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.     

Copper fungicide residues in Australian vineyard soils

Copper (Cu) concentrations were measured in Australian vineyard soils to assess the extent and magnitude of Cu accumulation resulting from the use of Cu-based fungicides and to indicate the likely risks to long-term soil fertility. Soil samples were collected from 98 vineyards across 10 grape-growing regions of Australia and analyzed for total Cu concentrations. Ninety-six percent of vineyards surveyed had elevated Cu concentrations in soil compared to the background Cu concentrations in nearby soil in its native state. Concentrations of total B, Co, Cr, Pb, and Zn were similar to background concentrations and below reported toxicity guideline values. Cu concentrations in Australian vineyard soils were generally much lower (6-150 mg kg (-1)) than those reported in the soils of vineyards in parts of Europe (i.e., 130-1280 mg kg (-1)). Concentrations of total Cu were generally below those concentrations reported to cause lethal effects to soil invertebrates; however, Cu exceeded concentrations known to cause sublethal effects (i.e., inhibit growth, affect reproduction, induce avoidance behavior) to those (or related) invertebrates.     

Effect of the addition of wine distillery wastes to vineyard soils on the adsorption and mobility of fungicides

In the present work, a study was made of the effect of the addition of liquid and solid wine distillery wastes (WLW and WSW) to vineyard soils on the adsorption and leaching of penconazole and metalaxyl, two fungicides of different hydrophobic character that are widely used in vine cultivation. The study of these processes is of great interest, since currently the green filter system is implemented simultaneously in vine cultivation and as an alternative to classic purification methods of such organic wastes. Three vineyard soils selected from the La Rioja region (NW Spain) were used. Adsorption isotherms of the 14C-labeled fungicides by the soils in aqueous medium and in WLW medium were obtained, together with the percolation curves of the fungicides in packed soil columns under saturated flow conditions. The adsorption and leaching of metalaxyl in a soil amended with WSW were also studied. The Freundlich Kf constants indicated an increase in the adsorption of both fungicides by the soils in WLW medium as compared to aqueous medium. The amounts of penconazole leached in the three soils when they were washed with water and WLW ranged between 3.18 and 39.3% and between 2.00 and 10.4%, respectively, of the total fungicide added to the columns. In the case of metalaxyl, these amounts represented 69.1-100 and 91.6-117%. Variations were also observed in the shape and parameters of the breakthrough curves obtained in both systems and in the presence of WSW. The soluble organic compounds of WLW must be retained by the soil components, creating new adsorbent hydrophobic surfaces, which increase the retention in the soil of the highly hydrophobic compound penconazole. In the case of metalaxyl, which is very water soluble, the soluble organic compounds of WLW seem to contribute to the increase in its leaching, whereas the WSW favors the opposite effect. The results obtained, indicating modifications in the adsorption and leaching of penconazole and metalaxyl in the presence of WLW and WSW, show that further studies should be carried out on the adsorption and mobility of the fungicides in soils from the vineyard zone, which in turn are used as a green filter purification system of wine wastes.     

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.     

Degradation of the fungicide metalaxyl and its non-extractable residue formation in soil clay and silt fractions

The proportion of organic matter and mineral composition are important factors determining the formation and type of non-extractable residues (NERs) of pesticides in soil. In this study, we investigated the enantioselectivity in degradation and NER formation of the chiral fungicide metalaxyl in soil particle size fractions (silt and clay). Microbial and extracellular enzyme activities during these processes were monitored in incubation of silt and clay samples isolated from sterilized and non-sterilized soil samples collected from a long-term agricultural field experimental site in Ultuna, Sweden. The temporal influence on the fate of the fungicide was noted by short-term (10-d) and long-term (92-d) incubations. Besides the acquisition of quantitative data with gas chromatography-mass spectrometry (GC/MS), stereoselective analyses were performed with chiral GC/MS. Quantitative results pointed to a higher metabolism rate of the pesticide through microbial activity than through extracellular enzyme activity. This was also confirmed by the enantioselective depletion of R-metalaxyl and the subsequent formation of R-metalaxyl acid in microbially active samples from non-sterilized soil. The silt fraction containing a high amount of organic matter exhibited a significant hydrolyzable proportion of metalaxyl NERs that was releasable under alkaline conditions. On the contrary, the clay fraction showed an enhanced affinity for covalently bound residues. Based on our results, we recommend differentiating between reversibly and irreversibly bound proportions of pesticides in persistence and environmental risk assessment because the reversible fraction contained potentially bioavailable amounts of residues that may be released under natural conditions.     

Spatial and vertical analysis of soil properties in a Mediterranean vineyard soil

Soil physical properties influence vineyard behaviour; therefore, the knowledge of their spatial variability is essential for making vineyard management decisions. Little work has been conducted at high spatial resolution on soil properties at depths lower than 0.30 m which is of special relevance to perennial crops. The objectives of this work were to (i) analyse the spatial and vertical variability of soil depth, particle size fractions and water‐holding capacity (WHC) by geostatistical techniques; (ii) study the causes of the variability, with additional information from classical soil sampling; and (iii) assess the significance of WHC through its relationship with vine vigour. The work was carried out in a vineyard of eight hectares within the D.O.Ca. Rioja (northern Spain). Soil variability was determined via grid sampling at three depth ranges (0–0.30, 0.30–0.60 and 0.60–0.90 m). A conventional soil survey provided additional information on soil variability. Clay, sand and silt fractions, soil organic matter content, WHC and pruning weight were determined. Most soil properties had strong or moderate spatial dependence, with the exceptions of sand at 0.30–0.60 m and silt in the topsoil. Topography and soil erosion caused the spatial variability of soil depth and contributed to the spatial distribution of particle size fractions in the topsoil, while the heterogeneity of parent material influenced the spatial pattern of soil properties at 0.60–0.90 m. The WHC and soil depth spatial distributions related well to that of vine vigour, demonstrating the importance of knowing the spatial variability of these soil properties.     

土层性质对铜和铅在土壤中保持和迁移的影响

The mobility and bioavailability of heavy metals in soils is largely governed by sorption and desorption phenomena.Cu2+ and Pb2+ are among the most potentially toxic heavy metals and they are present,often concomitantly,in many polluting spills and in agrochemicals.The objective was to assess and compare the competitive sorption and desorption capacities and sorption hysteresis of Cu2+ and Pb2+,as well as their migration through the profiles of four natural soils:a Humic Umbrisol,an Umbric Cambisol,an Endoleptic Luvisol and a Humic Cambisol.In all horizons Pb2+ was invariably sorbed and retained to a greater extent than Cu2+.The sorption and retention of Cu2+ were most in?uenced by pH,e?ective cation exchange capacity(CECe) and Mn oxide content.On the other hand,the fixation capacity of Pb2+ was most in?uenced by pH,CECe,and Mn oxide and organic matter contents.pH and CECe were the individual soil properties most markedly in?uencing Cu2+ and Pb2+ sorption and retention.In all the horizons Pb2+ exhibited greater hysteresis than Cu2+.In each soil the hysteresis in the A horizon was greater than that in the B horizon,except in the Bt horizon of the Endoleptic Luvisol,due to its high pH and vermiculite content.Based on migration indices,Pb2+ was less mobile than Cu2+ in the studied soils.     

Boron adsorption characteristics of some acidic alluvial soils in relation to soil properties

Abstract

We investigated boron (B) adsorption characteristics for 16 acid alluvial soils as a function of equilibrium B concentration (0–80 μg/mL) and the effect of soil properties on such adsorption. The adsorption data for the soils could be described by Freundlich, Temkin, and BET isotherm equations over the entire concentration ranges studied, and by Langmuir and Eadie‐Hofstee equations only over a limited range. In general, the B adsorption capacity and the energy of retention of the soils calculated from different equations are low, the average Langmuir adsorption maxima and bonding energy constant being 21.47 μg/g and 0.113 mL/μg, respectively, making B susceptible to leaching losses. Simple and multiple regression analysis show that the adsorption capacities are significantly influenced by organic carbon (C), cation exchange capacity (CEC), and different forms of aluminium (Al) content in soils. The energy related constants are also influenced by the forms of Al in soils. Existence of significant correlations between constants obtained from different equations confirmed the adsorption characteristics of the soils.     

Sorption and mobility of 14C-labeled imazaquin and metolachlor in four soils as influenced by soil properties

Aqueous batch-type sorption-desorption studies and soil column leaching studies were conducted to determine the influence of soil properties, soil and suspension pH, and ionic concentration on the retention, release, and mobility of [14C]imazaquin in Cape Fear sandy clay loam, Norfolk loamy sand, Rion sandy loam, and Webster clay loam. Sorption of [14C]metolachlor was also included as a reference standard. L-type sorption isotherms, which were well described by the Freundlich equation, were observed for both compounds on all soils. Metolachlor was sorbed to soils in amounts 2-8 times that of imazaquin, and retention of both herbicides was related to soil organic matter (OM) and humic matter (HM) contents and to herbicide concentration. Metolachlor retention was also related to soil clay content. Imazaquin sorption to one soil (Cape Fear) increased as concentration increased and as suspension pH decreased, with maximum sorption occurring in the vicinity of pK(a1) = (1.8). At pH levels below pK(a1) imazaquin sorption decreased as hydronium ions (H3O+) increased and competed for sites. NaCl was more effective than water in desorption of imazaquin at pH levels near the pK(a1). Mechanisms of bonding are postulated and discussed. The mobility of imazaquin through soil columns was in the order Rion > or = Norfolk > Cape Fear > or = Webster, whereas for metolachlor it was Rion > or = Norfolk > Webster > or = Cape Fear. Imazaquin was from 2 to 10 times as mobile as metolachlor.     

Phosphorus adsorption by a range of western Australian soils related to soil properties

Abstract

The capacity of 36 Western Australian soils to adsorb phosphorus (P) was measured by three different methods: P retention index (PRI), P buffering capacity (PBC), and P adsorption (PA). The P adsorption values measured by all three methods varied markedly with soil type. When the P adsorption values were correlated with several soil properties, using simple and multiple linear regressions, PRI, PBC, or PA values were found to be significantly correlated with the aluminium oxide content of the soils. In addition, PBC and PRI was correlated with organic carbon content. The role of aluminium oxide (Al₂O₃) in the soil was apparently more important in determining the P adsorption capacity of the soils than that of iron (Fe), even though the iron oxide (Fe₂O₃)content of all the soils studied was consistently higher than the aluminium oxide content. The relationship between P adsorption and the selected soil properties, as determined by multiple linear regression, explained 45–59% of the variation: arabic PRI = ‐10.87 + 9.94 organic C (%) + 160.02 Al₂O₃ (%), r² = 0.45.

arabic PBC = ‐0.004 + 1.532 organic C (%) + 22.26 Al₂O₃ (%), r² = 0.57.

arabic PA = 3.52 + 248.75 Al₂O₃ (%), r² = 0.59.

     

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.     

The relationship between copper accumulated in vineyard calcareous soils and soil organic matter and iron

The intensive use for over 100 years of copper sulphate (Bordeaux mixture) to fight mildew in vineyards has led to a substantial accumulation of copper (Cu) in surface soils. To assess the effects of such large concentrations, the surface soils of 10 Burgundy vineyards were sampled and analysed for total organic matter (carbon and nitrogen) and metal (copper and iron) contents. Physical (i.e. size fractionation) and chemical (sequential extraction) methods were used to determine the distribution of these elements. The most Cu‐contaminated plots showed the largest accumulation of organic carbon and Cu in the coarse sand and fine sand fractions. Copper was strongly correlated with organic carbon and organic nitrogen in the coarse sand fraction and with organic nitrogen in the fine sand fraction. Copper was also highly correlated with both Fe and organic nitrogen in the clay fraction but not significantly with organic carbon. The sequential extraction showed that Cu was bound mainly to the Fe oxides. However, in the most Cu‐contaminated plots, a part of added Cu was bound to organic matter. This study suggests that Cu protected indirectly the organic matter present in the coarse fractions against biodegradation, and therefore modified the distribution of organic carbon among the particle‐size fractions. Iron appeared as the main factor responsible for Cu accumulation in the clay fraction, mainly through inclusion of Cu in Fe oxyhydroxides and possibly in clay–humus complexes.     

Zinc adsorption characteristics of selected calcareous soils of Iran and their relationship with soil properties

Abstract

The apparent recovery of applied zinc (Zn) by plants is very low in calcareous soils of Iran because most of it is retained by the soil solids. Subsamples of 24 surface soil (clay 130–530 g kg^‐1; pH 7.7–8.4; electrical conductivity 0.63–3.10 dS m^‐1; organic matter 6.0–22.0 g kg^‐1; cation exchange capacity 8–20 cmol kg^‐1; calcium carbonate (CaCO₃) equivalent 180–460 g kg^‐1) representing 13 soil series in three taxonomic orders were equilibrated with zinc sulphate (ZnSO₄) solutions and the amount of Zn disappeared from solution after a 24‐h shaking period was taken as that adsorbed (retained) by the soil solids. The adsorption data were fitted to Freundlich (X=AC^B) and Langmuir [X=(K‐bC)/(1+K#lbC)] adsorption isotherms. Backward stepwiseprocedure was used to obtain regression equations with isotherms coefficients as dependent and soil properties as independent variables. Freundlich A and Langmuir K were found to be highly significantly related to pH and clay and increasing as these soil properties increased. But Langmuir b was related only to clay and Freundlich B showed no significant relationship with any of the properties studied. The distribution coefficient (also called maximum buffering capacity), calculated as the product of Langmuir K and b, was also found to be highly significantly related to pH and clay. It is concluded that pH and clay content of calcareous soils are the most influential soil properties in retention of Zn.     

Adsorption and mobility of linuron in soils as influenced by soil properties, organic amendments, and surfactants

Adsorption and mobility of the herbicide linuron (3-3, 4-dichlorophenyl-1-methoxy-1-methylurea) in 35 irrigated soils with organic matter (OM) contents in the 0.43-2.59% range and in four natural soils with OM contents in the 4.16-11.69% range were studied using the batch equilibration technique. The adsorption isotherms were found to conform to the Freundlich adsorption equation. The Freundlich constant, K, and the distribution coefficient, K(d), were seen to be highly significantly correlated (p < 0.001) with the OM content when all soils or only those with an OM content above 2% were considered. There was also a significant correlation of K and K(d) with the OM content (p < 0.05) and of K(d) with the clay and silt plus clay contents (p < 0.1) when the soils with a OM content below 2% were considered. On the basis of the R(f)() values obtained by soil TLC, the pesticide was found to be slightly mobile in 77% and moderately mobile in 23% of the soils studied. The results of the leaching of linuron in soil columns unmodified and modified with two organic agricultural amendments, a city refuse compost, and two surfactants (one of them cationic and the other anionic) revealed that the leaching rate and the mass transfer of the herbicide to water were affected, increasing or decreasing according to the characteristics of the amendments and the doses added. These results also point to the usefulness of selected organic materials and surfactants in the development of physicochemical methods for preventing the pollution of soils, sediments and aquifers by hydrophobic pesticides.     

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.     

Adsorption and desorption behavior of metalaxyl in intensively cultivated acid soils

Metalaxyl adsorption and desorption behavior in acid soils were evaluated via batch and stirred-flow chamber experiments. On the basis of batch experiments (adsorption curves of the Giles C-type), metalaxyl has a low affinity for acid soils. Also, as derived from batch and stirred-flow chamber tests, its adsorption in acid soils is dictated mainly by their organic matter and clay contents. The high correlation between these two variables makes it rather complicated to resolve their effects. Metalaxyl adsorption occurs largely (80-99%) via fast adsorption reactions. On the other hand, the pesticide is desorbed in variable proportions (30-100%). The desorption parameters obtained by fitting the results to a pseudo-first-order reaction were correlated with no edaphic variable; however, the q(0)/q(max) ratio, which is a measure of reversibility in the adsorption-desorption process, exhibited significant negative correlation with the organic matter and clay contents.     

Quantitative relationship between soil properties and adsorption of dissolved organic matter onto volcanic ash and non-volcanic ash soils

The formation of soil organo-mineral complexes is a key reaction in the carbon cycle in soil, since organic materials acquire a resistance to decomposition due to the formation of the complexes. Adsorption of dissolved organic matter (DOM) onto soil minerals provides a model of this important process. Adsorption of DOM onto samples from Andisols, Inceptisols, and Entisols in batch experiments was compared in terms of the quantitative relationship between the soil properties and the adsorption behavior of DOM. Adsorption behavior was effectively described by a linear initial mass (IM) isotherm, indicating that the adsorption efficiency did not appreciably decline in the range studied even though a large amount of DOM was applied to the soil samples. Samples from Andisols showed a particularly high efficiency of adsorption compared with those from other soils which contained a comparable amount of organic carbon. Explanatory variables useful to predict the efficiency parameter were investigated in 2 steps: firstly the degree of carbon accumulation in the soil samples was examined, and next an index for the amount of ligand exchange sites was examined in combination with the former indices. As a result, an index comprising the total carbon/clay (or total carbon/specific surface area) ratio and the amount of hydroxy ions in the soil extracts with NaF solution was eventually detected. The former represents the degree of carbon occupation on the soil surface, and the latter the amount of ligand exchange sites on labile aluminum. Although the mechanisms involved in the adsorption varied among soils, the selected index was significantly correlated with the adsorption efficiency.     

Andosols and soils with andic properties in the German soil taxonomy

The presence of soils with andic properties on German territory has been suspected for decades and there are numerous reports of sites where they may potentially occur. Andic properties, however, are not adequately represented by the German soil‐classification system. The German taxonomic category “Lockerbraunerde” has not been revised or reconciled with international taxonomic categories since the year 1957, when it was initially proposed. With this review, we show that there are true Andosols of both the silandic (allophane‐containing) and the aluandic (Al‐Humus‐dominated) type in Germany and that their properties differ substantially from other soils which merely exhibit low bulk density. By (1) comparing soil carbon storage between some German Andosols, Chernozems, and nonandic Cambisols with particularly low bulk density and (2) elucidation of the differential pedogenetic pathways leading to Andosol formation, we further demonstrate that Andosols are important objects of study in research issues of contemporary interest. We propose that appropriate measures be taken to lay the foundations for the protection and conservation of these soils, because they are valuable as archives of natural history and provide opportunities to study unique soil processes.