Jesús M. Marín-Benito

Field-scale dissipation of tebuconazole in a vineyard soil amended with spent mushroom substrate and its potential environmental impact

The persistence, mobility and degradation of tebuconazole were assessed under field conditions in a sandy clay loam soil amended with spent mushroom substrate (SMS) at two rates. The aim was to evaluate the environmental impact of the simultaneous application of SMS and fungicide in a vineyard soil. SMS is the pasteurized and composted organic material remaining after a crop of mushroom is produced. SMS is generated in increasing amounts in La Rioja region (Spain), and could be used as soil amendment in vineyard soils, where fungicides are also applied in large amounts. The study was carried out in 18 experimental plots (6 treatments and 3 replicates per treatment) over one year. Laboratory experiments were also conducted to verify the changes over time in the adsorption of fungicide by soils and in soil dehydrogenase activity caused by the fungicide and/or SMS. Tebuconazole dissipation followed biphasic kinetics with a rapid dissipation phase, followed by a slow dissipation phase. Half-life (DT50) values ranged from 8.2 to 12.4 days, with lower DT50 for amended soils when compared to the non-amended controls. The distribution of tebuconazole through the soil profile (0-50 cm) determined at 124, 209 and 355 days after its application indicated the higher mobility of fungicide to deeper soil layers in amended soils revealing the influence of solid and dissolved organic matter from SMS in this process. Tebuconazole might be available for biodegradation although over time only chemical or photochemical degradation was evident in surface soils. The results obtained highlight the interest of field and laboratory data to design rational applications of SMS and fungicide when they are jointly applied to prevent the possible risk of water contamination.

Effect of Spent Mushroom Substrate Amendment of Vineyard Soils on the Behavior of Fungicides: 1. Adsorption−Desorption of Penconazole and Metalaxyl by Soils and Subsoils

The effect of the addition of fresh and composted spent mushroom substrates (F-SMS and C-SMS) to vineyard soils on the adsorption-desorption of penconazole and metalaxyl was studied under laboratory conditions. SMS is a promising agricultural residue as an amendment to increase the soil organic matter (OM) content. It may also modify the behavior of fungicides applied to vineyards. Freundlich Kf adsorption constants of both fungicides by soils and subsoils from three experimental plots unamended and amended in the field ranged between 2.78 and 13.4 (penconazole) and 0.14 and 0.67 (metalaxyl) with scant differences for unamended soil and subsoil. However, Kf values of amended soils were higher than those corresponding to subsoils and generally higher than those of unamended soils (up to 2.3 times for penconazole and 1.3 times for metalaxyl). The influence of SMS treatment (fresh or composted) was observed in the adsorption of the most hydrophobic fungicide penconazole. Simple and multiple correlations between soil and subsoil properties and adsorption constants indicated the influence of the OM on the adsorption of both fungicides, together with the clay, silt, and CaCO(3) content for metalaxyl and the pH for penconazole. The results revealed changes in the adsorption-desorption processes of these fungicides, which could give rise to a decrease in the mobility of metalaxyl (highly water-soluble) and an increase in the retention of penconazole (more hydrophobic). These effects could have an impact on surface and/or groundwater contamination.

Effect of different organic amendments on the dissipation of linuron, diazinon and myclobutanil in an agricultural soil incubated for different time periods.

Dissipation kinetics of pesticides belonging to three chemical groups (linuron, diazinon and myclobutanil) was studied in an unamended agricultural soil and in this soil amended with three organic residues: sewage sludge (SS), grape marc (GM) and spent mushroom substrate (SMS). The soils were incubated with the residues outdoors for one and 12 months. Mineralized, extracted and non-extractable fractions were also studied for (14)C-linuron and (14)C-diazinon. The dissipation kinetics was fitted to single first-order or first-order multicompartment models. The dissipation rate (k) decreased in the order diazinon>linuron>myclobutanil, and DT50 values decreased for linuron (1.6-4.8 times) or increased for myclobutanil (1.7-2.6 times) and diazinon (1.8-2.3 times) in the amended soils relative to the unamended soil. The lowest DT50 values for the three pesticides were recorded in GM-amended soil, and the highest values in SMS-amended soil. After 12 months of soil incubation, DT50 values decreased in both the unamended and amended soils for linuron, but increased for the unamended and SMS-amended soil for diazinon and myclobutanil. A certain relationship was observed between the sorption of pesticides by the soils and DT50 values, although it was significant only for myclobutanil (p<0.05). Dissipation mechanism recorded the lowest mineralization of (14)C-pesticides in the GM-soil despite the highest dissipation rate in this soil. The extracted (14)C-residues decreased with incubation time, with increased formation of non-extractable residues, higher in amended soils relative to the unamended soil. Soil dehydrogenase activity was, in general, stimulated by the addition of the organic amendments and pesticides to the soil after one month and 12 months of incubation. The results obtained revealed that the simultaneous use of amendments and pesticides in soils requires a previous study in order to check the environmental specific persistence of these compounds and their effectiveness in amended soils.

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.

Use of raw or incubated organic wastes as amendments in reducing pesticide leaching through soil columns

Soil amendment with organic wastes is becoming a widespread management practice since it can effectively solve the problems of uncontrolled waste accumulation and improve soil quality. However, when simultaneously applied with pesticides, organic wastes can significantly modify the environmental behaviour of these compounds. This study evaluated the effect of sewage sludges (SS), grape marc (GM) and spent mushroom substrates (SMS) on the leaching of linuron, diazinon and myclobutanil in packed columns of a sandy soil with low organic matter (OM) content (<1%). Soil plus amendments had been incubated for one month (1 m) or 12 months (12 m). Data from the experimental breakthrough curves (BTCs) were fitted to the one-dimensional transport model CXTFIT 2.1. All three amendments reduced leaching of linuron and myclobutanil relative to unamended soil. SMS was the most effective in reducing leaching of these two compounds independent of whether soil was incubated for 1 m or 12 m. Soil amendments increased retardation coefficients (Rexp) by factors of 3 to 5 for linuron, 2 to 4 for diazinon and 3 to 5 for myclobutanil relative to unamended soil. Leaching of diazinon was relatively little affected by soil amendment compared to the other two compounds and both SS and SMS amendment with 1m incubation resulted in enhanced leaching of diazinon. The leaching data for linuron and myclobutanil were well described by CXTFIT (mean square error, MSE<4.9·10(-7) and MSE<7.0·10(-7), respectively) whereas those of diazinon were less well fitted (MSE<2.1·10(-6)). The BTCs for pesticides were similar in soils incubated for one month or one year, indicating that the effect of amendment on leaching persists over relatively long periods of time.

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

PurposeThe aim of this work was to study the temporal changes in the sorption–desorption 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 methodsSorption–desorption 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 2xa0% and 10xa0% 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 12xa0months of soil incubation with SMS under controlled conditions.Results and discussionAddition of amendments to soil increased soil sorption capacity of fungicides. Kd values increased with the hydrophobic character of fungicides (metalaxylu2009<u2009iprovalicarbu2009<u2009pyrimethanilu2009<u2009penconazole) at both amendment rates. The lower content of DOC and the higher degree of OC humification enhanced sorption of all fungicides by the soilu2009+u2009C-SMS with regard to the soilu2009+u2009F-SMS. In general, sorption of fungicides decreased after 6 and 12xa0months of soilu2009+u2009SMS 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 soilu2009+ SMS incubation time increased.ConclusionsThe 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 soilu2009+ 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.

Adsorption of pesticides by sewage sludge, grape marc, spent mushroom substrate and by amended soils

A comparative adsorption study of linuron, diazinon and myclobutanil, representing three classes of pesticides, by sewage sludge (SS), grape marc (GM) and spent mushroom substrate (SMS) and soils amended with these residues was carried out. The study assayed the effect of the nature of the residue, soil characteristics, pesticide properties and residue-soil incubation time on adsorption. Soil-residues were incubated outdoors for one month and 12 months. Adsorption was not related to pesticide hydrophobicity. For unamended soils, distribution coefficients (Kd) ranged between 1.77–6.60u2009mLu2009g−1 for linuron, 0.54–5.52u2009mLu2009g−1 for diazinon and 1.35–4.52u2009mLu2009g−1 for myclobutanil, and increased significantly for amended soils: up to 4.8 times for linuron, 6.9 times for diazinon and 5.3 times for myclobutanil. Kd values revealed the highest adsorption of linuron and diazinon by GM and of myclobutanil by SMS. These coefficients significantly changed after 12 months of incubation as compared to 1 month. The adsorption...

Effects of Wood Amendments on the Degradation of Terbuthylazine and on Soil Microbial Community Activity in a Clay Loam Soil

The herbicide terbuthylazine is widely used within the EU; however, its frequent detection in surface and groundwater, together with its intrinsic toxicological properties, may pose a risk both for human and environmental health. Organic amendments have recently been proposed as a possible herbicide sorbent in soil, in order to limit herbicide movement from soil to water. The environmental fate of terbuthylazine depends not only in its mobility but also in its persistence. The latter is directly dependent on microbial degradation. For this reason, the effects of pine and oak residues on terbuthylazine soil microbial community functioning and on the potential of this community for terbuthylazine degradation were studied. For this purpose, degradation kinetics, soil dehydrogenase activity and the number of live bacteria were assessed in a clay loam soil treated with terbuthylazine and either amended with pine or oak wood or unamended (sterilised and non-sterilised). At day 65, 85xa0% of the herbicide applied still persisted in the sterile soil, 73xa0% in the pine-amended one and 63xa0% in the oak-amended and unamended ones. Pine residues increased the sorption of terbuthylazine to soil and hampered microbial degradation owing to its high terbuthylazine sorption capacity and a decrease in the bioavailability of the herbicide. On the contrary, in the presence of oak residues, the herbicide sorption did not increase significantly. The overall results confirm the active role of the soil microbial community in terbuthylazine degradation in amended and unamended soils and in a liquid enrichment culture performed using an aliquot of the same soil as the inoculum. In this clay loam soil, in the absence of amendments, the herbicide was found to be quite persistent (t1/2u2009>u200995xa0days), while in the enrichment culture, the same natural soil bacterial community was able to halve terbuthylazine in 24xa0days. The high terbuthylazine persistence in this soil was presumably ascribable to its texture and in particular to the mineralogy of the clay fraction.

Assessment of spent mushroom substrate as sorbent of fungicides: influence of sorbent and sorbate properties.

The capacity of spent mushroom substrate (SMS) as a sorbent of fungicides was evaluated for its possible use in regulating pesticide mobility in the environment. The sorption studies involved four different SMS types in terms of nature and treatment and eight fungicides selected as representative compounds from different chemical groups. Nonlinear sorption isotherms were observed for all SMS-fungicide combinations. The highest sorption was obtained by composted SMS from Agaricus bisporus cultivation. A significant negative and positive correlation was obtained between the K(OC) sorption constants and the polarity index values of sorbents and the K(OW) of fungicides, respectively. The statistic revealed that more than 77% of the variability in the K(OW) could be explained considering these properties jointly. The other properties of both the sorbent (total carbon, dissolved organic carbon, or pH) and the sorbate (water solubility) were nonsignificant. The hysteresis values for cyprodinil (log K(OW)= 4) were for all the sorbents much higher (>3) than for other fungicides. This was consistent with the remaining sorption after desorption considered as an indicator of the sorption efficiency of SMS for fungicides. Changes in the absorption bands of fungicides sorbed by SMS observed by FTIR permitted establishing the interaction mechanism of fungicides with SMS. The findings of this work provide evidence for the potential capacity of SMS as a sorbent of fungicides and the low desorption observed especially for some fungicides, although they suggest that more stabilized or humified organic substrates should be produced to enhance their efficiency in environmental applications.

Effect of spent mushroom substrate amendment of vineyard soils on the behavior of fungicides: 2. mobility of penconazole and metalaxyl in undisturbed soil cores.

Mobility of fungicides penconazole and metalaxyl in unamended and amended vineyard soils with fresh and composted spent mushroom substrates (F-SMS and C-SMS) was studied. Experiments were performed in non-incubated and incubated (outdoors for 77 days) undisturbed soil cores under non-saturated flow conditions. Breakthrough curves (BTC) of metalaxyl leaching were delayed with regard to the tracer ion, and they showed an incomplete leaching in all soil cores after the addition of 2.5-4.5 pore volumes. A decrease of the maximum peak concentration in C-SMS soils with regard to unamended soils (up to 24-fold in Viana soil) and an increase in the fungicide retention by soils (up to 8-fold in the first segment of Viana soil core) was observed. However, a decrease (up to 2.6-fold in Sajazarra soil) or an increase (up to 1.4-fold in Aldeanueva soil) of the maximum peak concentration in F-SMS soils was observed. No leaching of penconazole was observed in all cases. After fungicide incubation in soil cores, the amounts of metalaxyl retained and leached decreased significantly by 1.24-37.8-fold and 1.17-302-fold, respectively, whereas no changes were observed for penconazole. Degradation of metalaxyl occurred in non-incubated soil and increased after incubation (two metalaxyl metabolites were detected in the leachates and the soil extracts), but it was not seen for penconazole in any case. In consequence, the addition of SMS as amendment to soil (especially C-SMS) enhanced adsorption of both fungicides, although metalaxyl could be available for degradation. This effect contributes to prevent groundwater contamination by metalaxyl, but it could contribute to increase the surface water contamination by penconazole, because adsorption protects this fungicide from degradation, increasing its persistence in soils.