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Abstract This study investigates the adsorption and dissipation of glyphosate and the formation/dissipation of AMPA in non-tilled (NT) and conventionally tilled (CT) soil at 0–5 and 5–20 cm depth. Glyphosate adsorption was mainly related to the different NT and CT soil properties (clay and amorphous Al oxides), whereas an effect of the soil management could not be identified. Glyphosate dissipation was initially fast, and it slowed down later. The initial glyphosate concentration in NT soil at 0–5 cm was significantly lower than the dose applied due to the interception by the weeds and crop residues. AMPA began to form early after treatment and persisted longer than glyphosate. The DT50 range was 8–18 days for glyphosate and 99–250 days for AMPA. Longer glyphosate and AMPA DT50 were observed in NT soil compared to CT soil but, for glyphosate, the difference was significant only at 5–20 cm. Higher glyphosate and AMPA concentrations were detected in NT than in CT soil at the end of the study at 0–5 cm. The differences in glyphosate and AMPA DT50 and persistence were mainly attributable to the influence of different NT and CT soil characteristics. However, other factors could have contributed to the different glyphosate and AMPA dynamics between the soils, like glyphosate wash-off from crop residues on NT soil with the rainfall, the delayed glyphosate return to the soil by weed root exudation or weeds decomposition, and the NT soil compaction which may have reduced the microbial degradation of glyphosate at low concentrations. Graphic abstract

ObjectivesMotor neuron disease (MND) is an incurable progressive neurodegenerative disease with limited treatment options. There is a pressing need for innovation in identifying therapies to take to clinical trial. Here, we detail a systematic and structured evidence-based approach to inform consensus decision making to select the first two drugs for evaluation in Motor Neuron Disease-Systematic Multi-arm Adaptive Randomised Trial (MND-SMART:NCT04302870), an adaptive platform trial. We aim to identify and prioritise candidate drugs which have the best available evidence for efficacy, acceptable safety profiles and are feasible for evaluation within the trial protocol.MethodsWe conducted a two-stage systematic review to identify potential neuroprotective interventions. First, we reviewed clinical studies in MND, Alzheimer’s disease, Huntington’s disease, Parkinson’s disease and multiple sclerosis, identifying drugs described in at least one MND publication or publications in two or more other diseases. We scored and ranked drugs using a metric evaluating safety, efficacy, study size and study quality. In stage two, we reviewed efficacy of drugs in MND animal models, multicellular eukaryotic models and human induced pluripotent stem cell (iPSC) studies. An expert panel reviewed candidate drugs over two shortlisting rounds and a final selection round, considering the systematic review findings, late breaking evidence, mechanistic plausibility, safety, tolerability and feasibility of evaluation in MND-SMART.ResultsFrom the clinical review, we identified 595 interventions. 66 drugs met our drug/disease logic. Of these, 22 drugs with supportive clinical and preclinical evidence were shortlisted at round 1. Seven drugs proceeded to round 2. The panel reached a consensus to evaluate memantine and trazodone as the first two arms of MND-SMART.DiscussionFor future drug selection, we will incorporate automation tools, text-mining and machine learning techniques to the systematic reviews and consider data generated from other domains, including high-throughput phenotypic screening of human iPSCs.

Oligodendrocytes are implicated in amyotrophic lateral sclerosis pathogenesis and display transactive response DNA-binding protein-43 (TDP-43) pathological inclusions. To investigate the cell autonomous consequences of TDP-43 mutations on human oligodendrocytes, we generated oligodendrocytes from patient-derived induced pluripotent stem cell lines harbouring mutations in the TARDBP gene, namely G298S and M337V. Through a combination of immunocytochemistry, electrophysiological assessment via whole-cell patch clamping, and three-dimensional cultures, no differences in oligodendrocyte differentiation, maturation or myelination were identified. Furthermore, expression analysis for monocarboxylate transporter 1 (a lactate transporter) coupled with a glycolytic stress test showed no deficit in lactate export. However, using confocal microscopy, we report TDP-43 mutation-dependent pathological mis-accumulation of TDP-43. Furthermore, using in vitro patch-clamp recordings, we identified functional Ca2+-permeable α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor dysregulation in oligodendrocytes. Together, these findings establish a platform for further interrogation of the role of oligodendrocytes and cellular autonomy in TDP-43 proteinopathy.

Oligodendrocytes are implicated in amyotrophic lateral sclerosis pathogenesis and display transactive response DNA-binding protein-43 (TDP-43) pathological inclusions. To investigate the cell autonomous consequences of TDP-43 mutations on human oligodendrocytes, we generated oligodendrocytes from patient-derived induced pluripotent stem cell lines harbouring mutations in the

Conservation agriculture, and in particular no-till systems, generally yield improvements in both soil characteristics (e.g. structure, and water holding capacity) and soil processes (such as runoff and hence erosion). Nevertheless, during the first years of no-till, the soil is prone to compaction due to the poor structure, missing ploughing activities, and passage of tractors and machinery, thus favouring surface runoff and soil erosion. Little information exists about the effect of no-till when applied during the transition period from conventional to conservation agriculture. This study aimed at analysing runoff and soil erosion in a non-tilled field in comparison with a tilled field during the transition period. The study was conducted at the Padova University Experimental Farm, in northeast Italy. Six sub-plots (2.5 m × 5 m) were established, three in a tilled field (CT plot) and three in a non-tilled field (NT plot). Each sub-plot was equipped with a runoff water collection system. Runoff was monitored during two sampling seasons: from May to October 2017 and May to September 2018. Runoff water volume was measured at each rainfall event, and the amount of sediment was quantified by drying the runoff samples. This technique is simple and inexpensive and suitable to be applied also in rural areas with inadequate infrastructures and economic resources. Two indices, runoff reduction benefits (RRB) and sediment reduction benefits (SRB), were computed. During the monitoring period, 24 runoff events occurred. NT practices coincided with reductions of over 50% in runoff volumes and 50% to 95% in sediment losses. Only the runoff event just after the CT soil harrowing produced a significantly lower runoff and sediment loss in CT than in NT field, due to the effect of soil tillage on surface roughness and rainfall infiltration. The average sediment concentration in NT was only 47% of CT. The RRB and SRB values confirmed a reduction in runoff and sediment loss in the NT compared with the CT plot, but SRB was greater than the RRB, indicating that the no-till regime showed a better control of sediment loss than it did the runoff amount. The reduced runoff and sediment yield in the NT plot could have important on-site benefits in terms of both sustainable soil management and surface water quality.

A soil and an organic biomix (soil/vine branch/garden compost 20/40/40) were used in this lab experiment to evaluate adsorption and degradation parameters for three pesticides (chlorpyrifos, metalaxyl and cymoxanil) used in a vineyard. Adsorption in the biomix material was higher than in the soil for the three pesticides and chlorpyrifos was the most adsorbed pesticide. The role of the organic carbon is essential for enhancing the adsortion of the three pesticides, especially for the most apolar chlorpyrifos. Degradation was generally faster in the biomix material than in the soil although the process was slower in the case of chlorpyrifos if compared with the other two chemicals, due to a more toxic effect of this pesticide on soil microflora and a larger adsorption of this pesticide on the organic biomix that reduces its availability for dissipation. Amendment with cheap and available organic wastes or a grass-covered management of soil in the vineyard could reduce the impact of pesticides in the vineyard ecosystem and contribute to the sustainable management of chemicals in the environment.

Glyphosate (GLP) has been the most frequently used herbicide worldwide, including Europe. Due to its systemic, post-emergence, and non-selective characteristics, it offers optimal weed control without the need of mechanical treatments. Therefore, it is widely used in no-till practices. However, increasing awareness of its potential harmful effect to human health and ecosystems has led numerous countries to restrict or, even, ban its use. The EPIC (Environmental Policy Integrated Climate mode) model has been selected as a screening tool to evaluate the vulnerability of groundwater to glyphosate contamination under different pedo-climatic and agronomic conditions across the Veneto Region (NE Italy), an area where the interaction of different pedo-climatic and agronomic conditions makes it difficult to predict site-specific GLP movement. The aim of this study was to evaluate the performance of a modified version of EPIC that includes a fast solution of Richards’ equation to predict GLP dynamics under shallow water table conditions. The experimental site was in Northeastern Italy and consisted of eight drainable lysimeters; 4 treatments, replicated twice, in factorial combination of two management practices (conventional -CV- and conservation -CA- agriculture) and two water table levels (60 and 120 cm). Degradation and movement of GLP in the soil profile were monitored in 2019 from May to September. The herbicide (144 mg m-2) was applied on bare soil in CV and on the cover crop (Secale cereale) in CA. Water samples were systematically collected at 15, 30 and 60 cm depth using suction cups, whose suction was regulated by an automated system that combined matric potential readings, provided by electronic tensiometers, with a vacuum regulator. Water samplings from groundwater were also performed. Soil samples were collected at 0-5 and 5-15 cm depth every other week. Weather and soil data were used as input to EPIC, while the GLP experimental results, along with yields, soil water content, evapotranspiration and water percolation data, were used to calibrate (from 2011 to 2017) and validate (from 2018 to 2019) the model. In all lysimeters, GLP reached the groundwater the day after the first irrigation event, with higher leaching in CV than in CA and at 120 than at 60 cm. After 40 days, GLP was almost completely dissipated in CA soil, while it was still detected in CV. EPIC was able to acceptably reproduce evapotranspiration (R2=0.76), yields (R2=0.74) and water percolation (R2= 0.59-0.90). In general, GLP predictions compared well with observations but the predictions in CV treatments were closer to observations than in CA treatments. This work showed the robustness of the modified EPIC, suggesting its use as a tool to assess the potential vulnerability of the groundwater under different management scenarios and water table levels.

Broad contamination of systemic herbicide glyphosate –GLP– (N-(phosphonomethyl) glycine) and its metabolite aminomethylphosphonic acid (AMPA) in soil and water has become one of the main environmental issues worldwide, raising awareness of the potential harmful effects to human health and ecosystems. Physical, chemical, and biological soil properties contribute to the complex interaction between GLP and the environment, that makes any prediction of adsorption, transport, and degradation dynamics still challenging.Within a wide project –SWAT– that tries to link GLP and AMPA dynamics through the vadose zone with groundwater contamination, the specific goals of this work are: 1. monitoring soil and water contamination of GLP and AMPA in agricultural lands; 2. identifying the driving factors leading to site-specific soil-water contaminant interactions.Two experimental sites were located in northeastern Italy (Conegliano and Valdobbiadene municipalities) in the winegrowing terroir of the Prosecco wine production, recently included in the UNESCO’s World Heritage List. Each site was equipped with two soil-water monitoring stations (25 m2 each), multi-sensor soil probes (temperature and water content) and suction lysimeters to monitor the full soil profile. Undisturbed soil cores were also collected and later analyzed for hydraulic, physical and chemical properties down to 70 cm. After GLP field contamination on November 2018 (0.188 g m-2), soil and water were systematically sampled from each site, starting immediately after contamination and thereafter at each rain event for 6 months. Adsorption coefficients (Kf) were estimated in laboratory in order to get information about GLP sorption to soil particles at different soil layers along the full soil profile. Site-specific dissipation kinetics (DT50) were also evaluated to better understand its decay rate.First results revealed that GLP transport was highly site specific and locally affected by preferential flows when intense rainfall events occurred (12 mm h-1 max rainfall intensity): GLP showed strong binding affinity to soil particles in the topsoil layer and it likely bypassed the porous matrix towards the deepest layers, where it was detected as in the surface one. The GLP dissipation dynamic was completed after 6 months of experimentation, whereas AMPA was still detected in the topsoil layer, attesting the full degradation after almost 300 days. Site-specific laboratory and field data will be integrated and further discussed to better understand the fate of glyphosate and AMPA in the vadose zone.

Glyphosate is the most used herbicide worldwide, especially in conservation agriculture, where the lack of mechanical weed control often necessitates chemical inputs. In conservation agriculture, the elimination of tillage operations leads to changes in soil physical, chemical, and biological properties. Consequently, herbicide environmental fate may be potentially altered relatively to conventional tillage systems. The aim of this study was, therefore, to investigate the effect of conservation agriculture and conventional tillage on the adsorption of glyphosate and on the dissipation of glyphosate and its primary metabolite aminomethylphosphonic acid (AMPA) at two depths, 0−5 and 5−20 cm.The field trial was conducted from October 2018 to April 2019 at the Padua University Experimental Farm, North-East Italy. Glyphosate was applied as a formulated product (Roundup Power 2.0) at a dose of 1.44 kg/ha of the active ingredient. The dissipation of glyphosate and the formation/dissipation of AMPA were followed for 182 days after their application. The concentrations of glyphosate and AMPA in the soil were analysed by Ultra-High Performance Liquid Chromatography coupled with mass spectrometry. The dissipation of glyphosate was described by the first-order multicompartment model (FOMC), whereas the model for AMPA was composed of an FOMC degradation model for glyphosate and the single first-order degradation model for AMPA. The estimated trend of concentrations over time for both glyphosate and AMPA were used to derive their DT50 (time required for 50% dissipation of the initial concentration).The results indicate an increase in glyphosate adsorption in non-tilled soil compared to the tilled soil, at both depths. Glyphosate initial dissipation was fast, followed by a slower decline. At 0–5 cm no significant difference was observed in glyphosate persistence between the two soil managements, whereas at 5–20 cm glyphosate was more persistent in non-tilled soil (DT50 18 days) than in tilled soil (DT50 8 days). The fast initial dissipation of glyphosate was reflected in an increase in the concentration of AMPA. AMPA persisted longer than glyphosate but, for this metabolite, no apparent effect was observed in response to the different soil management. The higher persistence of glyphosate under conservation tillage might increase the risk of on-site soil pollution due to the accumulation of this chemical, especially in the case of repeated applications of glyphosate. Nevertheless, high glyphosate adsorption observed in non-tilled soil may reduce the leaching potential to lower soil depths.This abstract falls in the group “Soil contamination” and the subgroup “Experimental assessment”.

This paper deals with the progress of an ongoing project, first reported in [1], on teaching non-Euclidean geometry at high school. The main goal of the research work is: (1) to show whether non-Euclidean geometries can be a tool to allow students to consolidate the knowledge of Euclidean geometry by developing it in a critical way; (2) to promote the understanding of the modern axiomatic method in geometry; and (3) to give students a new perspective on mathematics so that they can see it as a creative activity and a widely discussed topic with a historical background. The idea itself is not novel, but one of the main issues related to the state of the art is the lack of experimental studies with students. Specifically, up to the authors’ knowledge, there is only one study that has conducted an extensive experimentation with high-school students, showing data that seem to support the hypothesis (3): teaching non-Euclidean geometries lets students change their view of mathematics [2]. Experimental studies conducted with high-school students related to the first two points seem to be absent. For this reason, our aim is to gather further experimental evidence of the potential benefits of teaching non-Euclidean geometries at high school. The authors have carried out a pilot study based on class activities on non-Euclidean geometries that involved four sets of Italian high-school students (10-18-20-29 students). The pilot study was aimed to understand how to improve the class activities and, most importantly, how to better design useful questionnaires to collect data for the final experimental study. To gather data during the pilot study, the authors used, before and after the class activities, the Van Hiele geometry test as formulated by Usiskin [3] (translated in Italian) and questionnaires previously designed by the authors. The pilot study made us aware of some students’ misconceptions and difficulties. The paper reports on these findings and on how they led us to change some of the class activities proposed to the students and to elaborate the questionnaires in a different way. Moreover, the paper presents data that seem to support the hypothesis (3) as in [2]. References: [1] S. Benvenuti, A. Cardinali, "The mental telescope: understanding the geometry of Euclid by learning the non-Euclidean geometry", INTED2018 Proceedings. [2] P. Schiano, "Convinzioni e cambi di convinzioni degli studenti sugli errori e sullo sviluppo della conoscenza in matematica (studenti di età 14-18)", PhD thesis, Consortium between the University of Bologna, the University of Catania, the University of Pavia, the University “Federico II” of Napoli, the University of Bratislava, the University of Nitra, the University of Alicante, the University of Palermo, the University of Cipro, C.I.R.E “Centro interdipartimentale ricerche educative” Palermo. [3] Z. Usiskin, "Van Hiele Levels and Achievement in Secondary School Geometry", University of Chicago, 1982.

The multidisciplinary research project SWAT - Subsurface Water quality and Agricultural pracTices monitoring - has been set up to assess pesticides contamination risks for groundwater in the hills of Prosecco in the north-east of Italy. The unconfined aquifer underneath the typical Glera grape-variety vineyards of Valdobbiadene and Conegliano is used as water supply resource for human consumption. The principal aim of the project SWAT is to obtain a thorough information on the impact of contaminants coming from agricultural practices and infiltrating in the soil of well protection areas. Based on specifically designed field experiments, a study on water and solutes infiltration process is developed to understand the movement and evolution of chemical species in the vadose zone. A one-dimensional transport model for unsaturated media (BRTSim - Maggi, 2015) is used to simulate solute infiltration and estimate the soil hydraulic parameters. Monitoring activities started in November 2018 in two experimental sites (the Settolo site in Valdobbiadene and the Colnù site in Conegliano) near supply wells surrounded by vineyards. A mixture of Bromide and Glyphosate was identically applied on two parcels of 25 m2 for each experimental site to obtain information about spatial heterogeneity and to collect independently water and soil quality measurements. Porous cups, for the collection of infiltrating water, and capacitive sensors, to gauge temperature and Volumetric Water Content (VWC), were installed beneath the sectors at three depths (-0.1, -0.3, -0.7 m). In each site meteorological station provides hydrological data. At first, laboratory analysis on soil samples collected at the same depths gave a vertical distribution of the sector-specific soil texture that was used as input for Rosetta to obtain initial estimations of retention curve behaviour and the saturated hydraulic conductivity. These data allowed us to develop an open-loop simulation using the early meteorological observations as hydrological forcing. As the laboratory analysis on soil and water samples proceed and the number of in-situ measurements increases, different data windows are tested to improve the performances of the calibration procedure performed using PEST. In all tests a spin-up procedure is applied to mitigate the dependency of the results on the imposed initial data by repeating the first month of hydrological forcing three times. The results of the transport model using Rosetta parameters are already satisfactory in terms of VWC trends even if they are considerably shifted respect to the measured values. The calibration reduces the gap between model results and observations, but the behaviour seems to get worse in dry conditions. Improvements are achieved in the upper layer (-0.3 m) applying evapotranspiration along the root zone. The Bromide simulations agree with the infiltration behaviour: its movement is well represented up to -0.3 m, while at -0.7 m the observed values are overestimated. Ongoing investigations on the glyphosate dispersion process show limited infiltrating mass in the water collected samples.

Vegetated buffer strips (VBS) are recognized as a cost-effective way to reduce agricultural nonpoint-source pollution. In agroecosystems with high field fragmentation, only narrow VBS that partially compromise farmers' revenue are accepted. This study aimed to identify some ecosystem services as provided by VBS in terms of soil and water quality, and VBS performance in terms of wood for energy purposes. Buffer strip design (3 vs. 6 m wide) and composition were considered to define best practices for wood use at the farm level and for the local firewood market. Results showed that yearly wood pole production was 0.5 t 100 m, on average, ranging between a minimum of 0.22 t 100 m and a maximum of 0.72 t 100 m per row. Wood production had negligible effects on farmers' revenue. By contrast, water quality was enhanced, especially with 6-m-wide VBS. Specific subsidies for the maintenance of VBS increased total income despite a reduction in crop production (-17.5% in 6-m VBS with two rows). Subsidies might be better quantified at a site-specific level by taking into account all ecosystem services that are provided by VBS. Promising solutions to increase farmers' income are related to the wood seasoning process for firewood production; reducing the moisture content to

This study evaluates the effect of sewage amendment (SA) on the dissipation of terbuthylazine, its degradation compound desethyl-terbuthylazine, and S-metolachlor in the soil. The experiment was conducted at Padua Experimental Farm (Italy). Herbicides dissipation was evaluated in soils differently fertilized for three years: with inorganic fertilizer, with sewage sludge, and with a combination of them. Terbuthylazine and S-metolachlor were applied on sorghum as a formulated product at a dose of 2.8 L ha

Glyphosate is the most used pesticide worldwide and its impact on the environment is becoming increasingly significant. Glyphosate and its main metabolite AMPA are frequently detected in streams and rivers. In this study, an analytical method is presented that combines Ultra-High Performance Liquid Chromatography with mass spectrometry (UHPLC–ESI-MS/MS) for glyphosate and AMPA analysis in environmental water samples. The method was developed starting from an application of Waters Corporation, and involves the use of an alternative derivatizing reagent, the commercially available AccQ·Tag™ Ultra Derivatization Kit (Waters Corporation, Milford, MA, USA). The kit contains the derivatizing reagent 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC). Derivatization takes place directly in the injection vial and no sample pre-concentration is needed. The derivatization is simple, quick and robust, which fits well within the needs of a routine method for the analysis of glyphosate and AMPA. Derivatized glyphosate and AMPA were recorded in positive ion mode. The method demonstrates a good linear relationship in the concentration range from 0.2 μg/L for glyphosate and 0.05 μg/L for AMPA to 100 μg/L and an accurate recovery. The method developed has been successfully applied to the determination of glyphosate and AMPA in 23 runoff water samples collected from a field in the Po Valley (North-East Italy), an agricultural area where glyphosate is widely used.

Glyphosate is the most common herbicide worldwide, and its impact on the environment has increasingly been scrutinized. Glyphosate-based formulations can contain co-formulants, among which are surfactants. This study aimed to investigate whether the presence of an alkyl polyglucoside-based surfactant, Triton CG-110, affects the adsorption, leaching, and mineralisation of glyphosate in the soil. The experiments were conducted in two soils with different textures (sandy and clay) and in washed sand. Glyphosate and surfactant mixtures were applied at realistic field rates. Because of ponding and scarce leaching from the field soil, the leaching experiments were conducted only with washed sand. The results indicate a reduction of glyphosate adsorption in washed sand (from Kf = 13.5 to 3.99 μg1−1/n (ml)1/n g−1) and in sandy soil (from Kf = 165 to 90.8 μg1−1/ n (ml)1/n g−1) when using a Triton CG-110 concentration of 0.5 %, which corresponds to that of a spraying solution applied in the field, whereas adsorption in clay soil was unaffected. Triton CG-110 did not significantly affect glyphosate leaching in washed sand or mineralisation in any of the tested soils. The results indicate that Triton CG-110 is unlikely to significantly affect the environmental fate of glyphosate in the soil at environmentally relevant concentrations.

This study evaluates the dissipation of terbuthylazine, metolachlor, and mesotrione at different depths in soils with contrasting texture. The field trial was conducted at the Padua University Experimental Farm, north-east Italy. The persistence of three herbicides was studied in three different soil textures (clay soil, sandy soil, and loamy soil) at two depths (0-5 and 5-15 cm). Soil organic carbon content was highest in the clay (1.10%) followed by loam (0.67%) and sandy soil (0.24%); the pH of soils was sub-alkaline. Terbuthylazine, metolachlor, and mesotrione were applied on maize as a formulated product (Lumax®) at a dose of 3.5 L ha-1. Their dissipation in the treated plots was followed for 2 months after application. The concentrations of herbicides were analyzed by liquid chromatography-mass spectrometry. The dissipation of terbuthylazine, metolachlor, and mesotrione could be described by a pseudo first-order kinetics. Terbuthylazine showed the highest DT50, followed by metolachlor and mesotrione. Considering the tested soil, the highest DT50 value was found in clay soil for terbuthylazine and metolachlor, whereas for mesotrione there was no difference among soils. Significant differences were found between the two soil depths for terbuthylazine and metolachlor, whereas none were found for mesotrione. These results suggest that soil texture and depth have a strong influence on the dissipation of terbuthylazine and metolachlor, whereas no influence was observed on mesotrione because of its chemical and physical properties.

We describe a research project about the teaching of non-Euclidean geometries. Our intent is to show that non-Euclidean geometries can be a tool to promote the understanding of the modern axiomatic method in mathematics, to stimulate students' aptitudes to logical thinking and to allow students to consolidate the knowledge of Euclidean geometry by developing it in a critical way.

In alpine environments, colonies of snow vole (Chionomys nivalis Martins) cause strong pedoturbation, which may affect humification process and soil organic matter (SOM) cycling, with repercussions on the hormone‐like activity of organics. We investigated the effect of snow vole pedoturbation on the chemical and spectroscopic features of soil organic fractions, and the potential hormone‐like activity of humic and fulvic acids (HA, FA). The study site was located on the high‐mountain environment of the Majella massif (central Italy). Pedoturbated and regular soils were morphologically described and characterized for pH and content of total organic carbon, total extractable carbon, HA, and FA. Both HA and FA were extracted and investigated using attenuated total reflectance/Fourier transform infrared (ATR/FTIR), nuclear magnetic resonance with high‐resolution magic angle spinning (HRMAS‐NMR), and 1H‐13C heteronuclear single quantum coherence (HSQC). HA and FA were also tested for their auxin‐like and gibberellin‐like activities. Results provide evidences that bioturbated and regular soils contain a poorly decomposed SOM, but HA and FA with a well‐defined molecular structure. The HA and FA from both bioturbated and regular soils show a hormone‐like activity with a different allocation along the soil profile. In the regular soil, the highest auxin‐like activity was shown by HA and FA from Oe1 horizon, while gibberellin‐like activity was expressed by FA from Oe2 horizon. Burrowing activity determines a redistribution of organics throughout the profile with a relatively high auxin‐like activity in the FA from straw tunnel wall (STW) and gibberellin‐like activity in the HA from vole feces (VF). The relative high presence of carboxylic acids, amides, proteins, and amino acids in the FA from STW and the aromatic moieties in the HA from VF put evidences for their different behavior. The fact that snow vole activity has modified the chemical and biological properties of SOM in these soils otherwise considered governed only by low temperature has important ecological implications such as the preservation of soil fertility and vegetal biodiversity.

Biochar is used as soil amendment and enhancer of plant growth, but the mechanisms involved in grapevine are not understood. In this study, the short-term effects of amendments were evaluated in a trial combining three substrates (biochar, compost, peat-based media) with three doses (30, 70, 100%) along a time sequence on 1-year-old bare root cuttings of grapevine. Amendments were analyzed for elemental composition. Soil pH, electrical conductivity (EC), chlorophyll (CHL), flavonoids (FL), anthocyans (ANT) and nitrogen balance index (NBI) were measured.Biochar differed from other amendments for stable C structures, where nutrients and lignin residues were high in compost. Biochar increased soil pH, whereas biochar plus compost mixture augmented EC. The amended plants had detrimental effects on root, true and lateral leaves. Nevertheless, at the lowest rate biochar increased the primary shoot and total scion to root biomass ratio. Among biochemicals, ANT and NBI were mostly affected by biochar, while compost gave only slight increments. Thus, although biochar rate was not adequate for the shedding in open field our results suggest that biochar might be useful in nursery when used at low dosages.

Vegetative filter strips reduce herbicide runoff from cultivated fields owing to the ability of vegetation to delay surface runoff, promote infiltration, and adsorb herbicides. Previous research has shown that the annual runoff of each herbicide is typically less than 1 g ha-1. A model for the detection of the return period of rainfall events was recently proposed for a site in the north-eastern Po Valley, Italy. The return period model suggested that most of the herbicide loss by runoff (about 98%) is caused by a few, or even just one, extreme rainfall event with a return period of about 25-27 years, whereas ordinary events (4-5 each year) account for the rest. The present study aims to validate that model by comparing model predictions with the experimental results obtained in the 2010-2011 sampling season (independent test data), and to evaluate the effectiveness of the VFS. In addition, a 7-yr dataset of metolachlor and terbuthylazine concentration in real runoff events is summarised in order to highlight the medium-term magnitude of the pollution. Results show that on the Po Valley plain, 3-4 runoff events of low intensity are expected in spring-summer and that the consequent annual runoff of the herbicides metolachlor and terbuthylazine is about 0.5-0.7 g ha-1 yr-1. A summary shows that, owing to their chemical-physical properties, concentrations of the two herbicides are similar, both varying from about 0.01-300 microg l-1, with a potential pulse-like exposure risk for aquatic communities in waterways. This study showed that vegetative filter strips can reduce herbicide transfer to surface water by 90-98%, and should be suggested for environmental schemes at field and catchment scale.

Narrow vegetative filter strips proved to effectively reduce herbicide runoff from cultivated fields mainly due to the ability of vegetation to delay surface runoff, promote infiltration and adsorb herbicides. A field trial was conducted from 2007 to 2009 in north-east Italy in order to evaluate the effectiveness of various types of vegetative filter strips to reduce spring-summer runoff of the herbicides mesotrione, metolachlor and terbuthylazine, widely used in maize, and to evaluate the effect of the rainfall characteristics on the runoff volume and concentration. Results show that without vegetative filter strip the herbicide load that reaches the surface water is about 5–6 g ha −1 year −1 for metolachlor and terbuthylazine (i.e. 0.5–0.9% of the applied rate), confirming that runoff from flat fields as in the Po Valley can have a minor effect on the water quality, and that most of the risk is posed by a few, or even just one extreme rainfall event with a return period of about 25–27 years, causing runoff with a maximum concentration of 64–77 μg L −1 . Mesotrione instead showed rapid soil disappearance and was observed at a concentration of 1.0–3.8 μg L −1 only after one extreme (artificial) rainfall. Vegetative filter strips of any type are generally effective and can reduce herbicide runoff by 80–88%. Their effectiveness is steady even under severe rainfall conditions, and this supports their implementation in an environmental regulatory scheme at a catchment or regional scale.

In intensive agricultural systems runoff is one of the major potential diffuse pollution pathways for pesticides and poses a risk to surface water. Ditches are common in the Po Valley and can potentially provide runoff mitigation for the protection of watercourses. The effectiveness depends on ditch characteristics, so there is an urgent need for site-specific field trials. The use of a fugacity model (multimedia model) can allows recognition of the mitigation main processes. A field experiment was conducted in order to evaluate the mitigation capacity of a typical vegetated ditch, and results were compared with predictions by a fugacity model. To evaluate herbicide mitigation after an extreme runoff, the ditch was flooded with water containing mesotrione, S-metolachlor and terbuthylazine. Two other subsequent floods with uncontaminated water were applied 27 and 82 days later to evaluate herbicides release. Results show that the ditch can immediately reduce runoff concentration of herbicides by at least 50% even in extreme flooding conditions. The half-distances were about 250 m. As a general rule, a runoff of 1 mm from 5 ha is mitigated by 99% in 100 m of vegetated ditch. Herbicides retention in the vegetated ditch was reversible, and the second flood mobilized 0.03 0.2% of the previous one, with a concentration below the drinking water limit of 0.1 microg/ L. No herbicide was detected in the third flood, because the residual amount in the ditch was too low. Fugacity model results show that specific physical-chemical parameters may be used and a specific soil-sediment-plant compartment included for modelling herbicides behaviour in a vegetated ditch, and confirm that accumulation is low or negligible for herbicides with a half-life of 40 days or less. Shallow vegetated ditches can thus be included in a general agri-environment scheme for the mitigation of pesticides runoff together with wetlands and linear buffer strips. These structures are present in the landscape, and their environmental role can be exploited by proper management.

Introduction In intensive agriculture areas the use of pesticides can alter soil properties and microbial community structure with the risk of reducing soil quality. Materials and Methods In this study the fatty acid methyl esters (FAMEs) evolution has been studied in a factorial lab experiment combining five substrates (a soil, two aged composts and their mixtures) treated with a co-application of three pesticides (azoxystrobin, chlorotoluron and epoxiconazole), with two extraction methods, and two incubation times (0 and 58 days). FAMEs extraction followed the microbial identification system (MIDI) and ester-linked method (EL). Results and Discussion The pesticides showed high persistence, as revealed by half-life (t1/2) values ranging from 168 to 298 days, which confirms their recalcitrance to degradation. However, t1/2 values were affected by substrate and compost age down to 8 days for chlorotoluron in S and up to 453 days for epoxiconazole in 12M. Fifty-six FAMEs were detected. Analysis of variance (ANOVA) showed that the EL method detected a higher number of FAMEs and unique FAMEs than the MIDI one, whereas principal component analysis (PCA) highlighted that the monosaturated 18:1ω9c and cyclopropane 19:0ω10c/19ω6 were the most significant FAMEs grouping by extraction method. The cyclopropyl to monoenoic acids ratio evidenced higher stress conditions when pesticides were applied to compost and compost+soil than solely soil, as well as with final time. Conclusion Overall, FAMEs profiles showed the importance of the extraction method for both substrate and incubation time, the t1/2 values highlighted the effectiveness of solely soil and the less mature compost in reducing the persistence of pesticides.

Vegetated buffer strips alongside watercourses are commonly used to counteract diffuse pollution from agricultural activities. If properly designed, they can provide multiple environmental benefits by increasing wildlife habitats and biodiversity. Little attention has been paid to the effects of buffer strips on soil quality. This study was conducted to determine the impact of different buffer designs on soil biochemical parameters and to define relevant quality parameters for soil monitoring. We compared four buffer arrangements: 3 m wide grass buffer; 3 m grass with one tree row; 6 m grass with one tree row; 6 m grass with two tree rows; plus two controls: an adjacent maize crop field and a plot without buffer. Buffers were established 13 years ago at the Padua University Experimental Farm in the Po Valley, north-east Italy. Studied parameters included soil organic matter composition and soil microbial and enzymatic assays. As expected, control plots showed the lowest values for all the studied parameters. Among buffer designs, 3 m grass and 3 m grass with 1 tree row buffers gave the highest values. Multivariate analysis demonstrated that the increase of soil organic carbon content distinguished buffers from controls, whereas soil humic carbon quality parameters such as humic compounds apparent molecular weight, together with acetyl esterase (fluorescein test) enzyme activity, were discriminatory in separating buffer designs. These results are an important contribution to the knowledge base and can help to improve the management of these systems.

Compost biobeds can promote biodegradation of pesticides. The microbial community structure changes during the composting process, and simple methods can potentially be used to follow these changes. In this study the microbial identification (MIDI) and ester-linked (EL) procedures were used to determine the composition of fatty acid methyl esters (FAMEs) in composts aged 3 and 12 months, inoculated with 3 recalcitrant pesticides (azoxystrobin, chlorotoluron, and epoxyconazole and a coapplication of all three) after 0, 56, and 125 days of degradation. Pesticide persistence was high, and after 125 days the residue was 22 to 70% of the applied amount depending mostly on the composting age. Seventy-one FAMEs belonging to nine groups were detected. The EL method provided three times as many detections as did the MIDI method and was more sensitive for all FAME groups except alcohol. Thirty-six and five FAMEs were unique to the EL and MIDI methods, respectively. The extraction method was of importance. The EL method provided a higher number of detections for 57 FAMEs, and the MIDI method provided a higher number for 9 FAMEs, while the two methods were equal for 5 FAMEs; thus, the EL method provided a more uniform overall FAME profile. Effects of the other factors were not always clear. Inoculation with pesticide did not influence the FAME profile with the MIDI method, while it influenced cyclopropane and monounsaturated content with the EL method. Composting age and degradation time had an effect on some groups of FAMEs, and this effect was greater with the EL method. The use of some FAMEs as biomarkers to follow microbial community succession was likely influenced by the type of compost and other factors.

A 180 d laboratory experiment was conducted to investigate the degradation rates of chlorpyrifos (10 and 50 mg kg−1) and metalaxyl (100 mg kg−1) separately and co-applied in a biomix constituted by topsoil, vine-branches and urban-waste-garden compost. The effect of repeated application of metalaxyl was also investigated. Microbial biomass-C (MBC) content and metabolic quotient (qCO2) were measured to evaluate changes in microbial biomass size and activity induced by the presence of the two pesticides. Degradation rate decreased with increasing concentration of chlorpyrifos in all treatments. Metalaxyl half-life was significantly reduced in co-application with chlorpyrifos indicating a synergic interaction between the two pesticides in favour of enhanced degradation rate for metalaxyl but not for chlorpyrifos. Furthermore, repeated application resulted in a sharp reduction of metalaxyl half-life from 37 d after first application to 4 d after third application. MBC content was negatively influenced by the addition of pesticides but it started to recover immediately, in both separate and co-applied treatments, reaching the control value when pesticide residues were about 50% of the initial concentration. The qCO2 reached a steady-state after about 20 d in separately applied and 40 d in co-applied treatments, indicating a tendency to arrive at a new metabolic equilibrium. In conclusion, the biomix tested has been shown to degrade pesticides relatively fast and to have a microbial community that is varied enough to allow selection of those microorganisms able to degrade metalaxyl and chlorpyrifos.

A field experiment is reported to ascertain the drift of two pesticides (chlorpyrifos and metalaxyl) in a vineyard in Italian climatic conditions and the effect of mitigation measures, such as buffer zones and tree rows, on pesticide drift contamination in a small aquatic system located inside the field. Results indicated that, in typical Italian agricultural conditions, spray drift in vineyards occurs at a distance of more than 24 m and adequate buffer zones are required to protect surface water bodies from direct contamination. The presence of tree rows in front of the water body inside the agricultural field, against the main wind direction, resulted in a very high reduction of the spray drift and of the ecotoxicological risk for aquatic ecosystem. In addition, a comparison between the data obtained in the experiment and the Drift Calculator procedure showed that the model failed when the procedure is used for short distances. However, concordance was found in terms of maximum drift distances.

Biobeds provide a simple and cheap solution to reducing point-source contamination by pesticides from farm activities. In its original design, the Swedish biobed is a clay-lined pit in the ground filled with a biomixture of topsoil, peat and straw and covered with a grass layer. The straw stimulates the growth of lignin-degrading fungi and the formation and activity of ligninolytic enzymes which can degrade many different pesticides. Here we compared the behaviour of the chlorpyrifos pesticide in two biobeds of different composition: a Swedish biobed composed of 50%v vine straw, 25%v peat and 25%v Swedish soil; and an Italian biobed composed of 40%v vine straw, 40%v green compost and 20%v Italian soil. Microbial biomass was measured in the Italian biomix by the fumigation-extraction method. The microbial activity was estimated by measuring mineralisation of a synthetic lignin, 14C-de-hydrogenative polymerisate (14C-DHP) in the Swedish biomix. Microbial respiration was followed over time in both biomixes. Our results show that the chlorpyrifos half-lives were similar in both biomixes. The microbial biomass content was reduced by 25 and 50% with, respectively, 10 and 50 mg kg−1 chlorpyrifos in the Italian biomix. The respiration activity was affected only at 50 mg kg−1 chlorpyrifos in the Italian biomix. No effect was observed in the Swedish biomix despite the higher chlorpyrifos concentration of 100 mg kg−1. The mineralisation of 14C-DHP was not affected by the presence of chlorpyrifos in the Swedish biomix. These findings could be explained by the presence of chlorpyrifos-sensitive microorganisms in the Italian biomix and chlorpyrifos-resitant microorganisms in the Swedish biomix. The more robust microftora developed in the Swedish biomix may be explained by its lower nitrogen content, higher C/N ratio and lower pH, all of which are favourable for the development of lignin-degrading fungi and their activity. In Sweden more than 1000 biobeds are in practical use on farms and they have been shown to be efficient at reducing pesticide water-body contamination. The present study compares the capability of an Italian biomix for degrading pesticides to that shown by the Swedish original biomix in order to introduce this biological system for a sustainable Italian agriculture.