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.     

Parameters affecting extraction of selected fungicides from vineyard soils

This paper describes a sensitive method for the simultaneous quantification of eight commonly used grapevine fungicides in vineyard soils: cyprodinil, fludioxonil, metalaxyl, penconazole, pyrimethanil, procymidone, tebuconazole, and vinclozolin. The fungicides are extracted from the soil sample by sonication with water followed by shaking with ethyl acetate and are quantified by gas chromatography with mass spectrometry. Average extraction efficiencies in a sample of seven spiked, previously fungicide-free soils were > or =79% for all of the analytes, method precisions were > or =17%, and quantification limits were < or =50 microg/kg. However, because recoveries varied considerably from soil to soil, there is a need to control for soil matrix differences (mainly soil pH and exchangeable calcium content); as a consequence, soil fungicide contents must be quantified by the standard additions method. When the method was applied in this way to soil samples from vineyards belonging to the specified wine-growing region of Rias Baixas (Galicia, northwestern Spain) taken at the beginning of October (1 month after the crop's final treatment), levels of fludioxonil as high as 991 microg/kg were found, but at the start of the season (9 months after the previous crop's final treatment) only fludioxonil was detected at levels higher than its limit of quantification (45 and 52 microg/kg).     

Influence of pH and soil copper on adsorption of metalaxyl and penconazole by the surface layer of vineyard soils

The upper horizons of old vineyard soils have substantial copper contents due to the traditional use of copper-based fungicides. Total copper levels in eight vineyard soils in the Rías Baixas area of Galicia (northwestern Spain) ranged from 60 to 560 mg kg(-1) (mean +/- SD = 206 +/- 170 mg kg(-1)). The adsorption of the fungicides metalaxyl (pK(a) = 1.41) and penconazole (pK(a) = 2.83) by these soils was determined using fungicide solutions of pH 2.5 and 5.5, and desorption of fungicide adsorbed at pH 5.5 was also determined. In all cases, Freundlich equations were fitted to the data with R (2) > 0.96. Penconazole was adsorbed and retained more strongly than metalaxyl, with K(F) values more than an order of magnitude greater. In the desorption experiments, both fungicides exhibited hysteresis. Soil copper content hardly affected the adsorption of metalaxyl, but K(F) values for adsorption of penconazole increased at a rate of about 0.1 mL(n) (microg of penconazole)(1-n) (microg of Cu)(-1), which is attributed to the formation of Cu(2+)-penconazole complexes with greater affinity for soil colloids than penconazole itself. Because the dependence of K(F) for penconazole adsorption on copper content was the same at both pH values, complex formation appears not to have been affected by the solubilization of 6-17% of soil copper at pH 2.5. A similar copper dependence, or lack of dependence, was observed when 100-1000 mg kg(-1) of copper was added as Cu(NO(3))(2).2H(2)O to the solutions from which the fungicides were adsorbed.     

Effect of the addition of sewage sludge as a fertilizer on a sandy vineyard soil

Purpose

The application of sludge from wastewater in agriculture has increased in recent years, and it is therefore important to assess the effect that such treatment has on both the soil and the plant. The aim of the study described here was to ascertain whether there is a variation in the properties of the soil and to determine if this addition has an impact on the plant.

Materials and methods

The area of investigation was close to the municipality of Villarrubia de los Ojos (Ciudad Real). In this work, six samples were taken from the surface horizon in the studied plot at a depth of 35 cm. A further three samples were taken: (i) a surface horizon of a soil close to the area under investigation but without treatment (control sample), (ii) a sample of sludge from the wastewater treatment plant and (iii) a sample of the mixture used by farmers as fertilizer. Laboratory tests were conducted in accordance with the SCS-USDA (1972) guidelines. Trace element samples were analysed by X-ray fluorescence spectrophotometry (Philips PW 2404).

Results and discussion

The parcel of land studied is dominated by a sandy texture (88.3 % sand), and a decrease in pH was observed in areas in which the mixture (manure + sludge) was added (pH?=?8.0) compared to areas in which fertilizer was not applied (pH?=?8.5). It was observed that the addition of the compound led to an increase in the electrical conductivity of the soil. The trace elements can be organized into two groups based on the results obtained in this study. One group contains the trace elements that were only present in the rows that were treated with the fertilizer. The other group of trace elements was mobilized throughout the whole plot.

Conclusions

The application of sewage sludge on agricultural soils can be very useful as an organic amendment because it produces an increase in soil organic matter. However, sewage sludge must be applied with caution due to the changes in soil chemical properties (for example, pH and E.C.). The use of this type of waste for prolonged periods of time can cause problems of contamination in the soil.

     

Effect of undesalted dissolved organic matter from composts on persistence, adsorption, and mobility of cyhalofop herbicide in soils

The effect of undesalted dissolved organic matter (DOM) extracted from composts on the degradation, adsorption, and mobility of cyhalofop herbicide in soils was studied. A paddy-field sediment poor in organic matter (OM), an OM-rich forest soil, and DOM from agroindustrial or municipal waste compost were used. DOM increased the cyhalofop-acid but not the cyhalofop-butyl solubility in water. The degradation of cyhalofop-butyl in the sediment was slow, giving cyhalofop-acid as the only metabolite, whereas in forest soil, the process was faster, and three byproducts were detected. Soil pretreatment with DOM did not modify the degradation pattern but only reduced the adsorption of cyhalofop-butyl by soil, whereas it increased the adsorption of cyhalofop-acid. Among the cationic components of DOM solutions, the potassium ion seems to be related to the increased adsorption of the cyhalofop-acid in both OM-poor and OM-rich soils, yielding reversible complexes with the former and favoring hydrophobic interactions with the latter.     

Adsorption-desorption dynamics of cyprodinil and fludioxonil in vineyard soils

Cyprodinil and fludioxonil are new-generation fungicides that are employed to protect grapevines from botrytis and various rots. In this work, their adsorption and desorption dynamics in eight vineyard soils from Galicia (northwestern Spain) were examined in batch and column experiments. Both fungicides exhibited linear adsorption isotherms, with more ready adsorption (greater Kd) of fludioxonil. Kd values for cyprodinil were significantly correlated with soil organic matter content (r 2= 0.675, p < 0.01). Both pesticides exhibited adsorption-desorption hysteresis, but desorption was easier and more variable for cyprodinil (12-21%, RSD = 17%) than for fludioxonil (3-5%, RSD = 13%) and appeared to depend on the formation of irreversible bonds in the former case and on poor solubility in the latter. A linear adsorption model involving nonequilibrium conditions and an irreversible adsorption term was found to reproduce transport behavior accurately.     

The soils of the eastern hilly area and their suitability to vineyard in Friuli (Italy)

Typic Eutrochrepts (from “Flysch”), Typic Udifluvents (from alluvial deposits), Dystric Eutrochrepts and Plinthic Paleudults on old alluvial deposits and terraces were characterized. All soils investigated fall in the suitability class S2 or S3 for grape cultivation. Imperfect drainage and acidic reaction are most prominent soil limitations. Fertilization with organic matter, N and some microelements such as Zn, as well as drainage improvement, are the suggestions proposed in order to increase the soil fertility and the wine production.     

Influence of soil properties on the adsorption and mobility of metamitron

Abstract

The adsorption and mobility of herbicide, metamitron, in 41 soils samples from the province of Salamanca (Spain) was studied. Thirty‐four of the samples assayed were from irrigated soils and seven were from natural, uncultivated soils with organic matter contents above 3%. The correlations between the Freundlich K constants, Kd distribution coefficients, and Rf mobility parameters and the soils parameters were determined. Considering all the soils, the soils with organic matter contents above 2% or the soils with organic matter contents below 2%, significant correlations (p<0.001 to p<0.05) were found between K and Kd and the organic matter content of the soils. There were also a significant correlations (p<0.05) of K and Kd with clay+silt and clay contents of soils with organic matter contents below 2%. The adsorption of the herbicide by isolated soil components confirmed the results obtained with the soils and point to the importance of the exchangeable cation nature of the samples in the adsorption process. Based on Rf values obtained by TLC, the herbicide was found to be moderately mobile in 74% and mobile in 26% of the soils studied. The results of metamitron leaching by thin layer chromatography (TLC) and in undisturbed soil columns indicated the influence of organic matter content and of soil texture on the mobility of this herbicide.     

Studies on the adsorption and release of copper by soils

In a previous communication we¹⁾ reported the adsorption and subsequent release of adsorbed Cu⁺⁺ by two soils and a compost sample using fairly high concentrations of Cu⁺⁺ ions in the form of copper sulphate solution.     

Effect of macerating enzymes on red wine aroma at laboratory scale: exogenous addition or expression by transgenic wine yeasts.

The effects of a Trichoderma longibrachiatum endoglucanase and an Aspergillus nidulans endoxylanase on the concentration of free and bound volatiles, color, and phenolics during maceration in red wine vinification has been studied. Two different approaches have been considered for the utilization of these enzymes: (i) direct addition of the enzymes to must and (ii) inoculation of must with recombinant wine yeasts overexpressing these activities. An experimental design based on a Taguchi orthogonal array was carried out in order to evaluate the effects of the enzymatic treatments. The data show that these fungal activities are able to increase the concentrations of free and glycosidically bound flavor compounds, color, and phenolics to similar or greater extents as compared to a commercial pectolytic enzyme preparation. The effects of the two different ways of addition of the enzymes were not always equivalent. These enzymes could be considered to be of potential application in the red wine maceration process.     

Carbendazim adsorption on montmorillonite, peat and soils

The adsorption of carbendazim by peat and montmorillonite was studied as a function of the exchangeable cations and temperature. The adsorption on soils was also studied. The kinetics of carbendazim adsorption on peat showed that adsorption equilibrium was reached within 1 h. The order of adsorption of carbendazim on peat was as follows: H⁺-peat > Cu²⁺-peat > Co²⁺-peat > Mg²⁺-peat > K⁺-peat, and the thermodynamic parameters appeared to suggest an adsorption mechanism involving hydrogen bonds, although in the H⁺, Cu²⁺ and Co²⁺ samples a protonation process and adsorption of the protonated species were also likely. The kinetics of carbendazim adsorption on montmorillonite (mont.) showed that equilibrium was reached within 1 h. The order of adsorption was: H⁺-mont. > Cu²⁺-mont. > Co²⁺-mont. > Ca²⁺-mont., the adsorption on the H⁺ and Cu²⁺ samples being much greater than that on the other samples. For the H⁺ and Cu²⁺ samples, the thermodynamic parameters appeared to suggest a double mechanism: physical adsorption, and protonation and adsorption by ion exchange. The most probable mechanism for the adsorption of carbendazim on the Co²⁺ and Ca²⁺ samples was physical bonding. The capacity for adsorption of this fungicide on soil was dependent on the organic matter, nitrogen and clay content, as well as on the cation exchange capacity. No significant correlation was found with pH, C/N ratio or free iron content.     

Determination of phosphatase activities of soils and animal wastes

A method is described to determine acid and alkaline phosphatase activities from the rate of decomposition of p-nitrophenylphosphate in the presence of large amounts of organic matter, such as occur in the surface layers of soils or in animal wastes. The p-nitrophenol formed is separated by high pressure liquid chromatography on a cellulose column from p-nitrophenylphosphate and other organic compounds present in the soil or waste extract. After separation, p-nitrophenol is measured on-line in a spectrophotometric flow cell at a wavelength of 405 nm. In this way p-nitrophenol concentrations down to 0.1 μm can be measured, making it possible to work with substrate concentrations of 1 μm.

The necessity of correcting the phosphatase activity measured in this way for adsorption of enzyme, substrate (p-nitrophenylphosphate) and product (p-nitrophenol) is discussed.

Acid and alkaline phosphatases are inhibited strongly at phosphate concentrations greater than 0.1 mm, consequently substrate concentrations in the range of 0.01 to 0.1 mm were used.

The method was applied to a number of sandy soils and to pig slurry. Air drying or freeze drying of soils was found to decrease the phosphatase activity. Freeze drying did not affect the phosphatase activity of pig slurry. Michaelis-Menten kinetics were found to apply reasonably well. The resulting kinetic parameters are compared with values from the literature. Phosphatase activities are correlated with organic P and organic matter contents of soils and pig slurry.     

Effect of wetting and drying of soils on phosphate adsorption and resin extraction of soil phosphate

Sixteen topsoils from Denmark and the UK were subjected to two wetting and drying treatments: (i) moist incubation (wet), (ii) eleven wetting and drying cycles (W/D). The W/D treatment resulted in larger P adsorption and resin extraction of soil P than the wet treatment. The differences in P adsorption at the final concentration of 800 μM P were mainly above 20 per cent, whereas the differences in amount of resin-extracted P were mainly less than 20 per cent. The effects were positively correlated with the cation exchange capacity of inorganic components. Furthermore, the increase in rapidly released P was positively correlated with pH. It is suggested that wetting and drying effects on P adsorption and desorption are associated with changes in soil structure caused by rewetting of dry samples.     

Sulfate adsorption by variable charge soils: Effect of low-molecular-weight organic acids

Sulfate (SO₄ ^2–) movement and transport in soils has received considerable attention in recent years. In most soils, SO₄ ^2– coexists with a variety of natural organic compounds, especially organic acids. Studies were conducted to assess the effect of low-molecular-weight organic acids (eight aliphatic and five aromatic acids) on SO₄ ^2– adsorption by variable charge soils from Chile and Costa Rica. The effects of type of organic acid, pH, type of soil, and organic acid concentration were investigated. In one experiment, a 1.0 g soil sample was equilibrated with 25 ml 0, 0.5, 1.0, 2.0, 4.0, or 6.0 mM K₂SO₄ in 1 mM NaCl in the presence or absence of 5 mM citric acid. In the second set of experiments, the adsorption of 2 mM SO₄ ^2– in soils at pH 4 or pH 5 in the presence or absence of one of 13 organic acids at a concentration of 2 mM or 5 mM was studied. Results showed that citric acid significantly decreased SO₄ ^2– adsorption by the two soils. Sulfate adsorption decreased with increasing pH of the equilibrium solution. Aliphatic acids, with the exception of cis-aconitic acid, decreased the amount of SO₄ ^2– adsorbed by the two soils, with oxalic, tartaric, and citric acid showing the greatest effect. The differences in pH values of the equilibrium solutions in the presence and absence of organic acids were significantly, but negatively, correlated with the amount of SO₄ ^2– adsorbed, suggesting chemisorption of SO₄ ^2– and the release of hydroxide ions. The ionization fraction values of the organic acids at the equilibrium pH were correlated with the amounts of SO₄ ^2– adsorbed, suggesting that the protonation of surface hydroxyl groups of the mineral phase increased as the strength of the ionization of the acid increased, thus creating more positively charged surfaces. Received: 12 February 1997     

Aspects of the adsorption of pirimicarb by smectites and soils

A study was conducted to examine the adsorption and interaction mechanism of pirimicarb with smectites and soils. Studies were carried out in pesticide-smectite or soil-water systems and in pesticide-smectite-organic solvent systems, using homoionic samples of montmorillonite, smectites of different layer charge and soils with smectite in their clay fraction. The adsorption isotherms obtained at 30° and 45°C follow the empirical equation of Freundlich. In the adsorption of the pesticide by soils a highly significant correlation was seen between adsorption (distribution coefficient) and the content of smectite in them. In the studies in organic medium the formation of a smectite-pirimicarb bilayer complex with a basal d₀₀₁ spacing of 18.55 Å was observed; the formation of this is also related to the nature of the interlayer cation and the layer charge of the smectite. According to the I.R. results, the interlayer cations of the silicate and the oxygen atom of the C–O group of the pesticide molecule are involved in the interaction mechanism.     

Effects of industrial liquid wastes on dinitrogen fixation and microflora of soils and waters

Potential N₂-fixation was investigated in a number of samples representing soils and water courses under the effect of some industrial wastes in Helwan area of Egypt. Microbiological analysis of soil and water samples showed the general enrichment of fungi, actinomycetes and bacteria including N₂-fixers. Among asymbiotic N₂-fixers, azospirilla compared to azotobacters and clostridia were found to be present with rather higher densities in all samples tested. Generally, the microbial numbers increased by increasing the distance from the Industrial Complex at Helwan, which could be attributed to the high levels of salinity and total heavy metals near the factories. The results indicated that the industrial wastes near the factories exerted inhibitory effects on the acetylenereducing activity in soils, which seriously reduces their biological fertility. Such effects were decreased by getting away from the factories. Significantly negative correlations were recorded between densities of N₂-fixers or N₂-ase activity and salinity and total heavy metals content in both soil and water samples.     

Effect of phosphorus addition on onion plants grown in 13 soils of varying degree of weathering

Phosphorus (P) phytoavailability decreases with soil weathering, however P dynamics in high-P soils with relatively narrow differences in weathering and further addition of P is not known. In the present study, P dynamics and availability in soils varying in their chemical properties and P availability were examined. Onion plants were grown in 13 high-P soils at two P levels [Ρ0 and Ρ1]. Extractable P was assessed with Olsen, Mechlich-3, ammonium oxalate, and water soluble methods, as well as plant tissues P content and morphological features. Despite the initial high P content, all the measured parameters, including soil P, plant morphology, and P content, further increased at P1 compared to P0. Moreover, water soluble P, bulb weight, and plant P content exhibited greater differences between P0 and P1 in Alfisols. In conclusion, for high-P soils, P application could increase traits, such as onion bulb weight, especially for soils with higher weathering.     

Effect of flow rate on the adsorption and desorption of glyphosate,simazine and atrazine in columns of sandy soils

Adsorption and desorption of the herbicides glyphosate [N-phosphonomethyl-aminoaceticacid], simazine [6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-diamine] and atrazine [6-chloro-N²-ethyl-N⁴-isopropyl-1,3,5-triazine-2,4-diamine] were studied in four sandy soils from Western Australia. Distribution coefficients (K_ds) were calculated from breakthrough curves (BTCs) resulting from leaching step changes in concentrations through small saturated columns of soil at flow rates ranging from 0.3 to 30 m day^–1. A comparison was made with K_ds obtained after batch equilibrating solutions of the herbicides with the same soils. The K_ds of herbicides in soils decreased with increasing flow rate and most strongly for glyphosate in soils rich in clay content. Resulting increases in mobility of about 40–50% were estimated for simazine and atrazine and > 50% for glyphosate at flow rates of 3 m day^–1. Adsorption and desorption rates were estimated by fitting numerically simulated BTCs to experimental BTCs. Best fits were obtained with a time-dependent Freundlich adsorption equation. The resulting coefficient for time dependency in the equation suggests that the rates of adsorption and desorption are controlled mainly by diffusion in an adsorbing layer on or in soil particles.