Mulching vs. organic soil amendment: Effects on adsorption-desorption of herbicides.

Mulching and organic soil amendment are two agricultural practices that are being increasingly used to preserve soil from degradation, although they may modify the fate of herbicides when applied in soils subjected to these practices. This study has set out to compare the impact of both agricultural practices on the adsorption-desorption behaviour of the herbicides S-metolachlor (SMOC), foramsulfuron (FORAM), and thiencarbazone-methyl (TCM) involving winter wheat mulch residues at different stages of decomposition and particle size, and unamended soils or those amended with mulch. The Freundlich Kf adsorption constants of the three herbicides by mulches, and unamended and amended soils ranged between 1.34 and 65.8 (SMOC), 0-34.3 (FORAM), and 0.01-1.10 (TCM). The adsorption of the three compounds was significantly higher in mulches than in soils (unamended and amended). The adsorption of SMOC and FORAM increased significantly with mulch decomposition, with this positive impact also being observed on the adsorption of FORAM and TCM after mulch milling. Simple and multiple correlations between mulches, soils, and herbicide properties, and adsorption-desorption constants (Kf, Kd, Kfd) reflected the organic carbon (OC) content and/or dissolved organic carbon (DOC) content of the adsorbents as main variables controlling the adsorption and/or desorption of each herbicide. The statistic R2 revealed that >61 % of the variability in the adsorption-desorption constants could be explained by jointly considering the OC of mulches and soils and the hydrophobicity (for Kf) or water solubility of herbicides (for Kd or Kfd). The same trend observed for Kfd desorption constants as for Kf adsorption ones resulted in higher percentages of herbicide remaining adsorbed after desorption in amended soils (33 %-41 % of SMOC, 0 %-15 % of FORAM, and 2 %-17 % of TCM) than in mulches (< 10 %). The results reveal a higher efficiency of organic soil amendment than mulching as an agricultural practice for immobilising the herbicides studied when winter wheat mulch residues are used as a common adsorbent, and as a better strategy for avoiding groundwater contamination.

Changes in vineyard soil parameters after repeated application of organic-inorganic amendments based on spent mushroom substrate.

The changes of physicochemical and biochemical parameters of a silty loam (S1) and sandy loam (S2) vineyard soils added with spent mushroom substrate (SMS) or SMS composted with ophite (OF) as rock dust (SMS + OF) were studied. Two doses of SMS or SMS + OF (25 and 100 Mg ha-1) were applied for two consecutive years (2020-2021) and changes of soil physicochemical parameters, and dehydrogenase activity (DHA), respiration (RES), microbial biomass (BIO), and the phospholipid fatty acids (PLFAs) profile were assayed on a temporal basis. The results showed an increase in soil organic carbon (OC) content, total and mineralised N, P, and K, especially when the highest SMS dose was applied to soils. Repeated application caused OC content over time up to 2.3 times higher than initial content in the silty loam soil. This increase was not observed in sandy soil, possibly due to a higher bioavailability of OC, as indicated by the evolution of extractable humic acid/fulvic acid pools. In both soils, all biochemical parameters increased after amendment, being favoured both by the OC and by the presence of OF. Significant positive correlations were found between DHA, RES and BIO, and OC content especially in the first part and then levelled off after the second dose application. Total bacterial or fungal PLFAs patterns reflected the variation of BIO by SMS application. The higher growth of fungi vs. bacterial community in amended soils was recorded after the first SMS application, although the opposite effect occurred after the second application, with similar results in both soils. The findings indicate that the application of SMS or SMS + OF in vineyard soils could be an appropriate agronomic management practice for maintaining soil sustainability, although doses and application times of these amendments should first be evaluated depending on soil texture.

The role of two organic amendments to modify the environmental fate of S-metolachlor in agricultural soils.

S-metolachlor is a widely used herbicide that may contaminate groundwater when applied to irrigated crops, especially when the soil has a low organic carbon (OC) content. The objective here was to assess the capacity of two organic wastes, namely, green compost (GC) and pelletised organo-mineral manure fertilizer (PM), applied to two soils (S) with different textures at a rate of 10% dry weight to modify the fate of S-metolachlor. The herbicide's Freundlich adsorption coefficient (Kf) increased within a range of 3.2-8.2 times in S + GC and 3.8-6.8 times in S + PM. A positive correlation between adsorption and OC and the coefficient of variation of the OC normalised adsorption coefficients (Kfoc) higher than 20% indicated the evident influence on this process of soil OC content and its nature. The increase in adsorption did not prevent the dissipation of S-metolachlor in the amended soils, although the degradation rate decreased up to ~2 times or was not significantly modified across the different soil types. The S-metolachlor metabolites, metolachlor ethane sulfonic acid and metolachlor oxanilic acid, were detected in the herbicide's dissipation in the unamended soils, but they were not detected in the amended soils. The mobility experiments indicated leached amounts of S-metolachlor higher than 50% in unamended soil. The amounts decreased 1.1-1.7 times and 1.7-1.8 times in the S + GC and S + PM when a saturated flow was applied. Moreover, breakthrough curves indicated a slow leaching kinetics of herbicide in amended soils, with low concentrations continuously detected in the leachates together with a decrease in the maximum peak concentration. The results show the effect of the application of organic wastes especially in sandy soils to promote the immobilisation and/or degradation of S-metolachlor, avoiding its transfer to other environmental compartments.

Field measurement and modelling of chlorotoluron and flufenacet persistence in unamended and amended soils.

The dissipation and persistence of two cereals herbicides, chlorotoluron and flufenacet, were studied in a field experiment including three replicated plots of unamended soil (S), soil amended with spent mushroom substrate (S + SMS), and soil amended with green compost (S + GC), during the winter wheat cultivation campaign. The SMS and GC organic residues were applied to the soil at rates of 140 or 85 t residue ha-1, and herbicides were sprayed as Erturon® and Herold® formulations for chlorotoluron and flufenacet, respectively. Concentrations of both herbicides and of their metabolites were regularly measured in the three soil treatments (0-10 cm) from 0 to 339 days. The dissipation kinetics fitted well the single first order (SFO) model, except that of chlorotoluron that fitted the first order multi-compartment (FOMC) model better in the unamended soil. The dissipation rates of herbicides were lower in amended than in unamended soils. The results also showed that the DT50 of chlorotoluron (66.2-88.0 days) and flufenacet (117-145 days) under field conditions were higher than those previously obtained at laboratory scale highlighting the importance of the changing environmental conditions on the dissipation process. Similarly, the formation of chlorotoluron and flufenacet metabolites under field conditions was different from that previously observed in the laboratory. The performance of the MACRO pesticide fate model, parameterized with laboratory data, was then tested against field data. There was a very good agreement between measured and simulated chlorotoluron residue levels in the three soil treatments, while the ability of the model to reproduce the dissipation of flufenacet was good in the unamended soil and very good in S + SMS and S + GC soils. MACRO might be used to estimate the remaining amounts of herbicides in amended soils from degradation data previously obtained at laboratory scale. This would help to manage herbicide doses in different environmental conditions to preserve the sustainability of agricultural systems.

Mobility monitoring of two herbicides in amended soils: A field study for modeling applications.

This paper reports the mobility and total balance of chlorotoluron (CTL), flufenacet (FNC) and bromide ion (Br-) throughout a sandy soil profile after the application of spent mushroom substrate (SMS) and green compost (GC). Obtaining mobility dataset is crucial to simulate the herbicides' fate under amended soil scenarios by application pesticide leaching models with regulatory application (FOCUS models). The application of organic residues is nowadays increased to improve the crop yields and there is a gap in the simulations of this kind of amended scenarios. A two-year field experiment involving unamended soil (S) and SMS- or GC-amended soil plots was conducted. CTL, FNC, and Br- were annually applied and their residual concentrations were determined in soil profiles (0-100 cm) regularly sampled. In all the treatments the order of mobility is followed as FNC < CTL < Br-. SMS and GC increased herbicide retention in the top 10 cm by the higher organic carbon (OC) content than the unamended soil, and their ability to increase the soil's water-holding capacity and to decrease water percolation. Simultaneously dissolved organic carbon (DOC) content facilitated herbicide transport being it favoured by the initial soil moisture content and the rainfall shortly after the chemicals' initial application. Over the first year, residual amounts (<2.6%) of Br-, CTL and FNC were leached down to 90-100 cm depth in the three treatments. However, over the second year low CTL and FNC amounts (<1.0%) reached the bottom layer only in S + SMS although high Br- concentrations did so in the three treatments (<20%). According to the total balance of Br-, CTL, and FNC in the soil profiles other processes (degradation, mineralisation, bound residues formation, and/or crop uptake) different from leaching below 1 m depth might play a key role in their dissipation especially in the amended soil profiles. SMS and GC are likely to be used as organic amendments to preserve the soil and water quality but in the case of SMS, its higher DOC content could imply a higher potential risk for groundwater contamination than GC.

Modelling herbicides mobility in amended soils: Calibration and test of PRZM and MACRO.

Addition of organic residues to soil is a current farming practice but it is not considered in the modelling studies for pesticide risk assessment at regulatory level despite its potential impact on the pesticide dynamics in soil. Thus, the objective of this work was to examine and to compare the ability of PRZM and MACRO pesticide fate models to simulate soil water content, and bromide (Br-, tracer), chlorotoluron and flufenacet concentrations in the soil profiles (0-100 cm) of one agricultural soil, unamended (control soil, S), amended with spent mushroom substrate (S + SMS) or amended with green compost (S + GC). Based on a two-year field-scale dataset, the models were first calibrated against measurements of water and solutes contents in the soil profiles (first year) and then tested without any further model calibration by comparison with the field observations of the second year. In general, the performance of MACRO to simulate the whole dataset in the three soil treatments was higher than that of PRZM. MACRO simulated satisfactorily the water dynamics along the soil profiles whereas it was poorly described by the capacity model PRZM. Both models predicted very well the Br- mobility in control and amended soils after dispersion parameters were fitted to observations. No calibration was necessary to reproduce correctly herbicides vertical distribution in the control soil profile. In the amended soils, MACRO simulations were highly correlated to the observed vertical distribution of flufenacet and chlorotoluron, but calibration of the Kd of chlorotoluron was needed. On the contrary, modelling with PRZM required calibration of Kd and DT50 of both herbicides to obtain an acceptable agreement between observations and predictions in the amended soils. Kd and DT50 calibration was based on the initial dissolved organic carbon contents (DOC) of amended soils. It allowed to take into account the processes that decrease the herbicides sorption on the soil and enhance their bioavailability, but that are not described in PRZM and MACRO (such as the formation of herbicide-DOC mobile complexes). This work showed that models such as PRZM and MACRO are able to simulate the fate of pesticides in amended soils. However, before using these models as predictive tools in large amended soil conditions, and especially in the regulatory context, further modelling studies should focus on other pedoclimatic-pesticides-organic residues combinations, and on longer periods.

Organic carbon nature determines the capacity of organic amendments to adsorb pesticides in soil.

The spread of organic pollutants from soil to other environments is one important source of environmental pollution. The addition of organic amendments to soil is an interesting strategy to control pollutants leaching. However, the contribution of different carbon types of organic amendments to organic pollutants adsorption is not clear. Hence, the objective of this work was to determine the role of carbon types of organic amendments into the adsorption of four herbicides. To this extent, organic amendments were characterized by elemental analysis and 13C-NMR and adsorption-desorption isotherms of herbicides by the organic amendments and two soils amended with them were obtained. Adsorption coefficients were correlated with the organic carbon content of the organic amendments and the adsorption process was enhanced by the hydrophobicity of herbicides and the aliphatic and aromatic carbon of amendments. Organic amendments increased the adsorption of herbicides by soils but it is not possible to extrapolate results from one soil to another because organo-mineral interactions between soils and organic amendments can modify this process. Desorption isotherms of herbicides from organic amendments and/or amended soils presented hysteresis indicating the irreversible adsorption of herbicides. Desorption results indicated, the abundance of O-alkyl and N-alkyl groups in organic amendments enhanced the hysteresis in amended soils.

Transport of 14C-prosulfocarb through soil columns under different amendment, herbicide incubation and irrigation regimes.

This study sets out to evaluate the effect on the leaching of prosulfocarb through packed soil columns of applying green compost (GC) as an organic amendment (20% w/w), herbicide ageing over 28 days in the soil (incubation vs. no incubation), and two different irrigation regimes (saturated or saturated-unsaturated flows). Peak concentrations decreased after herbicide incubation in the columns for both unamended (S) and amended (S + GC) soils under both flow regimes. The leached amounts decreased when the herbicide was incubated for 28 days in S (2.1 and 1.9 times) and S + GC (2.9 and 1.6 times), under saturated or saturated-unsaturated flow, respectively. In the S columns, the total amounts retained (43.3%-60.8%) were lower than the ones obtained for the S + GC columns under saturated flow (77.4%-85.2%), suggesting a stronger interaction between the herbicide and the GC-amended soil. This behaviour was not observed under saturated-unsaturated flow, as the total amounts retained were similar in both the S and S + GC columns. Prosulfocarb was primarily retained in the first segment of the S (>28%) and S + GC (>43%) columns under all conditions. Incubation time did not greatly affect the herbicide retention, but it significantly increased the mineralized amount under saturated flow. The total balances of 14C-prosulfocarb were >73% and >80% in the S and S + GC columns, respectively, indicating that amendment decreased prosulfocarb loss by volatilization. Several factors, such as amendment, herbicide ageing and water flow, proved to be important for controlling the leaching of this herbicide through the soil profile.

Assessment of 14C-prosulfocarb dissipation mechanism in soil after amendment and its impact on the microbial community.

Adding organic amendments to soil could modify the bioavailability of herbicides and lead to changes in the microbial community's activity and structure. The objective here was to study the dissipation and total mass balance of 14C-labeled prosulfocarb applied at two rates (4 and 10 mg kg-1) in unamended and green compost (GC)-amended soil. Soil dehydrogenase activity (DHA) and phospholipid fatty acid (PLFA) profile analysis were determined to evaluate the effect of herbicide residues on microbial community's activity and structure over the dissipation period. The dissipation rate of prosulfocarb decreased after soil amendment due to higher herbicide adsorption by the amended soil. The 50% dissipation time (DT50) increased 1.7 times in the unamended soil when the concentration of prosulfocarb increased 2.5 times. The mass balance results indicate that the sum of water and organic extractable fractions represented the highest amounts up to the dissipation of 50% 14C-prosulfocarb. The 14C-herbicide was then mainly mineralized (up to 11%-31%) or formed non-extractable residues (up to 35%-44%). The amount of 14C-prosulfocarb residues extracted with methanol was slightly higher in amended soils than in unamended ones. 14C-prosulfocarb mineralization was higher in unamended soils than in amended ones. The formation of non-extractable residues was continuous, and increased over time. Soil DHA decreased in the unamended soil and was maintained in the GC-amended soil at the end of the assay. The microbial structure was barely disturbed over the prosulfocarb degradation process, although it was clearly influenced by the application of GC. The results obtained reveal the influence organic amendment has on herbicide bioavailability to decrease its biodegradation and buffer its impact on the soil microbial structure.

Previous degradation study of two herbicides to simulate their fate in a sandy loam soil: Effect of the temperature and the organic amendments.

A laboratory study was designed to assess the following: i) the degradation kinetics of chlorotoluron and flufenacet at two different temperatures, 6 °C and 16 °C, in an unamended agricultural soil and one amended with spent mushroom substrate (SMS) and green compost (GC), and ii) the formation of the main metabolites of both herbicides with potential risk for water pollution over degradation time. The aim was to determine the dependence of these herbicide degradations on temperature (Q10 factor) using kinetic parameters, which is essential information for the later simulation of herbicide environmental fate with FOCUS models. SMS and GC were applied in situ to the natural soil as organic amendments at rates of 140 or 85 t residue ha-1, respectively. Unamended and amended soils were taken from the 0-10 cm topsoil of experimental plots (three replicates/treatment) located on an agricultural farm. Samples of soil + herbicides were incubated at 6 °C or 16 °C under laboratory conditions. The degradation curves of chlorotoluron and flufenacet were fitted to single first-order and first-order multicompartment kinetic models, respectively. The flufenacet degradation, the more hydrophobic herbicide, was slower than that of chlorotoluron in all the treatments. The application of the organic amendments to soil increased the half-lives (DT50) for both herbicides incubated at 6 °C (1.3-1.9 times) and 16 °C (1.4-1.9 times) due to their higher sorption and lower bioavailability for degradation in amended soils. The herbicides recorded a faster degradation at 16 °C than at 6 °C (Q10 = 1.9-2.8) due to the increased microbial biomass and/or activity with temperature. The metabolites desmethyl chlorotoluron, flufenacet ESA and flufenacet OA were detected in all the soil treatments at both incubation temperatures. The determination of Q10 factors in amended soils is very valuable for generating accurate input data for pesticide fate models such as FOCUS in order to improve the evaluation of the leaching of herbicides and their transformation products, which is a relevant goal to maintain the sustainability of agricultural systems.

Influence of different agricultural management practices on soil microbial community over dissipation time of two herbicides.

Soil microbiology could be affected by the presence of pesticide residues during intensive farming, potentially threatening the soil environment. The aim here was to assess the dissipation of the herbicides triasulfuron and prosulfocarb, applied as a combined commercial formulation, and the changes in soil microbial communities (through the profile of phospholipid fatty acids (PLFAs) extracted from the soil) during the dissipation time of the herbicides under field conditions. The dissipation of herbicides and the soil microbial structure were assessed under different agricultural practices, such as the repeated application of herbicides (twice), in unamended and amended soils with two organic amendments derived from green compost (GC1 and GC2) and with non-irrigation and irrigation regimes. The results obtained indicate slower dissipation for triasulfuron than for prosulfocarb. The 50% dissipation time (DT50) decreased under all conditions for the second application of triasulfuron, although not for prosulfocarb. The DT50 values for both herbicides increased in the GC2 amended soil with the highest organic carbon (OC) content. The DT50 values decreased for prosulfocarb with irrigation, but not for triasulfuron, despite its higher water solubility. The herbicides did not have any significant effects on the relative population of Gram-negative and Gram-positive bacteria during the assay, but the relative abundance of Actinobacteria increased in all the soils with herbicides. At the end of the assay (215 days), the negative effects of herbicides on fungi abundance were significant (p < 0.05) for all the treatments. These microbiological changes were detected in non-irrigated and irrigated soils, and were more noticeable after the second application of herbicides. Actinobacteria could be responsible for the modification of herbicide degradation rates, which tend to be faster after the second application. This study makes a useful contribution to the evaluation of the soil environment and microbiological risks due to the long-term repeated application of herbicides under different agricultural management practices.

Dissipation of herbicides after repeated application in soils amended with green compost and sewage sludge.

Certain agricultural practices, such as the repeated application of herbicides or organic amendments to soil, can influence herbicide dissipation. This research has studied the effects of two repeated applications of mesotrione, pethoxamid, and triasulfuron on their dissipation rates in unamended soil (S) and soil amended with green compost (S+GC) or sewage sludge (S+SS). The dissipation experiment has also included an evaluation of the adsorption of the three herbicides by soils and of changes in soil dehydrogenase activity (DHA). The adsorption of the three herbicides by amended soils (Kf range 0.83-2.98) was higher than by unamended soil (Kf range 0.20-0.64). The adsorption coefficients (Kd) of mesotrione and triasulfuron were higher for S+SS, while that of pethoxamid was higher for S+GC, but no relationship between values for the time to 50% degradation (DT50) and adsorption coefficients could be determined. The repeated application of mesotrione decreased its dissipation rate in unamended soil (DT50 increased from 4.75 to 8.15 days) and amended soils (DT50 increased from 11.7 to 28.2 days in S+GC and from 17.7 to 37.9 in S+SS), whereas the repeated application of pethoxamid increased its dissipation rate in all the treatments, and the rate for triasulfuron increased only in amended soils. The highest DT50 values for pethoxamid (12.3 days) and triasulfuron (57.1 days) were in S+GC, and the lowest in S+SS (8.35 and 24.7 days). Soil DHA was stimulated by the presence of GC in the soil and by the first application of mesotrione. The second application of mesotrione and pethoxamid positively affected soil DHA, but this did not occur for triasulfuron. The repeated applications of herbicides and soil organic amendments have different effects on herbicide dissipation, adsorption, and soil DHA, and they should be taken into account when assessing soil quality and other potential environmental implications of pesticide use.

Pesticide fate modelling in conservation tillage: Simulating the effect of mulch and cover crop on S-metolachlor leaching.

Conservation tillage practices mainly based on cover crops and no-tillage with accumulation of crop residues at the soil surface (mulch) modify the environmental fate of pesticides. However, only few pesticide fate models are able to consider mulch of crop residues as well as the effect of intermediate cover crops. Thus, the objective was to develop an approach to model the effects of crop residues left at the soil surface and cover crops on the fate of pesticides. This approach consisted in (1) considering the crop residues as a soil layer with specific physical, hydrodynamic and pesticide-reactivity properties close to that of a high organic content soil layer, and (2) introducing a correction factor of the potential evapotranspiration, estimated through a calibration step, to take into account the reduction of soil evaporation by the presence of a mulch. This approach was developed using MACRO as support pesticide model. To assess the model performances, we used the data from a field experiment designed in an irrigated maize monoculture under conservation tillage. Soil water content, water percolates, soil temperature and S-metolachlor herbicide concentrations in the leachate at 1m depth were measured during two years. The approach chosen to simulate the mulch effects allowed MACRO to make acceptable predictions of the observed water percolation, soil temperature and to a less extent herbicide leaching. However, it showed a poor performance to simulate the soil water content. Results are discussed in terms of further modelling options to better assess the environmental risks of pesticides under conservation tillage. This approach remains to be tested against various soils, crops, pesticides and types of mulch.

Leaching of two fungicides in spent mushroom substrate amended soil: Influence of amendment rate, fungicide ageing and flow condition.

A study has been conducted on the leaching of two fungicides, tebuconazole and cymoxanil, in a soil amended with spent mushroom substrate (SMS), with an evaluation of how different factors influence this process. The objective was based on the potential use of SMS as a biosorbent for immobilizing pesticides in vulnerable soils, and the need to know how it could affect the subsequent transport of these retained compounds. Breakthrough curves (BTCs) for 14C-fungicides, non-incubated and incubated over 30days, were obtained in columns packed with an unamended soil (S), and this soil amended with SMS at rates of 5% (S+SMS5) and 50% (S+SMS50) under saturated and saturated-unsaturated flows. The highest leaching of tebuconazole (>50% of the total 14C added) was found in S when a saturated water flow was applied to the column, but the percentage of leached fungicide decreased when a saturated-unsaturated flow was applied in both SMS-amended soils. Also a significant decrease in leaching was observed for tebuconazole after incubation in the column, especially in S+SMS50 when both flows were applied. Furthermore, cymoxanil leaching was complete in S and S+SMS when a saturated flow was applied, and maximum peak concentrations were reached at 1pore volume (PV), although BTCs showed peaks with lower concentrations in S+SMS. The amounts of cymoxanil retained only increased in S+SMS when a saturated-unsaturated flow was applied. A more relevant effect of SMS for reducing the leaching of fungicide was observed when cymoxanil was previously incubated in the column, although mineralization was enhanced in this case. These results are of interest for extending SMS application on the control of the leaching of fungicides with different physicochemical characteristics after different ageing times in the soil and water flow conditions applied.

Impact of Spent Mushroom Substrates on the Fate of Pesticides in Soil, and Their Use for Preventing and/or Controlling Soil and Water Contamination: A Review.

Intensive crop production involves a high consumption of pesticides. This is a cause of major environmental concern because the presence of pesticides in water is becoming increasingly common. Physicochemical methods based on soil modification with organic residues have been developed to enhance the immobilization and/or degradation of pesticides in agricultural soils, which may control both the diffuse and the point pollution of soils and waters. This review summarizes the influence of spent mushroom substrate (SMS) on the environmental fate of pesticides when both are simultaneously applied in agriculture. The processes of adsorption, leaching and dissipation of these compounds in SMS-amended soils were evaluated at laboratory and field scale. Relationships were established between the experimental parameters obtained and the properties of the soils, the SMS, and the pesticides in order to determine the effect that the application of SMS in agricultural soils has on the environmental impact of pesticides. Accordingly, this review highlights the use of SMS as a strategy for the prevention and/or control of soil and water contamination by pesticides to strike a balance between agricultural development and the use of these compounds.

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.

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.

Influence of pine or oak wood on the degradation of alachlor and metalaxyl in soil.

The objective of this work was to study the influence pine or oak wood added to soil as an amendment (5% w/w) had on the degradation rate of two pesticides, alachlor and metalaxyl, with different hydrophobic character. The formation of pesticide metabolites and the soil dehydrogenase activity in non-amended and amended soil samples were also monitored. The degradation of metalaxyl followed first-order kinetics, while the degradation of alachlor followed first-order or biphasic kinetics in the soil samples studied. The results indicated that the degradation rate was slower for metalaxyl than for alachlor, and for both pesticides followed the order: pine amended soil < oak amended soil < non-amended soil. The faster degradation rate in non-amended soil was attributed to the higher sorption of pesticides by wood amended soils. The alachlor ethane sulfonic acid (ESA), and two metalaxyl metabolites (2-[(2,6-dimethylphenyl)-methoxyacetylamino]-propionic acid and N-(2,6-dimethylphenyl)-2-methoxy-acetamide) were detected during the incubation period. Soil dehydrogenase activity recorded close values in non-amended and amended soil treated with alachlor, but it was higher in wood amended soil treated with metalaxyl. Pine and oak wood increase the immobilization of the pesticides studied, but they also limit their bioavailability in soil by decreasing their degradation rate in amended soil.

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.