. Furthermore, the model allows testing possible combinations of enantiomer analysis (EA), compound specific isotope analysis (CSIA), and enantiomer specific isotope analysis (ESIA) to identify and assess isotope and enantiomer selective reaction mechanisms.

Stomatal behaviors reflect enantioselective phytotoxicity of chiral herbicide dichlorprop in Arabidopsis thaliana

Stomata in plants play vital roles in water transpiration and gas exchange necessary for photosynthesis, which are critical for the plants growth. Until now, however, the effect of chiral herbicides on the response of stomata was poorly understood. To unveil this puzzle, the enantioselective effect of chiral herbicide dichloroprop (DCPP) on stomata in Arabidopsis thaliana was investigated. It was found that (R)-DCPP preferentially promoted the extent of stomatal opening in Arabidopsis leaves, resulting in 59.84% enhancement at 0.3μmol·L−1 comparing to the control, where (S)- and (Rac)-DCPP exhibited no significant differences. Enantioselectivity was also observed in the response of stomata to DCPP. To better understand the mechanism involved, the reactive oxygen species (ROS) production and antioxidant system defense were measured. Interestingly, the ROS production in Arabidopsis leaves was also enantioselective. The (R)-DCPP treatments resulted in 6.08-fold enhancement compared with the control, whereas 1.35- and 2.51-fold increases occurred in (S)-DCPP and (Rac)-DCPP treatments, respectively. The promoting of stomatal opening was positively correlated with ROS production. In addition, the antioxidant system response provided evidence of oxidative stress and damage caused by DCPP. This study confirmed that the ROS produced by DCPP promoted stomatal opening and suggested a potential sight to elucidate the phytotoxicity of chiral herbicides.

Evaluation of the toxicity of ZnO nanoparticles to Chlorella vulgaris by use of the chiral perturbation approach.

The toxicity of ZnO nanoparticles (NPs) has been widely investigated because of their extensive use in consumer products. The mechanism of the toxicity of ZnO NPs to algae is unclear, however, and it is difficult to differentiate between particle-induced toxicity and the effect of dissolved Zn(2+). In the work discussed in this paper we investigated particle-induced toxicity and the effects of dissolved Zn(2+) by using the chiral perturbation approach with dichlorprop (DCPP) as chiral perturbation factor. The results indicated that intracellular zinc is important in the toxicity of ZnO NPs, and that ZnO NPs cause oxidative damage. According to dose-response curves for DCPP and the combination of ZnO NPs with (R)-DCPP or (S)-DCPP, the toxicity of DCPP was too low to perturb the toxicity of ZnO NPs, so DCPP was suitable for use as chiral perturbation factor. The different glutathione (GSH) content of algal cells exposed to (R)-DCPP or (S)-DCPP correlated well with different production of reactive oxygen species (ROS) after exposure to the two enantiomers. Treatment of algae with ZnO NPs and (R)-DCPP resulted in reduced levels of GSH and the glutathione/oxidized glutathione (GSH/GSSG) ratio in the cells compared with the control. Treatment of algae with ZnO NPs and (S)-DCPP, however, resulted in no significant changes in GSH and GSH/GSSG. Moreover, trends of variation of GSH and GSH/GSSG were different when algae were treated with ZnSO4·7H2O and the two enantiomers. Overall, the chiral perturbation approach revealed that NPs aggravated generation of ROS and that released Zn(2+) and NPs both contribute to the toxicity of ZnO NPs.

Study on the bindings of dichlorprop and diquat dibromide herbicides to human serum albumin by spectroscopic methods

The interactions of dichlorprop (DCP) and diquat dibromide (DQ) herbicides with human serum albumin (HSA) protein were studied by UV absorption, fluorescence, synchronous fluorescence and circular dichroism (CD) spectroscopy. Both DCP and DQ quenched the fluorescence emission spectrum of HSA through the static quenching mechanism. The Stern–Volmer quenching constant, binding constant, the number of binding sites and thermodynamic parameters were determined at 288K, 298K, 310K and 318K. In HSA-DCP and HSA-DQ systems, an increase in temperature led to a decrease in the Stern–Volmer quenching constant and binding constant. One binding site was obtained for DCP and DQ on HSA. It was found that DCP can bind to HSA with higher affinity than DQ. Negative ΔH and positive ΔS values were obtained for the binding processes between protein and herbicide molecules. This result displayed that electrostatic interactions play a major role in the formation of HSA-DCP and HSA-DQ complexes. The binding processes were exothermic reactions and spontaneous. In addition, synchronous fluorescence and CD spectra of HSA revealed that the binding of DCP to HSA did not cause a significant conformational change in protein, but the interaction of DQ with HSA led to an alteration in the protein structure.

Fast, simple and efficient supramolecular solvent-based microextraction of mecoprop and dichlorprop in soils prior to their enantioselective determination by liquid chromatography–tandem mass spectrometry

A simple, sensitive, rapid and economic method was developed for the quantification of enantiomers of chiral pesticides as mecoprop (MCPP) and dichlorprop (DCPP) in soil samples using supramolecular solvent-based microextraction (SUSME) combined with liquid chromatography coupled to mass spectrometry (LC-MS/MS). SUSME has been described for the extraction of chiral pesticides in water, but this is firstly applied to soil samples. MCPP and DCPP are herbicides widely used in agriculture that have two enantiomeric forms (R- and S-) differing in environmental fate and toxicity. Therefore, it is essential to have analytical methods for monitoring individual DCPP and MCPP enantiomers in environmental samples. MCPP and DCPP were extracted in a supramolecular solvent (SUPRAS) made up of dodecanoic acid aggregates, the extract was dried under a nitrogen stream, the two herbicides dissolved in acetate buffer and the aqueous extract directly injected in the LC-MS/MS system. The recoveries obtained were independent of soil composition and age of herbicide residues. The detection and quantitation limits of the developed method for the determination of R- and S-MCPP and R- and S-DCPP in soils were 0.03 and 0.1 ng g(-1), respectively, and the precision, expressed as relative standard deviation (n=6), for enantiomer concentrations of 5 and 100 ng g(-1) were in the ranges 4.1-6.1% and 2.9-4.1%. Recoveries for soil samples spiked with enantiomer concentrations within the interval 5-180 ng g(-1) and enantiomeric ratios (ERs) of 1, 3 and 9, ranged between 93 and 104% with standard deviations of the percent recovery varying between 0.3% and 6.0%. Because the SUPRAS can solubilize analytes through different type of interactions (dispersion, dipole-dipole and hydrogen bonds), it could be used to extract a great variety of pesticides (including both polar and non-polar) in soils.

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 1ngL−1 for R- and S-MCPP, and 4ngL−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]=5ngL−1 and [R-DCPP]=[S-DCPP]=15ngL−1) and 1.6–1.8% (100ngL−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 180ngL−1 at variable enantiomeric ratios (ER=1–9).

Evaluation of the role of the glutathione redox cycle in Cu(II) toxicity to green algae by a chiral perturbation approach

The effect of heavy metal toxicity on the environment is usually linked to changes in the glutathione redox cycle and oxidative damage as causative events. However, it is unknown whether changes in the glutathione redox cycle are a cause or result of Cu(II) toxicity. Herein, a new chiral perturbation strategy involving a chiral herbicide, dichlorprop (DCPP), as a perturbation factor was used. According to the dose–response fitting curve of DCPP and the combination with Cu(II), 40μM (R)-DCPP and (S)-DCPP, whose toxicities were low enough to not significantly perturb the Cu(II) toxicity, were selected as the chiral perturbation factor. When Scenedesmus obliquus was incubated with the chiral perturbation factor and 10μM Cu(II), chiral perturbation was observed in the chlorophyll content and the PAM chlorophyll fluorescence. Then, the role of the glutathione redox cycle in the toxicity of Cu(II) was evaluated with the chiral perturbation approach. The results revealed that the GSH differences in algae cells exposed to (R)-DCPP or (S)-DCPP were well correlated with the differences in the production of reactive oxygen species (ROS) after exposure to the two enantiomers. When (R)-DCPP or (S)-DCPP was added with Cu(II) to the algae culture, treatment with (R)-DCPP-Cu resulted in a decrease in the GSH content in algae cells compared to the control, whereas treatment with (S)-DCPP-Cu resulted in an increase in the GSH. The GSH/GSSG ratio and GR activity also showed similar enantioselectivities. The enantioselectivities would not exist if the changes of in glutathione redox cycle were the cause. Therefore, these data provide indirect evidence that ROS induced cell toxicity of Cu is a causative event, which results in the response of the glutathione redox cycle. These results also provided an implication that before sustainable detoxification strategies for heavy metal pollutants were proposed, it is better that the roles of ROS production and glutathione redox cycle are elucidated. In this case, the chiral perturbation strategy may be a good choice.

Enantioselectivity Tuning of Chiral Herbicide Dichlorprop by Copper: Roles of Reactive Oxygen Species

Reactive oxygen species (ROS) are considered to be the key players in cell toxicity. However, cross talk between the enantioselective toxicity of pesticides, heavy metals, and ROS is poorly understood. To decipher the puzzle, the effects of copper (Cu) on the enantioselective ecotoxicity of the chiral pesticide dichlorprop (DCPP) to Scenedesmus obliquus were investigated. The results showed that the presence of DCPP and Cu, both individually and in combination, caused a sudden increase of ROS. This in turn stimulated the response of antioxidant defenses, impaired subcellular structure and physiological function, and finally resulted in cell growth inhibition. In the absence of Cu, ROS production after exposure to the herbicidally active (R)-enantiomer was higher than that of the (S)-enantiomer, suggesting a preference for an (R)-enantiomer-induced production of ROS. When DCPP and Cu were both added to algae simultaneously, (R)-DCPP preferentially induced production of ROS was observed. However, the enantioselective induced production of ROS was reversed when DCPP was mixed with Cu for 24 h prior to addition to the algae solution. It was also found that the generation of ROS, antioxidant response, and growth inhibition rate in Scenedesmus obliquus were all (R)-enantiomer preferentially induced. These findings implied that ROS play a primary role in chemical contaminant toxicity, and interactions between contaminants can tune the enantioselectivity of chiral herbicides, which should be considered in future risk assessment.

Enantioselective Oxidative Damage of Chiral Pesticide Dichlorprop to Maize

To investigate the enantioselective oxidative damage of the pesticide dichlorprop (DCPP) to maize, young seedlings were exposed to solutions of DCPP enantiomers and racemate at different concentrations. Early root development was more influenced by (R)-DCPP than racemic (rac)- and (S)-DCPP. Inhibition rates of seed germination, seedling biomass, and root and shoot elongation were all in the order of (R)-DCPP > (rac)-DCPP > (S)-DCPP treatments. The antioxidant enzyme activities of superoxide dismutase (SOD) and peroxidase (POD) were significantly upregulated by exposure to lower concentrations of (R)-DCPP than (rac)- and (S)-DCPP. Direct determination of the formation of hydroxyl radical (•OH) with electron paramagnetic resonance (EPR) spectroscopy indicated that the •OH level in maize roots followed the order of (R)-DCPP > (rac)-DCPP > (S)-DCPP treatments. All of these results provide solicited evidence of the significant enantioselective phytotoxicity of DCPP to maize with a higher toxicity of (R)-DCPP than (S)- and (rac)-DCPP.

Enantioselective ecotoxicity of the herbicide dichlorprop and complexes formed with chitosan in two fresh water green algae

To reduce the leaching potential, to prevent groundwater contamination and to maintain the efficacy of a pesticide, natural polysaccharides have received increasing attention due to their biocompatibility and useful biological reactivity for controlled release formulations (CRFs) of pesticides. In this paper, the toxicities of the chiral herbicide dichlorprop (DCPP) and its complexes with chitosan molecules (DCPP-CS) and chitosan nanoparticles (DCPP-NP) to two different green algae were determined and compared. The inhibition rates of DCPP, DCPP-CS and DCPP-NP were determined at 24, 48, 72, 96, 120, 144, 168 h, and the results show that (S)-DCPP was more toxic to Chlorella vulgaris than (R)-DCPP, while the (R)-DCPP was more toxic to Scenedesmus obliquus than (S)-DCPP. The study also found that the chiral selectivity of DCPP to Chlorella vulgaris and Scenedesmus obliquus could be changed when DCPP was complexed with chitosan molecules (CS) or chitosan nanoparticles (NP). For Chlorella vulgaris, the order of inhibition was (R)-DCPP-CS > (S)-DCPP-CS and (R)-DCPP-NP > (S)-DCPP-NP; for Scenedesmus obliquus, the order was (S)-DCPP-CS > (R)-DCPP-CS and (S)-DCPP-NP > (R)-DCPP-NP. This phenomenon suggests that the enantioselective behaviors of chiral compounds might shift when interactions with other chiral receptors coexist in different biological environments. Additionally, chitosan molecules and chitosan nanoparticles also showed different toxicities, which could be ascribed to the difference in the physicochemical properties between CS and NP or the differences in the cell walls of the two fresh water green algae.

CEC enantioseparations on chiral monolithic columns: A study of the stereoselective degradation of (R/S)‐dichlorprop [2‐(2,4‐dichlorophenoxy)propionic acid] in soil

For the study of the stereoselective degradation of the herbicide 2-aryloxipropionic acid dichlorprop (DCPP) in soil, a porous monolithic chiral column (100 microm id) was prepared by in situ copolymerization of glycidyl methacrylate, methyl methacrylate and ethylene glycol dimethacrylate in the presence of formamide and 1-propanol as the porogen solvents. Subsequently, the epoxide groups at the surface of the monolith were reacted with (+)-1-(4-aminobutyl)-(5R,8S,10R)-terguride as the chiral selector. Optimum conditions for the herbicide resolution by CEC were found using mobile phases consisting of acetic acid/triethylamine mixtures in ACN-methanol (9:1 v/v). Under these conditions fully separation of DCPP enantiomers in the presence of clofibric acid (internal standard) was achieved in about 5 min. Experiments on the incubation of rac-DCPP in soil at room temperature showed the herbicide undergone during 23 incubation days to a degradation to levels </=20% of the initial concentration, with rates for (R)-DCPP slower than (S)-DCPP. More interesting results were observed when herbicide enantiomers were individually incubated. In both the experiments, the formation of the opposite isomer in the presence of the initial one, and reversed enantiomeric interconversion in the case of (S)-DCPP was observed. (R)-DCPP was found to be the most persistent isomer after incubation.

Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC–MS

A solid-phase microextraction (SPME) method was developed for the analysis of acidic pesticide residues in water. The method utilizes in situ derivatization with butylchloroformate (BuCF), followed by on-line SPME extraction using a PDMS fibre, and analysis by GC–MS. Derivatives of the phenoxy acids mechlorprop (MCPP), dichlorprop (DCPP), MCPA and 2,4-D and their phenol degradation products 4-chloro-2-methylphenol and 2,4-dichlorophenol (DCP) were identified. Detection limits at 0.16–2.3 μg/l were achieved. Optimization of derivatization, ion strength, extraction time, SPME-fibre, desorption time and temperature are described. Standard curves in the range 0.5–10.0 μg/l were fitted to a second-degree polynomial. Standard deviation ( n=5) was below 10% for the phenol derivatives, but 20–50% for the phenoxy acids. For method verification groundwater samples from a field experiment were screened for content of MCPP and compared to the results from the HPLC analysis. A good agreement was obtained with respect to identification of positive samples, even though concentrations measured by the SPME were lower than with HPLC. Even if the precision and accuracy do not meet the demands for a strictly quantitative analysis, the SPME method is suitable for screening, because it is cheap, it can be automated, and uses smaller amounts of potential harmful solvents. Also, the method is less labour-intensive, as it requires a minimum of sample preparation when compared to traditional analyses. The acidic pesticides bentazon, dicamba, bromoxynil, ioxynil, dinoseb and DNOC were included in the study but could not be analysed by the current method.

Determination of Mecoprop and Dichlorprop in Aqueous Soil Solutions by HPLC with DAD

A reverse phase high performance liquid chromatographic method was developed for the direct determination of mecoprop (MCPP) and dichlorprop (DCPP) in the presence of soil and peat constituents. Spiked aqueous soil or soil/peat samples were directly injected after centrifugation and filtration. The analytical sensitivity, 0.35 and 0.24 ng L-1, detection limit, 1.02 and 0.70 ng L-1, and precision, 1.28 and 0.80%, for MCPP and DCPP respectively, are very appropriate. The concentration ranges studied 0.0–94.2 ng L-1 for MCPP and 0.0–103.1 ng L-1 for DCPP are suitable for adsorption/desorption and mobility studies of these herbicides in soil. The two tests used to demonstrate the purity or otherwise of every chromatographic peak give valuable information.