M.S. Rodríguez-Cruz

Significance of the long-chain organic cation structure in the sorption of the penconazole and metalaxyl fungicides by organo clays

Sorption-desorption of two different hydrophobic fungicides, penconazole and metalaxyl, by a series of clay minerals layered and non-layered (montmorillonite, illite, kaolinite, muscovite, sepiolite and palygorskite) modified with the two-chain cationic surfactant, dihexadecyldimetylammonium (DHDDMA) was studied by first time in this work. DHDDMA-clays showed a good capacity to sorb both fungicides from water. Freundlich sorption constants (K(f)) increased 22-268-fold for penconazole and 4-112-fold for metalaxyl in relation to natural clays. High sorption irreversibility was observed for penconazole for all modified clays, while for metalaxyl this occurred only for some of the modified clays. Additionally, a comparative study of the sorption of the fungicides by clay minerals modified with organic cations of different structure was carried out by a statistical approach. Non-layered and layered clay minerals modified with the two-chain alkylammonium organic cation DHDDMA, and with single-chain organic cations octadecyltrimethylammonium (ODTMA) and hexadecylpyridinium (HDPY) were used as sorbents. The study indicated a significant linear regression between the distribution coefficients K(d) of fungicides and the organic carbon (OC) content of the organo clays (r(2)>or=0.80, p<0.001). According to this sorption of fungicides by partition between the aqueous solution and the organic medium created by the alkyl chains of the exchanged ammonium cations regardless of the type and structure of these cations is suggested. However, linear relationships between K(d) values of each pesticide by the different organo clays and their relative OC contents revealed higher increase in sorption for HDPY-clays (penconazole) and for ODTMA-clays (metalaxyl) pointing out different effectiveness of the OC provided by each organic cation. These effects were also supported by the values of K(d) relative to OC, K(d)(oc). The results evidenced the different relative weight of alkyl cations to make organo clays effective barriers to prevent the mobility of pesticides from a point source of pollution.

Sodium dodecyl sulphate-enhanced desorption of atrazine: effect of surfactant concentration and of organic matter content of soils.

A study was made of the adsorption-desorption of atrazine in aqueous medium in five soils with organic matter (OM) contents in the range 1.4-10.3% and also of the desorption of the herbicide in aqueous solutions of the anionic surfactant sodium dodecyl sulphate (SDS) at critical micelle concentrations (cmc) of 0.75, 1.50, 5 and 10. The adsorption and desorption isotherms in water together with the desorption isotherms in SDS solutions with concentrations of 0.75 and 1.50 cmc fit the Freundlich adsorption equation. All the desorption isotherms displayed hysteresis. The increase or reduction in hysteresis of the desorption isotherms in SDS solutions with respect to those of desorption in water depend on the SDS concentration and on the OM content of the soils. Below the cmc, SDS only increases the desorption of atrazine in the soil with the highest OM content (10.3%). However, above the cmc (5 and 10 cmc) the desorption of atrazine increases in all soils, the efficiency of desorption increasing with the OM content of the soils.

Comparison of Pesticide Sorption by Physicochemically Modified Soils with Natural Soils as a Function of Soil Properties and Pesticide Hydrophobicity

The objectives of this paper were to determine the efficiency of physicochemically modified soils with a surfactant in the sorption of pesticides, the stability against washing of the pesticides sorbed, and the effective sorption capacity of surfactant adsorbed by soils as a function of pesticide hydrophobicity and soil characteristics. Five soils of different characteristics and five pesticides (penconazole, linuron, alachlor, atrazine and metalaxyl) with different Kow values were selected and octadecyltrimethylammonium bromide (ODTMA) was chosen as model of cationic surfactants. Sorption-desorption isotherms were obtained and constants Kf and Kfd for natural soils (from Freundlich equation) and K and Kd for ODTMA-soils (from linear equation) were determined. Sorption on ODTMA-soils was higher than on natural soils. K increased 27–165 times for penconazole, 22–77 times for linuron, 7–14 times for alachlor, 9–23 times for atrazine, and 21–333 times for metalaxyl in relation to Kf. Sorption coefficients normalized to 100% of total organic matter (TOM) from organo soils KOM (K 100/%TOM), were always higher than those from natural soils KfOM (Kf 100/%OM), indicating that the organic matter (OM) derived from the ODTMA (OMODTMA) had a greater sorption capacity than the OM of the natural soil. KOM values were also higher than the Kow (octanol/water distribution coefficient) value for each pesticide. The similarity of the high KOM values for the sorption of each pesticide by the five soils and the linearity of isotherms point to a partitioning of the pesticides between surfactant and water. The use in this work of different soils and various pesticides, unusual in this type of investigation, allowed us to obtain equations to know the sorbed amount of a given pesticide by the surfactant-modified soils as a function of the OM content derived from the cation and the Kow of the pesticide. The results obtained are of interest when it becomes necessary to increase the sorption capacity of soils with low OM contents with a view to delaying pesticide mobility in soils from pollution point sources (high concentration in small area), and preventing the pollution of waters.

Use of raw or incubated organic wastes as amendments in reducing pesticide leaching through soil columns

Soil amendment with organic wastes is becoming a widespread management practice since it can effectively solve the problems of uncontrolled waste accumulation and improve soil quality. However, when simultaneously applied with pesticides, organic wastes can significantly modify the environmental behaviour of these compounds. This study evaluated the effect of sewage sludges (SS), grape marc (GM) and spent mushroom substrates (SMS) on the leaching of linuron, diazinon and myclobutanil in packed columns of a sandy soil with low organic matter (OM) content (<1%). Soil plus amendments had been incubated for one month (1 m) or 12 months (12 m). Data from the experimental breakthrough curves (BTCs) were fitted to the one-dimensional transport model CXTFIT 2.1. All three amendments reduced leaching of linuron and myclobutanil relative to unamended soil. SMS was the most effective in reducing leaching of these two compounds independent of whether soil was incubated for 1 m or 12 m. Soil amendments increased retardation coefficients (Rexp) by factors of 3 to 5 for linuron, 2 to 4 for diazinon and 3 to 5 for myclobutanil relative to unamended soil. Leaching of diazinon was relatively little affected by soil amendment compared to the other two compounds and both SS and SMS amendment with 1m incubation resulted in enhanced leaching of diazinon. The leaching data for linuron and myclobutanil were well described by CXTFIT (mean square error, MSE<4.9·10(-7) and MSE<7.0·10(-7), respectively) whereas those of diazinon were less well fitted (MSE<2.1·10(-6)). The BTCs for pesticides were similar in soils incubated for one month or one year, indicating that the effect of amendment on leaching persists over relatively long periods of time.

Study of the desorption of linuron from soils to water enhanced by the addition of an anionic surfactant to soil–water system

The influence of the addition of the anionic surfactant sodium dodecyl sulphate (SDS) to the soil-water-linuron system in the herbicide desorption from soils with different organic matter (OM) content to water have been studied. SDS was used at critical micelle concentrations (cmc) of 0.75, 1.50, 5 and 10. The adsorption-desorption isotherms of linuron in aqueous medium and in SDS solutions at concentration of 0.75 cmc fitted the Freundlich adsorption equation for all the soils studied. When the SDS concentration was 1.50 cmc only the desorption isotherms for the soils with OM content < or = 5.40% fit this equation and was not fulfilled by any of the soils when the SDS concentration was 5 or 10 cmc. All the desorption isotherms displayed hysteresis, the hysteresis coefficients of the desorption isotherms in SDS solutions always being lower than those of the desorption isotherms in water. The efficiency coefficients, defined as the relationship between the percentages of linuron desorbed in SDS solution and the percentages of linuron desorbed in water, range from 1.02 to 2.41 in the soil with the lowest OM content, and from 1.91 to 17.1 in the soil with the highest OM content. The results obtained indicate the enhancement of linuron desorption by the addition of SDS surfactant to soil-water system. The efficiency of SDS is seen as from surfactant concentrations below the cmc and varies with the surfactant concentration and with the soil OM content.

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 spent mushroom substrate applied to vineyard soil on the behaviour of copper-based fungicide residues.

The effect of the addition of spent mushroom substrate (SMS) to the soil as an amendment on the distribution and/or fate of copper from a copper-based fungicide applied to a vineyard soil in La Rioja (N. Spain) was studied. The study was carried out on experimental plots amended or not with SMS at rates of 40 and 100 t ha(-1). The variation in total Cu content in the topsoil (0-10 cm) and in the soil profile (0-50 cm), and the distribution of Cu in different fractions of the topsoil were studied as a function of the dose of Cu added (5 and 10 kg ha(-1)) and of the time elapsed since application (0-12 months). In addition, the changes in the chemical properties (solid organic carbon (OC), dissolved organic carbon (DOC) and pH) of the soils were studied. A greater capacity for Cu retention by the amended soils than by the unamended one was observed only when the fungicide was applied at the high dose. No effect of the amendment rate was noted on this retention capacity. The metal content in the topsoil decreased over time in step with the disappearance of the OC in the amended soil due to its oxidation, mineralization and/or leaching. This decrease in total Cu content was possibly due to the formation of soluble Cu complexes with the DOC, which facilitated its transport through the soil. A re-distribution of Cu in the different soil fractions was also observed over time, mainly from the organic to the residual fraction. The results obtained indicate that the increase in OC due to the application of SMS at the rates used does not lead to any significant increase in the persistence of Cu in the soil over time. Of greater interest would be the assessment of the risk for groundwater quality, owing to possible leaching of the fungicide enhanced by the SMS when SMS and Cu-based fungicides are jointly applied to vineyard soils.

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.

Field versus laboratory experiments to evaluate the fate of azoxystrobin in an amended vineyard soil

This study reports the effect that adding spent mushroom substrate (SMS) to a representative vineyard soil from La Rioja region (Spain) has on the behaviour of azoxystrobin in two different environmental scenarios. Field dissipation experiments were conducted on experimental plots amended at rates of 50 and 150 t ha(-1), and similar dissipation experiments were simultaneously conducted in the laboratory to identify differences under controlled conditions. Azoxystrobin dissipation followed biphasic kinetics in both scenarios, although the initial dissipation phase was much faster in the field than in the laboratory experiments, and the half-life (DT50) values obtained in the two experiments were 0.34-46.3 days and 89.2-148 days, respectively. Fungicide residues in the soil profile increased in the SMS amended soil and they were much higher in the top two layers (0-20 cm) than in deeper layers. The persistence of fungicide in the soil profile is consistent with changes in azoxystrobin adsorption by unamended and amended soils over time. Changes in the dehydrogenase activity (DHA) of soils under different treatments assayed in the field and in the laboratory indicated that SMS and the fungicide had a stimulatory effect on soil DHA. The results reveal that the laboratory studies usually reported in the literature to explain the fate of pesticides in amended soils are insufficient to explain azoxystrobin behaviour under real conditions. Field studies are necessary to set up efficient applications of SMS and fungicide, with a view to preventing the possible risk of water contamination.