Recycling organic residues in soils as amendments: Effect on the mobility of two herbicides under different management practices.

The addition of organic residues to soil to increase its organic matter content is considered as a viable option for sustainable food production in soils sensitive to degradation and erosion. However, the recycling of these organic residues in agricultural soils needs to be previously appraised because they can modify the behaviour of pesticides when they are simultaneously applied in agricultural practices. This study evaluated the changes in the mobility and persistence of two herbicides, triasulfuron and prosulfocarb, after two repeated applications in field experimental plots in an unamended soil and one amended with green compost (GC) for seven months. Different factors were studied: i) soil without amendment (S), ii) soil amended with two doses of GC (∼12 t C ha-1, S + GC1 and 40 t C ha-1, S + GC2), and iii) soils unamended and amended with different irrigation conditions: non-irrigated and with additional irrigation (2.8 mm per week). After the first application of herbicides, the results initially indicated no significant effects of soil treatments or irrigation conditions for triasulfuron mobility in agreement with the residual concentrations in the soil profile. The effect of irrigation was noted after one month of herbicide application and the effect of the soil treatment was significant after two months because the persistence of triasulfuron in S + GC2 was maintained until 50% of the applied amount. For prosulfocarb, the influence of soil amendment was significant for the initial persistence of the herbicide in S + GC2, higher than in S or S + GC1, in agreement with its adsorption constants for this soil. However, dissipation or leaching of the herbicide over time was not inhibited in this soil. After the repeated application of herbicides, the influence of the treatment of soils and/or irrigation was significant for the leaching and dissipation of both herbicides. The initial dissipation/degradation or leaching of herbicides was higher than after the first application, although persistence was maintained after five months of application in amended soils for triasulfuron and in unamended and amended soils for prosulfocarb. The results confirm that high doses of GC increased the persistence of both herbicides. This practice may offer the possibility of applying a tailored dose of GC to soil for striking a balance between residual concentrations and the soil agronomic effect.

Application of green compost as amendment in an agricultural soil: Effect on the behaviour of triasulfuron and prosulfocarb under field conditions.

Herbicides are essential in agricultural systems for maintaining crop yields, as weeds compromise grain production. Furthermore, the application of organic amendments to soil is an increasingly frequent agricultural practice for avoiding irreversible soil degradation. However, this practice could modify the behaviour of the herbicides applied, with implications for their absorption by weeds. This study evaluated the dissipation, persistence and mobility of the herbicides triasulfuron and prosulfocarb in a sandy clay loam soil unamended and amended with green compost (GC) in a field experiment using single or combined commercial formulations of both herbicides. The study was carried out in experimental plots (eight treatments × three replicates) corresponding to unamended soil and soil amended with GC, untreated and treated with the herbicide formulations Logran®, Auros® and Auros Plus® over 100 days. The half-life (DT50) of triasulfuron applied individually was 19.4 days, and increased in the GC-amended soil (46.7 days) due to its higher adsorption by this soil, although non-significant differences between DT50 values were found when it was applied in combination with prosulfocarb. Prosulfocarb dissipated faster than triasulfuron under all the conditions assayed, but non-significant differences were observed for the different treatments. The analysis of the herbicides at different soil depths (0-50 cm) after their application confirmed the leaching of both herbicides to deeper soil layers under all conditions, although larger amounts of residues were found in the 0-10 and 10-20 cm layers. The application of GC to the soil increased the persistence of both herbicides, and prevented the rapid leaching of triasulfuron in the soil, but the leaching of prosulfocarb was not inhibited. The influence of single or combined formulations was observed for triasulfuron, but not for prosulfocarb. The results obtained highlight the interest of obtaining field data to design rational joint applications of GC and herbicides to prevent the possible decrease in their effectiveness for weeds or the risk of water contamination.

Study of processes influencing bioavailability of pesticides in wood-soil systems: Effect of different factors.

Lignocellulosic wastes and by-products containing lignin are now available in large amounts from forestry and industrial activities, and could be promising organic materials for the biosorption of pesticides by soils in order to reduce point-source pollution. Adding these materials to soil requires understanding the process of pesticide sorption-desorption by wood-soils, as sorption capacity could increase, with changes in pesticide bioavailability and final fate. The objective of this work was to study the effect that pine and oak wood added to soils had on the sorption/desorption of the pesticides linuron, alachlor, and metalaxyl. Experiments were conducted with two sandy loam and sandy clay soils each amended with two wood doses (5% and 50%) after different incubation times (0, 5 and 12 months). A low wood dose (5%) had no significant impact on the sorption (Kf) of alachlor, but Kf increased for linuron (up to 5.4-1.7 times) and metalaxyl (up to 4.4 and 8.6 times) in all wood-soil systems. The results were not significantly different after different incubation times. The desorption results indicated that wood decreases the sorption irreversibility of alachlor, and increases that of linuron and metalaxyl, with a varying effect of the wood-soil incubation time. The addition of a high wood dose to soil (50%) was more significant for increasing the sorption of all the pesticides, and the sorbed amounts remaining after desorption (>49% for linuron, >33% for alachlor and >6% for metalaxyl), although there was no apparent discrimination between the two types of woods. The role of the nature of the organic carbón (Koc values) for sorption was evidenced for alachlor and metalaxyl, but not for linuron. These outcomes are of interest for extending wood application to soil as a barrier for avoiding environmental risk by point-source pollution due to the use and management of pesticides in farming systems.

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.

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.

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.

Tratamiento perioperatorio de una niña con origen anómalo de la arteria coronaria izquierda desde la arteria pulmonar (Síndrome de Alcapa) / No disponible

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Enhanced retention of linuron, alachlor and metalaxyl in sandy soil columns intercalated with wood barriers.

A study has been made of the effect a reactive barrier made of pine (softwood) or oak (hardwood) wood intercalated in a sandy soil column has on the retention of linuron, alachlor and metalaxyl (pesticides with contrasting physicochemical characteristics). The leaching of pesticides has been carried out under a saturated flow regime and breakthrough curves (BTCs) have been obtained at flow rates of 1 m Lmin(-1) (all pesticides) and 3 m Lmin(-1) (linuron). The cumulative curves in the unmodified soil indicate a leaching of pesticides >80% of the total amount of compound added. After barrier intercalation, linuron leaching decreases significantly and a modification of the leaching kinetics of alachlor and metalaxyl has been observed. The theoretical R factors increased ∼2.6-3.3, 1.2-1.6-fold, and 1.4-1.7-fold and the concentration of the maximum peak decreased ∼6-12-fold, 2-4-fold and 1.2-2-fold for linuron, alachlor and metalaxyl, respectively. When considering the three pesticides, significant correlations have been found between the theoretical retardation factor (R) and the pore volume corresponding to the maximum peaks of the BTCs (r=0.77; p<0.05) or the total volume leached (r=-0.78; p<0.05). The results reveal the efficacy of reactive wood barriers to decrease the leaching of pesticides from point sources of pollution depends on the type of wood, the hydrophobicity of the pesticide and the adopted water flow rate. Pine was more effective than oak in decreasing the leaching of hydrophobic pesticide linuron or in decreasing the maximum peak concentration of the less hydrophobic pesticides in soils. Efficacy of these wood barriers was limited for the least hydrophobic pesticide metalaxyl.

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.

Influence of clay mineral structure and surfactant nature on the adsorption capacity of surfactants by clays.

Adsorption of three surfactants of different nature, Triton X-100 (TX100) (non-ionic), sodium dodecylsulphate (SDS) (anionic) and octadecyltrimethylammonium bromide (ODTMA) (cationic) by four layered (montmorillonite, illite, muscovite and kaolinite) and two non-layered (sepiolite and palygorskite) clay minerals was studied. The objective was to improve the understanding of surfactant behaviour in soils for the possible use of these compounds in remediation technologies of contaminated soils by toxic organic compounds. Adsorption isotherms were obtained using surfactant concentrations higher and lower than the critical micelle concentration (cmc). These isotherms showed different adsorption stages of the surfactants by the clay minerals, and were classified in different subgroups of the L-, S- or H-types. An increase in the adsorption of SDS and ODTMA by all clay minerals is observed up to the cmc of the surfactant in the equilibrium solution is reached. However, there was further TX100 adsorption when the equilibrium concentration was well above the cmc. Adsorption constants from Langmuir and Freundlich equations (TX100 and ODTMA) or Freundlich equation (SDS) were used to compare adsorption of different surfactants by clay minerals studied. These constants indicated the surfactant adsorption by clay minerals followed this order ODTMA>TX100>>SDS. The adsorption of TX100 and ODTMA was higher by montmorillonite and illite, and the adsorption of SDS was found to be higher by kaolinite and sepiolite. Results obtained show the influence of clay mineral structure and surfactant nature on the adsorption capacity of surfactants by clays, and they indicate the interest to consider the soil mineralogical composition when one surfactant have to be selected in order to establish more efficient strategies for the remediation of soils and water contaminated by toxic organic pollutants.

Seasonal and time variability of heavy metal content and of its chemical forms in sewage sludges from different wastewater treatment plants.

Sewage sludges obtained from seven wastewater treatment plants from the province of Salamanca, Spain, were periodically sampled to determine seasonal and time variation of their elemental composition over 2000 to 2002. The aim of this paper was to provide additional insight to evaluate the potential environmental impact following soil incorporation of these materials as amendments. Aqua regia extractable metals (pseudo total content) of Cd, Cr, Cu, Ni, Pb and Zn were determined and furthermore, the main chemical forms of metals within the sludge were evaluated using a five-step fractionation procedure. All the studied sludges displayed high fertility properties due to their richness of OC, P and K. Total mean concentrations of Cd, Cr, Cu, Ni, Pb and Zn in the sludges were within the regulation of the Spanish legislation. Using an multifactor analysis of variance, significant differences between Cr, Cu, Ni, Pb and Zn pseudo total contents (p<0.01) of sludges at different sites were found while the Cd content was statistically similar. Also significant differences were found between these pseudo total contents of heavy metals in samples collected along the time after three years (0.001

Modification of clay barriers with a cationic surfactant to improve the retention of pesticides in soils.

In this work, the efficiency of reactive clay barriers in the immobilisation of organic pesticides in a sandy soil was studied. Reactive barriers were prepared by modification of montmorillonite, kaolinite and palygorskite clay minerals, and of a clayey soil with the cationic surfactant octadecyltrimethylammonium bromide (ODTMA). Percolation curves of the pesticides linuron, atrazine and metalaxyl of different hydrophobic character, were obtained in columns packed with a natural sandy soil with these barriers intercalated under saturated flow conditions. The cumulative curves in the unmodified soil indicated a leaching of pesticides greater than 85% of the total amount of compound added. After barrier intercalation, the breakthrough curves (BTC) indicated a dramatic decrease in the amounts of linuron leached in all columns and a significant modification of the leaching kinetics of atrazine and metalaxyl. Retardation factors, R, of the pesticides in the columns were significantly correlated with the organic matter content (OM) derived from the ODTMA of the organo clay/soil barriers (r2>or=0.78). Significant correlations were also found between these R factors and the pore volume values corresponding to the maximum peaks of the BTCs (r2=0.83; p<0.01) or the total volumes leached (r2=0.44; p<0.05) for the pesticides atrazine and metalaxyl. The results obtained point to the interest in the use of reactive clay barriers for almost complete immobilisation of hydrophobic pesticides or for decreasing the leaching of moderately hydrophobic pesticides coming from point-like sources of pollution. These barriers would avoid the generation of elevated concentrations of these compounds in the soils due to their rapid washing.

Surfactant-enhanced desorption of atrazine and linuron residues as affected by aging of herbicides in soil.

In the present work, we studied the efficiency of two surfactants, one anionic (SDS) and other non-ionic (Triton X-100), in the desorption of atrazine and linuron after 0, 3, and 9 months of soil-herbicide aging time. Batch desorption studies were conducted in soil-water and in soil-water-surfactant systems. The kinetic pattern of desorption was biphasic, a slow desorption following an initial fast phase. Both phases followed first-order kinetics. The desorption rate of the first phase (K1) was very low in water for both herbicides and always increased in the presence of surfactants. At zero time, K1 increased 9- and 8-fold (atrazine), and 24- and 17-fold (linuron) in the presence of the two surfactants, respectively. Desorption rates decreased with the increase in the aging time in all three desorption systems. After 9 months of soil-herbicide aging time, DT25 for linuron was 6.85 h (SDS) and 41.7 h (Triton X-100) and for the atrazine it was only possible determine in SDS solution (17.2h). The amount of desorbed herbicide in the different systems varied from 35.6-12.5% (water), 87.9-46.2% (SDS), and 63.2-18.0% (Triton X-100) for atrazine and 8.02-3.94% (water), 69.9-41.3% (SDS), and 58.1-34.8% (Triton X-100) for linuron. The ratio of amount desorbed in surfactant solution and in water for the different aging times of the herbicides was greater for the desorption of linuron than that of atrazine. For both herbicides, it was always greater with SDS than with Triton X-100, and was higher when desorption of the residues aged for 9 months was carried out. The results indicate the interest of surfactants for increasing the desorption of atrazine and linuron from soils polluted with these compounds after a long aging time in the soil. Therefore, they indicate the possibility to use the pump-and-treat remediation technique for pesticides in soils with a long history of pollution. The enhanced desorption achieved will be governed by the hydrophobic character of the herbicide, the nature of the surfactant used, the aging time, and the characteristics of soils.

A comparative study of adsorption of an anionic and a non-ionic surfactant by soils based on physicochemical and mineralogical properties of soils.

In the present work we performed a comparative study on the adsorption of the surfactants sodium dodecyl sulphate (SDS) (anionic), and octylphenoxypolyethoxyethanol (Triton X-100) (non-ionic) to 18 soils with organic matter (OM) and clay fraction contents varying over a broad range. The objective of the study was to gain further insight into the influence of the physicochemical and mineralogical properties of soils on the adsorption of surfactants by soils. Adsorption isotherms were obtained using concentrations below the critical micellar concentration (cmc) of the surfactants. The adsorption coefficients, Kf, determined from the Freundlich equation were lower for SDS (range 1.77-82.1, mean value 36.3) than for Triton X-100 (range 0.01-913, mean value 257). Simple and multiple correlation coefficients were obtained between Kf values and soil characteristics. The results obtained indicate the influence of the OM content on the adsorption of SDS (r=0.64, p<0.01) and of the clay fraction content on that of Triton X-100 (r=0.83, p<0.001). Additionally, we observed a preferential adsorption of SDS by the 1:1 mineral kaolinite (r=0.54, p<0.05), while Triton X-100 was adsorbed mainly by the 2:1 minerals, montmorillonite (r=0.66, p<0.01) and illite (r=0.87, p<0.001). According to the influence of different soil parameters on adsorption, different mechanisms of adsorption are proposed for each surfactant. Our findings point to the interest of considering the physicochemical properties of soils and also the mineralogy of the soil clay fraction when selecting a surfactant in technologies involving enhanced solubilization and removal of contaminants from soils and sediments.

Atrazine and alachlor inputs to surface and ground waters in irrigated corn cultivation areas of Castilla-Leon region, Spain.

The inputs of atrazine and alachlor herbicides to surface and ground waters from irrigated areas dedicated to corn cultivation in the Castilla-León (C-L) region (Spain) as related to the application of both herbicides were studied. Enzyme-linked immunosorbent assays (ELISA) were used for monitoring the atrazine and alachlor concentrations in 98 water samples taken from these areas. Seventy-nine of the samples were of ground waters and 19 were of surface waters. The concentration ranges of the herbicides detected in the study period (October 1997-October 1998) were 0.04-25.3 microg L(-1) in the surface waters and 0.04-3.45 microg L(-1) in the ground waters for atrazine, and 0.06-31.9 microg L(-1) in the surface waters and 0.05-4.85 microg L(-1) in the ground waters in the case of alachlor. The highly significant correlation observed between the concentrations of both herbicides in the surface waters (r = 0.89, p < 0.001) pointed to a parallel transport of atrazine and alachlor to these waters. A study was made of the temporal evolution of the concentrations of both herbicides, and it was found a maximum recharge of atrazine in the ground waters for April 1998 and of alachlor in October 1997 and October 1998. The temporal evolution of the concentrations of both herbicides in surface waters was parallel. The highly significant correlations observed between atrazine concentrations determined by ELISA and by HPLC (r = 0.92, p < 0.001) and between alachlor concentrations also determined by both methods (r = 0.96, p < 0.001) confirmed the usefulness of ELISA for monitoring both herbicides in an elevated number of samples. Using HPLC, the presence in some waters of the alachlor ethanesulfonate (ESA) metabolite was found at a concentration range of 0.52-4.01 microg L(-1). However the interference of ESA in the determination of alachlor by ELISA was negligible. The inputs of atrazine and alachlor to waters found in this study, especially the inputs to ground waters, could pose a risk for human health considering that some waters, though sporadically, are even used for human consumption.

Enhanced desorption of herbicides sorbed on soils by addition of Triton X-100.

A study of the desorption of atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine) and linuron [1-methoxy-1-methyl-3-(3,4-dichlorophenyl)urea] adsorbed on soils with different organic matter (OM) and clay contents was conducted in water and in the presence of the non-ionic surfactant Triton X-100 at different concentrations. The aim was to gain insight into soil characteristics in surfactant-enhanced desorption of herbicides from soils. Adsorption and desorption isotherms in water, in all Triton X-100 solutions for atrazine, and in solutions of 0.75 times the critical micelle concentration (cmc) and 1.50cmc for linuron fit the Freundlich equation. All desorption isotherms showed hysteresis. Hysteresis coefficients decreased for linuron and increased or decreased for atrazine in Triton X-100 solutions. These variations were dependent on surfactant concentration and soil OM and clay contents. In the soil-water-surfactant system desorption of linuron from all soils was always greater than in the soil-water system but for atrazine this only occurred at concentrations higher than 50cmc. For the highest Triton X-100 concentration (100cmc), the desorption of the most hydrophobic herbicide (linuron) was increased more than 18-fold with respect to water in soil with an OM content of 10.3% while the atrazine desorption was increased 3-fold. The effect of Triton X-100 on the desorption of both herbicides was very low in soil with a high clay content. The results indicate the potential use of Triton X-100 to facilitate the desorption of these herbicides from soil to the water-surfactant system. They also contribute to better understanding of the interactions of different molecules and surfaces in the complex soil-herbicide-water surfactant system.

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.

Significance of soil properties in the adsorption and mobility of the fungicide metalaxyl in vineyard soils.

Adsorption and mobility of the fungicide metalaxyl were studied in 16 vineyard soils from the La Rioja region (Spain), with organic matter (OM) contents in the 0.31--1.37% range, and in 7 natural soils with OM contents in the 3.30--8.24% range. Adsorption isotherms were obtained using the batch equilibrium technique, and mobility was studied by soil thin-layer chromatography (soil-TLC). In all cases, the adsorption isotherms fit the Freundlich equation. The values of the K(f) constants were low in the vineyard soils (0.01--0.64) and increased in the natural soils (1.05--2.83). The n(f) values were in general lower than unity. K(f) constants were significantly correlated (p < 0.001) with the OM content when all of the soils were considered. According to the determination coefficient, r(2), OM would account for 88% of the variance in adsorption. When the vineyard soils alone were considered, a significant correlation was seen between K(f) and the OM and clay contents; both parameters, varying simultaneously, explain 80% of the variance in adsorption. Study of the mobility of metalaxyl with soil-TLC indicated that in vineyard soils the fungicide has the potential for being highly mobile in 19% of the soils and mobile in 81% of them. In natural soils, the fungicide has the potential for being moderately mobile or mobile in 86 and 14% of the soils, respectively. This type of behavior of metalaxyl indicates that in vineyards soils of the La Rioja region (Spain) with low OM contents, where application of the compound is continuous, a leaching of the fungicide from the soil to groundwaters could potentially occur. These results should be borne in mind when metalaxyl is to be used in the soils of this region.