Eva Pose-Juan

Pesticide residues in vineyard soils from Spain: Spatial and temporal distributions

Spatial and temporal evaluations of seventeen pesticides and some of their degradation products were carried out in seventeen vineyard soils from La Rioja region (Spain). The soils were sampled in March, June and October 2012, and the pesticides were selected among those previously detected in surface and ground waters from the same area. All pesticides were detected in some of the soils in the three different areas of La Rioja at the different sampling times, with only the metalaxyl metabolite, CGA-62826, not being detected in any of the soils sampled in October. The highest concentrations were determined for the fungicides metalaxyl (11.5 μg kg(-1)) and triadimenol (26.1 μg kg(-1)), the herbicides fluometuron (174.6 μg kg(-1)) and terbuthylazine (403.3 μg kg(-1)), and the insecticide methoxyfenozide (4.61 μg kg(-1)). While the highest total concentration of pesticides was detected in March, the highest number of positive detections was recorded in June (46), as opposed to 26 and 19 in March and October, respectively. Significant differences were detected in the concentrations of herbicides in soils from the three areas in La Rioja, but this was not the case for the fungicides and the insecticides. The study revealed a more intensive use of herbicides in March, while the use of insecticides and fungicides probably depended on the specific needs of crops and/or the onset of diseases. The results are consistent with the residues found in waters in the region, and highlight the need to implement strategies for more efficient application of these compounds to avoid risk of water contamination.

Pesticide residues in groundwaters and soils of agricultural areas in the Águeda River Basin from Spain and Portugal

This research has evaluated the agricultural impact of the use of pesticides in small agricultural areas in the Águeda river basin, which straddles the Spanish-Portuguese border. Sixteen pesticides frequently used in the area, including herbicides, fungicides and insecticides and some of their degradation products, were monitored in 52 groundwater samples and 42 soil samples taken around them, using a developed multi-residual analytical method based on SPE-LC-MS. Sampling was carried out in two different seasons (winter and summer). The results indicated the presence of pesticides at several levels, both in groundwaters and soils. Thirteen of the pesticides studied were detected in one or more of the groundwater samples analysed, but only three pesticides were detected in the soil samples. Terbuthylazine, cyprodinil, tebuconazole and chlorpyrifos were the pesticides most frequently detected in groundwaters, whereas terbuthylazine, metalaxyl and tebuconazole were the sole compounds detected in soils. The distribution of the concentrations in groundwaters indicated that up to 80% and 70% of the samples collected in the summer on the Spanish and Portuguese sides, respectively, exceed the quality standards of 0.1 µg L−1 for one or more individual compounds and, in turn, up to 64% and 40% exceed the quality standards of 0.5 µg L−1 for all compounds. The presence of pesticide residues in the groundwaters and soils analysed may well be explained by the use of these compounds in agricultural practices.

Application of mesotrione at different doses in an amended soil: Dissipation and effect on the soil microbial biomass and activity

The aim of this work was to estimate the dissipation of mesotrione applied at three doses (2, 10 and 50 mg kg(-1) dw) in an unamended agricultural soil, and this same soil amended with two organic residues (green compost (C) and sewage sludge (SS)). The effects of herbicide and organic residue on the abundance and activity of soil microbial communities were also assessed by determining soil microbial parameters such as biomass, dehydrogenase activity (DHA), and respiration. Lower dissipation rates were observed for a higher herbicide dose. The highest half-life (DT50) values were observed in the SS-amended soil for the three herbicide doses applied. Biomass values increased in the amended soils compared to the unamended one in all the cases studied, and increased over the incubation period in the SS-amended soil. DHA mean values significantly decreased in the SS-amended soil, and increased in the C-amended soil compared to the unamended ones, under all conditions. At time 0 days, respiration values were significantly higher in SS-amended soils (untreated and treated with mesotrione) than in the unamended and C-amended soils. The effect of mesotrione on soil biomass, DHA and respiration was different depending on incubation time and soil amendment and herbicide dose applied. The results support the need to consider the possible non-target effects of pesticides and organic amendments simultaneously applied on soil microbial communities to prevent negative impacts on soil quality.

Effect of different rates of spent mushroom substrate on the dissipation and bioavailability of cymoxanil and tebuconazole in an agricultural soil.

Physicochemical methods to immobilize pesticides in vulnerable soils are currently being developed to prevent water contamination. Some of these methods include the use of different organic residues to modify soils because they could limit the transport of pesticides and/or facilitate their dissipation. Spent mushroom substrate (SMS) may be used for these purposes. Accordingly a study was conducted under laboratory conditions to know the dissipation and bioavailability of the fungicides cymoxanil and tebuconazole over time in a vineyard soil amended with two rates of spent mushroom substrate (SMS) (5% and 50% (w/w)), selected to prevent the diffuse or point pollution of soil. The dissipation of cymoxanil was more rapid than that of tebuconazole in the different soils studied. The dissipation rate was higher in the amended soil than in the unamended one for both compounds, while no significant differences were observed between the amended soils in either case. An apparent dissipation occurred in the amended soil due to the formation of non-extractable residues. Bound residues increased with incubation time for tebuconazole, although a proportion of this fungicide was bioavailable after 303days. The major proportion of cymoxanil was tightly bound to the amended soil from the start, although an increasing fraction of bound fungicide was bioavailable for mineralization. Soil dehydrogenase activity was significantly affected by SMS application and incubation time; however, it was not significantly modified by fungicide application. The significance of this research suggests that SMS applied at a low or high rate to agricultural soil can be used to prevent both the diffuse or point pollution of soil through the formation of non-extractable residues, although more research is needed to discover the time that fungicides remain adsorbed into the soil decreasing either bioavailability (tebuconazole) or mineralization (cymoxanil) in SMS-amended soils.

Pesticides and degradation products in groundwaters from a vineyard region: optimization of a multiresidue method based on SPE and GC-MS.

A reliable multiresidue method based on solid phase extraction was developed using GC-MS to determine and quantify 34 pesticides, including herbicides, fungicides, insecticides, and some of their degradation products, in groundwater in a vineyard region of La Rioja (northern Spain). Different parameters were optimized and good recoveries (65-108% range) and precisions (12-19% range) were achieved with spiked water samples for a concentration of 0.1 μg/L. The experimental results showed an excellent linearity (r(2) > 0.99) over the 0.1-1.5 μg/L range. The detection limits of the proposed method were 1-37 ng/L for most of the compounds studied. The methodology has been successfully applied to the analysis of groundwater samples from vineyard areas in La Rioja and the presence of pesticides, especially fungicides and herbicides, at several concentration levels was revealed. Terbuthylazine, its metabolite desethyl-terbuthylazine, and fluometuron were the pesticides most frequently detected in higher concentrations. Overall and taking into consideration the European Union maximum residue limit of pesticides in groundwater, 16 of the 34 compounds included in this study were detected in concentrations over that limit in at least one of the samples analyzed.

Seasonal distribution of herbicide and insecticide residues in the water resources of the vineyard region of La Rioja (Spain)

Pesticides are needed to maintain high production in the vineyard area of La Rioja (Spain), and monitoring their spatial distribution is a priority for preserving the quality of natural resources. Accordingly, the purpose of this work was to conduct a study to evaluate the presence and seasonal distribution of herbicide and insecticide residues in ground and surface waters in this region. The monitoring network comprised 12 surface waters and 78 groundwaters, covering the three subareas (63,593ha) into which the vineyard region is divided. The quality of natural waters was examined through the analysis of twenty-two herbicides, eight of their main degradation products, and eight insecticides. Pesticides were extracted by solid-phase extraction, and analysed by gas chromatography-mass spectrometry or by liquid-chromatography-mass spectrometry. The results reveal the presence of most of the herbicides and insecticides included in the study in one or more of the samples collected during the four campaigns. The herbicide terbuthylazine and its metabolite desethylterbuthylazine were the compounds more frequently detected (present in >65% of the samples across all the campaigns). Other compounds detected in >50% of the samples in one sampling campaign were the herbicides fluometuron, metolachlor, alachlor and ethofumesate. Insecticides were present in a small number of samples, with only pirimicarb being detected in >25% of the samples in March and June campaigns. The results reveal that the sum of compounds detected (mainly herbicides) was higher than 0.5μgL-1 in >50% of the samples, especially in the campaigns with the highest application of these compounds. A possible recovery of the quality of the waters was detected outside the periods of crop cultivation, although more monitoring programmes are needed to confirm this trend with a view to preventing and/or maintaining the sustainability of natural resources.

Development of a procedure for the multiresidue analysis of pesticides in vineyard soils and its application to real samples

A procedure for multiresidue analysis was developed for the extraction and determination of 17 pesticides, including herbicides, fungicides, and insecticides, as well as certain degradation products, in vineyard soils from La Rioja region (Spain). Different solvents and mixtures were tested in spiked pesticide-free soils, and pesticides were comparatively evaluated by gas chromatography with mass spectrometry and liquid chromatography with mass spectrometry. Recoveries >70%, with relative standard deviations <9%, were obtained when a mixture of methanol/acetone or a mixture of methanol/CaCl2 0.01 M for the most polar compounds was selected as the extraction solvent. Method validation was accomplished with acceptable linearity (r(2) ≥ 0.987) within the concentration range of 0.005-1 μg/mL corresponding to 1.667-333.4 μg/kg and 0.835-167.1 μg/kg for liquid chromatography with mass spectrometry and gas chromatography with mass spectrometry, respectively, and detection limits <0.4 μg/kg for the compounds were studied. The extraction method was applied to 17 real vineyard soil samples, and terbuthylazine and its metabolite desethylterbuthylazine were the most ubiquitous compounds, as they were detected in the 100% of the soils analyzed. The presence of fungicides was also high, and the presence of insecticides was lower than other pesticides. The results confirm the usefulness of the optimized procedure for monitoring residues in vineyard soils.

Influence of Herbicide Triasulfuron on Soil Microbial Community in an Unamended Soil and a Soil Amended with Organic Residues

The effect of organic amendments and pesticides on a soil microbial community has garnered considerable interest due to the involvement of microorganisms in numerous soil conservation and maintenance reactions. The aim of this work was to assess the influence on a soil microbial community of the simultaneous application of the herbicide triasulfuron at three doses (2, 10, and 50 mg kg-1), with an organic amendment [sewage sludge (SS) or green compost (GC)]. Dissipation kinetics, soil microbial biomass, dehydrogenase activity (DHA) and respiration, and the profile of phospholipid fatty acids (PLFAs) extracted from the soil, were determined in unamended (S) soil and amended (S+SS and S+GC) ones. Triasulfuron dissipation followed the single first-order kinetics model. Half-life (DT50) values were higher in the amended soils than in the unamended one for the 10 and 50 mg kg-1 doses. The dissipation rates were lower in the S+GC soil for the three herbicide doses applied. In general, soil biomass, DHA and respiration values increased in SS- and GC-amended soils compared to the unamended one. DHA values decreased (S and S+SS) or increased (S+GC) with the incubation time of soil with herbicide at the different doses applied. Respiration values increased with the herbicide doses applied and decreased with the incubation time, although maximum values were obtained for soils treated with the highest dose after 70 days of incubation. PLFA analysis indicated different effects of triasulfuron on the soil microbial community structure depending on the organic amendments. While the increasing triasulfuron doses resulted in deeper alterations in the S soil, the time after triasulfuron application was the most important variation in the S+SS and S+GC soils. The overall results indicate that the soil amendment has an effect on herbicide dissipation rate and the soil microbial community. Initially, a high dose of triasulfuron had detrimental effects on the soil microbial community, which is important in the case of the long-term use of this compound.

Predicting release and transport of pesticides from a granular formulation during unsaturated diffusion in porous media

The release and transport of active ingredients (AIs) from controlled-release formulations (CRFs) have potential to reduce groundwater pesticide pollution. These formulations have a major effect on the release rate and subsequent transport to groundwater. Therefore the influence of CRFs should be included in modeling non-point source pollution by pesticides. We propose a simplified approach that uses a phase transition equation coupled to the diffusion equation that describes the release rate of AIs from commercial CRFs in porous media; the parameters are as follows: a release coefficient, the solubility of the AI, and diffusion transport with decay. The model gives acceptable predictions of the pesticides release from commercial CRFs in diffusion cells filled with quartz sand. This approach can be used to study the dynamics of the CRF-porous media interaction. It also could be implemented in fate of agricultural chemical models to include the effect of CRFs.

Dissipation of herbicides after repeated application in soils amended with green compost and sewage sludge

Certain agricultural practices, such as the repeated application of herbicides or organic amendments to soil, can influence herbicide dissipation. This research has studied the effects of two repeated applications of mesotrione, pethoxamid, and triasulfuron on their dissipation rates in unamended soil (S) and soil amended with green compost (S+GC) or sewage sludge (S+SS). The dissipation experiment has also included an evaluation of the adsorption of the three herbicides by soils and of changes in soil dehydrogenase activity (DHA). The adsorption of the three herbicides by amended soils (Kf range 0.83-2.98) was higher than by unamended soil (Kf range 0.20-0.64). The adsorption coefficients (Kd) of mesotrione and triasulfuron were higher for S+SS, while that of pethoxamid was higher for S+GC, but no relationship between values for the time to 50% degradation (DT50) and adsorption coefficients could be determined. The repeated application of mesotrione decreased its dissipation rate in unamended soil (DT50 increased from 4.75 to 8.15 days) and amended soils (DT50 increased from 11.7 to 28.2 days in S+GC and from 17.7 to 37.9 in S+SS), whereas the repeated application of pethoxamid increased its dissipation rate in all the treatments, and the rate for triasulfuron increased only in amended soils. The highest DT50 values for pethoxamid (12.3 days) and triasulfuron (57.1 days) were in S+GC, and the lowest in S+SS (8.35 and 24.7 days). Soil DHA was stimulated by the presence of GC in the soil and by the first application of mesotrione. The second application of mesotrione and pethoxamid positively affected soil DHA, but this did not occur for triasulfuron. The repeated applications of herbicides and soil organic amendments have different effects on herbicide dissipation, adsorption, and soil DHA, and they should be taken into account when assessing soil quality and other potential environmental implications of pesticide use.