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).     

Effect of the simultaneous addition of beta-cyclodextrin and the herbicide norflurazon on its adsorption and movement in soils

The effects of beta-cyclodextrin (BCD) on the sorption-desorption and transport processes of the herbicide norflurazon (NFL) in soils of different characteristics when both are applied simultaneously have been investigated. Adsorption-desorption studies of NFL on six soils of very different characteristics in the presence of BCD have been performed using a batch equilibration method and correlated to its mobility in homogeneous hand-packed soil columns. NFL determinations were undertaken by HPLC equipped with a diode array detector at a wavelength of 220 nm. BCD was also analyzed by HPLC with fluorimetric detection using a postcolumn reaction. The interaction of NFL with BCD yielded the formation of an inclusion complex in solution. When this complex is applied to soils, a large decrease in NFL adsorption capacity and an increase in its desorption were observed, due to the higher tendency of NFL-BCD complexes to remain in solution. The results obtained in adsorption and soil column experiments indicated that the influence of BCD on NFL mobility and availability depends on the different affinities of BCD to be sorbed on soils of different characteristics and on the concentration of BCD used. The lower the concentration of BCD added, the more tenaciously it adheres to the soil, and most of the BCD molecules would be adsorbed, providing a coating to soil particles that acts as a bridge between NFL and the soil surface, acting as an adsorbent and retarding the mobility of the herbicide. At higher concentrations of BCD, or in soils where its adsorption is very low, most of the BCD molecules are in the aqueous phase and NFL molecules tend to be complexed with BCD in solution, acting then as a solubilizing agent.     

硫酸根离子添加顺序对可变电荷土壤吸附铜离子的影响

研究了SO2-4添加顺序对三种可变电荷土壤(昆明铁质砖红壤、徐闻砖红壤和江西红壤)吸附Cu2+的影响,作为对照,也研究了其对恒电荷土壤(黄棕壤、棕壤)以及两种不同矿物(高岭石与针铁矿)吸附铜离子的影响。实验结果表明,在同等条件下,SO2-4添加顺序对两类表面性质不同的土壤吸附Cu2+有着不同的影响。对于恒电荷土壤,SO2-4添加顺序对土壤吸附Cu2+几乎没有影响。同等pH条件下,对可变电荷表面而言,加入CuSO4者具有最高的Cu2+吸附率;对昆明砖红壤、徐闻砖红壤以及针铁矿和高岭石而言,先加入Cu2+者相对先加入SO2-4者Cu2+吸附率更高;对江西红壤而言,上述这个次序则刚好相反。SO2-4浓度和有机质去除对同等pH条件下铜离子吸附率高低的排序并无实质性影响。     

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.     

Influence of copper on the adsorption and desorption of paraquat, diquat, and difenzoquat in vineyard acid soils

Retention of the cationic herbicides paraquat (PQ), diquat (DQ), and difenzoquat (DFQ) in two vineyard soils with a different management history and retention capacity was examined. The influence of copper on the ability of the soils to retain the herbicides was determined by comparing the results of adsorption and desorption tests on untreated and Cu-enriched soil samples, and also on soils that were previously treated with EDTA to extract native copper. The three herbicides were strongly adsorbed by both soils. Soil 1 exhibited linear adsorption isotherms for PQ and DFQ with partition coefficients, KD, of 1.28 x 103 and 1.37 x 103 L kg-1, respectively, and a Freundlich-type isotherm for DQ with a linearized partition coefficient, KD*, of 1.01 x 103 L kg-1. On the other hand, soil 2 exhibited curved isotherms and smaller KD* values (viz. 106, 418, and 28 L kg-1 for PQ, DQ, and DFQ, respectively). Using EDTA to extract copper from the soils released new sites for the herbicides to bind. The three herbicides exhibited strong hysteresis in the adsorption-desorption process. Extracting copper decreased the percent desorption of PQ and DQ; on the other hand, it decreased the affinity of DFQ for the resulting vacant adsorption sites. Similarly, competitive adsorption tests with copper and the herbicides revealed that the metal was only capable of displacing DFQ from adsorption sites. The behavior of this herbicide in the soils was consistent with a specific adsorption model. The disparate behavior of the two soils toward the herbicides was a result of the adsorption sites in soil 1 being less extensively occupied than those of soil 2 in the adsorption tests. The effect of copper on the adsorption of DFQ in the two soils was acceptably reproduced by an adsorption model involving Coulombic and specific sorption with competition from the metal.     

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.     

Effect of organic amendments on the retention and mobility of imazaquin in soils

The influence of two organic amendments consisting of an urban waste compost (SUW) and a commercial amendment from olive mill wastes (OW) was assessed on the sorption properties and leaching of the ionizable herbicide imazaquin on four soils with different physicochemical characteristics. A loamy sand soil (CR), a loam soil (P44), a silt loam soil (AL), and a clay soil (TM), with low-medium organic matter contents, were chosen. Sorption-desorption experiments were performed on the original soils and on a mixture of these soils with the organic amendments at a rate of 6.25% (w/w). These mixtures were used just after preparation and after aging for 3 months. Imazaquin adsorption was higher on AL soil because of its high content of amorphous iron oxides, whereas it was related to the soils' organic matter (OM) contents on TM and CR soils and to acid pH on P44 soil. Addition of exogenous OM to soils caused a decrease in the adsorption of the herbicide with the only exception of CR soil, due to blocking of adsorptive surfaces and/or equilibrium pH rise. The extent of this decrease was dependent only on the nature of the added amendment on AL soil. The adsorbed amounts of imazaquin on aged organic fertilized soils were usually fairly close to that on original soils. Results of soil column experiments indicate that addition of exogenous organic matter cannot be considered as a regular practice for retarded movement of imazaquin.     

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.     

施用堆肥对葡萄园土壤中敌草隆残留与迁移的影响

Diuron is frequently detected in surface- and groundwater under the vineyards, where organic amendments are often used, in Burgundy of France. Undisturbed column experiments were conducted to study the influence of three composted organic amendments on diuron leaching through columns of two vineyard soils from Vosne-Roman′ee(VR, calcareous Cambisol) and Beaujolais(Bj, sandy Leptosol), France. Bromide(used as non-reactive tracer) and diuron breakthrough curves(BTCs) were analyzed using convectivedispersive equation(CDE), two-region(mobile-immobile, MIM) and two-site models. No influence of the composts was observed on the bromide recovery rates. The CDE model described well the bromide BTCs for all columns of the Bj soil and seven of the VR soil, suggesting a homogeneous water flow. However, for five VR soil columns, the MIM model fitted better, suggesting a partition of the water flow(15%–50% of matrix flow). The texture, the coarse material content and the tillage of the VR soil could explain this heterogeneity. However, for all columns, diuron leaching was greater through the Bj soil(46%–68%) than the VR soil(28%–39%). The compost addition resulted in a contrasting effect on diuron leaching: no difference or a decrease was observed for the VR soil, probably due to an increase of adsorption sites, whereas no difference or an increase was observed for the Bj soil possibly because of interactions and/or competition of diuron with the compost water-extractable organic matter which could facilitate its transport. All the diuron BTCs were best described using the two-site model, suggesting a large proportion of time-dependent sorption sites(30%–50%). The soil type and the nature of the amendments had contrasting influences on diuron transport. Composts with a high water-soluble fraction must be avoided in sandy soils to reduce the risk of groundwater contamination.     

Cadmium adsorption as influenced by poultry manure addition in soils of South-Western Nigeria

Soil contamination with heavy metals is of great concern worldwide because of its negative effects on human health and environment. The objective of this study was to evaluate the influence of poultry manure on cadmium (Cd) adsorption characteristics in soils from ten different land uses and to determine the effects of Cd adsorption on soil properties. Laboratory experiments were carried out using Cd concentrations ranging from 0 to 160 mg Cd L^?1 and poultry manure rates ranging from 0 to 8% w/w basis. Results showed that all the soils exhibited varying capacity to adsorb Cd with values ranging from 28.78 to 130.2 mgkg^?1; 126.2 to 153.5 mgkg^?1 and 126.2 to 156.1 mgkg^?1 for 0%, 4% and 8% poultry manure at 160 mgkg^?1 initial Cd concentrations, respectively. Lowest Cd adsorbed (28.78 mgkg^?1) was recorded in samples from 6 months fallow and highest (156.1 mgkg^?1) from vegetable field. On the average, capacity to adsorb Cd was 72.1%, 99.7% and 95.3% with 0%, 4% and 8% applied poultry manure, respectively. Organic carbon, CEC, pH were significantly correlated with Cd adsorption. Poultry manure use will increase Cd adsorption and decrease Cd in the environment.     

Effect of liming and air-drying on the adsorption of phosphate by some acid soils

The effect of liming the A and B horizons of a number of acid soils on the subsequent adsorption of phosphate by soils retained moist or allowed to dry was investigated. Air-drying increased the phosphate adsorption capacity but the reason was not clear. When A horizons were maintained moist, incubation with lime for six weeks increased phosphate adsorption by four samples and had no effect on another. When A horizons were air-dried, the effect was considerably reduced or reversed. For B horizons, which had considerably greater phosphate adsorption capacities than A horizons, liming decreased phosphate adsorption irrespective of whether the soils remained moist or were dried. The relative decrease in adsorption was, however, greater when the soils were dried. In a more detailed study using one acid soil it was shown that incubation of the soil with lime for six weeks had no effect on phosphate adsorption by moist A and B horizons but after 36 weeks incubation liming decreased adsorption by the moist samples. If soils were dried then liming decreased phosphate adsorption after six or 36 weeks incubation. Such relative effects of liming on phosphate adsorption were confounded by the fact that air-drying greatly increased the phosphate adsorption capacity of the unlimed soil. The drying effect was at least partially reversible following rewetting of the soil. Results were interpreted in terms of the lime-induced increase in soil pH causing (i) the surface charge conferred on soil oxide surfaces to become more negative (thus decreasing phosphate adsorption) and (ii) the precipitation of exchangeable Al as hydroxy-Al polymers resulting in the formation of new, highly active, adsorbing surfaces (thus increasing phosphate adsorption). Phosphate adsorption by moist limed soils can, therefore, be increased, decreased or unaffected depending on the relative magnitudes of these two processes. It is suggested that after liming, and/or air-drying, crystallization of amorphous materials progressively decreases their surface area and adsorbing capacity. Thus, liming tends to decrease phosphate adsorption when the soils are dried.     

Mobility of copper and zinc fractions in fungicide-amended vineyard sandy soils

The purpose of this study was to evaluate the mobility of copper (Cu) and zinc (Zn) in the profile and distribution of sandy soil fractions from vineyards. Soil samples were collected from two vineyards of different ages (14 and 30 years) and a natural field area in the south of Brazil. The chemical characteristics, Cu levels and Zn levels, were analyzed in the soils by extraction with ethylenediamine tetraacetic acid (EDTA) using the 3050B method of USEPA and by chemical fractionation. Cu and Zn were accumulated in the vineyard soils, especially in the uppermost soil layers and in the soil from the oldest vineyard. Approximately, 75% of the total Cu was extracted by EDTA, but only 30% of the total Zn was extracted by EDTA. Most of the Cu, especially in the oldest vineyard, was distributed in the mineral-associated fraction, which is characterized by low geochemical mobility, but another important part of the Cu was distributed in the soil organic matter. Most of the Zn in the soil was distributed in the residual and mineral-associated fractions, which are characterized by low mobility and have potential for causing toxicity to plants.     

硫酸盐对锌和镉在可变电荷土壤上吸附的影响

SO4^2- and Zn^2 or Cd^2 were added to three variable charge soils in different sequences.In one sequence sulfate was added first ,and in the other,Zn^2 or Cd^2 first.The addition of sulfate to the system invariably caused an increase in adsorption of the heavy metal added,with the effect more remarkable whn the soil reacted with the sulfate prior to the metal.the shift in pH50 for both Zn and Cd adsorption was aslo comparatively larger in the first sequence of reactions .It was suggested that the increase in negative charge density and the resultant negative potential of the soil were the primary cause of the pronounced effect of sulfate on adsorption of Zn or Cd,and the formaiton of the ternary surface complex-S-SO4-M might also play a role in the effect.     

Effect of plant litter addition on element leaching in young sandy soils

The knowledge about element leaching and biogeochemical cycles during initial stages of soil development is very limited. Therefore, we studied the effects of parent material characteristics and plant litter addition on element leaching from young sandy soils in a microcosm experiment. Our objective was to evaluate the function of young soils as a source and/or sink for nutrients during initial pedogenesis and to identify main processes which are involved in the initial development of biogeochemical cycles. The main research questions were: (1) How do differences in parent material characteristics affect nutrient leaching?; and (2) How is nutrient leaching of young soils influenced by litter addition of different plant functional groups (e.g., legume and grass species)? Combined treatments of two minimally weathered parent materials (pure sand and loamy sand) with plant litter of two plant species (Lotus corniculatus L. and Calamagrostis epigejos L.) were investigated in a soil column experiment. In addition, control columns with parent material or plant litter only were included. Carbonate weathering as a main source for calcium leaching was induced by the moderately acidic irrigation solution used in the experiment. It was 7.5 fold greater for the loamy sand parent material compared to the pure sand despite lower carbonate contents in the loamy sand. Leaching of K was very low for both parent materials but greater for the loamy sand parent material, likely due to transfer processes from fixed to exchangeable potassium forms in the clay minerals of the loamy sand. Plant litter addition generally increased leaching losses. Carbonate dissolution was intensified by both plant litter types, especially by L. corniculatus, very likely due to H⁺ released during nitrification of N released from plant litter and an increase in partial pressure of CO₂ from microbial respiration. In contrast, K was largely retained in the soils, probably due to fixation by clay minerals and microbial immobilization. Only the pure sand treated with L. corniculatus litter leached K, resulting in 4–6 fold greater leaching losses compared to all other treatments. Nitrogen released from L. corniculatus litter was almost completely nitrified and was nearly doubled as compared to that from C. epigejos, resulting in greater N leaching. The results of our study allow identifying the general function and processes of vegetation patches in young ecosystems formed as a result of initial parent material characteristics and invading vegetation with respect to litter decomposition, soil solution composition, nutrient retention and leaching, and effects on the soil mineral phase. These patterns are not mere additive effects of parent materials plus plant litter, but reflect differences in biogeochemical process intensities and could result in an increasing heterogeneity of soil properties, nutrient availability, and element leaching fluxes with time.     

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.     

Microbial response to the addition of glucose in low-fertility soils

Addition of soluble organic substrates to soil has been shown to either increase or restrict the rate of microbial CO₂–C evolution. This has been attributed to a priming effect resulting from accelerated or decreased turnover of the soil organic matter including the soil microflora. We investigated microbial responses to small glucose-C additions (10–50 μg C g¹ soil) in arable soils either amended or not with cellulose. An immediate CO₂–C release between 0 and 69 h (equivalent to 59% of glucose-C applied) was measured. However, only half of the CO₂–C respired could be attributed to the utilisation of glucose-C substrate, based on the percentage of ¹⁴C–CO₂ evolved after the addition of a ¹⁴C-labelled glucose tracer. Thus, although no evidence of an immediate release of ‘extra’ C above the rate applied as glucose-C was observed, the pattern of decomposition for ¹⁴C-glucose suggested utilisation of an alternate C source. Based on this, a positive priming effect (1.5 to 4.3 times the amount CO₂–C evolved that was attributed to glucose-C decomposition) was observed for at least 170 h in non-cellulose-amended soil and 612 h in cellulose-amended soil. Two further phases of microbial activity in cellulose-amended soils were attributed to either activation of different microbial populations or end-product inhibition of cellulase activity after glucose addition. During these subsequent phases, a negative priming effect of between 0.1 and 1.5 times was observed. Findings indicate that the response of the microbial community to small additions of soluble organic C substrate is not consistent and support the premise that microbial response varies in a yet to be predicted manner between soil type and ecosystems. We hypothesise that this is due to differences in the microbial community structure activated by the addition of organic C and the timing of soluble organic substrate addition with respect to the current dissolved organic C status of the soil.