Batch adsorption of herbicides from aqueous solution onto diverse reusable materials and granulated activated carbon.

This study reports the kinetics and isotherms of the adsorption of five herbicides, MCPA, mecoprop-P, 2,4-D, fluroxypyr and triclopyr, from aqueous solutions onto a range of raw and pyrolysed waste materials originating from an industrial setting. The raw waste materials investigated demonstrated little capability for any herbicide adsorption. Granulated activated carbon (GAC) was capable of the best removal of the herbicides, with >95% removal observed. A first order kinetic model fitted the data best for GAC adsorption of 2,4-D, while a pseudo-first order model fitted the data best for GAC adsorption of fluroxypyr and triclopyr, indicating that adsorption was via physisorption. A pseudo-second order kinetic model fitted the GAC adsorption of MCPA and mecoprop-P, which is indicative of chemisorption. The adsorption of the herbicides in all cases was best described by the Freundlich model, indicating that adsorption occurred onto heterogeneous surfaces.

Mechanisms of the enantioselective effects of phenoxyalkanoic acid herbicides DCPP and MCPP.

Phenoxyalkanoic acids (PAAs), synthetic indole-3-acetic acid (IAA) auxin mimics, are widely used as herbicides. Many PAAs are chiral molecules and show strong enantioselectivity in their herbicidal activity; however, there is a lack of understanding of mechanisms driving enantioselectivity. This study aimed to obtain a mechanistic understanding of PAA enantioselectivity using dichlorprop and mecoprop as model PAA compounds. Molecular docking, in vitro 3H-IAA binding assay, and surface plasmon resonance analysis showed that the R enantiomer was preferentially combined with TIR1-IAA7 (Transport Inhibitor Response1- Auxin-Responsive Protein IAA7) than the S enantiomer. In vivo tracking using 14C-PAAs showed a greater absorption of the R enantiomer by Arabidopsis thaliana, and further comparatively enhanced translocation of the R enantiomer to the nucleus where the auxin co-receptor is located. These observations imply that TIR1-IAA7 is a prior target for DCPP and MCPP, and that PAA enantioselectivity occurs because the R enantiomer has a stronger binding affinity for TIR1-IAA7 as well as a greater plant absorption and translocation capability than the S enantiomer. The improved understanding of PAA enantioselectivity is of great significance, as the knowledge may be used to design "green" molecules, such as R enantiomer enriched products, leading to improved plant management and environmental sustainability.

The auxin herbicide mecoprop-P in new light: Filling the data gap for dicotyledonous macrophytes.

Mecoprop-P (MCPP-P) is an auxin herbicide which has been used against dicotyledonous weed plants since the 1980s. While fate and monitoring data of MCPP-P in the aquatic environment revealing concentrations up to 103 µg/L in freshwaters are well documented, only very few toxicity data and no studies with dicotyledonous macrophytes have been published in open literature so far. To fill up this essential data gap, a microcosm study was conducted in order to test the sensitivity of nine dicotyledonous and one Ceratophyllales macrophyte species. The plant species were exposed to seven MCPP-P concentrations ranging from 8 to 512 µg/L for 21/22 days in one microcosm per concentration, and two further microcosms served as controls. Plant preparation was adapted to each species and endpoints were measured to calculate growth rates. Data were generated to obtain effect concentrations (ECX) which then were used to construct species sensitivity distribution curves (SSD). Eight species proved to be sensitive to MCPP-P in the tested concentration range with EC50 values ranging from 46.9 µg/L for Ranunculus aquatilis to 656.4 µg/L MCPP-P for Ludwigia repens. Taking the EC50 values of this study and published data for autotrophic organisms into account, a hazard concentration (HC5) of 2.7 µg/L was derived from the SSD curve, while an SSD curve without dicotyledonous macrophytes resulted in an about 100 times higher HC5 (360.8 µg/L MCCP-P). This confirms that a re-evaluation for old auxin herbicides by including dicotyledonous test species into the environmental risk assessment may be indicated. Furthermore, the use of MCPP-P in bitumen felts as protection against rooting by plants is not in the focus of any risk regulation so far. This application, however, can lead to high run-off concentrations that can enter surface waters easily, exceeding the new regulatory acceptable concentration values.

Novel esterquat-based herbicidal ionic liquids incorporating MCPA and MCPP for simultaneous stimulation of maize growth and fighting cornflower.

Modern agricultural practices are often based on the use of mixtures of specific herbicides to achieve efficient crop protection. The major drawbacks of commercial herbicidal formulations include the necessity to incorporate toxic surfactants and high volatility of active substances. Transformation of herbicides into herbicidal ionic liquids (HILs) seems to be a promising alternative which allows to almost completely reduce volatility due to ionic interactions. In the scope of this research, we transformed (2-methyl-4-chlorophenoxy)acetic acid (MCPA) into a quaternary ester (esterquat) with the use of derivatives of 2-dimethylaminoethanol. The obtained esterquats were later coupled with (±)-2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) in the form of an anion. The combination of MCPA and MCPA is commonly applied in the UK, EU countries and also in the USA to increase the spectrum of targeted weed species. In the framework of this study, novel HILs with an esterquat moiety incorporating a long alkyl chain (C8, C9, C10, C11, C12, C14) were prepared and characterized in terms of basic physicochemical properties (solubility and volatility) as well as biodegradability. Their phytotoxicity was assessed towards cornflower (Centaurea cyanus) as a model weed and maize (Zea mays) as a crop plant. The presence of the esterquat cation contributed to satisfactory solubility in water and other low polar solvents, which eliminates the need to add exogenous adjuvants. Further experiments indicated that the tested HILs stimulated the germination stage of maize and maintained high herbicidal activity towards cornflower. No significant differences in terms of properties were observed in case of HILs which included alkyl substituents with an odd number of carbon atoms. Future studies should be focused on structural modifications in order to improve the biodegradability as well as field studies for evaluation of commercial applications.

Occurrence and transformation of phenoxy acids in aquatic environment and photochemical methods of their removal: a review.

The article presents the behavior of phenoxy acids in water, the levels in aquatic ecosystems, and their transformations in the water environment. Phenoxy acids are highly soluble in water and weakly absorbed in soil. These highly mobile compounds are readily transported to surface and groundwater. Monitoring studies conducted in Europe and in other parts of the world indicate that the predominant phenoxy acids in the aquatic environment are mecoprop, 4-chloro-2-methylphenoxyacetic acid (MCPA), dichlorprop, 2,4-dichlorophenoxyacetic acid (2,4-D), and their metabolites which are chlorophenol derivatives. In water, the concentrations of phenoxy acids are effectively lowered by hydrolysis, biodegradation, and photodegradation, and a key role is played by microbial decomposition. This process is determined by the qualitative and quantitative composition of microorganisms, oxygen levels in water, and the properties and concentrations of phenoxy acids. In shallow and highly insolated waters, phenoxy acids can be decomposed mainly by photodegradation whose efficiency is determined by the form of the degraded compound. Numerous studies are underway on the use of advanced oxidation processes (AOPs) to remove phenoxy acids. The efficiency of phenoxy acid degradation using AOPs varies depending on the choice of oxidizing system and the conditions optimizing the oxidation process. Most often, methods combining UV radiation with other reagents are used to oxidize phenoxy acids. It has been found that this solution is more effective compared with the oxidation process carried out using only UV.

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.

Preparation and Characterization of Herbicide Mecoprop Imprinted Polymer and Its Application as a Selective Sorbent in Water Sample.

Bulk polymerization method was used to prepare a homogeneous molecularly imprinted polymer (MIP) for the specific extraction of herbicide mecoprop (MCPP). Thereafter, the binding performance of this functional polymer was evaluated under optimal condition, compared to a non-imprinted polymer. From the Scatchard plot analysis, two types of binding sites were detected in the MIP, the high affinity binding sites with a KD (equilibrium dissociation constant) of 6.4 µM and the low affinity ones with a KD of 55.9 µM. In addition, the possibility of using synthesized MIP for MCPP extraction from environmental aqueous samples was explored. The adsorption capacity of MIP in spiked bottled water and groundwater samples showed that the polymer could effectively extract MCPP from bottled water and groundwater (p < 0.05) with the recovery of 70.5% and 65.1%, respectively, demonstrating the potential of imprinted polymers for cost-effective and effective water treatment.

Transformation, CO2 formation and uptake of four organic micropollutants by carrier-attached microorganisms.

A tiered process was developed to assess the transformation, CO2 formation and uptake of four organic micropollutants by carrier-attached microorganisms from two municipal wastewater treatment plants. At the first tier, primary transformation of ibuprofen, naproxen, diclofenac, and mecoprop by carrier-attached microorganisms was shown by the dissipation of the target compounds and the formation of five transformation products using LC-tandem MS. At the second tier, the microbial cleavage of the four organic micropollutants was confirmed with 14C-labeled micropollutants through liquid scintillation counting of the 14CO2 formed. At the third tier, microautoradiography coupled with fluorescence in situ hybridization (MAR-FISH) was used to screen carrier-attached microorganisms for uptake of the four radiolabeled micropollutants. Results from the MAR-FISH screening indicated that only a small fraction of the microbial community (≤1‰) was involved in the uptake of the radiolabeled micropollutants and that the responsible microorganisms differed between the compounds. At the fourth tier, the microbial community structure of the carrier-attached biofilms was analyzed by 16S rRNA gene amplicon sequencing. The sequencing results showed that the MAR-FISH screening targeted ∼80% of the microbial community and that several taxonomic families within the FISH-probed populations with MAR-positive signals (i.e. Firmicutes, Gammaproteobacteria, and Deltaproteobacteria) were present in both biofilms. From the broader perspective of organic micropollutant removal in biological wastewater treatment, the MAR-FISH results of this study indicate a high degree of microbial substrate specialization that could explain differences in transformation rates and patterns between micropollutants and microbial communities.

Effects on metabolic parameters in young rats born with low birth weight after exposure to a mixture of pesticides.

Pesticide exposure during fetal life can lead to low birth weight and is commonly observed in reproductive toxicology studies. Associations have also been found in low birth weight babies born from pesticide-exposed gardeners. Since low birth weight is also linked to metabolic disorders, it can be speculated that early life exposure to pesticides could increase the risk of becoming obese or developing diabetes later in life. We have analyzed potential long-term effects of gestational and lactational exposure to a low dose mixture of six pesticides that individually can cause low birth weight: Cyromazine, MCPB, Pirimicarb, Quinoclamine, Thiram, and Ziram. Exposed male offspring, who were smaller than controls, displayed some degree of catch-up growth. Insulin and glucagon regulation was not significantly affected, and analyses of liver and pancreas did not reveal obvious histopathological effects. Efforts towards identifying potential biomarkers of metabolic disease-risk did not result in any strong candidates, albeit leptin levels were altered in exposed animals. In fat tissues, the key genes Lep, Nmb and Nmbr were altered in high dosed offspring, and were differentially expressed between sexes. Our results suggest that early-life exposure to pesticides may contribute to the development of metabolic disorders later in life.

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.

Degradation of mecoprop in polluted landfill leachate and waste water in a moving bed biofilm reactor.

Mecoprop is a common pollutant in effluent-, storm- and groundwater as well as in leachates from derelict dumpsites. Thus, bioremediation approaches may be considered. We conducted batch experiments with moving bed biofilm (MBBR)-carriers to understand the degradation of mecoprop. As a model, the carriers were incubated in effluent from a conventional wastewater treatment plant which was spiked to 10, 50 and 100 µg L-1 mecoprop. Co-metabolic processes as well as mineralization were studied. Initial mecoprop concentration and mecoprop degradation impacted the microbial communities. The removal of (S)-mecoprop prevailed over the (R)-mecoprop. This was associated with microbial compositions, in which several operational taxonomic units (OTUs) co-varied positively with (S)-mecoprop removal. The removal-rate constant of (S)-mecoprop was 0.5 d-1 in the 10 µg L-1 set-up but it decreased in the 50 and 100 µg L-1 set-ups. The addition of methanol prolonged the removal of (R)-mecoprop. During mecoprop degradation, 4-chloro-2-methylphenol was formed and degraded. A new metabolite (4-chloro-2-methylphenol sulfate) was identified and quantified.

Methods comparison, transport and distribution of polar herbicides in the Baltic Sea.

Two LC-MS/MS methods including different sample preparation and quantitative processes showed a good agreement for analysis of the herbicides MCPA, mecoprop, isoproturon, bentazon and chloridazon, and the metabolite chloridazon-methyl-desphenyl (CMD) in estuarine waters. Due to different sensitivity of the methods only one could be used to analyze marine samples. The transport of these compounds to the Baltic Sea via ten German estuaries and their distribution between coastal water and sediments was studied. The results showed that all selected compounds can be transported to the Baltic Sea (0.9-747ng/L). Chloridazon, bentazon, isoproturon and CMD were detected (0.9-8.9ng/L) in the coastal waters and chloridazon and isorproturon in the sediments (5-136pg/g d.w.). Levels of contaminants in the sediments could be influenced by the total organic carbon content. Concentrations observed in the Baltic Sea are most likely not high enough to cause acute effects, but long term effect studies are strongly recommended.

Degradation and enantiomeric fractionation of mecoprop in soil previously exposed to phenoxy acid herbicides - New insights for bioremediation.

Phenoxy acid-contaminated subsoils are common as a result of irregular disposal of residues and production wastes in the past. For enhancing in situ biodegradation at reducing conditions, biostimulation may be an effective option. Some phenoxy acids were marketed in racemic mixtures, and biodegradation rates may differ between enantiomers. Therefore, enantio-preferred degradation of mecoprop (MCPP) in soil was measured to get in-depth information on whether amendment with glucose (BOD equivalents as substrate for microbial growth) and nitrate (redox equivalents for oxidation) can stimulate bioremediation. The degradation processes were studied in soil sampled at different depths (3, 4.5 and 6m) at a Danish urban site with a history of phenoxy acid contamination. We observed preferential degradation of the R-enantiomer only under aerobic conditions in the soil samples from 3- and 6-m depth at environmentally relevant (nM) MCPP concentrations: enantiomer fraction (EF)<0.5. On the other hand, we observed preferential degradation of the S-enantiomer in all samples and treatments at elevated (µM) MCPP concentrations: EF>0.5. Three different microbial communities were discriminated by enantioselective degradation of MCPP: 1) aerobic microorganisms with little enantioselectivity, 2) aerobic microorganisms with R-selectivity and 3) anaerobic denitrifying organisms with S-selectivity. Glucose-amendment did not enhance MCPP degradation, while nitrate amendment enhanced the degradation of high concentrations of the herbicide.

Selective and Sensitive Chemiluminescence Determination of MCPB: Flow Injection and Liquid Chromatography.

Two new chemiluminescence (CL) methods are described for the determination of the herbicide 4-(4-chloro-o-tolyloxy) butyric acid (MCPB). First, a flow injection chemiluminescence (FI-CL) method is proposed. In this method, MCPB is photodegraded with an ultraviolet (UV) lamp and the photoproducts formed provide a great CL signal when they react with ferricyanide in basic medium. Second, a high-performance liquid chromatography chemiluminescence (HPLC-CL) method is proposed. In this method, before the photodegradation and CL reaction, the MCPB and other phenoxyacid herbicides are separated in a C18 column. The experimental conditions for the FI-CL and HPLC-CL methods are optimized. Both methods present good sensitivity, the detection limits being 0.12 µg L(-1) and 0.1 µg L(-1) (for FI-CL and HPLC-CL, respectively) when solid phase extraction (SPE) is applied. Intra- and interday relative standard deviations are below 9.9%. The methods have been satisfactorily applied to the analysis of natural water samples. FI-CL method can be employed for the determination of MCPB in simple water samples and for the screening of complex water samples in a fast, economic, and simple way. The HPLC-CL method is more selective, and allows samples that have not been resolved with the FI-CL method to be solved.

Low pressure UV/H2O2 treatment for the degradation of the pesticides metaldehyde, clopyralid and mecoprop - Kinetics and reaction product formation.

The degradation kinetics of three pesticides - metaldehyde, clopyralid and mecoprop - by ultraviolet photolysis and hydroxyl radical oxidation by low pressure ultraviolet hydrogen peroxide (LP-UV/H2O2) advanced oxidation was determined. Mecoprop was susceptible to both LP-UV photolysis and hydroxyl radical oxidation, and exhibited the fastest degradation kinetics, achieving 99.6% (2.4-log) degradation with a UV fluence of 800 mJ/cm(2) and 5 mg/L hydrogen peroxide. Metaldehyde was poorly degraded by LP-UV photolysis while 97.7% (1.6-log) degradation was achieved with LP-UV/H2O2 treatment at the maximum tested UV fluence of 1000 mJ/cm(2) and 15 mg/L hydrogen peroxide. Clopyralid was hardly susceptible to LP-UV photolysis and exhibited the lowest degradation by LP-UV/H2O2 among the three pesticides. The second-order reaction rate constants for the reactions between the pesticides and OH-radicals were calculated applying a kinetic model for LP-UV/H2O2 treatment to be 3.6 × 10(8), 2.0 × 10(8) and 1.1 × 10(9) M(-1) s(-1) for metaldehyde, clopyralid and mecoprop, respectively. The main LP-UV photolysis reaction product from mecoprop was 2-(4-hydroxy-2-methylphenoxy) propanoic acid, while photo-oxidation by LP-UV/H2O2 treatment formed several oxidation products. The photo-oxidation of clopyralid involved either hydroxylation or dechlorination of the ring, while metaldehyde underwent hydroxylation and produced acetic acid as a major end product. Based on the findings, degradation pathways for the three pesticides by LP-UV/H2O2 treatment were proposed.

Examining impacts of current-use pesticides in Southern Ontario using in situ exposures of the amphipod Hyalella azteca.

In situ exposures with Hyalella azteca were used to assess impacts of current-use pesticides in Southern Ontario, Canada. Exposures were conducted over 2 growing seasons within areas of high pesticide use: 1 site on Prudhomme Creek and 3 sites on Twenty Mile Creek. Three sites on Spencer Creek, an area of low pesticide use, were added in the second season. Surface water samples were collected every 2 wk to 3 wk and analyzed for a suite of pesticides. Hyalella were exposed in situ for 1 wk every 4 wk to 6 wk, and survival and acetylcholinesterase (AChE) activity were measured. Pesticides in surface waters reflected seasonal use patterns: lower concentrations in spring and fall and higher concentrations during summer months. Organophosphate insecticides (chlorpyrifos, azinphos methyl, diazinon) and acid herbicides (2,4-dichlorophenoxyacetic acid [2,4-D], mecoprop) were routinely detected in Prudhomme Creek, whereas neutral herbicides (atrazine, metolachlor) dominated the pesticide signature of Twenty Mile Creek. Spencer Creek contained fewer pesticides, which were measured at lower concentrations. In situ effects also followed seasonal patterns: higher survival and AChE activity in spring and fall, and lower survival and AChE activity during summer months. The highest toxicity was observed at Prudhomme Creek and was primarily associated with organophosphates. The present study demonstrated that current-use pesticides in Southern Ontario were linked to in situ effects and identified sites of concern requiring further investigation.

Selection of organic process and source indicator substances for the anthropogenically influenced water cycle.

An increasing number of organic micropollutants (OMP) is detected in anthropogenically influenced water cycles. Source control and effective natural and technical barriers are essential to maintain a high quality of drinking water resources under these circumstances. Based on the literature and our own research this study proposes a limited number of OMP that can serve as indicator substances for the major sources of OMP, such as wastewater treatment plants, agriculture and surface runoff. Furthermore functional indicators are proposed that allow assessment of the proper function of natural and technical barriers in the aquatic environment, namely conventional municipal wastewater treatment, advanced treatment (ozonation, activated carbon), bank filtration and soil aquifer treatment as well as self-purification in surface water. These indicator substances include the artificial sweetener acesulfame, the anti-inflammatory drug ibuprofen, the anticonvulsant carbamazepine, the corrosion inhibitor benzotriazole and the herbicide mecoprop among others. The chemical indicator substances are intended to support comparisons between watersheds and technical and natural processes independent of specific water cycles and to reduce efforts and costs of chemical analyses without losing essential information.

Mecoprop (MCPP) removal in full-scale rapid sand filters at a groundwater-based waterworks.

Contamination by the herbicide mecoprop (MCPP) was detected in groundwater abstraction wells at Kerteminde Waterworks in concentrations up to 0.08µg/L. MCPP was removed to below detection limit in a simple treatment line where anaerobic groundwater was aerated and subsequently filtered by primary and secondary rapid sand filters. Water quality parameters were measured throughout the waterworks, and they behaved as designed for. MCPP was removed in secondary rapid sand filters--removal was the greatest in the sand filters in the filter line with the highest contact time (63 min). In these secondary sand filters, MCPP concentration decreased from 0.037 µg/L to below the detection limit of 0.01 µg/L. MCPP was removed continuously at different filter depths (0.80 m). Additionally, biodegradation, mineralisation and adsorption were investigated in the laboratory in order to elucidate removal mechanisms in the full-scale system. Therefore, microcosms were set up with filter sand, water and (14)C-labelled MCPP at an initial concentration of 0.2 µg/L. After 24 h, 79-86% of the initial concentration of MCPP was removed. Sorption removed 11-15%, while the remaining part was removed by microbial processes, leading to a complete mineralisation of 13-18%. Microbial removal in the filter sand was similar at different depths of the rapid sand filter, while the amount of MCPP which adsorbed to the filter sand after 48 h decreased with depth from 21% of the initial MCPP in the top layer to 7% in the bottom layer. It was concluded that MCPP was removed in secondary rapid sand filters at Kerteminde Waterworks, to which both adsorption and microbial degradation contributed.

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.

Effects of chlorophenoxy herbicides and their main transformation products on DNA damage and acetylcholinesterase activity.

Persistent pesticide transformation products (TPs) are increasingly being detected among different environmental compartments, including groundwater and surface water. However, there is no sufficient experimental data on their toxicological potential to assess the risk associated with TPs, even if their occurrence is known. In this study, the interaction of chlorophenoxy herbicides (MCPA, mecoprop, 2,4-D and dichlorprop) and their main transformation products with calf thymus DNA by UV-visible absorption spectroscopy has been assessed. Additionally, the toxicity of the chlorophenoxy herbicides and TPs was also assessed evaluating the inhibition of acetylcholinesterase activity. On the basis of the results found, it seems that AChE is not the main target of chlorophenoxy herbicides and their TPs. However, the results found showed that the transformation products displayed a higher inhibitory activity when compared with the parent herbicides. The results obtained in the DNA interaction studies showed, in general, a slight effect on the stability of the double helix. However, the data found for 4-chloro-2-methyl-6-nitrophenol suggest that this transformation product can interact with DNA through a noncovalent mode.