Retention and transport of mecoprop on acid sandy-loam soils.

Interaction with soil components is one of the key processes governing the fate of agrochemicals in the environment. In this work, we studied the adsorption / desorption and transport of mecoprop (methylchlorophenoxypropionic acid or MCPP) in four acid sandy-loam soils with different organic matter contents. Kinetics of adsorption and adsorption/desorption at equilibrium were studied in batch experiments, whereas transport was studied in laboratory columns. Adsorption and desorption were found to be linear or nearly-linear. The kinetics of mecoprop adsorption were relatively fast in all cases (less than 24h). Adsorption and desorption were adequately described by the linear and Freundlich models, with KF values that ranged from 0.7 to 8.8Ln µmol1-nkg-1 and KD values from 0.3 to 3.6Lkg-1. The results of the transport experiments showed that the retention of mecoprop by soil was very low (less than 6.2%). The retention of mecoprop by the soils in all experiments increased with organic matter content. Overall, it was observed that mecoprop was weakly adsorbed by the soils, what would result in a high risk of leaching of this compound in the environment.

Urea Fertilizer and pH Influence on Sorption Process of Flumetsulam and MCPA Acidic Herbicides in a Volcanic Soil.

The aim of this study was to evaluate the influence of urea fertilizer and pH on the sorption process of two acidic herbicides, flumetsulam (2',6'-difluoro-5-methyl[1,2,4]triazolo[1,5-a]pyrimidine-2-sulfonanilide) and MCPA (4-chloro--tolyloxyacetic acid), on an Andisol. Urea reduced the adsorption of MCPA but not that of flumetsulam. The Freundlich parameter of MCPA decreased from 8.5 to 5.1 mg L kg. This finding could be attributed to an increase in dissolved organic C due to an initial increase in soil pH for urea application. The higher acidic character of MCPA compared with that of flumetsulam produced a greater hydrolysis of urea, leading to a further pH increase. A marked effect of pH on the adsorption of both herbicides was observed. The organic C distribution coefficient () values for flumetsulam were in the range of 74 to 10 L kg, while those of MCPA were in the range of 208 to 45 L kg. In the kinetic studies, the pseudo-second-order model appeared to fit the data best ( > 0.994). The initial adsorption rates () ranged from 20.00 to 4.59 mg kg h for flumetsulam and from 125.00 to 25.60 mg kg hfor MCPA. Both herbicides were adsorbed rapidly during the first stage of the sorption process, and the rates of sorption were dependent on pH. The application of the Elovich and Weber-Morris models led us to conclude that mass transfer through the boundary layer and, to a lesser degree, intraparticle diffusion were influenced by the chemical character of the herbicide. These results suggest that urea application could increase leaching of acid herbicides in soils.

Contamination of rice field water with sulfonylurea and phenoxy herbicides in the Muda Irrigation Scheme, Kedah, Malaysia.

The purpose of the present study was to investigate the potential risk of herbicide contamination (2,4-dichlorophenoxy (2,4-D), 2-methyl-4-chlorophenoxyacetic acid (MCPA), metsulfuron, bensulfuron, and pyrazosulfuron) in the rice fields of the Muda Irrigation Scheme, Kedah, Malaysia. The study included two areas with different irrigation water sources namely non-recycled (N-RCL) and recycled (RCL) water. Periodic water sampling was carried out from the drainage canals during the planting period of the wet season 2006/2007 and dry season 2007. The HPLC-UV was used to detect herbicide residues in the water samples collected from the rice fields. The results showed that the concentration of sulfonylurea herbicides such as bensulfuron and metsulfuron in the rice field was 0.55 and 0.51 µg/L, respectively. The potential risk of contamination depended on the actual dosage of each herbicide applied by farmers to their rice fields. The potential risk of water pollution by the five herbicides studied in the area with RCL water tended to be more widespread compared to the area with N-RCL water due to surface water runoff with higher levels of weedicides to the surrounding areas. During the two seasons, 50-73% of the water samples collected from the area receiving RCL water contained the five herbicides studied at concentrations of more than 0.05 µg/L, and this percentage was higher than that from the areas receiving N-RCL water (45-69%). During the wet season, the overall total mean concentration of the eight herbicides found in the samples collected from the area with RCL water (6.27 µg/L) was significantly higher (P < 0.01) than that from the area receiving N-RCL water (2.39 µg/L). Meanwhile, during the dry season, there was no significant difference (P > 0.05) in the herbicide concentrations between the areas receiving RCL (6.16 µg/L) and N-RCL water (7.43 µg/L) water.

Chiral and isotope analyses for assessing the degradation of organic contaminants in the environment: Rayleigh dependence.

The Rayleigh equation is frequently used to describe isotope fractionation as a function of conversion. In this article we propose to draw a parallel between isotope and enantiomeric enrichments and derive a set of conditions that allow the use of the Rayleigh approach to describe the enantiomeric enrichment-conversion dependencies. We demonstrate an implementation of the Rayleigh equation for the enantioselective enzymatic hydrolysis of Mecoprop-methyl, Dichlorprop-methyl, and dimethyl-methylsuccinate by lipases from Pseudomonas fluorescens, Pseudomonas cepacia, and Candida rugosa. The data obtained for all the studied reactions gave good fits to the Rayleigh equation, with a linear regression R(2) > 0.96. In addition to that, our analysis of four microcosm studies on the hydrolysis of the individual enantiomers of Dichloroprop methyl, Lactofen, Fenoxaprop-ethyl, and Metalaxyl reported in the literature by other research groups revealed a suitability of the Rayleigh dependence. Two dimensional plots describing the isotope fractionation versus enantiomeric enrichment are demonstrated for all studied cases. Processes not accompanied by enantiomeric enrichment (acid and base hydrolysis) and by isotope enrichment (transesterification) are demonstrated, their 2-D plots are either horizontal or vertical which can illuminate concealed degradation pathways.

The effects of woodchip- and straw-derived biochars on the persistence of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) in soils.

Sorption and degradation are the primary processes controlling the efficacy and runoff contamination risk of agrochemicals. This study assessed the influence of two biochars, made from woodchips and straw at a pyrolysis temperature of 725°C and applied to a loamy sand and a sandy soil in the concentration of 5.3 g 100 g(-1) sandy soil and 4.1 g 100 g(-1) loamy sand soil, or 53 t ha(-1) for both soil types, on degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA). Soils were spiked with 50 mg MCPA kg(-1) soil. In the sandy soil, significantly more MCPA remained after 100 days if amended with straw-derived biochar in comparison to wood-derived biochar. Both biochars types significantly increased urease activity (p<0.05) after 37 days in the loamy sand soil, but these differences disappeared after 100 days. A root and shoot elongation test demonstrated that the soils containing straw-derived biochar and spiked with MCPA, showed the highest phytotoxicity. Both biochars were found to retard MCPA degradation in loamy sand and sandy soils. This effect could not be explained only by sorption processes due to comparatively low developed micro/mesoporous structure of both biochars shown by BET surface analysis. However, an enhanced MCPA persistence and soil toxicity in sandy soil amended with straw biochar was observed and further studies are needed to reveal the responsible mechanisms.

Coupling of solvent-based de-emulsification dispersive liquid-liquid microextraction with high performance liquid chromatography for simultaneous simple and rapid trace monitoring of 2,4-dichlorophenoxyacetic acid and 2-methyl-4-chlorophenoxyacetic acid.

A simple, rapid, and efficient sample pretreatment technique, based on solvent-based de-emulsification dispersive liquid-liquid microextraction (SD-DLLME), followed by high performance liquid chromatography (HPLC) has been developed for simultaneous preconcentration and trace detection of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in water and urine samples. Some parameters such as acidity of solution, the amount of salt, type, and volume of extraction solvents, type of disperser/de-emulsifier solvent, and its volume were investigated and optimized. Under optimum extraction conditions, the limits of detections (LODs) of this method for MCPA and 2,4-D were 0.2 and 0.6 µg L(-1) (based on 3S(b)/m) in water and 0.4 and 1.6 µg L(-1) in urine, respectively. Furthermore, dynamic linear range of this method for MCPA and 2,4-D was 1-300 and 2-400 µg L(-1), repectively. Finally, the applicability of the proposed method was evaluated by extraction and determination of the herbicides in urine and different water samples.

Possible source term of high concentrations of mecoprop-p in leachate and water quality: impact of climate change, public use and disposal.

Mecoprop-p herbicide is often found in wells and water abstractions in many areas around Europe, the UK inclusive. There is a growing environmental and public health concern about mecoprop-p herbicide pollution in ground and surface water in England. Reviews suggest that extensive work has been carried out on the contribution of mecoprop-p herbicides from agricultural use whilst more work needs to be carried out on the contribution of mecoprop-p herbicide from non-agricultural use. The study covers two landfill sites in Weaver/Gowy Catchment. Mecoprop-p herbicide concentrations in the leachate quality range between 0.06 and 290 microg l1 in cells. High concentration ofmecoprop-p herbicide in the leachate quality suggests that there is a possible source term in the waste stream. This paper addresses the gap by exploring possible source terms of mecoprop-p herbicide contamination on landfill sites and evaluates the impact of public purchase, use and disposal alongside climate change on seasonal variations in mecoprop-p concentrations. Mecoprop-p herbicide was found to exceed the EU drinking water quality standards at the unsaturated zone/aquifer with observed average concentrations ranging between 0.005 and 7.96 microg l1. A route map for mecoprop-p herbicide source term contamination is essential for mitigation and pollution management with emphasis on both consumer and producer responsibility towards use of mecoprop-p product. In addition, improvement in data collection on mecoprop-p concentrations and detailed seasonal herbicide sales for non-agricultural purposes are needed to inform the analysis and decision process.

Enantioselective stable isotope analysis (ESIA) of polar herbicides.

Assessing the environmental fate of chiral micropollutants such as herbicides is challenging. The complexity of aquatic systems often makes it difficult to obtain hydraulic mass balances, which is a prerequisite when assessing degradation based on concentration data. Elegant alternatives are concentration-independent approaches like compound-specific isotope analysis or enantiospecific concentration analysis. Both detect degradation-induced changes from ratios of molecular species, either isotopologues or enantiomers. A combination of both-enantioselective stable isotope analysis (ESIA)-provides information on (13)C/(12)C ratios for each enantiomer separately. Recently, Badea et al. demonstrated for the first time ESIA for the insecticide α-hexachlorocyclohexane. The present study enlarges the applicability of ESIA to polar herbicides such as phenoxy acids: 4-CPP ((RS)-2-(4-chlorophenoxy)-propionic acid), mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid), and dichlorprop (2-(2,4-dichlorophenoxy)-propionic acid). Enantioselective gas chromatography-isotope ratio mass spectrometry was accomplished with derivatization prior to analysis. Precise carbon isotope analysis (2σ ≤ 0.5‰) was obtained with ≥7 ng C on column. Microbial degradation of dichlorprop, 2-(2,4-dichlorophenoxy)-propionic acid by Delftia acidovorans MC1 showed pronounced enantiomer fractionation, but no isotope fractionation. In contrast, Badea et al. observed isotope fractionation, but no enantiomeric fractionation. Hence, the two lines of evidence appear to complement each other. They may provide enhanced insight when combined as ESIA.

Ultrasound-assisted emulsification microextraction combined with injection-port derivatization for the determination of some chlorophenoxyacetic acids in water samples.

An efficient method based on ultrasound-assisted emulsification microextraction followed by injection-port derivatization GC analysis was developed to determine 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-methylphenoxyacetic acid (MCPA) in natural water samples. In this procedure, 12.5 µL of 1-undecanol was injected slowly into a 12 mL home-designed centrifuge glass vial containing an aqueous sample of the analytes located inside an ultrasonic water bath. The resulting emulsion was centrifuged, and 1 µL of the separated organic solvent together with 1 µL of the derivatization reagent were injected into a GC equipped with a flame ionization detector. Several factors that influence the derivatization and extraction were optimized. Under the optimal conditions, the LODs were 0.33 and 1.7 µg/L for MCPA and 2,4-D, respectively. Preconcentration factors of 670 and 836 were obtained for MCPA and 2,4-D, respectively. The precision of the proposed method was evaluated in terms of repeatability, which was <5.7% (n = 5). The applicability of the proposed method was evaluated by extraction and determination of chlorophenoxyacetic acids from some natural waters, which indicated that the matrices of natural waters have no significant effect on the extraction and derivatization efficiency of this method.

Impact of wheat straw biochar addition to soil on the sorption, leaching, dissipation of the herbicide (4-chloro-2-methylphenoxy)acetic acid and the growth of sunflower (Helianthus annuus L.).

Biochar addition to agricultural soils might increase the sorption of herbicides, and therefore, affect other sorption-related processes such as leaching, dissipation and toxicity for plants. In this study, the impact of wheat straw biochar on the sorption, leaching and dissipation in a soil, and toxicity for sunflower of (4-chloro-2-methylphenoxy)acetic acid (MCPA), a commonly used ionizable herbicide, was investigated. The results showed that MCPA sorption by biochar and biochar-amended soil (1.0wt% biochar) was 82 and 2.53 times higher than that by the non-amended soil, respectively. However, desorption of MCPA from biochar-amended soil was only 1.17 times lower than its desorption in non-amended soil. Biochar addition to soil reduced both MCPA leaching and dissipation. About 35% of the applied MCPA was transported through biochar-amended soil, while up to 56% was recovered in the leachates transported through non-amended soil. The half-life value of MCPA increased from 5.2d in non-amended soil to 21.5 d in biochar-amended soil. Pot experiments with sunflower (Helianthus annuus L.) grown in MCPA-free, but biochar-amended soil showed no positive effect of biochar on the growth of sunflower in comparison to the non-amended soil. However, biochar itself significantly reduced the content of photosynthetic pigments (chlorophyll a, b) in sunflower. There was no significant difference in the phytotoxic effects of MCPA on sunflowers between the biochar-amended soil and the non-amended soil. Furthermore, MCPA had no effect on the photosynthetic pigment contents in sunflower.

Use of a new hybrid sol-gel zirconia matrix in the removal of the herbicide MCPA: a sorption/degradation process.

A class II hybrid sol-gel material was prepared starting from zirconium(IV) propoxide and 2,4-pentanedione and its catalytic activity in the removal of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) was revealed. The thermal and structural characterization, performed by thermogravimetry, differential thermal analysis, and diffuse reflectance Fourier transform infrared spectroscopy, demonstrated the hybrid nature of the material. The structure of the material can be described as a polymeric network of zirconium oxo clusters, on the surface of which large part of Zr(4+) ions are involved in strong complexation equilibria with acetylacetonate (acac) ligands. The incubation of MCPA in the presence of this material yielded an herbicide removal fraction up to 98%. A two-step mechanism was proposed for the MCPA removal, in which a reversible first-order adsorption of the herbicide is followed by its catalytic degradation. The nature of the products of the MCPA catalytic degradation as well as the reaction conditions adopted do not support typical oxidation pathways involving radicals, suggesting the existence of a different mechanism in which the Zr(4+):acac enol-type complex can act as Lewis acid catalyst.

FI on-line chemiluminescence reaction for determination of MCPA in water samples.

This paper reports an economic, simple, and rapid FI-CL method for the determination of MCPA. This method requires simple instrumentation and it is fast enough to be used in routine analyses. A chemiluminescence signal is generated by reaction between photodegraded MCPA and ferricyanide solution in alkaline medium. All physical and chemical parameters in the flow injection chemiluminescence system were optimized in the experimental setting. To eliminate interference, a solid-phase extraction stage with SDB-1 cartridges and ethanol elution is applied. The signal-MCPA concentration relation is linear in concentration intervals between 0.0015 and 0.6 µg·mL(-1). The calibration lines are statistically similar in different working conditions: standards with ethanol without extraction and standards with ethanol and extraction, allowing standards to be excluded from the extraction step, which simplifies the process. The detection limit (DL) is 0.5 ng·mL(-1), which is the same order as the maximum limit established in legislation regarding pesticide limits in water destined for human consumption. A DL of 0.13 ng·mL(-1) can be reached if a sample of 100 mL is preconcentrated. The interday variance coefficient is 3% and the sample throughput is 90 h(-1). The water analysis method is efficient with relative error percentages lower than 5% with respect to the added concentration.

Reverse micelle-mediated dispersive liquid-liquid microextraction of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-methylphenoxyacetic acid.

A supramolecular solvent consisting of reverse micelles of decanoic acid, dispersed in a continuous phase of tetrahydrofuran:water, was proposed as an efficient microextraction technique for extraction of selected chlorophenoxy acid herbicides from water samples prior to high-performance liquid chromatography UV determination. The disperser solvent (1.0 mL tetrahydrofuran) containing 20 mg decanoic acid was rapidly injected into 10.0 mL of water sample. After centrifugation, the reverse micelle-rich phase (25 ± 0.5 µL) was floated at top of the home-designed centrifuge tube. The solvent was collected and 20 µL of it was injected into high-performance liquid chromatography for analysis. The results showed that the in situ solvent formation and extraction process can be completed in a few seconds. Under the optimal conditions, limits of detection of the method for 4-chloro-2-methylphenoxyacetic acid and 2,4-dichlorophenoxyacetic acid were in the range of 0.5-0.8 µg L(-1) and the repeatability of the proposed method, expressed as relative standard deviation, varied in the range of 2.5-3.2%. Linearity was found to be in the range of 1-200 µg L(-1) and the preconcentration factors were between 148 and 157. The mean percentage recoveries exceeded 92.0% for all the spiking levels in real water samples.

Dissipation and residue of MCPA (4-chloro-2-ethylphenoxyacetate) in wheat and soil.

A rapid and simple HPLC method has been developed for the quantitation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in both wheat and soil samples. Samples were extracted in acidic media and cleaned up by solid-phase extraction with C(18) cartridges before HPLC-DAD detection. The limits of detection and quantification of MCPA were 0.02 ng and 0.01 mg/kg for both wheat and soil. The mean recoveries ranged from 87.1% to 98.2%, and the RSDs ranged from 0.604% to 3.44% for the three spiked levels (0.01, 0.1, 0.5 mg/kg). The proposed method was successfully applied to the analysis of MCPA residues in wheat and soil samples from an experimental field. The dissipation half-lives in soil were calculated to be 3.22 days (Beijing) and 3.10 days (Tianjin), respectively. Direct confirmation of the analytes in real samples was achieved by gas chromatography-mass spectrometry. The results indicated that at harvest time, the residues of MCPA in wheat were well below the maximum residue levels and were safe to apply in wheat.

Adsorption and desorption processes of MCPA in Polish mineral soils.

Studies on the adsorption and desorption of MCPA (4-chloro-2-methylophenoxyacetic acid) were performed in soil horizons of three representative Polish agricultural soils. The Hyperdystric Arenosol, the Haplic Luvisol and the Hypereutric Cambisol were investigated in laboratory batch experiments. Initially, both the adsorption and desorption proceeded rapidly, and either the equilibrium was reached after approximately 30 min or the process slowed down and continued at a slow rate. In the latter case, the equilibrium was reached after 8 hours. Data on the adsorption/desorption kinetics fitted well to the two-site kinetic model. The measured sorption and desorption isotherms were of L-type. The sorption distribution coefficients (K(ads) (d)) were in the range of 0.75--0.97 for Ap soil horizons and significantly lower in deeper soil layers. The corresponding desorption coefficients (K(des) (d)) were higher and ranged from 1.02 to 2.01. Both the adsorption and desorption of MCPA in all soil horizons was strongly and negatively related to soil pH. It appears that hydrophobic sorption plays a dominant role in the MCPA retention in topsoils whereas hydrophilic sorption of MCPA anions is the dominant adsorption mechanism in subsoils.

Remediation of waters contaminated with MCPA by the yeasts Lipomyces starkeyi entrapped in a sol-gel zirconia matrix.

A single-stage sol-gel route was set to entrap yeast cells of Lipomyces starkeyi in a zirconia (ZrO(2)) matrix, and the remediation ability of the resulting catalyst toward a phenoxy acid herbicide, 4-chloro-2-methylphenoxyacetic acid (MCPA), was studied. It was found that the experimental procedure allowed a high dispersion of the microorganisms into the zirconia gel matrix; the ZrO(2) matrix exhibited a significant sorption capacity of the herbicide, and the entrapped cells showed a degradative activity toward MCPA. The combination of these effects leads to a nearly total removal efficiency (>97%) of the herbicide at 30 °C within 1 h incubation time from a solution containing a very high concentration of MCPA (200 mg L(-1)). On the basis of the experimental evidence, a removal mechanism was proposed involving in the first step the sorption of the herbicide molecules on the ZrO(2) matrix, followed by the microbial degradation operated by the entrapped yeasts, the metabolic activity of which appear enhanced under the microenvironmental conditions established within the zirconia matrix. Repeated batch tests of sorption/degradation of entrapped Lipomyces showed that the removal efficiency retained almost the same value of 97.3% after 3 batch tests, with only a subsequent slight decrease, probably due to the progressive saturation of the zirconia matrix.

Determination of 4-chloro-2-methylphenoxyacetic acid residues in wheat and soil by ultra-performance liquid chromatography/tandem mass spectrometry.

A rapid, highly sensitive, and selective method was developed for the identification and quantitation of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) in wheat plants, wheat grain, and soil by ultra-performance LC/MS/MS. MCPA was extracted from the sample (5 or 10 g) with acetonitrile, and an aliquot was taken for cleanup with primary secondary amine. Two precursor product ion transitions for MCPA were measured and evaluated to provide maximum confidence in the results. Average recoveries from wheat plants, wheat grain, and soil fortified at levels of 0.01-1.0 mg/kg ranged from 75.1 to 93.9%, with RSD(r) values of 3.0-9.3% and RSDR values of 3.1-8.7%. Coefficients of determination of R2 > or = 0.9994 were obtained for wheat and soil matrix calibration curves at MCPA levels of 0.01-5.0 microg/mL. Under conditions of electrospray ionization in the negative-ion mode, the ion at m/z 141 was monitored for quantitation; the parent ion at m/z 199 was also measured. The LOD values for MCPA in wheat plants, wheat grain, and soil were determined to be 0.005, 0.004, and 0.004 mg/kg, respectively, and corresponding LOQ values were 0.02, 0.01, and 0.01 mg/kg. This method can be used to determinate MCPA residues in wheat products and soils.

Study on the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chloro-phenoxyacetic sodium (MCPA sodium) in natural agriculture-soils of Fuzhou, China using capillary electrophoresis.

A new method of analyzing trace 2,4-Dichlorophenoxyacetic acid (2,4-D) and 2-methy-4-chloro-lphenoxyacetic sodium (MCPA sodium) in soils by capillary electrophoresis (CE) has been developed in this study. The optimum analytical conditions including chemical component and concentration of buffer solution, pH, separation voltage and sample injection time were studied in detail. Under the optimum conditions, 2,4-D and MCPA sodium in soils can be speedy separated and determined within 20 min with detection limits of 0.15 microg/g (2,4-D) and 0.25 microg/g (MCPA sodium) , a RSD (n=6)<5% and a recovery>89%. With the help of analytical method developed in this study, the degradations of 2,4-D and MCPA sodium in natural agriculture-soils of Fuzhou were studied. The experimental results indicated that the degradations of 2,4-D and MCPA sodium follow first-order kinetics with degradation constants of 0.1509 day(-1) (2,4-D) and 0.2722 day(-1) (MCPA sodium) respectively. The degradation half-life were calculated to be 4.6 days (2,4-D) and 2.6 days (MCPA sodium) at 27 degrees C, implied that 2,4-D and MCPA sodium can be speedy degraded in natural agriculture-soils of Fuzhou, China.

Determination of the phenoxyacid herbicides MCPA, mecoprop and 2,4-D in kidney tissue using liquid chromatography with electrospray tandem mass spectrometry.

An analytical method was developed to determine the phenoxyacid herbicides 2,4-D, MCPA and mecoprop in kidney tissue from animals where poisoning is suspected. Samples were Soxhlet extracted using diethyl ether and the extracts cleaned-up using anion exchange solid phase extraction cartridges. Analysis was performed using liquid chromatography with negative-ion electrospray tandem mass spectrometry (LC-MS/MS). The method was evaluated by analysing control kidney samples fortified at 1 and 5 mg/kg. Mean recoveries ranged from 82 to 93% with relative standard deviations from 3.2 to 19%. The limit of detection was estimated to be 0.02 mg/kg.

Dissipation of mecoprop-P, isoproturon, bentazon and S-metolachlor in heavy metal contaminated acidic and calcareous soil before and after EDTA-based remediation.

The ability of contaminated farmland soils reclaimed by remediation to dissipate pesticides and thus to mitigate their unwanted environmental effects, i.e., leaching and run-off, was studied. Novel EDTA-based soil washing technology (EDTA and process waters recycling; no toxic emissions) removed 79 and 73% of Pb from acidic and calcareous soil with 740 and 2179 mg kg-1 Pb, respectively. The dissipation kinetics of four herbicides: mecoprop-P, isoproturon, bentazon and S-metolachlor was investigated under field conditions in beds with maize (Zea mays) and barley (Hordeum vulgare). The biphasic First-Order Multi-Compartment (FOMC) model was used to fit experimental data and calculate the herbicides' half-life (DT50) in soil. Remediation significantly (up to 64%) decreased dehydrogenase activity assessed as a marker of soil microbial activity and prolonged the DT50 of herbicides in acidic soils from 16% (isoproturon) to 111% (S-metachlor). Remediation had a less significant effect on herbicide dissipation in calcareous soils; i.e., mecoprop-P DT50 increased by 3%, while isoproturon and S-metachlor DT50 decreased by 29%. Overall, the dissipation from remediated soils was faster than the average DT50 of tested herbicides published in the Pesticides Properties DataBase. Results demonstrate that EDTA-based remediation of the studied soils does not pose any threat of extended herbicide persistence.