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.     

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.     

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 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.     

甲硫嘧磺隆在土壤中的吸附和解吸特性研究

Methiopyrsulfuron is a new low-rate sulfonylurea herbicide for weed control in wheat; however, there is a lack of published information on its behavior in soils. In this study, methiopyrsulfuron adsorption and desorption were measured in seven soils sampled from Heilongjiang, Shandong, Jiangxi, Sichuan, Anhui, and Chongqing provinces of China using a batch equilibrium method. The Freundlich equation was used to described its adsorption and desorption. Adsorption isotherms were nonlinear with the values of Kf-ads, the Freundlich empirical constant indicative of the adsorption capacity, ranging from 0.75 to 2.46, suggesting that little of this herbicide was adsorbed by any of the seven soils. Soil pH and organic matter content (OM) were the main factors influencing adsorption; adsorption was negatively correlated with pH and positively correlated with OM. Methiopyrsulfuron desorption was hysteretic on the soils with high OM content and low pH.     

Adsorption,Desorption And Mobility of Fomesafen in Chinese Soils

Fomesafen, 5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide, is used widely for weed control in soybeans since its introduction to China. Little information is available on its adsorption, desorption and movement in Chinese soils. The adsorption, desorption and mobility of fomesafen in six Chinese soils was studied. Adsorption isotherms agreed with the Freundlich equation very well. The results of regressionanalysis indicated that soil pH was more important than organic matter for fomesafen adsorption. Fomesafen was more readily desorbed from soils with 0.01 M CaSO₄ solution. Soil TLC and column leaching studies showed that fomesafen and its metabolites was less mobile in Chinese soils. About 89.82% of applied fomesafen and its metabolites still remained in upper 5 cm layer 60 days after treatment under field conditions.     

Dissipation of fungicides in a vineyard soil amended with different spent mushroom substrates

The degradation kinetics and formation of metabolites for fungicides of different chemical classes (iprovalicarb, metalaxyl, penconazole, and pyrimethanil) and determination of bound residues for metalaxyl and penconazole were studied in both an unamended vineyard soil and in the same soil amended with two spent mushroom substrates (composted (C-SMS1) and fresh (F-SMS2)). The degradation kinetics was fitted to single first-order or first-order multicompartment patterns. Degradation rates decreased in C-SMS1-amended soils for all fungicides as compared to unamended soil, but in F-SMS2-amended soils, they decreased only for iprovalicarb and penconazole. The DT(50) values were higher by up to 1.8 (metalaxyl), 3.8 (pyrimethanil), 4.1 (iprovalicarb), and >1000 (penconazole) times in the soil plus C-SMS1 compared to those for soil plus F-SMS2 or unamended soil. The dissipation mechanism recorded the highest mineralization in the unamended soil for (14)C-metalaxyl and (14)C-penconazole, with the highest formation of nonextractable residues in the F-SMS2-amended soil for (14)C-metalaxyl. The results are consistent with (1) the chemical characteristics of each SMS (total and soluble organic carbon) controlling sorption and the bioavailability of fungicides and (2) the microbial activity of SMS-amended soils, which affects fungicide biodegradation. The findings of this work highlight the potential of SMS amendments with different characteristics to decrease or increase the degradation rate of a fungicide in a vineyard soil.     

Adsorption and desorption of arsenate in Louisiana rice soils

Adsorption and desorption of arsenic (As) in the soil are dominant parameters that affect the mobility and bioavailability of arsenic. Batch arsenate adsorption and desorption experiments were conducted using soils collected from three Louisiana, USA, aquaculture ponds representing different crayfish farming and rice cultural practices. Arsenate adsorption behavior in the soils was investigated using Freundlich and Langmuir sorption equations. Results demonstrated that the Langmuir isotherm model was the best fit based on statistical correlation with soil properties governing adsorption, for the entire range of arsenate concentrations for all soils. Adsorption of As(V) was governed by soil physicochemical properties especially Fe and Al oxides, clay and organic matter. Desorption of As(V) was initially fast, but with increasing incubation times desorption occurred progressively slower. Chemical fractionation of arsenic in the soils showed that the most mobile fraction represented 4.74–5.18% of the total arsenic. A part of this mobile fraction could potentially be taken up by rice and enter the food chain, but would require additional research to quantify.     

Organic matter effects on phase partition of 1,3-dichloropropene in soil

The fumigant 1,3-dichloropropene (1,3-D), in combination with chloropicrin, is considered a major replacement to methyl bromide (MeBr). This study was conducted to better understand phase partitioning of 1,3-D and the role of organic matter in its adsorption to soil. Partition of 1,3-D between air and water (K(H)), and between soil and water (K(f)), was determined by quantifying the concentration in both phases upon equilibrium. At 20 degrees C, the K(H) values of (Z)- and (E)-1,3-D were 0.052 and 0.033, respectively. In four California and Florida soils, the K(f) values of 1,3-D isomers ranged from 0.39 to 8.55, and the K(oc) values ranged from 18 to 60. The relatively high K(H) and low K(f) imply that 1,3-D is highly mobile in most soils after subsurface application. Adsorption of 1,3-D in native soils and soils amended with manure compost increased with increasing soil organic matter content. This suggests that organic wastes may be applied to soil to increase 1,3-D adsorption, thus reducing its potential for offsite movement.     

动物粪液中可溶性磷在土壤中的吸附和迁移特性研究

农田土壤施用动物粪肥引入了大量的可溶性有机物、有机磷和无机磷,了解这些可溶性物质在土壤中的相对移动性及它们之间的相互作用有助于指导农田养分管理。本研究从粪液中分离获得含水溶性无机磷、有机磷和有机物（碳）的溶液,选择了具不同质地和有机质含量的4个土壤（含高量有机质的黄筋泥、含低量有机质的黄筋泥、淡涂泥和清水沙）,应用等温吸附和土柱模拟淋洗方法研究了可溶性有机碳、无机磷和有机磷共存条件下,粪液中可溶性有机态磷和无机态磷在土壤中的吸附和迁移特性。吸附试验表明,可溶性有机物（碳）的存在大大降低了土壤对有机态磷和无机态磷的吸附,表明施用液态有机肥比施用化肥具有更大的磷流失风险。供试土壤对无机态磷的吸附强度高于有机态磷,但对二者的吸附量大小为:黄筋泥>淡涂泥>清水沙;并与粘粒含量、氧化铁含量呈正相关。有机质较高的土壤对有机磷的吸附明显低于有机质低的土壤。淋洗试验表明,在供试土壤中,这3种可溶性物质在土壤中吸持(包括生物吸持)的顺序为:可溶性无机磷>可溶性有机碳>可溶性有机磷;有机态磷比无机态磷更易在土壤中迁移。     

Sorption behavior of triazole fungicides in Indian soils and its correlation with soil properties

Adsorption-desorption of triazole fungicides, hexaconazole [2-(2,4-dichlorophenyl)-1-(1H-1,2,4,-triazol-1-yl) hexan-2-ol], triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl) butan-2-one], and penconazole[1-(2,4-dichloro-beta-propyl phenethyl)-1H-1,2,4-triazole] was studied in five Indian soils using batch method. The adsorption isotherms fitted very well to the Freundlich equation. Adsorption of various triazole fungicides increased in this order: triadimefon > hexaconazole > penconazole. The product of the Freundlich adsorption constants, K(f)(1/n), showed good correlation with the soil organic carbon (OC) content, suggesting that soil OC is the main controlling factor for triazoles adsorption. Clay and silt content of the soil also affected the adsorption constants. Adsorption of hexaconazole and triadimefon was nearly reversible in two low OC soils (soil 3, soil 5) where 90-100% of the sorbed fungicides was released in a single washing step. Otherwise, desorption of triazole fungicides showed hysteresis, and 30-60% of the triazole fungicides were retained by the soil after single washing. IR spectra showed that H-bonds and charge-transfer bonds between humic acid and fungicides probably operated as mechanisms of adsorption.     

Degradation and adsorption of fosthiazate in soil

Adsorption and degradation behavior of a pesticide in soil has a strong effect on its environmental fate as well as efficacy for pest control. Fosthiazate is an organophosphate compound that is currently under development as a nonfumigant nematicide. In this study, we evaluated adsorption and degradation kinetics of fosthiazate in three U.S. soils with different properties. Adsorption of fosthiazate in mineral soil was negligibly weak but appeared to increase with soil organic matter (OM) content. The half-life (T(1/2)) of fosthiazate ranged from 0.5 to 1.5 months in nonsterile soils but was prolonged to 1-3 months after sterilization. Degradation of fosthiazate in soil appeared to be caused by both chemical and microbial transformations. The persistence of fosthiazate generally decreased with increasing soil pH, but increased with increasing soil OM and clay contents. This results suggest that fosthiazate may have an enhanced leaching potential in acidic soils with low OM content, and its efficacy in high pH soils may not last as long as in neutral soils because of faster degradation.     

Adsorption and desorption of atrazine, desethylatrazine, deisopropylatrazine, and hydroxyatrazine in vegetated filter strip and cultivated soil

Adsorption and desorption of atrazine and its metabolites in vegetated filter strip soil (VFS) has not been evaluated, yet these data are needed to predict the transport of these compounds through the VFS. Adsorption and desorption parameters for atrazine, desethylatrazine (DEA), deisopropylatrazine (DIA), and hydroxyatrazine (HA) were compared between a cultivated Houston Black clay (CS) and an adjacent 12-year-old VFS established in a mixed stand of bermudagrass [Cynodon dactylon (L.) Pers.] and buffalograss [Buchloe dactyloides (Nutt. Engelm)]. Adsorption and desorption isotherms were determined by batch equilibrium. The evaluated chemical and physical properties of the VFS and CS were similar with the exception of a 1.7-fold increase in the organic carbon content of the VFS. Adsorption and desorption coefficients for atrazine were at least 59% higher in VFS than in CS. The adsorption coefficient for HA was 48% higher in VFS compared with CS, but desorption was not statistically different between soils. Adsorption and desorption coefficients for DEA and DIA were not statistically different between soils. The predicted order of mobility in CS is HA < atrazine = DIA = DEA. In VFS, the predicted order of mobility is HA < atrazine = DIA < DEA. These data indicate that the higher organic carbon in VFS will likely retard the transport of atrazine and HA to surface and ground waters; however, the transport rates of DEA and DIA will be similar between soils.     

[A环-U-14C]丙酯草醚在土壤中的迁移和淋溶

在实验室模拟条件下,采用同位素成像及液体闪烁测量技术对[A环-U-14C]丙酯草醚在7种土壤中的迁移和淋溶特性进行了研究。结果显示:[A环-U1-4C]丙酯草醚在7种土壤(S1~S7)薄板层析中的Rf值分别为0.36、0.27、0.21、0.31、0.30、0.15和0.24,这表明丙酯草醚在S1中属于中等移动农药,而在其余6种土壤中均属于不易移动农药。结果还表明,[A环-U1-4C]丙酯草醚在7种土壤中随水(最大降雨量200mm/24h)的淋溶性较弱,在S1和S4中其主要分布在0~6cm土层,其余5种土壤中则主要分布在0~4cm土层。丙酯草醚在7种供试土壤中的最大淋溶量峰值均出现在0~2cm表层。因此,从迁移和淋溶特性看,田间使用丙酯草醚不易对地下水造成污染。     

Adsorption-desorption of atrazine on four soils of Hyderabad

The adsorption-desorption equilibrium of atrazine (2-chloro, 4-ethylamino, 6-isopropyl amino-1, 3, 5 triazine) was studied by the batch equilibration method at 27 ± 1 °C on four soils of Hyderabad. Adsorption isotherms conformed to the Freundlich equation (A = KC^1/n ). K increased in the same order as the organic C content of the soils. Desorption studies were conducted by repeated replacement of 5 mL of the supernatant equilibrium solutions after adsorption, with 0.01 M CaCl₂. Desorption isotherms showed considerable hysteresis which was more prominent when the desorption was carried out with higher adsorbed concentration of atrazine. Desorption from the lowest level of adsorbed atrazine (3 to 5 μg g^?1 soil) was close to the adsorption isotherm. The cumulative desorption after four desorption steps covering five days was significantly different at the 1% level, for different initial adsorbed concentrations of atrazine. Desorption was significantly higher at the lowest adsorbed level of atrazine. The soils differed significantly at 6% level for desorption and the amount desorbed decreased in the inverse order of organic C. Desorption isotherms also conformed to Freundlich equation but K andn values were both higher than that for adsorption and increased with increase in initially adsorbed concentration of atrazine. Desorption thus confirmed the irreversible nature of the adsorption of atrazine on these soils. The quantitative factors and reasons for desorption are discussed.     

Influence of Increasing Soil Copper Concentration on the Susceptibility of Phosphomonoesterase and Urease to Heat Disturbance

The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO₄ ^2– and PO₄ ^3–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K _f was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.     

Effect of Calcium on the Soil Adsorption of Cadmium and Zinc in Some Spanish Sandy Soils

Castellón Plain is a natural area with an extension of 464 km², situated in Castellón (eastern coast of Spain), with an important number of ceramic industries which generate waste waters containing cadmium and zinc. In this paper, equilibrium adsorption isotherms have been obtained to examine the behaviour of cadmium and zinc in three selected soils of Castellón Plain (Spain) by means of batch experiments. Both metals exhibit non-linear adsorption isotherms with adsorption maximum beyond the dissolved concentration range considered in this study. Statistical analysis showed that data fit slighty better to Freundlich linearization than that of Langmuir. Adsorption coefficients obtained from Freundlich approximation were calculated to evaluate the relative cadmium and zinc distribution between solution and studied soils obtaining coefficients ranging from 5200 to 5900 μg kg^-1μg l^{-1 -n} for cadmium and from 3500 to 43200 μg kg^-1μg l^{-1 -n} for zinc. The effects of salt concentration and calcium competition for adsorption sites were investigated providing different concentrations of CaCl₂ in background solutions. Adsorption capacities of cadmium and zinc in the studied soils decreased when the salt concentration increased. A tenfold increase in calcium concentration reduced the cadmium adsorption capacity approximately by one third whereas the Ca²⁺ ion does not seem a significant competitor with Zn²⁺ for adsorption sites in soils with high organic matter content, where precipitation of zinc can be expected.     

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).     

Adsorption of Cry1Ab protein isolated from Bt transgenic rice on bentone, kaolin, humic acids, and soils

Adsorption on a soil matrix of the insecticidal protein from Bacillus thuringiensis ( Bt) transgenic plants affects their accumulation and release and, hence, bioavailability in soil. Cry1Ab protein isolated from Bt transgenic rice was used to evaluate the adsorption and desorption on bentone, kaolin, and humic acids (HAs). The adsorption equilibrium of Cry1Ab protein was reached within 1-2 h for bentone and kaolin and within 4-8 h for HAs. The adsorption isotherms were better described by linear expressions ( R (2) >/= 0.973) rather than by the Freundlich model. No saturation was observed, even at the maximum concentration used (3.71 microg mL (-1)). The adsorbed protein was not easily desorbed at the used protein concentrations (0.18-3.71 microg mL (-1)); more than 50-70%, 70-80%, and 90% of the adsorbed protein remained on HAs, kaolin, and bentone, respectively, after washing with water. Adsorption and desorption of the Cry1Ab protein were further studied using five soils, and the isotherms were also well-described by linear equations ( p < 0.05). Adsorption of the Cry1Ab protein on soils was positively related to the soil organic matter content.