Changes in the sorption–desorption of fungicides over time in an amended sandy clay loam soil under laboratory conditions

Purpose

The aim of this work was to study the temporal changes in the sorption?Cdesorption of fungicides in a sandy clay loam soil amended with spent mushroom substrate (SMS) under controlled laboratory conditions and the influence that fungicides properties and soil characteristics have on these processes. Soil amendment with SMS is becoming a widespread management practice since it can effectively solve the problems of uncontrolled SMS accumulation and disposal and improve soil quality. However, when simultaneously applied with pesticides, SMS can significantly modify the environmental behaviour of these compounds.

Materials and methods

Sorption?Cdesorption isotherms of metalaxyl, penconazole, pyrimethanil and iprovalicarb for unamended and amended vineyard soils from La Rioja (Spain) were obtained. Composted SMS (C-SMS) and fresh SMS (F-SMS) from cultivation of different mushrooms were used as amendments at 2?% and 10?% rates. Soil parameters (organic carbon (OC), dissolved organic carbon (DOC), humic acid (HA) and fulvic acid (FA)) and sorption (Kf, nf, Kd, Koc) and desorption (Kfd, nfd, H) parameters of fungicides were determined over 0, 6 and 12?months of soil incubation with SMS under controlled conditions.

Results and discussion

Addition of amendments to soil increased soil sorption capacity of fungicides. Kd values increased with the hydrophobic character of fungicides (metalaxyl?<?iprovalicarb?<?pyrimethanil?<?penconazole) at both amendment rates. The lower content of DOC and the higher degree of OC humification enhanced sorption of all fungicides by the soil?+?C-SMS with regard to the soil?+?F-SMS. In general, sorption of fungicides decreased after 6 and 12?months of soil?+?SMS incubation, although the humification degree of the remaining OC expressed by HA/FA increased. This might indicate that the OC content was more important for fungicide sorption than the changes in its nature with the incubation time. SMS addition favoured desorption of metalaxyl and iprovalicarb, in general, whereas irreversible sorption of penconazole and pyrimethanil increased. However, the opposite trends were observed when the soil?+ SMS incubation time increased.

Conclusions

The results show an increase in sorption of all fungicides by amending soil with composted or fresh SMS. However, desorption of fungicides increases or decreases depending on the properties of fungicides and soil?+ SMS. Changes in both processes with the incubation time are more related to the OC content of the amended soil than to the evolution of its nature. These outcomes are of interest for extending SMS application to soil with minimal or no environmental risk when used simultaneously with fungicides.     

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 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.     

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).     

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.     

Effect of Seaweeds on Degradation of DDT in Soils

There are concerns over the environmental risks posed by Cu-based fungicide use, and there is community and regulatory pressure on viticultural industries to restrict the use of Cu-based fungicides. This study assesses the relative environmental risks posed by Cu-based and alternative synthetic organic fungicide compounds used in Australian vineyards, giving particular consideration to their adverse effects on soil microbial activity and how risks vary across different viticultural regions. The study was guided by key steps in the ecological risk assessment framework to analyse the risks of Cu-based fungicides towards soil organisms and involved four key steps: (1) problem formulation, (2) analysis (characterise exposure and effects), (3) risk characterisation and (4) risk assessment. There is evidence of a build-up of Cu-based fungicide residues in Australian vineyard soils, although this has occurred over many years, thus allowing the availability of Cu in the soil to be attenuated over time due to aging processes. On the whole, it appears that Cu-based fungicide residues are currently unlikely to pose a significant risk to soil organisms in Australian vineyard soils. However, there are indicators that continued applications of Cu-based fungicides may well have implications on the use of impacted land for sustainable agricultural production. Further detailed studies are required to enable a more definitive characterisation of the risks posed by Cu-based fungicide residues, such as establishing a clearer link between the laboratory and agricultural settings, investigating effects on other indicators of microbial activity and biodiversity and understanding the resilience of soil microbes to additional stressors. The challenge for agricultural industries and governments, both in Australia and globally, is to formulate appropriate plans to reduce the risks associated with Cu-based fungicide use. Further research is required to consider the relative risks of a wide range of alternative fungicide compounds to ensure that they pose a lower environmental risk than the Cu-based fungicides they may replace.     

Procedure for the measurement of soil inputs of plant-protection agents washed off through vineyard canopy by rainfall

Soil inputs produced by rainfall waters washed off through a Ribeiro vineyard (Galicia, northwestern Spain) confirmed that levels recovered are <5% of the added fungicides. Laboratory studies showed that some fungicides were degraded in the ODS cartridge used for the collection of fungicides washed off by rainfall. Procymidone wash-off data obtained in the vineyard can be explained by a first-order rate mass transfer model. A procedure for the collection of wash-off waters based on octadecylsilane solid phase extraction, followed by an analytical method of reverse-phase liquid chromatography with diode array detection is presented for the evaluation of fungicide inputs into soils after being washed off vineyards by rainfalls. Quality parameters of the analytical method yielded good precision (RSD < 10%) and low detection limits (ranging between 1 and 21 microg/L).     

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.     

Effects of the phenylamide fungicides, mefenoxam and metalaxyl, on the microbiological properties of a sandy loam and a sandy clay soil

The objective of the study was to compare ecotoxicological data obtained from laboratory experiments on the side-effects of three phenylamide fungicides, pure metalaxyl (racemic mixture of R- and S-enantiomers), formulated metalaxyl and mefenoxam (only active R-enantiomer) on the chemical and biochemical parameters of two soils of different type and origin. The purpose of the comparison was to determine to what extent mefenoxam, developed as alternative to metalaxyl, can affect the activity of soil micro-organisms and their processes, and to elucidate the differences between the effects of pure and formulated metalaxyl. The dynamics of the quantitative changes in biochemical parameters induced by the addition of these fungicides at their recommended field rate were determined in a sandy clay soil from Cameroon and a sandy loam soil from Germany, during a 120-day incubation experiment. The type of soil significantly influenced the effect of these fungicides on the soil parameters studied. Incorporation of these fungicides generally stimulated the activity of phosphatases and ß-glucosidase, mineralization and the availability of N and most plant nutrients in soils. The activity of dehydrogenase and the availability of NO₃^- were generally adversely affected. Among the fungicides tested, the stimulation was more pronounced with mefenoxam followed by formulated metalaxyl.     

Enhanced non-extractable residue formation of 14C-metalaxyl catalyzed by an immobilized laccase

We studied the influence of an immobilized laccase from Trametes versicolor on non-extractable residue (NER) formation of the systemic fungicide ¹⁴C-metalaxyl in soil. We added the enzyme (130 mU/g DW) to soil sterilized by gamma irradiation and observed that the amount of NER (6.3 % of applied radioactivity) after 10 days of incubation was enhanced about twofold compared to the sterile soil without laccase addition. Residues formed within samples without enhanced enzyme activity were mainly bound via ester linkages to all fractions of humic matter, i.e., fulvic acids, humic acids, non-humines, and humines, respectively. In contrast, residues formed in presence of immobilized laccase were more strongly bound by covalent linkages such as ether and C-C bonds, especially to humic acids. After chemical degradation of the humic matter, it could be observed that all NER contained the first major transformation product, i.e., metalaxyl acid. The findings underline that the residue formation of metalaxyl in soil may be partly catalyzed by immobilized extracellular oxidative enzymes through oxidative coupling reactions within the humic matter.     

Persistence, fate, and metabolism of [(14)C]metalaxyl in typical Indian soils

The biodegradation of ring-labeled [(14)C]metalaxyl in six Indian soils was examined. The total recovery of radioactivity from soil was 100 +/- 6% of the applied radioactivity. Volatile organics and (14)CO(2) were detected at lower levels. This suggests that neither mineralization nor volatilization is a major route of metalaxyl dissipation. The most rapid degradation of metalaxyl was observed in Bannimantap soil, in which the half-life of metalaxyl was 36 days. An inverse relationship was found when half-lives were plotted against microbial biomass and soil clay content. However, soil total organic carbon did not correlate with metalaxyl persistence. Five metabolites detected by thin-layer chromatography were more polar than metalaxyl.     

Correlations between pesticide transformation rate and microbial respiration activity in soil of different ecosystems

Cecil sandy loam soils (ultisol) from forest (coniferous and deciduous), pasture, and arable ecosystems were sampled (0-10 cm) in the vicinity of Athens, Georgia, USA. Soil from each site was subdivided into three portions, consisting of untreated soil (control) as well as live and sterile samples treated with the fungicide metalaxyl and the herbicide propachlor at 10 mg kg^-1 soil. Pesticide transformation rate, basal respiration (basal) and substrate-induced respiration (SIR) rates, and microbial metabolic quotient (qCO₂) were measured for the initial application of metalaxyl [methyl-N-(2,6-dimethylphenyl)-N-(metoxyacetyl)-DL-alaninate] or propachlor (2-chloro-N-isopropyl-acetanilide) at 22°C and 60% water holding capacity. Positive correlations were found for the following: metalaxyl transformation rate constant (K_met) and basal (r=0.73); K_met and SIR (r=0.83); propachlor transformation rate constant (K_pr) and basal (r=0.89); and K_pr and SIR (r=0.91). Regression analysis of pesticide transformation rate and soil respiration activity, coupled with specific soil properties (pH, C_org, and clay content), revealed a positive correlation between K and SIR for C_org (r=0.88 and 0.98, for metalaxyl and propachlor, respectively). qCO₂s were not significantly different (P=0.05) in propachlor-amended and pesticide-free soils. Metalaxyl amendment resulted in a change in the ecophysiological status of the soil microbial community as expressed by qCO₂. The qCO₂ values in metalaxyl-amended soils were significantly greater (P=0.05) in pine forest (by 25%) and arable and pasture (by 20%) soils compared to unamended soils. Differences in qCO₂ values may represent the magnitude of pesticide-induced disturbance. The duration of this disturbance was greater in the pine forest soil (48 days) compared to arable and pasture soils (21 and 15 days, respectively).     

Fate of diuron and terbuthylazine in soils amended with two-phase olive oil mill waste

The addition of organic amendments to soil increases soil organic matter content and stimulates soil microbial activity. Thus, processes affecting herbicide fate in the soil should be affected. The objective of this work was to investigate the effect of olive oil production industry organic waste (alperujo) on soil sorption-desorption, degradation, and leaching of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] and terbuthylazine [N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine], two herbicides widely used in olive crops. The soils used in this study were a sandy soil and a silty clay soil from two different olive groves. The sandy soil was amended in the laboratory with fresh (uncomposted) alperujo at the rate of 10% w/w, and the silty clay soil was amended in the field with fresh alperujo at the rate of 256 kg per tree during 4 years and in the laboratory with fresh or composted alperujo. Sorption of both herbicides increased in laboratory-amended soils as compared to unamended or field-amended soils, and this process was less reversible in laboratory-amended soils, except for diuron in amended sandy soil. Addition of alperujo to soils increased half-lives of the herbicides in most of the soils. Diuron and terbuthylazine leached through unamended sandy soil, but no herbicide was detected in laboratory-amended soil. Diuron did not leach through amended or unamended silty clay soil, whereas small amounts of terbuthylazine were detected in leachates from unamended soil. Despite their higher sorption capacity, greater amounts of terbuthylazine were found in the leachates from amended silty clay soils. The amounts of dissolved organic matter from alperujo and the degree of humification can affect sorption, degradation, and leaching of these two classes of herbicides in soils. It appears that adding alperujo to soil would not have adverse impacts on the behavior of herbicides in olive production.     

Influence of metalaxyl- and mefenoxam-based fungicides on chemical and biochemical attributes of soil quality under field conditions in a southern humid forest zone of Cameroon

A field experiment was conducted to study the changes in the chemical and biochemical attributes of soil quality resulting from a single application of metalaxyl- and mefenoxam-based fungicides applied as their EC and WPC formulations at the commercially recommended application rate under tropical rainforest field conditions. No significant change in soil pH was observed with fungicide application. Microbial activity indices (available P, available N and specific enzymatic systems) were more sensitive indicators of change. Acid and alkaline phosphatase, and β-Glucosidase activities in soil were affected at different levels with application of fungicides. However, use of metalaxyl and mefenoxam is not likely to harm the soil quality, in general. Simple correlations done between physico-chemical and microbial properties did not produce any significant relationship.     

A hot-spot approach applied to nitrification in tropical acid soils

Several authors have reported that nitrification in acid soils may be restricted to microsites having a more favorable pH. The aim of this study was to propose a conceptual model of the functioning of nitrification in hot-spots, and to test it with the experimental data obtained in laboratory conditions using twelve tropical unamended and -amended soils with a wide range of pH (from 4.2 to 6.9). Nitrification was also measured in two selected soils where the pH was adjusted from 3.5 to 6.2. The model characterizes the relationship between the nitrification rates in unamended and -amended soils as a function of pH. It is based upon the assumption that nitrification of the coming from N mineralization occurs in the hot-spot (RN_h), and the nitrification of the added occurs in the hot-spot and also in its adjacent surrounding region (RN_s). The experimental design was chosen to be able to estimate both nitrification rates. Soil acidity limited nitrification more in -amended soils than in unamended ones. From our approach, this is due to less favorable conditions for nitrification in the region surrounding the hot-spot. The effect of self-induced acidity on nitrification was not noticeable neither in unamended nor in -amended treatments. The model described well three observations made in the experiments: (i) the minimum pH for nitrification to occur was lower for RN_h (pH<4.2) than for RN_s (pH<4.7), (ii) the RN_h/RN_s ratio increased with the decrease of pH (from 1.5 at pH 6 to 8.5 at pH 4), and (iii) for a given pH, the RN_h/RN_s ratio increased with the decrease of the initial pH of the soil. Among the soil parameters determined in this study (i.e. exchangeable Al, EDTA-extractable Cu and Zn, total C and N), only pH was related to nitrification. However, for a given pH, nitrification varied 3-fold among soils, depending upon their initial pH. This suggests that soil pH as determined on bulk soil is not suitable to predict nitrification in each individual soil, because it is not representative of the acidity level within the hot-spot.     

Microbial activities during the early stage of laboratory decomposition of tropical leaf litters: the effect of interactions between litter quality and exogenous inorganic nitrogen

The comparative decomposition of tropical leaf litters (e.g. Andropogon gayanus, Casuarina equisetifolia, Faidherbia albida) of different qualities was investigated under laboratory conditions during a 60-day incubation period conducted with a typical oxisol. Total CO₂-C, soil inorganic N, microbial biomass (fumigation-extraction), -glucosidase and dehydrogenase activities were determined over the incubation to assess how they responded to the addition of inorganic N (+N). Cumulative CO₂-C evolved from the litter-amended soils was higher than that recorded for the unamended control soil. For the unfertilized treatment (0 N), correlation coefficients calculated between initial chemical data and CO₂ flux during the first day of incubation were r =0.963 for water soluble-C and 0.869 for soluble carbohydrates (P <0.05). At the end of the incubation, the amounts of CO₂-C in the F. albida- and A. gayanus-amended soils were higher than that in the C. equisetifolia-amended treatment. Cumulative net N immobilization increased during the first 30 days of incubation, the amounts being similar for A. gayanus- and C. equisetifolia-amended soil and higher than that recorded in the F. albida-amended treatment. Soil microbial biomass and enzyme activities increased in the litter-amended soils during the first 15 days of incubation and decreased (except for the dehydrogenase activity) thereafter. The addition of inorganic N modified the patterns of CO₂-C respiration and net N immobilization. The magnitude of these modifications varied according to the litter quality. The use of an accurate indicator based on several litter components to predict the amplitude of organic material decomposition is discussed.     

Factors affecting triadimefon degradation in soils

The degradation of triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one] was studied in two soils, mollisol and inseptisol, under varying conditions of moisture and temperature, and the role of cow manure amendment and soil sterilization on fungicide degradation was ascertained. The soil moisture content affected the pathway followed for triadimefon degradation. In nonflooded soils (60% water-holding capacity), triadimefon was reduced to triadimenol, and in flooded soils, it was metabolized to the diol derivative [1-(1H-1,2,4-triazol-1-yl)-3,3-dimethylbutan-2-one-1,4-diol]. In nonflooded soils, triadimefon was more persistent in soil having more organic carbon content (mollisol), and the amendment of cow manure (5%) further enhanced its persistence. On the contrary, in flooded soil systems, the higher the soil organic carbon content was, the less persistent was the fungicide, and amendment of cow manure further enhanced its degradation. Triadimefon degradation was faster at 35 degrees C than at 27 degrees C. Triadimefon degradation in soils was mediated by the microorganisms, and no triadimefon degradation was observed in sterile soils. Triadimefon (1 mg/kg) did not affect soil phosphatase activity in either of the soils; however, soil dehydrogenase activity was significantly reduced, especially in mollisol soil.     

Enzyme activities in vineyard soils long-term treated with copper-based fungicides

Copper-based fungicides have been applied in vineyard soils for a long time, which has resulted in increasing soil Cu concentration. However, information relating to non-target effects of these fungicides on microorganisms of these soils is scarce. The aim of this study was to determine the potential enzyme activities of vineyard soils in relation to Cu content and evaluate the potential risks of long-term application of Cu-based fungicides. For this purpose, a wide range of soil samples, having different total, exchangeable and bioavailable Cu contents, were collected from six regions of quality wines located in the NW Iberian Peninsula, and the activity of dehydrogenase, β-glucosidase, urease and phosphatase were measured. Overall, the results obtained indicate adverse effects of Cu on dehydrogenase, β-glucosidase and phosphatase activities and an inconsistent effect on urease activity. Threshold Cu concentrations at which changes in the enzyme activities became evident were 150-200 mg total Cu kg⁻¹ and 60-80 mg bioavailable Cu kg⁻¹.     

Soil organic carbon and microbial communities respond to vineyard management

The farming practices in vineyards vary widely, but how does this affect vineyard soils? The main objective of this study was to evaluate the effects of vineyard management practices on soil organic matter and the soil microbial community. To this end, we investigated three adjacent vineyards in the Traisen valley, Austria, of which the soils had developed on the same parent material and under identical environmental/site conditions but were managed differently (esp. tillage, fertilizer application, cover crops) for more than 10 yrs. We found that topsoil bulk density (BD) decreased with increasing tillage intensity, while subsoil BD showed the opposite trend. Soil organic carbon (SOC) stocks in 0–50 cm depth increased from 10 kg m^?2 in an unfertilized and frequently tilled vineyard to 17 kg m^?2 in a regularly fertilized but less intensively tilled vineyard. Topsoil microbial biomass per unit SOC, estimated by the sum of microbial phospholipid fatty acids (PLFAs), followed this trend, albeit not statistically significantly. Principal component analysis of PLFA patterns revealed that the microbial communities were compositionally distinct between different management practices. The fungal PLFA marker 18:2ω6,9 was highest in the vineyard with the lowest amount of extractable Cu (by 0.01 m CaCl₂), and the bacterial‐to‐fungal biomass ratio was positively correlated with extractable Cu. Our results indicate that tillage and fertilizer application of vineyards can strongly affect vineyard soil properties such as BD and SOC stocks and that the application of Cu‐based fungicides may impair soil fungal communities.     

Determination of fungicide residues in field-grown strawberries following different fungicide strategies against gray mold (Botrytis cinerea)

In a 2 year experiment, residues in field-grown strawberries were investigated from the fungicides fenhexamid, pyrimethanil, tolylfluanid, and kresoxim-methyl resulting from different strategies, as regards the dose, number, and time of fungicide applications. Kresoxim-methyl was only used the first year and in full or no dose to control powdery mildew. In the first year, the highest concentrations analyzed were 0.66 mg kg(-1) for pyrimethanil and 0.63 mg kg(-1) for fenhexamid resulting from the use of recommended dose rates and a preharvest interval (PHI) of 10 days, thus not exceeding the Danish maximum residue limit (MRL) of 1 mg kg(-1). Tolylfluanid was used no later than 21 days before harvest, which left residue contents in the berries of 0.48 mg kg(-1), a value well below the MRL of 5 mg kg(-1). In the second year, fungicide residues found in the samples were generally lower, 0.39 and 0.03 mg kg(-1) for pyrimethanil and fenhexamid, respectively. No residues of kresoxim-methyl were found in any of the samples from the field trials, indicating that kresoxim-methyl residues had declined to a level well below the detection limit within the 28 day period between the last application and the harvest.