M. Sonia Rodríguez-Cruz

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.

Pesticide residues in vineyard soils from Spain: Spatial and temporal distributions

Spatial and temporal evaluations of seventeen pesticides and some of their degradation products were carried out in seventeen vineyard soils from La Rioja region (Spain). The soils were sampled in March, June and October 2012, and the pesticides were selected among those previously detected in surface and ground waters from the same area. All pesticides were detected in some of the soils in the three different areas of La Rioja at the different sampling times, with only the metalaxyl metabolite, CGA-62826, not being detected in any of the soils sampled in October. The highest concentrations were determined for the fungicides metalaxyl (11.5 μg kg(-1)) and triadimenol (26.1 μg kg(-1)), the herbicides fluometuron (174.6 μg kg(-1)) and terbuthylazine (403.3 μg kg(-1)), and the insecticide methoxyfenozide (4.61 μg kg(-1)). While the highest total concentration of pesticides was detected in March, the highest number of positive detections was recorded in June (46), as opposed to 26 and 19 in March and October, respectively. Significant differences were detected in the concentrations of herbicides in soils from the three areas in La Rioja, but this was not the case for the fungicides and the insecticides. The study revealed a more intensive use of herbicides in March, while the use of insecticides and fungicides probably depended on the specific needs of crops and/or the onset of diseases. The results are consistent with the residues found in waters in the region, and highlight the need to implement strategies for more efficient application of these compounds to avoid risk of water contamination.

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 1.77–6.60 mL g−1 for linuron, 0.54–5.52 mL g−1 for diazinon and 1.35–4.52 mL g−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...

Effect of the modification of natural clay minerals with hexadecylpyridinium cation on the adsorption–desorption of fungicides

Clay minerals, montmorillonite (M), illite (I), kaolinite (K), muscovite (Mu), sepiolite (S) and atapulgite (A), modified with the organic cation hexadecylpyridinium (HDPY) were studied as sorbents of two fungicides of different hydrophobicity, penconazole and metalaxyl, using adsorption–desorption isotherms. The Freundlich constant values were low for the adsorption of the fungicides by natural clays and increased when the minerals were saturated with the organic cation. In HDPY-M, the K f constant increased 190-fold for the adsorption of penconazole and 67-fold for the adsorption of metalaxyl. Adsorption of the fungicides by the organo-clays at an initial concentration of 25 µg/mL was related to their organic matter content, the highest adsorption values being found in HDPY-M, HDPY-I and HDPY-A, and the increase in adsorption was greatest for the more hydrophobic fungicide penconazole. Desorption of fungicides from modified clays pointed to a high degree of stability for penconazole adsorbed by HDPY-M. In the remaining samples, the stability of this pesticide was low and the stability of metalaxyl adsorbed by all the organo-clays was also low. The results obtained point to the potential value of clay minerals modified with HDPY for immobilising pesticides with different degrees of hydrophobicity. Of special interest is the HDPY-M sample, which could be considered for use in clay barriers aimed at protection of soil and water pollution by hydrophobic pesticides.

Physicochemical study of the sorption of pesticides by wood components.

The sorption-desorption and interaction mechanisms of three non-ionic (linuron, alachlor, and metalaxyl) and two ionic (paraquat and dicamba) pesticides by three commercial lignins (hydrophobic macromolecule) and cellulose (hydrophilic macromolecule) as wood components were studied. Wood is a low-cost and environmentally friendly material proposed in recent years to immobilize pesticides in soils. The influence of sorbent and pesticide properties and the identification of the functional groups of the organic molecules involved in sorption were evaluated by a statistical approach and by Fourier transform infrared spectroscopy. The sorption isotherms of non-ionic pesticides by the lignins and cellulose fit the Freundlich model, and those of the ionic pesticides also fit the Langmuir model. The sorption constants of pesticides by cellulose were 62-, 9-, 24-, 119-, and 3-fold lower than those for the sorption by lignins. A predictive model of pesticide sorption indicated that 88.5% of the variability in the sorption coefficient normalized to the organic carbon content could be explained in terms of the variability of the polarity index and the octanol-water partition coefficient of sorbent and sorbate. The greater irreversibility observed for ionic pesticides was attributed to the involvement of simultaneous interaction mechanisms. The results obtained contribute the knowledge of sorption capacity of pesticides by lignin/cellulose, the main components of woods and ubiquitous materials in the environment.

Effect of different wood pretreatments on the sorption-desorption of linuron and metalaxyl by woods.

The sorption-desorption of two different pesticides, linuron and metalaxyl, by woods was studied. Sorbent/solution ratio and sorption kinetics were also determined. Untreated wood and water, NaOH, HCl, and octadecyltrimethylammonium bromide (ODTMA) treated pine (softwood) and oak (hardwood) were used as sorbents. Linuron and metalaxyl were sorbed by untreated woods up to 80 and 40%, respectively, in a short time when the sorbent/solution ratio of 1:10 was used. Sorption of pesticides was significantly higher by pine, having higher lignin content, than by oak. Freundlich sorption constants (K(f)) were 96.2 and 74.4 (linuron) and 8.28 and 4.95 (metalaxyl) for untreated pine and oak woods and increased 1.04-2.35-fold (linuron) and 1.33-2.17-fold (metalaxyl) when woods were treated. The sorption was higher by HCl- and ODTMA-treated woods. Additionally, Freundlich desorption constants also indicated greater sorption irreversibility of both pesticides for treated woods than for untreated woods. The results revealed wood residues as a promising, low-cost, and environmentally friendly material to immobilize pesticides in soils, preventing water contamination. Wood treatments aimed at removing soluble wood extracts or at modifying wood chemical structure could increase their sorption capacity.

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.