Coexistence of microplastics and Foramsulfuron in soil: effects on herbicide persistence and soil functionality

Coexistence of microplastics and Foramsulfuron in soil: effects on herbicide persistence and soil functionality | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Coexistence of microplastics and Foramsulfuron in soil: effects on herbicide persistence and soil functionality Maria Vittoria Pinna, Stefania Diquattro, Enrico Buscaroli, Daniela Pezzolla, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8539415/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Microplastics (MPs) in agricultural soils pose a major environmental issue since they persist and alter the soil chemical and physical properties, affecting its overall health. Applying digestate to soil may introduce MPs, which can adsorb agrochemicals, and alter their behaviour. This study examined Foramsulfuron (FRS) degradation and adsorption in two soils (S1 and S2), with and without MPs and digestate (D) amendment. The results showed that MPs prolonged FRS half-life (+ 17% in S1 and + 21% in S2 relative to the control), whereas D reduced it by 10% in both soils. The experimental FRS adsorption isotherm data fitted with the Freundlich equation. The low K fa values (between 1.07 and 2.05 µmol (1−1/n) kg − 1 L 1/n ) suggested limited herbicide adsorption in soils, which increased with MPs and D in the order (S) < (S + MPs) < (S + D + MPs). In S1, MPs and D enhanced adsorption hysteresis, while in S2, MPs reduced the soil's FRS retention capacity. The effects of the copresence of FRS and MPs on soil functionality were evaluated by quantifying dehydrogenase, β-glucosidase, and urease activities at 3-, 10- and 24-days post-herbicide application. In the short term (3 days after FRS treatment), these enzymatic activities were stimulated by FRS, MPs, and D, likely due to added carbon and energy sources for soil microbes. The effects varied by soil type, exposure time, and interactions between treatments. This study demonstrated that MPs and digestate amendment significantly influenced herbicide fate, persistence, and soil microbial activity. Organic pollutants Agrochemicals Agricultural soil Organic amendment Adsorption Enzymatic activities Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction The accumulation of plastics in agricultural soils represents a significant environmental concern, as their residues contribute significantly to the presence of microplastics [MPs, plastic fragments or particles with a diameter < 5 mm, predominantly composed of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), and polyvinyl chloride (PVC); Yang et al. 2021 ]. These MPs persist in the soil, where they can alter the chemical and physical properties (Peng et al. 2025 ), the carbon, nitrogen, and phosphorus cycles (Sakin et al. 2025 ) and negatively affect soil microbial communities and overall soil health (Liu et al. 2023 ; Liu et al. 2025 ). Such impacts are attributable to the intrinsic physicochemical properties of MPs (e.g. hydrophobicity, surface charge, and functional groups). Recent data estimate that the agricultural sector consumes approximately 12.5 million tonnes of plastic annually, making it the sector that contributes most (14% of global plastic pollution) to the spread of plastic residues in the environment (Wanner 2021 ). Although agricultural plastic mulching represents a well-recognized source of MPs in soil (Zhang et al. 2022 ), the potential input due to the use of organic amendments, such as contaminated digestates, should not be overlooked (Corradini et al. 2019 ; Azizi et al. 2021 ). Mahon et al. ( 2017 ) found that, despite partial removal of MPs during anaerobic digestion, their accumulation within biosolids is inevitable. More recently, Dronjak et al. ( 2025 ) reported that compost and digestate from municipal wastes and agri-food industry, as well as horse manure and sewage sludge from wastewater treatment plant, contained between 7 and 550 micro and macroplastics particles per gram, with concentrations varying according to their origin and treatment process. Their findings also indicated that anaerobic digestion accumulated more plastic than aerobic treatments. The land application of digestate is widely regarded as a sustainable practice, as it improves soil physical properties, fertility, and productivity while contributing to waste reduction and resource recovery. Therefore, assessing the presence of MPs in the digestate and their potential environmental impacts needs great attention. The composition of digestate derived from anaerobic digestion of organic waste depends largely on the type of feedstock employed and may be a source of other contaminants such as agrochemicals (Porterfield et al. 2023 ), anyway present in the soil because of their widespread use in agricultural production (Sabzevari and Hofman 2022 ). The environmental fate of these compounds is influenced by biotic and abiotic degradation, adsorption and transport processes, which complicate the prediction and assessment of the risks associated with their use (Fouad et al. 2024). Furthermore, co-occurring pollutants such as plastic residues, that can adsorb and transport agrochemicals, interfere with their performance and influence their toxicological effects (Rodríguez-Seijo et al. 2019 ; Cheng et al. 2020 ; Sun et al. 2021 ). Ni et al. ( 2023 ), in a recent study on the adsorption of amide herbicides on biodegradable and non-biodegradable microplastics originating from agricultural plastic films, highlighted that MPs, especially biodegradable types, exhibit significantly higher adsorption capacities compared to other adsorbents, e.g., soil, sediment, mineral, straw, and biochar. As MPs degrade, changes in particle size and surface properties can promote the release of previously adsorbed pollutants, which in turn affects their bioavailability and ecotoxicity in soil (Hu et al. 2023 ; 2021 ; Tan et al. 2025 ). Consequently, growing attention is being directed toward the potential cotransport and release of the adsorbed agrochemicals by MPs in soils. The adsorption capacity and type of interaction between MPs and agrochemicals depend on their respective structures and properties (Qin et al. 2021 ). Generally, the adsorption of organic pollutants on MPs can be attributed to partitioning or surface adsorption phenomena due to electrostatic, π-π or van der Waals interactions, as well as hydrogen bond formation (Mo et al. 2021 ; Lan et al. 2022 ; Liu et al. 2022 ). For example, a recent study reported that the adsorption of atrazine by MPs (specifically PS, PE, and PP, both young and aged) in batch experiments is due to a combination of physical and chemical adsorption mechanisms (Wang et al. 2022 ). Studies have shown that atrazine adsorption in soil significantly intensified in the presence of MPs derived from polyethylene film, with effects directly related to the MPs quantity and aging degree (Song et al. 2023 ). Microplastics can also decrease the soil adsorption capacity of several agrochemicals ( e.g. 2,4-D, dichlorprop, diuron, flufenacet, simazine, thiacloprid) and thereby accelerate their leaching, enhancing the potential of groundwater contamination (Wu et al. 2025 ). The occurrence of MPs, alone or in combination with agrochemicals, may influence the activity and health of biotic components, although these aspects remain insufficiently investigated to date. Evidence from the literature shows that the effects of MPs are dependent on multiple factors, including their quantity, polymer type, particle size, aging degree, surface characteristics, and experimental conditions such as exposure time, coexisting pollutants, presence of soil amendments and soil properties. For example, Gao et al. ( 2024 ) discovered that MPs promoted the degradation of nicosulfuron herbicide, increased its accumulation in earthworms, and altered the composition, diversity, and functionality of the microbial communities. Similarly, Wu et al. (2024) found that the co-exposure to MPs with imidacloprid and flumioxazin influenced soil microorganisms and the processes related to carbon, nitrogen, and phosphorus cycles, with outcomes either nullified or amplified compared to individual exposures. Interestingly, the agrochemicals exerted a leading role in shaping the microbial responses under co-exposure conditions. In this context, the aim of this work was to study the degradation and adsorption-desorption processes of Foramsulfuron (FRS) in two soils, with different chemical-physical properties (i.e. pH, organic matter content and texture), contaminated and not with MPs, specifically PE, PP, PS, and PLA (polylactic acid), and amended and not with a digestate (itself potentially capable of modifying the behaviour of the herbicide in the soil). FRS, a sulfonylurea herbicide used post-emergently, is selective for maize and active against the most common grasses and broadleaf weeds species, with authorized use in Europe until 2035. Despite its widespread use, no studies are currently available regarding its adsorption-desorption in amended or unamended soils, nor on the potential impact of the combined action of FRS and MPs on soil functionality. Our working hypothesis posited that the combined incorporation of MPs and digestate into soil could impact the mobility of FRS and affect soil fertility and biological activity. For this reason, the effects of the copresence of FRS and MPs on soil functionality were evaluated by quantifying, after herbicide application, the activities of selected enzymes, such as dehydrogenase, β-glucosidase, and urease, which are widely recognized as bioindicators of soil health and ecosystem multifunctionality (Alkorta et al. 2003 ). Assessing the effects of MPs on the herbicide persistence, as well as their combined impact on soil health, will be crucial to rate the environmental hazard posed by these pollutants. Materials and Methods Soil and digestate origin, sampling procedures, and experimental design Two soils from different locations were chosen for the experimental set-up: S1 soil was from Casalina, Perugia province, Italy [42°57'33.5" N; 12°22'23.6" E], and S2 soil was from Cadriano University farm, Bologna, Italy [44°33'7.98"N; 11°24'38.26"E]. In January 2024, five subsamples of topsoil (0–20 cm) were randomly collected from the two sites (in an area over approximately 0.35 ha) and mixed to form a composite sample of 5 kg: S1 and S2. The first, S1, was an agricultural unpolluted soil, while S2 soil was chosen because it had not been treated with any plant pharmaceutical for 60 years and had never been covered with any mulching sheet. S1 and S2 soils were air dried, sieved (< 2 mm) and characterized. Particle size analysis identified the soil S1 as silty clay loam (USDA texture classification, 12% sand, 52% silt and 36% clay) and soil S2 as loam (USDA texture classification, 35% sand, 42% silt and 23% clay). Soil samples were prepared by adding to 500 g of control soils (S1 and S2) a mix of MPs containing PE, PP, PS and PLA at size of 5 mm (prepared in accordance with Dominici et al. 2019 ; Gomez-Caturla et al. 2022 ; Luzi et al. 2020 ) to reach a final concentration of 0.045% (consistent with an average concentration commonly detected in agricultural soils; S1 + MPs and S2 + MPs; Li et al. 2024 ). Additional treatments (S1 + D + MPs and S2 + D + MPs) were prepared by amending the respective MPs-contaminated soils with digestate (D) at an application rate of 6.7 g kg − 1 soil (dry weight basis, after freeze-drying and grinding), reaching a N concentration equivalent to 340 kg N ha − 1 . The digestate used in the present study was collected from a biogas plant, operating under dry anaerobic digestion and mesophilic conditions (37–45°C), where the organic fraction of municipal solid waste was co-treated with lignocellulosic biomass, e.g. urban green waste, for approximately 25 days. Subsequently, the digestate obtained was aerobically stabilized and characterized (Table S1 ). All samples were maintained at 60% WHC and subjected to dry/rewetting cycles for 30 days. Soil samples were air-dried after incubation and chemical analyses were performed to assess the effects of MPs and digestate on soil chemical properties (Table 1 ). Soil pH and electrical conductivity (EC) were determined in aqueous suspension at a solid-liquid ratio of 1:5 (w/v). The carbonate content (CaCO 3 ) was quantified by gas-volumetric determination of CO 2 released by treating a soil sample with hydrochloric acid (Colombo and Miano, 2015 ). The zero point of charge (ZPC) was determined following the method of Sakurai et al. ( 1988 ). Effective cation exchange capacity (CEC) and exchangeable bases (i.e., Na, K, Mg, Ca) were determined according to the Italian Official method (Colombo and Miano, 2015 ). The concentration of dissolved organic carbon (DOC) was quantified following the procedure described by Manzano et al. ( 2020 ), while total organic carbon (TOC) and total nitrogen were measured with a CN analyser (Leco CN 828), employing Soil LCRM Leco part no. 502–697 as the calibration sample. The concentration of pseudo-total potentially toxic elements (PTEs, Table 1 ) was quantified after soil digestion with HNO 3 /HCl (3:1 v/v) and microwave mineralization (Milestone UltraWave SRC Technology). FRS degradation For each sample [control soils (S1 and S2), soils contaminated with MPs (S1 + MPs and S2 + MPs), and soils contaminated with MPs and treated with digestate (S1 + D + MPs and S2 + D + MPs)], 2.5 g of soil were suspended in 5 mL of an aqueous FRS solution (215 µM) in polyallomer centrifuge tubes. Foramsulfuron ([2-[[[[(4,6-Dimethoxy-2-pyrimidinyl) amino] carbonyl]amino]sulfony]-4-(formylamino)-N,N-dimethylbenzamide], CAS 173159-57-4, FRS, Fig. 1 ) was supplied by LabStandard® (≥ 95% purity). The samples were kept at 25 ± 2°C under stirring and aliquots were collected at different times intervals (each 24 h). The supernatant was separated from the solid phase by centrifugation at ~ 2200 g for 10 min, pipetted off, filtered (Syringe Filters 25 mm FLL/MLSPP, NY 0.45 µm, GVS Abluo) and subsequently analysed by HPLC. The solvents were of HPLC grade and were used without further purification. The degradation rate was determined by monitoring the disappearance of FRS, as a function of time, in aqueous herbicide-soil suspensions prepared from different soil sample. Kinetic data were fitted using a first-order rate equation: ln C/C 0 =-k obs .t where C (µM) represents the concentration of the herbicide at the t time, C 0 the initial herbicide concentration, and k obs the first-order rate degradation constant. FRS adsorption-desorption FRS adsorption isotherms were obtained on all soil samples using a batch equilibrium method. Each soil samples (2.5 g) were placed in polyallomer centrifuge tubes with 5 mL of aqueous herbicide solution at initial concentration of 60, 120, 180, and 240 µM. Although these concentrations exceed typical environmental levels, they were selected to ensure analytical sensitivity, especially during desorption. The tubes were shaken in an end-over-end shaker at 25 ± 2°C for 24 h. After the contact period, the suspensions were centrifuged at ~ 2200 g for 10 min and the supernatant was collected, filtered (Syringe Filters 25 mm FLL/MLSPP, NY 0.45 µm, GVS Abluo) and immediately analysed. The FRS amount adsorbed was calculated as the difference between the initial and final concentrations of herbicide in solution. Immediately after the adsorption process 2.5 mL of the supernatant solution were withdrawn. The remaining slurry was again brought to 5 mL by adding 2.5 mL of water, equilibrated for 24 h, and centrifuged. These steps (supernatant withdrawing, and replacing with water, and re-equilibrating) were repeated four times consecutively. The concentration of herbicide in each desorption solution was determined, and the amount of herbicide adsorbed on the soil after each desorption step was calculated by difference. The experimental data were fitted using the logarithmic form of the Freundlich equation (the most common model used to describe herbicide adsorption on heterogeneous surfaces, Chen et al. 1999 ): log C s = log K fa + 1/n a log C e where C s (µmol kg − 1 ) is the amount of herbicide adsorbed, C e (µM) is the equilibrium concentration in solution, and log K fa and 1/n a are empirical constants representing the intercept and the slope of the isotherm, respectively. K fa [µmol (1−1/n) kg − 1 L 1/n ] is a constant that reflects the soil’s ability to adsorb the agrochemical in the specific adsorbent/adsorbate combination, while 1/n a (dimensionless) represents the intensity or heterogeneity of the adsorption process. The hysteresis coefficient, H, for the adsorption-desorption process was calculated according to the formula: H = 1/n d /1/n a where1/n a and 1/n d are the Freundlich slopes obtained for the adsorption and desorption isotherms, respectively. HPLC Analyses The FRS concentration was measured by HPLC. The analytical system consisted of a Waters 1515 pump equipped with a Waters 2487 UV/VIS programmable detector operating at 240 nm, a Breeze chromatography software, an end-capped µBondapak C18 analytical column (10 mm, 3.9x300 mm). The eluant was a mixture of acetonitrile and water (40:60, v/v), previously brought to pH 2.7 with phosphoric acid, at a flow rate of 0.5 mL min − 1 . Under these chromatographic conditions, the retention time was 6.9 min. An external standard was used for the FRS quantitative determination. The herbicide Limit of Detection (LOD) and Limit of Quantification (LOQ) were 2.21.10 − 7 mol L − 1 , and 7.27.10 − 7 mol L − 1 , respectively. Effects of pollutants on some enzymatic activities The effects of MPs and FRS on soil selected enzymatic activities were evaluated in mesocosm experiments. For each treatment, 150 g of soil were treated with 15 mL of an aqueous solution containing 8 mg of herbicide, corresponding to the lowest concentration of FRS used in the adsorption-desorption test (treatments: S + FRS, S + MPs + FRS, S + D + MPs + FRS). Controls soils without herbicide were obtained by adding 15 mL of ultrapure water to 150 g of soil samples (treatments: S; S + MPs, S + D + MPs). Enzymatic activities, i.e. dehydrogenase (DHG), β-glucosidase (GLU) and urease (URE), were determined in triplicate soil samples taken from each mesocosm at 3 (T1), 10 (T2) and 24 days (T3) from the addition of herbicide. To determine DHG, soil samples were treated with a solution of triphenyltetrazolium chloride and incubated at 30°C for 24 h, GLU activity was quantified after incubation of soil samples with p-nitrophenyl glucoside, while URE activity was determined after incubation of soil samples with urea (Alef and Nannipieri 1995 ). Statistical analysis All analyses were performed in triplicate on soil samples collected from each treatment and results are reported as mean values ± standard deviations in Tables and Figures. Differences among treatments were evaluate using one-way analysis of variance (ANOVA), followed by a Tukey’s post hoc test when significant P-values were detected ( P < 0.05). Before the ANOVA, data normality was assessed using the Shapiro-Wilk tests. Statistical analyses were carried out using the Sigma Plot Software (SPSS Inc., Chicago, II, USA). Principal component analysis (PCA) was conducted on standardized data to identify relationships among soil chemical variables and to evaluate the overall effects of MPs and digestate treatments on soil properties. Results and discussion Effects of MPs and digestate on soil chemicals properties The addition of MPs to soil caused a slight increase in pH value of S1 and S2, detectable even after the addition of digestate (Table 1 ). The enhancement of soil aeration and porosity caused by the addition of MPs (de Souza Machado et al. 2019; Lozano et al. 2021 ), together with the release of alkaline additives (e.g. carbonates and metal stearates) and residual inorganic compounds from MPs into the soil has been reported to elevate soil pH (Waldman and Rillig 2020 ). Though, as previously emphasized, the effects of MPs depend on their amount, particle size, aging, surface characteristics, and exposure time and properties of soil, our results are consistent with those of Sakin et al. ( 2025 ), who reported pH increases in soils with different polymer type and ages of MPs. In both soils, electrical conductivity (EC, Table 1 ), resulted unaffected by MPs addition, whereas digestate induced a fair increase in EC of S + D + MPs soils (+ 17% in S1 and + 21% in S2). MPs can represent a carbon source and provide habitat for soil microbes, thereby stimulating microbial activity and promoting the degradation of organic matter (Liu et al. 2023 ). Consistently, total organic carbon and DOC increased in both soils in the presence of MPs (Table 1 ). In S1, MPs enhanced TOC by 7% and DOC by 8% compared to the control, while in S2 the addition of MPs resulted in a 13% increase in DOC, despite the TOC remaining unchanged. The ability of MPs to increase soil aeration was likely responsible for enhancing the transformation of organic matter into soluble organic substrates (Zhang et al. 2023 ), which provided a plausible explanation for the observed DOC enrichment. These results agree with previous reports on the effects of MPs exposure on soil C dynamics (Xiang et al. 2024 ). In particular, Peng et al. ( 2025 ) observed an enhancement in pH and TOC, as well as a reduction of exchangeable K, following the incorporation into soil of several MPs, among which PLA. Furthermore, a meta-analysis of 337 cases from 33 studies conducted by Liu et al. ( 2025 ) confirmed that MPs increased organic matter and DOC content, highlighting however that the effect was polymer-dependent: PS significantly increased organic matter, but PLA decreased it. As expected, the application of digestate increased soil total organic carbon (Table 1 ): by 14% in S1, with a rise of 30% in DOC, whereas in S2 TOC and DOC increased by approximately 15% and 40% respectively, compared to the control soil. Likely, due to the immobilisation of nitrogen within the microbial biomass (de la Fuente et al. 2013 ), neither the presence of MPs nor the addition of digestate significantly affected the total nitrogen content in both soils. Depending on the feedstock used for the anaerobic digestion, the digestate may be a source of potentially toxic elements (PTEs, i.e. Cd, Cu, Pb, Zn, As) which, when their concentrations are high, pose serious risks of soil pollution (Dragicevic et al. 2018 ). As reported in Table 1 , the addition of digestate increased Pb concentration in both soils, by 31% in S1 and 36% in S2, respectively. Nonetheless, the pseudo total concentrations of PTEs (including Pb) remained below the contamination thresholds set by Italian legislation (Ministerial Decree, 2019). Overall, the combined presence of MPs and digestate altered soil chemical properties and carbon dynamics, while not inducing critical risks of PTEs contamination under the experimental conditions. Effects of MPs and digestate on FRS degradation and adsorption-desorption processes Degradation The co-existence of MPs and herbicides in agricultural environments is a common occurrence (Rodríguez-Seijo et al. 2019 ; Cheng et al. 2020 ; Sun et al. 2021 ). To evaluate the effect of MPs on the degradation of FRS, a controlled laboratory experiment was conducted, and the related kinetic data reported in Table 2. In both soils, whether added with MPs and treated or untreated with the digestate, FRS proved to be a non-persistent herbicide with half-lives ranging from 11 to 15 days. FRS, classified as a sulfonylurea herbicide, undergoes degradation predominantly through chemical hydrolysis and microbial metabolism, with the rate influenced by factors such as pH, temperature, humidity, and microbial activity (Grey and McCullough 2017). Consistently with findings previously reported, although for different families of herbicides and mixtures of MPs (Chen et al. 2025 ; Tang 2025 ), the present study also demonstrated that MPs reduced the FRS degradation rate. It is plausible that the increased half-life of FRS observed in the presence of MPs (+ 17% in S1 and + 21% in S2 relative to the control) may be at least partially attributed to the rise in soil pH, since the degradation of this compound is favoured under acidic conditions. Conversely, treatment with digestate reduced the half-life of the herbicide by 10% respect to the control in both soils, whereas in the combined treatment (S + D + MPs) the decrease was equal to 30% in S1 and 26% in S2 compared with the corresponding S + MPs. Given that pH values were the same in S + MPs and S + D + MPs, the increase in the degradation rate observed following digestate amendment is likely related to the stimulation of microbial activity, which increased herbicide degradation (Su et al. 2019 ; Marín-Benito et al. 2019 ; Barba et al. 2019 ). Adsorption Along with degradation, adsorption represents a key process governing the environmental fate of agrochemicals in soil (Arias-Estevez et al. 2008). FRS adsorption was described using the empirical Freundlich equation (r ≥ 0.99, Table 3 ). In general, K fa values were low (between 1.07 and 2.05 µmol (1−1/n) kg − 1 L 1/n , Table 3 ), suggesting a very limited adsorption of herbicide in all soils, while the 1/n a values (Table 3 ), were consistent with the limited range of 1/n a values reported for FRS adsorption in soils with organic carbon contents between 0.47 and 1.47% (EFSA, 2016). Table 3 Freundlich parameters (mean ± SD) for the adsorption and desorption of FRS in control soils (S1 and S2), soils treated with MPs (S1 + MPs and S2 + MPs) and soils treated with MPs and digestate (S1 + D + MPs and S2 + D + MPs) Adsorption S1 S1 + MPs S1 + D + MPs S2 S2 + MPs S2 + D + MPs K fa 2.05 ± 0.33 1.38 ± 0.24 1.37 ± 0.23 1.07 ± 0.15 2.06 ± 0.28 1.83 ± 0.46 1/n a 0.94 ± 0.03 1.05 ± 0.04 1.09 ± 0.04 1.05 ± 0.02 0.93 ± 0.03 1.02 ± 0.06 r a 0.996 0.990 0.987 0.996 0.996 0.993 Desorption Ci (µM) 60 K fd 14.6 ± 4.79 15.4 ± 4.22 28.6 ± 0.41 26.5 ± 0.48 14.3 ± 0.36 29.1 ± 1.70 1/n d 0.35 ± 0.07 0.28 ± 0.08 0.14 ± 0.02 0.14 ± 0.02 0.32 ± 0.01 0.17 ± 0.01 H 0.37 0.27 0.13 0.13 0.34 0.17 120 K fd 4.69 ± 1.17 8.74 ± 3.99 40.9 ± 3.86 14.1 ± 2.65 18.4 ± 1.51 26.3 ± 3.67 1/n d 0.73 ± 0.08 0.57 ± 0.10 0.21 ± 0.02 0.45 ± 0.03 0.36 ± 0.02 0.32 ± 0.03 H 0.78 0.54 0.19 0.43 0.39 0.31 180 K fd 0.48 ± 0.31 5.62 ± 0.02 37.8 ± 1.88 19.2 ± 2.03 18.1 ± 1.27 33.5 ± 4.11 1/n d 1.29 ± 0.15 0.74 ± 0.01 0.34 ± 0.02 0.42 ± 0.02 0.45 ± 0.01 0.36 ± 0.02 H 1.37 0.70 0.31 0.40 0.48 0.35 240 K fd 0.69 ± 0.02 6.14 ± 0.13 10.4 ± 0.36 17.6 ± 1.00 4.38 ± 1.05 23.2 ± 1.64 1/n d 1.16 ± 0.00 0.72 ± 0.01 0.66 ± 0.01 0.49 ± 0.02 0.77 ± 0.06 0.48 ± 0.02 H 1.23 0.68 0.60 0.47 0.83 0.47 a Correlation coefficient FRS is a weak acid (pK a = 4.6, Fig. 1 ), it predominantly exists in its anionic form at the pH values of studied soils (Table 1 ), and it is therefore weakly adsorbed by negatively charged soil constituents. For S1 soil, the Freundlich parameter 1/n a < 1 (characteristic of L-type isotherms, Giles et al. 1960 ; Table 3 and Fig. 2 ) suggested a relatively high affinity of FRS for soil at low concentrations. With increasing herbicide concentration, adsorption declined, likely due to fewer available adsorption sites. Conversely, for S2 soil, the Freundlich parameter 1/n a > 1 (distinctive of S-type isotherms, Table 3 and Fig. 2 ), indicated a lower FRS affinity for soil at low concentrations. Adsorption increased as herbicide concentration rised, probably because of cooperative interactions among adsorbed organic species that stabilized the sorbate on soil solid surfaces, thereby enhancing the herbicide affinity for the latter (Sposito 1984 ). The Freundlich adsorption constant K fa alone cannot be directly compared between different adsorption systems when the exponent 1/n a in the Freundlich equation varies. To enable a meaningful comparison, data should be normalized by calculating the amount adsorbed (C s ) at a standardized equilibrium concentration (C e ) using the Freundlich equation. This approach considers both K fa and 1/n a allowing for valid comparisons of adsorption capacities across different systems (Chen et al. 1999 ). The calculated C s at a common C e (i.e. 60 µM), was higher in S1 (96.21 µmol kg − 1 ) than in S2 (78.78 µmol kg − 1 ) indicating a greater affinity of S1 for the herbicide. The lower pH PZC of S1 compared to S2 indicated a prevalence of net negative charges in soil S1, which should result in a greater electrostatic repulsion of FRS, however the higher amount of organic matter in S1 (+ 61% compared to S2), as well as the its higher clay content relative to S2 may have contributed to the higher herbicide adsorption observed in S1 (Wauchope et al. 2002 ; Pusino et al. 2000 ; 2004 ). Both MPs and digestate influenced the herbicide adsorption (Table 3 ). The calculated C s at the common C e concentration (60 µM), increased in both soils in the order: C s -(S) < C s -(S + MPs) < C s -(S + D + MPs) resulting equal (119 µmol kg − 1 ) in both soils treated with MPs and digestate (S + D + MPs). Several authors observed differing effects of MPs on the soil adsorption of agrochemicals, reporting an increase (Tan et al. 2025 ), a reduction (Wu et al. 2025 ) or no significant effect (Sunta et al. 2025). These differences depended on the type, quantity, aging degree of MPs, and the specific agrochemical considered. Different mechanisms have been invoked to interpret the adsorption of agrochemicals on MPs (Mo et al. 2021 ; Lan et al. 2022 ; Liu et al. 2022 ). Our results seem to indicate that in soil S1 + MPs, the increased total organic carbon and the decreased pH PZC compared to S1 (Table 1 ) imply that the adsorption of FRS was likely due to hydrophobic interactions. Conversely, in S2 + MPs, considering that in this soil the pH PZC was higher than the pH value (Table 1 ), the dominant adsorption mechanism appeared to be electrostatic attraction. The adsorption process to soil protected FRS from degradation, and the increased herbicide retention capacity in the presence of MPs was therefore responsible for the increased herbicide half-life measured in the S + MPs soils (Table 2). The highest adsorption of FRS, equal in both soils, was detected in the S + D + MPs systems (Table 3 and Fig. 2 ), likely due to lipophilic interactions arising from their higher organic carbon content compared to the control soils (+ 14% in S1 + D + MPs and + 15% in S2 + D + MPs, Table 1 ). This result agrees with previous studies documenting that organic amendments increase the agrochemical adsorption capacity of soils (Rodríguez-Cruz et al. 2006 ; Fenoll et al. 2010 ) and confirms that the content of organic carbon in the digestate can be considered a key factor influencing the adsorption of agrochemicals in amended soils (Wauchope et al. 2002 ). Furthermore, the treatment of soils with digestate increased DOC (Table 1 ). The adsorption on soil components of this soluble organic fraction, creating new hydrophobic surfaces, may have contributed to the enhanced adsorption of herbicide (Cox et al. 2004 ). Desorption The parameters for FRS Freundlich desorption, determined at different concentration values, along with the calculated hysteresis coefficients (H), are listed in Table 3 . Overall, the K fd values were higher than the corresponding K fa , indicating that a greater amount of herbicide was retained by the soil during desorption compared to equilibrium adsorption. The fragmentation of soil particles, induced by reiterated centrifugation, resuspension, and prolonged agitation in the batch method (Delle Site 2001 ), which increased the number of available adsorption sites during the desorption, accounted for this finding. Additionally, degradative processes and formation of bound residues contributed to this outcome. Regarding hysteresis coefficients, no hysteresis is theoretically observed when H = 1. In practice, hysteresis is not considered significant when H lies between 0.7 and 1 (Mamy and Barriuso 2007 ). On the other hands, if H is greater than 1, a phenomenon that may be due to experimental artifacts or changes in the adsorption sites, desorption is favoured over adsorption. The desorption of FRS showed varying degree of hysteresis (Table 3 ), depending on the soil type and herbicide concentration used, indicating that the adsorption process was only partially reversible. Regarding soil S1, the highest hysteresis coefficient was recorded in the control, suggesting that herbicide desorption occurred more readily in this soil than in S1 + MPs and S1 + D + MPs. FRS adsorption in S1 was practically reversible except at the lowest herbicide concentration, where a certain degree of hysteresis was detected. The addition of MPs and especially digestate to the soil appeared to make adsorption more hysteretic, suggesting that soils where FRS is more adsorbed also retain more. This result, likely due to the formation of irreversible bonds between the herbicide molecule and the organic matter of which S1 + D + MPs is richest, supports the role of organic carbon of the digestate in soil dynamics of FRS. The adsorption of FRS showed a certain degree of hysteresis in both S2 and S2 + D + MPs, whereas hysteresis was negligible (H = 0.83, Table 3 ) when MPs were present alone at the highest herbicide concentration. In general, H calculated in S2 + MPs resulted higher than that in the control soil and in the soil treated with digestate and MPs (at the same initial concentration of herbicide, Table 3 ), indicating that in S2 the soil’s capacity to retain FRS was reduced by MPs. This result suggests that MPs can also lead to greater mobility of the herbicide in the environment, increasing the risk of migration to groundwater or other environmental matrices. Moreover, if compared with what was observed in soil S1, it points up that the effects of MPs must be assessed on a case-by-case basis. Our results highlighted that MPs and digestate altered the environmental fate of FRS in soil. Microplastics tended to prolong the half-life of the herbicide, while digestate promoted its degradation likely due to the stimulation of microbial activity. The effects on adsorption-desorption were different in the two soils and seemed to be governed by their intrinsic properties (i.e. pH, texture, organic matter). Effects of MPs, digestate, and FRS on soil enzymatic activities Enzyme activities are widely recognized as indicators of soil functionality, because they are closely linked to nutrient cycling processes, such as those related to carbon and nitrogen cycles, and are highly sensitive to changes in soil physical-chemical characteristics and contamination levels. Therefore, these activities provide useful insights into soil quality and ecosystem health. The effects of FRS, MPs, and D on soil microbial functioning were assessed through the activities of three representative enzymes, i.e., dehydrogenase (DHG, reflecting the oxidative activity of intact microbial cells), β-glucosidase (GLU, responsible for the cleavage of β 1–4 glycosidic bonds) and urease (URE, involved in the hydrolytic NH 4 + release from urea). Enzyme activities were determined at 3 (T1), 10 (T2) and 24 (T3) days from the addition of herbicide to soils (Figs. 3 and 4 ). In S1 soil, FRS, likely utilized by soil microorganisms as carbon source (Vandana et al. 2012 ), initially (i.e. T1) stimulated DHG activity, which increased by 40% compared to the control up to 10 days from treatment with the herbicide, and decreased by 17% at 24 days from the contact (Fig. 3 ). Although dependent on soil characteristics and experimental conditions, conflicting results are reported in the literature regarding the impact of sulfonylurea herbicides on DHG. For example, mesosulfuron methyl and iodosulfuron methyl showed short-lived harmful effects on dehydrogenase (Kaur et al. 2023 ), whereas a DHG increase, immediately after the treatment with mixtures containing azimsulfuron, flucetosulfuron, ethoxysulfuron, and bensulfuron methyl, was reported by Meher et al. ( 2021 ), with whom our results agree. On the other hand, Caraba et al. ( 2024 ) noticed an inhibitory effect of nicosulfuron on DHG activity at 14 days from treatment with herbicide. At 3 days, the highest dehydrogenase activity was found in S1 + D + MPs + FRS (double compared to the control, Fig. 3 ), indicating that the digestate, by modifying the chemical-physical properties of the soil and supplying nutrients and nitrogen, increased its biological properties, as confirmed by the high DHG value in S1 + D + MPs (about 1.5 times compared to the control) at T3. Literature data report variable impacts of MPs on DHG activity, including stimulation, inhibition as well as no effect, as a function of the polymer type and dose (Lian et al. 2024 ), particle shape and aging degree of MPs (Yi et al. 2021 ). In our study, increases in DHG activity of 33 and 68% compared to the control were initially measured (time = 3 and 10 days) in S1 + MPs, suggesting that MPs can also provide carbon and energy sources for microorganisms. The co-presence of MPs and FRS also initially stimulated DHG, increasing it by 18% (T1) and 26% (T2), but led to a reduction after 24 days (–13%, T3) in S1 + MPs + FRS compared to the control (Fig. 3 ). This result suggests that the initial positive impact of FRS and MPs alone on DHG is attenuated when both are present together and over time. Due to the lower organic matter content of S2 (38% less than in S1), a general lower DHG activity was measured in this soil compared to S1 (Fig. 4 ). These findings confirm that the effect of herbicides and MPs on DHG depends on soil chemical characteristics (i.e., pH and organic carbon content). In soil S2 both contaminants, whether applied individually or together, did not cause substantial short-term changes in DHG compared to the control, even when the soil was amended with digestate. At T3, the positive impact of the digestate was evident: in S2 + D + MPs soil DHG increased by 48% compared to the control soil (Fig. 4 ). Three days after herbicide treatment, GLU increased in both soils (Figs. 3 and 4 ). In S1, increases of 70, 78, and 95% compared to the control soil were recorded in the presence of FRS, FRS and MPs, and FRS, MPs, and D. In S2, GLU was doubled in S2 + FRS and S2 + MPs + FRS, and 2.25-fold higher S2 + D + MPs + FRS compared to the untreated soil, highlighting a short-term stimulatory action of the herbicide on this enzymatic activity. Representing FRS a carbon source for microorganisms, the GLU increase was marked in S2, the soil where FRS was less adsorbed. This result is consistent with observations reported by some authors for other agrochemicals (i.e. Tomkiel et al. 2019 ; Zhang et al. 2021 ). MPs did not seem to negatively influence GLU in S1, rather at t = 10 d they even had a stimulating effect, whereas GLU increased by 69% compared to the control in S2 + MPs as early as 3 days post-herbicide treatment. This underscores that the effect of MPs was also soil-dependent. In both soils and in the short term, the co-presence of MPs and FRS did not seem to have a detrimental effect on GLU, which was further increased by the presence of digestate. This stimulation was consistent with the increase of soil organic carbon and DOC derived from the organic amendment, that can also improve soil physical properties (Xiao et al. 2023 ) and provide organic and inorganic nutrients required for enzymes synthesis (Ge et al. 2010 ). FRS enhanced URE activity by 25 and 48% in S1 and S2, respectively, at 10 days from its application (Figs. 3 and 4 ). This activation of URE several days after herbicide application, observed by other authors for mixtures containing mesosulfuron and iodosulfuron (Baćmaga et al. 2015 ) and for treatments based on diclosulam and cloransulam-methyl (Zhang et al. 2021 ), may be due to the carbon and nitrogen supply for microorganisms from the sulfonylurea herbicide FRS. Microorganisms, following herbicide application, secreted more urease, whose action resulted appreciably activated (Fisher et al. 2017 ). In agreement with Baćmaga et al. ( 2015 ) and Zhang et al. ( 2021 ), the effect of FRS was irrelevant 24 days after treatment with the herbicide. Initially, MPs slightly reduced URE in S1, whereas an increase of 32% compared to the control soil was measured in S1 + MPs at the end of the experiment (T3, Fig. 3 ). On the other hand, an URE augment of 39% compared to the control soil was determined in S2 + MPs at T2. Probably, the increased soil organic carbon content and DOC, due to the addition of MPs promoted microbial metabolism and URE activity. Our findings agree with Ding et al. ( 2021 ) and Liu et al. ( 2017 ), who observed a positive impact of MPs, particularly at low doses, on soil urease. The highest urease activity was measured at T2 in MPs + D treatment, corresponding to + 36 and + 63% (compared to untreated soil, Figs. 3 and 4 ) in S1 and S2, respectively. The supply of nutrients and nitrogen provided by digestate accounts for the increased URE activity (and DHG activity) produced by the combination of MPs and digestate. PCA accounted for 90% of the total variance in S1 and 95% in S2 (Figs. 5 and 6 ). PC1 accounted for 61% (S1) and 85% (S2) of the variance and mainly separated the treatments at 3, 10 and 24 days. In contrast, PC2 explained 29% (S1) and 10% (S2) of the total variance and was mainly correlated with the addition of FRS to the soil, thereby highlighting the impact of the herbicide on enzymatic activities. Overall, these results indicated that FRS, MPs, and digestate mainly stimulated DHG, GLU, and URE in the short term, with the magnitude and duration of these effects controlled by soil properties and herbicide adsorption capacity. The PCA confirmed that exposure time and FRS addition were the main drivers of variability in enzymatic responses, highlighting complex, time-dependent interactions between herbicide, MPs, digestate, and soil properties. Conclusions This study demonstrates that MPs and digestate can significantly influence the persistence of FRS in soil. The combined presence of MPs, digestate, and FRS does not exert a markedly negative impact on key soil enzymatic activities in the short term. Instead, the observed increases in dehydrogenase, β-glucosidase, and urease activities indicate rather that MPs may serve as supplementary sources of carbon and energy for soil microorganisms. These effects, however, are influenced by soil properties, exposure duration, and the specific interactions among the different treatments. Overall, these findings provide insights into the behaviour of FRS, for which there are no data in the literature, in soils contaminated by MPs and amended with organic materials, underlining the necessity to consider multiple factors when assessing the environmental risks associated with herbicide and microplastic co-exposure in agricultural soils. Further investigations may concern long-term studies to assess chronic and cumulative effects of microplastics, digestate, and FRS on soil health, while extending investigations to diverse soil types to enhance the generalizability of findings. Moreover, changes in soil microbial communities as well as the impact on plants and soil fauna could be assessed. Declarations Acknowledgements Not applicable Funding The financial support of the National Recovery and Resilience Plan (NRRP), Mission 4, Component 2, Investment 1.1, call for tender No. 104 published on 2.02.2022 by the Italian Ministry of University and Research (MUR) funded by the European Union – Next Generation EU – Project Title “Impacts of microplastics, antibiotics and pesticides in soil amended with digestates - 3IMPACT” – CUP J53D23010170006 - Grant Assignment Decree No. 1048 adopted on 14.07.2023 by the Italian Ministry of University and Research (MUR), is gratefully acknowledged. Authors’ contributions Maria Vittoria Pinna: Investigation, Conceptualization, Methodology, Formal analysis, Data curation, Writing - original draft preparation; Stefania Diquattro: Investigation, Methodology, Formal analysis, Data curation, Writing - original draft preparation; Enrico Buscaroli: Formal analysis, Writing - reviewing and Editing; Daniela Pezzolla: Resources, Writing - reviewing and Editing; Paola Castaldi: Investigation, Conceptualization, Methodology, Resources, Writing - reviewing and Editing. Data availability The authors confirm that all the data supporting the findings of this study are included within the manuscript. The raw data used in this study will be made available upon reasonable request. Ethical approval This study did not involve human and/or animal subjects. Consent to participate This study did not involve human subjects, so clinical trial registration is not applicable. Consent to publish The authors confirm that this manuscript represents their original, unpublished work; has not been previously published; and is not currently being considered by any other journal. All authors have reviewed and approved the manuscript and consent to its submission. Competing interests The authors declare no competing interests. Data availability Data will be made available on reasonable request. Clinical trial number: not applicable. References Alef K, Nannipieri P (1995) Enzyme activities. Methods in applied soil microbiology and biochemistry, p.pp. 311–373. https://doi.org/10.1016/B978-0-12-513840-6.X5014-9 Alkorta I, Aizpurua A, Riga P, Albizu I, Am´ezaga I, Garbisu C (2003) Soil enzyme activities as biological indicators of soil health. 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J Hazard Mater 455:131603. https://doi.org/10.1016/j.jhazmat.2023.131603 Sposito G (1984) Inorganic and organic solute adsorption in soil. The surface chemistry of soils. Oxford University Press, Oxford, UK, pp 113–153. Chap. 4 Su W, Hao H, Ding M, Wu R, Xu H, Xue F, Lu C (2019) Adsorption and degradation of imazapic in soils under different environmental conditions. PLoS ONE 14:e0219462. https://doi.org/10.1371/journal.pone.0219462 Sun W, Meng Z, Li R, Zhang R, Jia M, Yan S, Tian S, Zhou Z, Zhu W (2021) Joint effects of microplastic and dufulin on bioaccumulation, oxidative stress and metabolic profile of the earthworm (Eisenia fetida). Chemosphere 263:128171. https://doi.org/10.1016/j.chemosphere.2020.128171 Šunta U, Prosenc F, Soderžnik KZ, Griessler Bulc T, Bavcon Kralj M (2025) Impact of microalgal biomass and microplastics on the sorption behaviour of pesticides in soil: a comparative study. Environ Sci Eur 37:57. https://doi.org/10.1186/s12302-025-01100-1 Tan G, Tang DWS, Silva V, Mu H, Qin S, Rima O, Geisse V, Yang X (2025) Co-occurrence of multiple contaminants: Unentangling adsorption behaviour in agricultural soils. Environ Pollut 373:126118. https://doi.org/10.1016/j.envpol.2025.126118 Tang KHD (2025) Effects of microplastics on bioavailability, persistence and toxicity of plant pesticides: an agricultural perspective. Agriculture 15:356. https://doi.org/10.3390/agriculture15040356 Tomkiel M, Baćmaga M, Borowik A, Kucharski J, Wyszkowska J (2019) Effect of a mixture of flufenacet and isoxaflutole on population numbers of soil-dwelling microorganisms, enzymatic activity of soil, and maize yield. J Environ Sci Health Part B 54(10):832–842. https://doi.org/10.1080/03601234.2019.1636601 Vandana LJ, Rao PC, Padmaja G (2012) Effect of herbicides and nutrient management on soil enzyme activity. New Facet 21 st Century Plant Breed. 5:51–58 Waldman WR, Rillig MC (2020) Microplastic research should embrace the complexity of secondary particles. Environ Sci Technol 54(13):7751–7753. https://doi.org/10.1021/acs.est.0c02194 Wang Y, Liu C, Wang F, Sun Q (2022) Behavior and mechanism of atrazine adsorption on pristine and aged microplastics in the aquatic environment: Kinetic and thermodynamic studies. Chemosphere 292:133425. https://doi.org/10.1016/j.chemosphere.2021.133425 Wanner P (2021) Plastic in agricultural soils – a global risk for groundwater systems and drinking water supplies? – a review. Chemosphere 264:128453. https://doi.org/10.1016/j.chemosphere.2020.128453 Wauchope RD, Yeh S, Linders JBHJ, Kloskowski R, Tanaka K, Rubin B, Katayama A, Kördel W, Gerstl Z, Lane M, Unsworth JB Pesticide soil sorption parameters: theory, measurement, uses, limitations and reliability. Pest Manag Sci 58:419–445., Song C, Wang X, Ma D, Shan Y, Ren Y, Hu X, Cui H, Ma J (2002) Y (2024) Combined effects of mulch film-derived microplastics and pesticides on soil microbial communities and element cycling. J Hazard Mater 466:133656. https://doi.org/10.1016/j.jhazmat.2024.133656 Wu S, Bohme A, Ulrich N, Chen Z, Schaffer A, Jahnke A (2025) The vertical migration of a pesticide mixture in sandy soil is strongly driven by their sorption behavior and can be altered by polyethylene microplastics. J Hazard Mater 494:138511. https://doi.org/10.1016/j.jhazmat.2025.138511 Xiang Y, Rillig MC, Pe˜nuelas J, Sardans J, Liu Y, Yao B, Li Y (2024) Global responses of soil carbon dynamics to microplastic exposure: a data synthesis of laboratory studies. Environ Sci Tech 58(13):5821–5831. https://doi.org/10.1021/acs.est.3c06177 Xiao QQ, He BP, Wang S (2023) Effect of the different fertilization treatments application on Paddy soil enzyme activities and bacterial community composition. Agronomy-Basel 13:712. https://doi.org/10.3390/agronomy13030712 Yang L, Zhang Y, Kang S, Wang Z, Wu C (2021) Microplastics in soil: a review on methods, occurrence, sources, and potential risk. Sci Total Environ 780:146546. https://doi.org/10.1016/j.scitotenv.2021.146546 Yi M, Zhou S, Zhang L, Ding S (2021) The effects of three different microplastics on enzyme activities and microbial communities in soil. Water Environ Res 93(1):24–32. https://doi.org/10.1002/wer.1327 Zhang GH, Liu D, Lin JJ, Kumar A, Jia KT, Tian XX, Yu ZG, Zhu B (2023) Priming effects induced by degradable microplastics in agricultural soils. Soil Biol Biochem 180:109006. https://doi.org/10.1016/j.soilbio.2023.109006 Zhang MG, Tan MM, Ji R, Ma RH, Li HL (2022) Current situation and ecological effects of microplastic pollution in soil. Rev Environ Contam Toxicol 260:11. https://doi.org/10.1007/s44169-022-00012-y Zhang Y, Zhang J, Shi B, Li B, Du Z, Wang J, Zhu L, Wang J (2021) Effects of cloransulam-methyl and diclosulam on soil nitrogen and carbon cycle-related microorganisms. J Hazard Mater 418:126395. https://doi.org/10.1016/j.jhazmat.2021.126395 Table 1 Table 1 is available in the Supplementary Files section. Supplementary Files Table1.docx TableS1.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8539415","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":573817778,"identity":"0996e3a1-768a-477a-9457-5402dc9ec69f","order_by":0,"name":"Maria Vittoria Pinna","email":"","orcid":"","institution":"University of Sassari: Universita degli Studi di Sassari","correspondingAuthor":false,"prefix":"","firstName":"Maria","middleName":"Vittoria","lastName":"Pinna","suffix":""},{"id":573817779,"identity":"46537ae5-ce71-48cf-b4ce-7214f7ce503b","order_by":1,"name":"Stefania Diquattro","email":"","orcid":"","institution":"University of 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1","display":"","copyAsset":false,"role":"figure","size":195673,"visible":true,"origin":"","legend":"\u003cp\u003eChemical structure and selected physicochemical properties of FRS\u003c/p\u003e","description":"","filename":"Figure1.png","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/81b732ea9a35a1923739662d.png"},{"id":100546705,"identity":"1017418a-84ef-4990-98a9-4db99136d16a","added_by":"auto","created_at":"2026-01-19 08:12:00","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":275226,"visible":true,"origin":"","legend":"\u003cp\u003eFRS adsorption isotherms on control soils (S), soils treated with MPs (S+MPs) and soils added with MPs and digestate (S+D+MPs)\u003c/p\u003e","description":"","filename":"Figure2.png","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/da3843bc221a1f091550b47b.png"},{"id":100546181,"identity":"88bb60fc-ca77-4784-b628-1a94151d610d","added_by":"auto","created_at":"2026-01-19 08:00:18","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":414725,"visible":true,"origin":"","legend":"\u003cp\u003eDehydrogenase (DHG), β-glucosidase (GLU), and urease (URE) activity in control soil (S1), in soil added with MPs (S1+MPs), and in soil added with MPs and digestate (S1+D+MPs), treated (+ FRS) and not with FRS at 3 (T1), 10 (T2) and 24 (T3) days from the treatment with herbicide. For each enzyme activity, different lowercase letters indicate statistically significant differences between treatments at the same time, while uppercase letters denote statistically significant differences over time for the same treatment, according to Tukey’s test (\u003cem\u003eP\u003c/em\u003e \u0026lt; 0.05)\u003c/p\u003e","description":"","filename":"Figure3.png","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/a428df7a364f2eef2f1edb2d.png"},{"id":100428999,"identity":"147707b2-ca0d-42f2-bde1-2e0b3e36d907","added_by":"auto","created_at":"2026-01-16 14:27:23","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":395767,"visible":true,"origin":"","legend":"\u003cp\u003eDehydrogenase (DHG), β-glucosidase (GLU), and urease (URE) activity in control soil (S2), in soil added with MPs (S2+MPs), and in soil added with MPs and digestate (S2+D+MPs), treated (+ FRS) and not with FRS at 3 (T1), 10 (T2) and 24 (T3) days from the treatment with herbicide. For each enzyme activity, different lowercase letters indicate statistically significant differences between treatments at the same time, while uppercase letters denote statistically significant differences over time for the same treatment, according to Tukey’s test (\u003cem\u003eP \u003c/em\u003e\u0026lt; 0.05)\u003c/p\u003e","description":"","filename":"Figure4.png","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/be3db0e0ede550c0ecd35ca6.png"},{"id":100546170,"identity":"fcbafbd2-ad8d-4073-9bc3-981e95a7c25c","added_by":"auto","created_at":"2026-01-19 08:00:15","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":486641,"visible":true,"origin":"","legend":"\u003cp\u003ePCA plot of enzymatic activities data in control soil (S1), in soil added with MPs (S1+MPs), and in soil added with MPs and digestate (S1+D+MPs), treated (+FRS) and not with FRS, at 3 (T1), 10 (T2) and 24 days (T3) from the treatment with herbicide\u003c/p\u003e","description":"","filename":"Figure5.png","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/bad3a566a6a5152f2925b8ca.png"},{"id":100429003,"identity":"71b67947-159b-4a7e-93c7-dd877e517421","added_by":"auto","created_at":"2026-01-16 14:27:23","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":476835,"visible":true,"origin":"","legend":"\u003cp\u003ePCA plot of enzymatic activities data in control soil (S1), in soil added with MPs (S1+MPs), and in soil added with MPs and digestate (S1+D+MPs), treated (+FRS) and not with FRS, at 3 (T1), 10 (T2) and 24 days (T3) from the treatment with herbicide\u003c/p\u003e","description":"","filename":"Figure6.png","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/01956d4ecfb2ed2eaddb7b6a.png"},{"id":102745208,"identity":"2feaac28-9e6b-4a35-ae2d-5888297b9fcb","added_by":"auto","created_at":"2026-02-16 08:44:01","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2928165,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/d3168def-47e3-4fb0-aa85-bf1bb2a38b94.pdf"},{"id":100546570,"identity":"1096f25c-c0c1-4f21-9fde-2bb87b4df8bd","added_by":"auto","created_at":"2026-01-19 08:10:53","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":19825,"visible":true,"origin":"","legend":"","description":"","filename":"Table1.docx","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/9f276b8b2b4d6bb268e6dbe4.docx"},{"id":100546292,"identity":"3049ccf0-8508-4fe6-b79a-437c956aabf3","added_by":"auto","created_at":"2026-01-19 08:05:00","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":14832,"visible":true,"origin":"","legend":"","description":"","filename":"TableS1.docx","url":"https://assets-eu.researchsquare.com/files/rs-8539415/v1/13f07f069fdbb9bbd354d626.docx"}],"financialInterests":"","formattedTitle":"Coexistence of microplastics and Foramsulfuron in soil: effects on herbicide persistence and soil functionality","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe accumulation of plastics in agricultural soils represents a significant environmental concern, as their residues contribute significantly to the presence of microplastics [MPs, plastic fragments or particles with a diameter\u0026thinsp;\u0026lt;\u0026thinsp;5 mm, predominantly composed of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), and polyvinyl chloride (PVC); Yang et al. \u003cspan citationid=\"CR77\" class=\"CitationRef\"\u003e2021\u003c/span\u003e]. These MPs persist in the soil, where they can alter the chemical and physical properties (Peng et al. \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e2025\u003c/span\u003e), the carbon, nitrogen, and phosphorus cycles (Sakin et al. \u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e2025\u003c/span\u003e) and negatively affect soil microbial communities and overall soil health (Liu et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Liu et al. \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2025\u003c/span\u003e). Such impacts are attributable to the intrinsic physicochemical properties of MPs (e.g. hydrophobicity, surface charge, and functional groups).\u003c/p\u003e \u003cp\u003eRecent data estimate that the agricultural sector consumes approximately 12.5\u0026nbsp;million tonnes of plastic annually, making it the sector that contributes most (14% of global plastic pollution) to the spread of plastic residues in the environment (Wanner \u003cspan citationid=\"CR72\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Although agricultural plastic mulching represents a well-recognized source of MPs in soil (Zhang et al. \u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), the potential input due to the use of organic amendments, such as contaminated digestates, should not be overlooked (Corradini et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Azizi et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Mahon et al. (\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2017\u003c/span\u003e) found that, despite partial removal of MPs during anaerobic digestion, their accumulation within biosolids is inevitable. More recently, Dronjak et al. (\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2025\u003c/span\u003e) reported that compost and digestate from municipal wastes and agri-food industry, as well as horse manure and sewage sludge from wastewater treatment plant, contained between 7 and 550 micro and macroplastics particles per gram, with concentrations varying according to their origin and treatment process. Their findings also indicated that anaerobic digestion accumulated more plastic than aerobic treatments. The land application of digestate is widely regarded as a sustainable practice, as it improves soil physical properties, fertility, and productivity while contributing to waste reduction and resource recovery. Therefore, assessing the presence of MPs in the digestate and their potential environmental impacts needs great attention.\u003c/p\u003e \u003cp\u003eThe composition of digestate derived from anaerobic digestion of organic waste depends largely on the type of feedstock employed and may be a source of other contaminants such as agrochemicals (Porterfield et al. \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e2023\u003c/span\u003e), anyway present in the soil because of their widespread use in agricultural production (Sabzevari and Hofman \u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The environmental fate of these compounds is influenced by biotic and abiotic degradation, adsorption and transport processes, which complicate the prediction and assessment of the risks associated with their use (Fouad et al. 2024). Furthermore, co-occurring pollutants such as plastic residues, that can adsorb and transport agrochemicals, interfere with their performance and influence their toxicological effects (Rodr\u0026iacute;guez-Seijo et al. \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Cheng et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Sun et al. \u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Ni et al. (\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2023\u003c/span\u003e), in a recent study on the adsorption of amide herbicides on biodegradable and non-biodegradable microplastics originating from agricultural plastic films, highlighted that MPs, especially biodegradable types, exhibit significantly higher adsorption capacities compared to other adsorbents, e.g., soil, sediment, mineral, straw, and biochar.\u003c/p\u003e \u003cp\u003eAs MPs degrade, changes in particle size and surface properties can promote the release of previously adsorbed pollutants, which in turn affects their bioavailability and ecotoxicity in soil (Hu et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Tan et al. \u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e2025\u003c/span\u003e). Consequently, growing attention is being directed toward the potential cotransport and release of the adsorbed agrochemicals by MPs in soils. The adsorption capacity and type of interaction between MPs and agrochemicals depend on their respective structures and properties (Qin et al. \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Generally, the adsorption of organic pollutants on MPs can be attributed to partitioning or surface adsorption phenomena due to electrostatic, π-π or van der Waals interactions, as well as hydrogen bond formation (Mo et al. \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Lan et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Liu et al. \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). For example, a recent study reported that the adsorption of atrazine by MPs (specifically PS, PE, and PP, both young and aged) in batch experiments is due to a combination of physical and chemical adsorption mechanisms (Wang et al. \u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Studies have shown that atrazine adsorption in soil significantly intensified in the presence of MPs derived from polyethylene film, with effects directly related to the MPs quantity and aging degree (Song et al. \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). Microplastics can also decrease the soil adsorption capacity of several agrochemicals (\u003cem\u003ee.g.\u003c/em\u003e 2,4-D, dichlorprop, diuron, flufenacet, simazine, thiacloprid) and thereby accelerate their leaching, enhancing the potential of groundwater contamination (Wu et al. \u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e2025\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe occurrence of MPs, alone or in combination with agrochemicals, may influence the activity and health of biotic components, although these aspects remain insufficiently investigated to date. Evidence from the literature shows that the effects of MPs are dependent on multiple factors, including their quantity, polymer type, particle size, aging degree, surface characteristics, and experimental conditions such as exposure time, coexisting pollutants, presence of soil amendments and soil properties. For example, Gao et al. (\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2024\u003c/span\u003e) discovered that MPs promoted the degradation of nicosulfuron herbicide, increased its accumulation in earthworms, and altered the composition, diversity, and functionality of the microbial communities. Similarly, Wu et al. (2024) found that the co-exposure to MPs with imidacloprid and flumioxazin influenced soil microorganisms and the processes related to carbon, nitrogen, and phosphorus cycles, with outcomes either nullified or amplified compared to individual exposures. Interestingly, the agrochemicals exerted a leading role in shaping the microbial responses under co-exposure conditions.\u003c/p\u003e \u003cp\u003eIn this context, the aim of this work was to study the degradation and adsorption-desorption processes of Foramsulfuron (FRS) in two soils, with different chemical-physical properties (i.e. pH, organic matter content and texture), contaminated and not with MPs, specifically PE, PP, PS, and PLA (polylactic acid), and amended and not with a digestate (itself potentially capable of modifying the behaviour of the herbicide in the soil). FRS, a sulfonylurea herbicide used post-emergently, is selective for maize and active against the most common grasses and broadleaf weeds species, with authorized use in Europe until 2035. Despite its widespread use, no studies are currently available regarding its adsorption-desorption in amended or unamended soils, nor on the potential impact of the combined action of FRS and MPs on soil functionality. Our working hypothesis posited that the combined incorporation of MPs and digestate into soil could impact the mobility of FRS and affect soil fertility and biological activity. For this reason, the effects of the copresence of FRS and MPs on soil functionality were evaluated by quantifying, after herbicide application, the activities of selected enzymes, such as dehydrogenase, β-glucosidase, and urease, which are widely recognized as bioindicators of soil health and ecosystem multifunctionality (Alkorta et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2003\u003c/span\u003e). Assessing the effects of MPs on the herbicide persistence, as well as their combined impact on soil health, will be crucial to rate the environmental hazard posed by these pollutants.\u003c/p\u003e"},{"header":"Materials and Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n \u003ch2\u003eSoil and digestate origin, sampling procedures, and experimental design\u003c/h2\u003e\n \u003cp\u003eTwo soils from different locations were chosen for the experimental set-up: S1 soil was from Casalina, Perugia province, Italy [42\u0026deg;57\u0026apos;33.5\u0026quot; N; 12\u0026deg;22\u0026apos;23.6\u0026quot; E], and S2 soil was from Cadriano University farm, Bologna, Italy [44\u0026deg;33\u0026apos;7.98\u0026quot;N; 11\u0026deg;24\u0026apos;38.26\u0026quot;E]. In January 2024, five subsamples of topsoil (0\u0026ndash;20 cm) were randomly collected from the two sites (in an area over approximately 0.35 ha) and mixed to form a composite sample of 5 kg: S1 and S2. The first, S1, was an agricultural unpolluted soil, while S2 soil was chosen because it had not been treated with any plant pharmaceutical for 60 years and had never been covered with any mulching sheet. S1 and S2 soils were air dried, sieved (\u0026lt;\u0026thinsp;2 mm) and characterized. Particle size analysis identified the soil S1 as silty clay loam (USDA texture classification, 12% sand, 52% silt and 36% clay) and soil S2 as loam (USDA texture classification, 35% sand, 42% silt and 23% clay).\u003c/p\u003e\n \u003cp\u003eSoil samples were prepared by adding to 500 g of control soils (S1 and S2) a mix of MPs containing PE, PP, PS and PLA at size of 5 mm (prepared in accordance with Dominici et al. \u003cspan class=\"CitationRef\"\u003e2019\u003c/span\u003e; Gomez-Caturla et al. \u003cspan class=\"CitationRef\"\u003e2022\u003c/span\u003e; Luzi et al. \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e) to reach a final concentration of 0.045% (consistent with an average concentration commonly detected in agricultural soils; S1\u0026thinsp;+\u0026thinsp;MPs and S2\u0026thinsp;+\u0026thinsp;MPs; Li et al. \u003cspan class=\"CitationRef\"\u003e2024\u003c/span\u003e). Additional treatments (S1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs and S2\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs) were prepared by amending the respective MPs-contaminated soils with digestate (D) at an application rate of 6.7 g kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e soil (dry weight basis, after freeze-drying and grinding), reaching a N concentration equivalent to 340 kg N ha\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The digestate used in the present study was collected from a biogas plant, operating under dry anaerobic digestion and mesophilic conditions (37\u0026ndash;45\u0026deg;C), where the organic fraction of municipal solid waste was co-treated with lignocellulosic biomass, e.g. urban green waste, for approximately 25 days. Subsequently, the digestate obtained was aerobically stabilized and characterized (Table \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eAll samples were maintained at 60% WHC and subjected to dry/rewetting cycles for 30 days. Soil samples were air-dried after incubation and chemical analyses were performed to assess the effects of MPs and digestate on soil chemical properties (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). Soil pH and electrical conductivity (EC) were determined in aqueous suspension at a solid-liquid ratio of 1:5 (w/v). The carbonate content (CaCO\u003csub\u003e3\u003c/sub\u003e) was quantified by gas-volumetric determination of CO\u003csub\u003e2\u003c/sub\u003e released by treating a soil sample with hydrochloric acid (Colombo and Miano, \u003cspan class=\"CitationRef\"\u003e2015\u003c/span\u003e). The zero point of charge (ZPC) was determined following the method of Sakurai et al. (\u003cspan class=\"CitationRef\"\u003e1988\u003c/span\u003e). Effective cation exchange capacity (CEC) and exchangeable bases (i.e., Na, K, Mg, Ca) were determined according to the Italian Official method (Colombo and Miano, \u003cspan class=\"CitationRef\"\u003e2015\u003c/span\u003e). The concentration of dissolved organic carbon (DOC) was quantified following the procedure described by Manzano et al. (\u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e), while total organic carbon (TOC) and total nitrogen were measured with a CN analyser (Leco CN 828), employing Soil LCRM Leco part no. 502\u0026ndash;697 as the calibration sample.\u003c/p\u003e\n \u003cp\u003eThe concentration of pseudo-total potentially toxic elements (PTEs, Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e) was quantified after soil digestion with HNO\u003csub\u003e3\u003c/sub\u003e/HCl (3:1 v/v) and microwave mineralization (Milestone UltraWave SRC Technology).\u003c/p\u003e\n\u003c/div\u003e\n\u003ch3\u003eFRS degradation\u003c/h3\u003e\n\u003cp\u003eFor each sample [control soils (S1 and S2), soils contaminated with MPs (S1\u0026thinsp;+\u0026thinsp;MPs and S2\u0026thinsp;+\u0026thinsp;MPs), and soils contaminated with MPs and treated with digestate (S1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs and S2\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs)], 2.5 g of soil were suspended in 5 mL of an aqueous FRS solution (215 \u0026micro;M) in polyallomer centrifuge tubes. Foramsulfuron ([2-[[[[(4,6-Dimethoxy-2-pyrimidinyl) amino] carbonyl]amino]sulfony]-4-(formylamino)-N,N-dimethylbenzamide], CAS 173159-57-4, FRS, Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e) was supplied by LabStandard\u0026reg; (\u0026ge;\u0026thinsp;95% purity).\u003c/p\u003e\n\u003cp\u003eThe samples were kept at 25\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u0026deg;C under stirring and aliquots were collected at different times intervals (each 24 h). The supernatant was separated from the solid phase by centrifugation at ~\u0026thinsp;2200 g for 10 min, pipetted off, filtered (Syringe Filters 25 mm FLL/MLSPP, NY 0.45 \u0026micro;m, GVS Abluo) and subsequently analysed by HPLC. The solvents were of HPLC grade and were used without further purification.\u003c/p\u003e\n\u003cp\u003eThe degradation rate was determined by monitoring the disappearance of FRS, as a function of time, in aqueous herbicide-soil suspensions prepared from different soil sample. Kinetic data were fitted using a first-order rate equation:\u003c/p\u003e\n\u003cp\u003eln C/C\u003csub\u003e0\u003c/sub\u003e =-k\u003csub\u003eobs\u003c/sub\u003e.t\u003c/p\u003e\n\u003cp\u003ewhere C (\u0026micro;M) represents the concentration of the herbicide at the t time, C\u003csub\u003e0\u003c/sub\u003e the initial herbicide concentration, and k\u003csub\u003eobs\u003c/sub\u003e the first-order rate degradation constant.\u003c/p\u003e\n\u003ch3\u003eFRS adsorption-desorption\u003c/h3\u003e\n\u003cp\u003eFRS adsorption isotherms were obtained on all soil samples using a batch equilibrium method. Each soil samples (2.5 g) were placed in polyallomer centrifuge tubes with 5 mL of aqueous herbicide solution at initial concentration of 60, 120, 180, and 240 \u0026micro;M. Although these concentrations exceed typical environmental levels, they were selected to ensure analytical sensitivity, especially during desorption. The tubes were shaken in an end-over-end shaker at 25\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u0026deg;C for 24 h. After the contact period, the suspensions were centrifuged at ~\u0026thinsp;2200 g for 10 min and the supernatant was collected, filtered (Syringe Filters 25 mm FLL/MLSPP, NY 0.45 \u0026micro;m, GVS Abluo) and immediately analysed. The FRS amount adsorbed was calculated as the difference between the initial and final concentrations of herbicide in solution.\u003c/p\u003e\n\u003cp\u003eImmediately after the adsorption process 2.5 mL of the supernatant solution were withdrawn. The remaining slurry was again brought to 5 mL by adding 2.5 mL of water, equilibrated for 24 h, and centrifuged. These steps (supernatant withdrawing, and replacing with water, and re-equilibrating) were repeated four times consecutively. The concentration of herbicide in each desorption solution was determined, and the amount of herbicide adsorbed on the soil after each desorption step was calculated by difference.\u003c/p\u003e\n\u003cp\u003eThe experimental data were fitted using the logarithmic form of the Freundlich equation (the most common model used to describe herbicide adsorption on heterogeneous surfaces, Chen et al. \u003cspan class=\"CitationRef\"\u003e1999\u003c/span\u003e):\u003c/p\u003e\n\u003cp\u003elog C\u003csub\u003es\u003c/sub\u003e = log K\u003csub\u003efa\u003c/sub\u003e + 1/n\u003csub\u003ea\u003c/sub\u003e log C\u003csub\u003ee\u003c/sub\u003e\u003c/p\u003e\n\u003cp\u003ewhere C\u003csub\u003es\u003c/sub\u003e (\u0026micro;mol kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) is the amount of herbicide adsorbed, C\u003csub\u003ee\u003c/sub\u003e (\u0026micro;M) is the equilibrium concentration in solution, and log K\u003csub\u003efa\u003c/sub\u003e and 1/n\u003csub\u003ea\u003c/sub\u003e are empirical constants representing the intercept and the slope of the isotherm, respectively. K\u003csub\u003efa\u003c/sub\u003e [\u0026micro;mol\u003csup\u003e(1\u0026minus;1/n)\u003c/sup\u003e kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eL\u003csup\u003e1/n\u003c/sup\u003e] is a constant that reflects the soil\u0026rsquo;s ability to adsorb the agrochemical in the specific adsorbent/adsorbate combination, while 1/n\u003csub\u003ea\u003c/sub\u003e (dimensionless) represents the intensity or heterogeneity of the adsorption process.\u003c/p\u003e\n\u003cp\u003eThe hysteresis coefficient, H, for the adsorption-desorption process was calculated according to the formula:\u003c/p\u003e\n\u003cp\u003eH\u0026thinsp;=\u0026thinsp;1/n\u003csub\u003ed\u003c/sub\u003e/1/n\u003csub\u003ea\u003c/sub\u003e\u003c/p\u003e\n\u003cp\u003ewhere1/n\u003csub\u003ea\u003c/sub\u003e and 1/n\u003csub\u003ed\u003c/sub\u003e are the Freundlich slopes obtained for the adsorption and desorption isotherms, respectively.\u003c/p\u003e\n\u003ch3\u003eHPLC Analyses\u003c/h3\u003e\n\u003cp\u003eThe FRS concentration was measured by HPLC. The analytical system consisted of a Waters 1515 pump equipped with a Waters 2487 UV/VIS programmable detector operating at 240 nm, a Breeze chromatography software, an end-capped \u0026micro;Bondapak C18 analytical column (10 mm, 3.9x300 mm). The eluant was a mixture of acetonitrile and water (40:60, v/v), previously brought to pH 2.7 with phosphoric acid, at a flow rate of 0.5 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Under these chromatographic conditions, the retention time was 6.9 min. An external standard was used for the FRS quantitative determination. The herbicide Limit of Detection (LOD) and Limit of Quantification (LOQ) were 2.21.10\u003csup\u003e\u0026minus;\u0026thinsp;7\u003c/sup\u003e mol L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and 7.27.10\u003csup\u003e\u0026minus;\u0026thinsp;7\u003c/sup\u003e mol L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively.\u003c/p\u003e\n\u003ch3\u003eEffects of pollutants on some enzymatic activities\u003c/h3\u003e\n\u003cp\u003eThe effects of MPs and FRS on soil selected enzymatic activities were evaluated in mesocosm experiments. For each treatment, 150 g of soil were treated with 15 mL of an aqueous solution containing 8 mg of herbicide, corresponding to the lowest concentration of FRS used in the adsorption-desorption test (treatments: S\u0026thinsp;+\u0026thinsp;FRS, S\u0026thinsp;+\u0026thinsp;MPs\u0026thinsp;+\u0026thinsp;FRS, S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs\u0026thinsp;+\u0026thinsp;FRS). Controls soils without herbicide were obtained by adding 15 mL of ultrapure water to 150 g of soil samples (treatments: S; S\u0026thinsp;+\u0026thinsp;MPs, S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs). Enzymatic activities, i.e. dehydrogenase (DHG), \u0026beta;-glucosidase (GLU) and urease (URE), were determined in triplicate soil samples taken from each mesocosm at 3 (T1), 10 (T2) and 24 days (T3) from the addition of herbicide. To determine DHG, soil samples were treated with a solution of triphenyltetrazolium chloride and incubated at 30\u0026deg;C for 24 h, GLU activity was quantified after incubation of soil samples with p-nitrophenyl glucoside, while URE activity was determined after incubation of soil samples with urea (Alef and Nannipieri \u003cspan class=\"CitationRef\"\u003e1995\u003c/span\u003e).\u003c/p\u003e\n\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\n \u003ch2\u003eStatistical analysis\u003c/h2\u003e\n \u003cp\u003eAll analyses were performed in triplicate on soil samples collected from each treatment and results are reported as mean values\u0026thinsp;\u0026plusmn;\u0026thinsp;standard deviations in Tables and Figures. Differences among treatments were evaluate using one-way analysis of variance (ANOVA), followed by a Tukey\u0026rsquo;s post hoc test when significant P-values were detected (\u003cem\u003eP\u003c/em\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05). Before the ANOVA, data normality was assessed using the Shapiro-Wilk tests. Statistical analyses were carried out using the Sigma Plot Software (SPSS Inc., Chicago, II, USA). Principal component analysis (PCA) was conducted on standardized data to identify relationships among soil chemical variables and to evaluate the overall effects of MPs and digestate treatments on soil properties.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003eEffects of MPs and digestate on soil chemicals properties\u003c/h2\u003e \u003cp\u003eThe addition of MPs to soil caused a slight increase in pH value of S1 and S2, detectable even after the addition of digestate (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The enhancement of soil aeration and porosity caused by the addition of MPs (de Souza Machado et al. 2019; Lozano et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), together with the release of alkaline additives (e.g. carbonates and metal stearates) and residual inorganic compounds from MPs into the soil has been reported to elevate soil pH (Waldman and Rillig \u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Though, as previously emphasized, the effects of MPs depend on their amount, particle size, aging, surface characteristics, and exposure time and properties of soil, our results are consistent with those of Sakin et al. (\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e2025\u003c/span\u003e), who reported pH increases in soils with different polymer type and ages of MPs. In both soils, electrical conductivity (EC, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), resulted unaffected by MPs addition, whereas digestate induced a fair increase in EC of S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs soils (+\u0026thinsp;17% in S1 and +\u0026thinsp;21% in S2).\u003c/p\u003e \u003cp\u003eMPs can represent a carbon source and provide habitat for soil microbes, thereby stimulating microbial activity and promoting the degradation of organic matter (Liu et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). Consistently, total organic carbon and DOC increased in both soils in the presence of MPs (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). In S1, MPs enhanced TOC by 7% and DOC by 8% compared to the control, while in S2 the addition of MPs resulted in a 13% increase in DOC, despite the TOC remaining unchanged. The ability of MPs to increase soil aeration was likely responsible for enhancing the transformation of organic matter into soluble organic substrates (Zhang et al. \u003cspan citationid=\"CR79\" class=\"CitationRef\"\u003e2023\u003c/span\u003e), which provided a plausible explanation for the observed DOC enrichment. These results agree with previous reports on the effects of MPs exposure on soil C dynamics (Xiang et al. \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). In particular, Peng et al. (\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e2025\u003c/span\u003e) observed an enhancement in pH and TOC, as well as a reduction of exchangeable K, following the incorporation into soil of several MPs, among which PLA. Furthermore, a meta-analysis of 337 cases from 33 studies conducted by Liu et al. (\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2025\u003c/span\u003e) confirmed that MPs increased organic matter and DOC content, highlighting however that the effect was polymer-dependent: PS significantly increased organic matter, but PLA decreased it.\u003c/p\u003e \u003cp\u003eAs expected, the application of digestate increased soil total organic carbon (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e): by 14% in S1, with a rise of 30% in DOC, whereas in S2 TOC and DOC increased by approximately 15% and 40% respectively, compared to the control soil. Likely, due to the immobilisation of nitrogen within the microbial biomass (de la Fuente et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2013\u003c/span\u003e), neither the presence of MPs nor the addition of digestate significantly affected the total nitrogen content in both soils.\u003c/p\u003e \u003cp\u003eDepending on the feedstock used for the anaerobic digestion, the digestate may be a source of potentially toxic elements (PTEs, i.e. Cd, Cu, Pb, Zn, As) which, when their concentrations are high, pose serious risks of soil pollution (Dragicevic et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). As reported in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, the addition of digestate increased Pb concentration in both soils, by 31% in S1 and 36% in S2, respectively. Nonetheless, the pseudo total concentrations of PTEs (including Pb) remained below the contamination thresholds set by Italian legislation (Ministerial Decree, 2019).\u003c/p\u003e \u003cp\u003eOverall, the combined presence of MPs and digestate altered soil chemical properties and carbon dynamics, while not inducing critical risks of PTEs contamination under the experimental conditions.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eEffects of MPs and digestate on FRS degradation and adsorption-desorption processes\u003c/h2\u003e \u003cdiv id=\"Sec12\" class=\"Section3\"\u003e \u003ch2\u003eDegradation\u003c/h2\u003e \u003cp\u003eThe co-existence of MPs and herbicides in agricultural environments is a common occurrence (Rodr\u0026iacute;guez-Seijo et al. \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Cheng et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Sun et al. \u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). To evaluate the effect of MPs on the degradation of FRS, a controlled laboratory experiment was conducted, and the related kinetic data reported in Table\u0026nbsp;2.\u003c/p\u003e \u003cp\u003eIn both soils, whether added with MPs and treated or untreated with the digestate, FRS proved to be a non-persistent herbicide with half-lives ranging from 11 to 15 days. FRS, classified as a sulfonylurea herbicide, undergoes degradation predominantly through chemical hydrolysis and microbial metabolism, with the rate influenced by factors such as pH, temperature, humidity, and microbial activity (Grey and McCullough 2017). Consistently with findings previously reported, although for different families of herbicides and mixtures of MPs (Chen et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2025\u003c/span\u003e; Tang \u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e2025\u003c/span\u003e), the present study also demonstrated that MPs reduced the FRS degradation rate. It is plausible that the increased half-life of FRS observed in the presence of MPs (+\u0026thinsp;17% in S1 and +\u0026thinsp;21% in S2 relative to the control) may be at least partially attributed to the rise in soil pH, since the degradation of this compound is favoured under acidic conditions. Conversely, treatment with digestate reduced the half-life of the herbicide by 10% respect to the control in both soils, whereas in the combined treatment (S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs) the decrease was equal to 30% in S1 and 26% in S2 compared with the corresponding S\u0026thinsp;+\u0026thinsp;MPs. Given that pH values were the same in S\u0026thinsp;+\u0026thinsp;MPs and S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs, the increase in the degradation rate observed following digestate amendment is likely related to the stimulation of microbial activity, which increased herbicide degradation (Su et al. \u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Mar\u0026iacute;n-Benito et al. \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Barba et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2019\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003eAdsorption\u003c/h2\u003e \u003cp\u003eAlong with degradation, adsorption represents a key process governing the environmental fate of agrochemicals in soil (Arias-Estevez et al. 2008). FRS adsorption was described using the empirical Freundlich equation (r\u0026thinsp;\u0026ge;\u0026thinsp;0.99, Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e). In general, K\u003csub\u003efa\u003c/sub\u003e values were low (between 1.07 and 2.05 \u0026micro;mol\u003csup\u003e(1\u0026minus;1/n)\u003c/sup\u003e kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eL\u003csup\u003e1/n\u003c/sup\u003e, Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e), suggesting a very limited adsorption of herbicide in all soils, while the 1/n\u003csub\u003ea\u003c/sub\u003e values (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e), were consistent with the limited range of 1/n\u003csub\u003ea\u003c/sub\u003e values reported for FRS adsorption in soils with organic carbon contents between 0.47 and 1.47% (EFSA, 2016).\u003c/p\u003e \u003cp\u003e\u003cimg 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\"\u003e\u003c/p\u003e\u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eFreundlich parameters (mean\u0026thinsp;\u0026plusmn;\u0026thinsp;SD) for the adsorption and desorption of FRS in control soils (S1 and S2), soils treated with MPs (S1\u0026thinsp;+\u0026thinsp;MPs and S2\u0026thinsp;+\u0026thinsp;MPs) and soils treated with MPs and digestate (S1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs and S2\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs)\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"9\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAdsorption\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eS1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eS1\u0026thinsp;+\u0026thinsp;MPs\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eS1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eS2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eS2\u0026thinsp;+\u0026thinsp;MPs\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003eS2\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eK\u003csub\u003efa\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.05\u0026thinsp;\u0026plusmn;\u0026thinsp;0.33\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.38\u0026thinsp;\u0026plusmn;\u0026thinsp;0.24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.37\u0026thinsp;\u0026plusmn;\u0026thinsp;0.23\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.07\u0026thinsp;\u0026plusmn;\u0026thinsp;0.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e2.06\u0026thinsp;\u0026plusmn;\u0026thinsp;0.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1.83\u0026thinsp;\u0026plusmn;\u0026thinsp;0.46\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1/n\u003csub\u003ea\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.94\u0026thinsp;\u0026plusmn;\u0026thinsp;0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.05\u0026thinsp;\u0026plusmn;\u0026thinsp;0.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.09\u0026thinsp;\u0026plusmn;\u0026thinsp;0.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.05\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.93\u0026thinsp;\u0026plusmn;\u0026thinsp;0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1.02\u0026thinsp;\u0026plusmn;\u0026thinsp;0.06\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003er\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.996\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.990\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.987\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.996\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.996\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.993\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDesorption\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCi (\u0026micro;M)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eK\u003csub\u003efd\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e14.6\u0026thinsp;\u0026plusmn;\u0026thinsp;4.79\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e15.4\u0026thinsp;\u0026plusmn;\u0026thinsp;4.22\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e28.6\u0026thinsp;\u0026plusmn;\u0026thinsp;0.41\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e26.5\u0026thinsp;\u0026plusmn;\u0026thinsp;0.48\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e14.3\u0026thinsp;\u0026plusmn;\u0026thinsp;0.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e29.1\u0026thinsp;\u0026plusmn;\u0026thinsp;1.70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1/n\u003csub\u003ed\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.35\u0026thinsp;\u0026plusmn;\u0026thinsp;0.07\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.28\u0026thinsp;\u0026plusmn;\u0026thinsp;0.08\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.14\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.14\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.32\u0026thinsp;\u0026plusmn;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.17\u0026thinsp;\u0026plusmn;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.37\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.27\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.34\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.17\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eK\u003csub\u003efd\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e4.69\u0026thinsp;\u0026plusmn;\u0026thinsp;1.17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e8.74\u0026thinsp;\u0026plusmn;\u0026thinsp;3.99\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e40.9\u0026thinsp;\u0026plusmn;\u0026thinsp;3.86\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e14.1\u0026thinsp;\u0026plusmn;\u0026thinsp;2.65\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e18.4\u0026thinsp;\u0026plusmn;\u0026thinsp;1.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e26.3\u0026thinsp;\u0026plusmn;\u0026thinsp;3.67\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1/n\u003csub\u003ed\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.73\u0026thinsp;\u0026plusmn;\u0026thinsp;0.08\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.57\u0026thinsp;\u0026plusmn;\u0026thinsp;0.10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.21\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.45\u0026thinsp;\u0026plusmn;\u0026thinsp;0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.36\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.32\u0026thinsp;\u0026plusmn;\u0026thinsp;0.03\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.78\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.54\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.19\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.43\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.39\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.31\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e180\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eK\u003csub\u003efd\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.48\u0026thinsp;\u0026plusmn;\u0026thinsp;0.31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e5.62\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e37.8\u0026thinsp;\u0026plusmn;\u0026thinsp;1.88\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e19.2\u0026thinsp;\u0026plusmn;\u0026thinsp;2.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e18.1\u0026thinsp;\u0026plusmn;\u0026thinsp;1.27\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e33.5\u0026thinsp;\u0026plusmn;\u0026thinsp;4.11\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1/n\u003csub\u003ed\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.29\u0026thinsp;\u0026plusmn;\u0026thinsp;0.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.74\u0026thinsp;\u0026plusmn;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.34\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.42\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.45\u0026thinsp;\u0026plusmn;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.36\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.37\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.48\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.35\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e240\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eK\u003csub\u003efd\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.69\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6.14\u0026thinsp;\u0026plusmn;\u0026thinsp;0.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e10.4\u0026thinsp;\u0026plusmn;\u0026thinsp;0.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e17.6\u0026thinsp;\u0026plusmn;\u0026thinsp;1.00\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e4.38\u0026thinsp;\u0026plusmn;\u0026thinsp;1.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e23.2\u0026thinsp;\u0026plusmn;\u0026thinsp;1.64\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1/n\u003csub\u003ed\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.16\u0026thinsp;\u0026plusmn;\u0026thinsp;0.00\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.72\u0026thinsp;\u0026plusmn;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.66\u0026thinsp;\u0026plusmn;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.49\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.77\u0026thinsp;\u0026plusmn;\u0026thinsp;0.06\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.48\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.23\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.68\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.47\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.83\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.47\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003ctfoot\u003e \u003ctr\u003e\u003ctd colspan=\"9\"\u003e\u003csup\u003ea\u003c/sup\u003e Correlation coefficient\u003c/td\u003e\u003c/tr\u003e \u003c/tfoot\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eFRS is a weak acid (pK\u003csub\u003ea\u003c/sub\u003e = 4.6, Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), it predominantly exists in its anionic form at the pH values of studied soils (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), and it is therefore weakly adsorbed by negatively charged soil constituents. For S1 soil, the Freundlich parameter 1/n\u003csub\u003ea\u003c/sub\u003e \u0026lt; 1 (characteristic of L-type isotherms, Giles et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e1960\u003c/span\u003e; Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) suggested a relatively high affinity of FRS for soil at low concentrations. With increasing herbicide concentration, adsorption declined, likely due to fewer available adsorption sites. Conversely, for S2 soil, the Freundlich parameter 1/n\u003csub\u003ea\u003c/sub\u003e \u0026gt; 1 (distinctive of S-type isotherms, Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e), indicated a lower FRS affinity for soil at low concentrations. Adsorption increased as herbicide concentration rised, probably because of cooperative interactions among adsorbed organic species that stabilized the sorbate on soil solid surfaces, thereby enhancing the herbicide affinity for the latter (Sposito \u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e1984\u003c/span\u003e). The Freundlich adsorption constant K\u003csub\u003efa\u003c/sub\u003e alone cannot be directly compared between different adsorption systems when the exponent 1/n\u003csub\u003ea\u003c/sub\u003e in the Freundlich equation varies. To enable a meaningful comparison, data should be normalized by calculating the amount adsorbed (C\u003csub\u003es\u003c/sub\u003e) at a standardized equilibrium concentration (C\u003csub\u003ee\u003c/sub\u003e) using the Freundlich equation. This approach considers both K\u003csub\u003efa\u003c/sub\u003e and 1/n\u003csub\u003ea\u003c/sub\u003e allowing for valid comparisons of adsorption capacities across different systems (Chen et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e1999\u003c/span\u003e). The calculated C\u003csub\u003es\u003c/sub\u003e at a common C\u003csub\u003ee\u003c/sub\u003e (i.e. 60 \u0026micro;M), was higher in S1 (96.21 \u0026micro;mol kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) than in S2 (78.78 \u0026micro;mol kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) indicating a greater affinity of S1 for the herbicide. The lower pH\u003csub\u003ePZC\u003c/sub\u003e of S1 compared to S2 indicated a prevalence of net negative charges in soil S1, which should result in a greater electrostatic repulsion of FRS, however the higher amount of organic matter in S1 (+\u0026thinsp;61% compared to S2), as well as the its higher clay content relative to S2 may have contributed to the higher herbicide adsorption observed in S1 (Wauchope et al. \u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Pusino et al. \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2000\u003c/span\u003e; \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2004\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eBoth MPs and digestate influenced the herbicide adsorption (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The calculated C\u003csub\u003es\u003c/sub\u003e at the common C\u003csub\u003ee\u003c/sub\u003e concentration (60 \u0026micro;M), increased in both soils in the order: C\u003csub\u003es\u003c/sub\u003e-(S)\u0026thinsp;\u0026lt;\u0026thinsp;C\u003csub\u003es\u003c/sub\u003e-(S\u0026thinsp;+\u0026thinsp;MPs)\u0026thinsp;\u0026lt;\u0026thinsp;C\u003csub\u003es\u003c/sub\u003e-(S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs) resulting equal (119 \u0026micro;mol kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) in both soils treated with MPs and digestate (S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs). Several authors observed differing effects of MPs on the soil adsorption of agrochemicals, reporting an increase (Tan et al. \u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e2025\u003c/span\u003e), a reduction (Wu et al. \u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e2025\u003c/span\u003e) or no significant effect (Sunta et al. 2025). These differences depended on the type, quantity, aging degree of MPs, and the specific agrochemical considered. Different mechanisms have been invoked to interpret the adsorption of agrochemicals on MPs (Mo et al. \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Lan et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Liu et al. \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Our results seem to indicate that in soil S1\u0026thinsp;+\u0026thinsp;MPs, the increased total organic carbon and the decreased pH\u003csub\u003ePZC\u003c/sub\u003e compared to S1 (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) imply that the adsorption of FRS was likely due to hydrophobic interactions. Conversely, in S2\u0026thinsp;+\u0026thinsp;MPs, considering that in this soil the pH\u003csub\u003ePZC\u003c/sub\u003e was higher than the pH value (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), the dominant adsorption mechanism appeared to be electrostatic attraction. The adsorption process to soil protected FRS from degradation, and the increased herbicide retention capacity in the presence of MPs was therefore responsible for the increased herbicide half-life measured in the S\u0026thinsp;+\u0026thinsp;MPs soils (Table\u0026nbsp;2).\u003c/p\u003e \u003cp\u003eThe highest adsorption of FRS, equal in both soils, was detected in the S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs systems (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e), likely due to lipophilic interactions arising from their higher organic carbon content compared to the control soils (+\u0026thinsp;14% in S1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs and +\u0026thinsp;15% in S2\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). This result agrees with previous studies documenting that organic amendments increase the agrochemical adsorption capacity of soils (Rodr\u0026iacute;guez-Cruz et al. \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Fenoll et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2010\u003c/span\u003e) and confirms that the content of organic carbon in the digestate can be considered a key factor influencing the adsorption of agrochemicals in amended soils (Wauchope et al. \u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e2002\u003c/span\u003e). Furthermore, the treatment of soils with digestate increased DOC (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The adsorption on soil components of this soluble organic fraction, creating new hydrophobic surfaces, may have contributed to the enhanced adsorption of herbicide (Cox et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2004\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003eDesorption\u003c/h2\u003e \u003cp\u003eThe parameters for FRS Freundlich desorption, determined at different concentration values, along with the calculated hysteresis coefficients (H), are listed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e. Overall, the K\u003csub\u003efd\u003c/sub\u003e values were higher than the corresponding K\u003csub\u003efa\u003c/sub\u003e, indicating that a greater amount of herbicide was retained by the soil during desorption compared to equilibrium adsorption. The fragmentation of soil particles, induced by reiterated centrifugation, resuspension, and prolonged agitation in the batch method (Delle Site \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2001\u003c/span\u003e), which increased the number of available adsorption sites during the desorption, accounted for this finding. Additionally, degradative processes and formation of bound residues contributed to this outcome. Regarding hysteresis coefficients, no hysteresis is theoretically observed when H\u0026thinsp;=\u0026thinsp;1. In practice, hysteresis is not considered significant when H lies between 0.7 and 1 (Mamy and Barriuso \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2007\u003c/span\u003e). On the other hands, if H is greater than 1, a phenomenon that may be due to experimental artifacts or changes in the adsorption sites, desorption is favoured over adsorption. The desorption of FRS showed varying degree of hysteresis (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e), depending on the soil type and herbicide concentration used, indicating that the adsorption process was only partially reversible. Regarding soil S1, the highest hysteresis coefficient was recorded in the control, suggesting that herbicide desorption occurred more readily in this soil than in S1\u0026thinsp;+\u0026thinsp;MPs and S1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs. FRS adsorption in S1 was practically reversible except at the lowest herbicide concentration, where a certain degree of hysteresis was detected. The addition of MPs and especially digestate to the soil appeared to make adsorption more hysteretic, suggesting that soils where FRS is more adsorbed also retain more. This result, likely due to the formation of irreversible bonds between the herbicide molecule and the organic matter of which S1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs is richest, supports the role of organic carbon of the digestate in soil dynamics of FRS.\u003c/p\u003e \u003cp\u003eThe adsorption of FRS showed a certain degree of hysteresis in both S2 and S2\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs, whereas hysteresis was negligible (H\u0026thinsp;=\u0026thinsp;0.83, Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e) when MPs were present alone at the highest herbicide concentration. In general, H calculated in S2\u0026thinsp;+\u0026thinsp;MPs resulted higher than that in the control soil and in the soil treated with digestate and MPs (at the same initial concentration of herbicide, Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e3\u003c/span\u003e), indicating that in S2 the soil\u0026rsquo;s capacity to retain FRS was reduced by MPs. This result suggests that MPs can also lead to greater mobility of the herbicide in the environment, increasing the risk of migration to groundwater or other environmental matrices. Moreover, if compared with what was observed in soil S1, it points up that the effects of MPs must be assessed on a case-by-case basis.\u003c/p\u003e \u003cp\u003eOur results highlighted that MPs and digestate altered the environmental fate of FRS in soil. Microplastics tended to prolong the half-life of the herbicide, while digestate promoted its degradation likely due to the stimulation of microbial activity. The effects on adsorption-desorption were different in the two soils and seemed to be governed by their intrinsic properties (i.e. pH, texture, organic matter).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003eEffects of MPs, digestate, and FRS on soil enzymatic activities\u003c/h2\u003e \u003cp\u003eEnzyme activities are widely recognized as indicators of soil functionality, because they are closely linked to nutrient cycling processes, such as those related to carbon and nitrogen cycles, and are highly sensitive to changes in soil physical-chemical characteristics and contamination levels. Therefore, these activities provide useful insights into soil quality and ecosystem health. The effects of FRS, MPs, and D on soil microbial functioning were assessed through the activities of three representative enzymes, i.e., dehydrogenase (DHG, reflecting the oxidative activity of intact microbial cells), β-glucosidase (GLU, responsible for the cleavage of β 1\u0026ndash;4 glycosidic bonds) and urease (URE, involved in the hydrolytic NH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e release from urea). Enzyme activities were determined at 3 (T1), 10 (T2) and 24 (T3) days from the addition of herbicide to soils (Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn S1 soil, FRS, likely utilized by soil microorganisms as carbon source (Vandana et al. \u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e2012\u003c/span\u003e), initially (i.e. T1) stimulated DHG activity, which increased by 40% compared to the control up to 10 days from treatment with the herbicide, and decreased by 17% at 24 days from the contact (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). Although dependent on soil characteristics and experimental conditions, conflicting results are reported in the literature regarding the impact of sulfonylurea herbicides on DHG. For example, mesosulfuron methyl and iodosulfuron methyl showed short-lived harmful effects on dehydrogenase (Kaur et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2023\u003c/span\u003e), whereas a DHG increase, immediately after the treatment with mixtures containing azimsulfuron, flucetosulfuron, ethoxysulfuron, and bensulfuron methyl, was reported by Meher et al. (\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), with whom our results agree. On the other hand, Caraba et al. (\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2024\u003c/span\u003e) noticed an inhibitory effect of nicosulfuron on DHG activity at 14 days from treatment with herbicide. At 3 days, the highest dehydrogenase activity was found in S1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs\u0026thinsp;+\u0026thinsp;FRS (double compared to the control, Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e), indicating that the digestate, by modifying the chemical-physical properties of the soil and supplying nutrients and nitrogen, increased its biological properties, as confirmed by the high DHG value in S1\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs (about 1.5 times compared to the control) at T3. Literature data report variable impacts of MPs on DHG activity, including stimulation, inhibition as well as no effect, as a function of the polymer type and dose (Lian et al. \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2024\u003c/span\u003e), particle shape and aging degree of MPs (Yi et al. \u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). In our study, increases in DHG activity of 33 and 68% compared to the control were initially measured (time\u0026thinsp;=\u0026thinsp;3 and 10 days) in S1\u0026thinsp;+\u0026thinsp;MPs, suggesting that MPs can also provide carbon and energy sources for microorganisms. The co-presence of MPs and FRS also initially stimulated DHG, increasing it by 18% (T1) and 26% (T2), but led to a reduction after 24 days (\u0026ndash;13%, T3) in S1\u0026thinsp;+\u0026thinsp;MPs\u0026thinsp;+\u0026thinsp;FRS compared to the control (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). This result suggests that the initial positive impact of FRS and MPs alone on DHG is attenuated when both are present together and over time.\u003c/p\u003e \u003cp\u003eDue to the lower organic matter content of S2 (38% less than in S1), a general lower DHG activity was measured in this soil compared to S1 (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). These findings confirm that the effect of herbicides and MPs on DHG depends on soil chemical characteristics (i.e., pH and organic carbon content). In soil S2 both contaminants, whether applied individually or together, did not cause substantial short-term changes in DHG compared to the control, even when the soil was amended with digestate. At T3, the positive impact of the digestate was evident: in S2\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs soil DHG increased by 48% compared to the control soil (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThree days after herbicide treatment, GLU increased in both soils (Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). In S1, increases of 70, 78, and 95% compared to the control soil were recorded in the presence of FRS, FRS and MPs, and FRS, MPs, and D. In S2, GLU was doubled in S2\u0026thinsp;+\u0026thinsp;FRS and S2\u0026thinsp;+\u0026thinsp;MPs\u0026thinsp;+\u0026thinsp;FRS, and 2.25-fold higher S2\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs\u0026thinsp;+\u0026thinsp;FRS compared to the untreated soil, highlighting a short-term stimulatory action of the herbicide on this enzymatic activity. Representing FRS a carbon source for microorganisms, the GLU increase was marked in S2, the soil where FRS was less adsorbed. This result is consistent with observations reported by some authors for other agrochemicals (i.e. Tomkiel et al. \u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Zhang et al. \u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). MPs did not seem to negatively influence GLU in S1, rather at t\u0026thinsp;=\u0026thinsp;10 d they even had a stimulating effect, whereas GLU increased by 69% compared to the control in S2\u0026thinsp;+\u0026thinsp;MPs as early as 3 days post-herbicide treatment. This underscores that the effect of MPs was also soil-dependent. In both soils and in the short term, the co-presence of MPs and FRS did not seem to have a detrimental effect on GLU, which was further increased by the presence of digestate. This stimulation was consistent with the increase of soil organic carbon and DOC derived from the organic amendment, that can also improve soil physical properties (Xiao et al. \u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e2023\u003c/span\u003e) and provide organic and inorganic nutrients required for enzymes synthesis (Ge et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2010\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eFRS enhanced URE activity by 25 and 48% in S1 and S2, respectively, at 10 days from its application (Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). This activation of URE several days after herbicide application, observed by other authors for mixtures containing mesosulfuron and iodosulfuron (Baćmaga et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2015\u003c/span\u003e) and for treatments based on diclosulam and cloransulam-methyl (Zhang et al. \u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), may be due to the carbon and nitrogen supply for microorganisms from the sulfonylurea herbicide FRS. Microorganisms, following herbicide application, secreted more urease, whose action resulted appreciably activated (Fisher et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). In agreement with Baćmaga et al. (\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2015\u003c/span\u003e) and Zhang et al. (\u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), the effect of FRS was irrelevant 24 days after treatment with the herbicide. Initially, MPs slightly reduced URE in S1, whereas an increase of 32% compared to the control soil was measured in S1\u0026thinsp;+\u0026thinsp;MPs at the end of the experiment (T3, Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). On the other hand, an URE augment of 39% compared to the control soil was determined in S2\u0026thinsp;+\u0026thinsp;MPs at T2. Probably, the increased soil organic carbon content and DOC, due to the addition of MPs promoted microbial metabolism and URE activity. Our findings agree with Ding et al. (\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2021\u003c/span\u003e) and Liu et al. (\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), who observed a positive impact of MPs, particularly at low doses, on soil urease. The highest urease activity was measured at T2 in MPs\u0026thinsp;+\u0026thinsp;D treatment, corresponding to +\u0026thinsp;36 and +\u0026thinsp;63% (compared to untreated soil, Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e) in S1 and S2, respectively. The supply of nutrients and nitrogen provided by digestate accounts for the increased URE activity (and DHG activity) produced by the combination of MPs and digestate.\u003c/p\u003e \u003cp\u003ePCA accounted for 90% of the total variance in S1 and 95% in S2 (Figs.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e). PC1 accounted for 61% (S1) and 85% (S2) of the variance and mainly separated the treatments at 3, 10 and 24 days. In contrast, PC2 explained 29% (S1) and 10% (S2) of the total variance and was mainly correlated with the addition of FRS to the soil, thereby highlighting the impact of the herbicide on enzymatic activities.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eOverall, these results indicated that FRS, MPs, and digestate mainly stimulated DHG, GLU, and URE in the short term, with the magnitude and duration of these effects controlled by soil properties and herbicide adsorption capacity. The PCA confirmed that exposure time and FRS addition were the main drivers of variability in enzymatic responses, highlighting complex, time-dependent interactions between herbicide, MPs, digestate, and soil properties.\u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusions","content":"\u003cp\u003eThis study demonstrates that MPs and digestate can significantly influence the persistence of FRS in soil. The combined presence of MPs, digestate, and FRS does not exert a markedly negative impact on key soil enzymatic activities in the short term. Instead, the observed increases in dehydrogenase, β-glucosidase, and urease activities indicate rather that MPs may serve as supplementary sources of carbon and energy for soil microorganisms. These effects, however, are influenced by soil properties, exposure duration, and the specific interactions among the different treatments.\u003c/p\u003e \u003cp\u003eOverall, these findings provide insights into the behaviour of FRS, for which there are no data in the literature, in soils contaminated by MPs and amended with organic materials, underlining the necessity to consider multiple factors when assessing the environmental risks associated with herbicide and microplastic co-exposure in agricultural soils. Further investigations may concern long-term studies to assess chronic and cumulative effects of microplastics, digestate, and FRS on soil health, while extending investigations to diverse soil types to enhance the generalizability of findings. Moreover, changes in soil microbial communities as well as the impact on plants and soil fauna could be assessed.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements \u003c/strong\u003eNot applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e The financial support of the National Recovery and Resilience Plan (NRRP), Mission 4, Component 2, Investment 1.1, call for tender No. 104 published on 2.02.2022 by the Italian Ministry of University and Research (MUR) funded by the European Union \u0026ndash; Next Generation EU \u0026ndash; Project Title \u0026ldquo;Impacts of microplastics, antibiotics and pesticides in soil amended with digestates - 3IMPACT\u0026rdquo; \u0026ndash; CUP J53D23010170006 - Grant Assignment Decree No. 1048 adopted on 14.07.2023 by the Italian Ministry of University and Research (MUR), is gratefully acknowledged.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eAuthors\u0026rsquo; contributions\u003c/strong\u003e Maria Vittoria Pinna: Investigation, Conceptualization, Methodology, Formal analysis, Data curation, Writing - original draft preparation; Stefania Diquattro: Investigation, Methodology, Formal analysis, Data curation, Writing - original draft preparation; Enrico Buscaroli: Formal analysis, Writing - reviewing and Editing; Daniela Pezzolla: Resources, Writing - reviewing and Editing; Paola Castaldi: Investigation, Conceptualization, Methodology, Resources, Writing - reviewing and Editing.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e The authors confirm that all the data supporting the findings of this study are included within the manuscript. The raw data used in this study will be made available upon reasonable request.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eEthical approval\u003c/strong\u003e This study did not involve human and/or animal subjects.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to participate\u003c/strong\u003e This study did not involve human subjects, so clinical trial registration is not applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to publish\u003c/strong\u003e The authors confirm that this manuscript represents their original, unpublished work; has not been previously published; and is not currently being considered by any other journal. All authors have reviewed and approved the manuscript and consent to its submission. \u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e The authors declare no competing interests.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e Data will be made available on reasonable request.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eClinical trial number:\u003c/strong\u003e not applicable.\u003c/p\u003e\n\n"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAlef K, Nannipieri P (1995) Enzyme activities. 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J Hazard Mater 418:126395. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jhazmat.2021.126395\u003c/span\u003e\u003cspan address=\"10.1016/j.jhazmat.2021.126395\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Table 1","content":"\u003cp\u003eTable 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Organic pollutants, Agrochemicals, Agricultural soil, Organic amendment, Adsorption, Enzymatic activities","lastPublishedDoi":"10.21203/rs.3.rs-8539415/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8539415/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eMicroplastics (MPs) in agricultural soils pose a major environmental issue since they persist and alter the soil chemical and physical properties, affecting its overall health. Applying digestate to soil may introduce MPs, which can adsorb agrochemicals, and alter their behaviour. This study examined Foramsulfuron (FRS) degradation and adsorption in two soils (S1 and S2), with and without MPs and digestate (D) amendment. The results showed that MPs prolonged FRS half-life (+\u0026thinsp;17% in S1 and +\u0026thinsp;21% in S2 relative to the control), whereas D reduced it by 10% in both soils. The experimental FRS adsorption isotherm data fitted with the Freundlich equation. The low K\u003csub\u003efa\u003c/sub\u003e values (between 1.07 and 2.05 \u0026micro;mol\u003csup\u003e(1\u0026minus;1/n)\u003c/sup\u003e kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eL\u003csup\u003e1/n\u003c/sup\u003e) suggested limited herbicide adsorption in soils, which increased with MPs and D in the order (S) \u0026lt; (S\u0026thinsp;+\u0026thinsp;MPs) \u0026lt; (S\u0026thinsp;+\u0026thinsp;D\u0026thinsp;+\u0026thinsp;MPs). In S1, MPs and D enhanced adsorption hysteresis, while in S2, MPs reduced the soil's FRS retention capacity. The effects of the copresence of FRS and MPs on soil functionality were evaluated by quantifying dehydrogenase, β-glucosidase, and urease activities at 3-, 10- and 24-days post-herbicide application. In the short term (3 days after FRS treatment), these enzymatic activities were stimulated by FRS, MPs, and D, likely due to added carbon and energy sources for soil microbes. The effects varied by soil type, exposure time, and interactions between treatments. This study demonstrated that MPs and digestate amendment significantly influenced herbicide fate, persistence, and soil microbial activity.\u003c/p\u003e","manuscriptTitle":"Coexistence of microplastics and Foramsulfuron in soil: effects on herbicide persistence and soil functionality","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-16 14:27:14","doi":"10.21203/rs.3.rs-8539415/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"62f10bf7-067c-43b1-aadd-95244608a5ce","owner":[],"postedDate":"January 16th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-02-08T23:44:46+00:00","versionOfRecord":[],"versionCreatedAt":"2026-01-16 14:27:14","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8539415","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8539415","identity":"rs-8539415","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}