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IntroductionEmerging contaminants in irrigation wastewater can cause bioaccumulation in crops, posing health risks to humans and other living organisms. The extent to which different emerging contaminants (ECs) are taken up by plants varies depending on the physicochemical properties of the contaminants and the type of crops grown.MethodsThis study investigated the fate of emerging contaminants (ECs), particularly pharmaceuticals, in durum wheat grown on soils irrigated with treated wastewater in southern Italy. The experiment was conducted in lysimeters irrigated with wastewater during previous crop cycles, assessing the presence and distribution of ECs in both soil and plant tissues. Three different levels of exposure to ECs were compared: freshwater irrigation (FW), wastewater treated to European average contaminant levels (TWWx1), and a triple dose of contaminants (TWWx3).ResultsThe behavior of 12 different ECs in the plant-soil complex was analyzed and found variable. Fluconazole and carbamazepine were found to have higher uptake concentrations in the plant, with accumulation observed in the plant and grain, especially in the TWWx3 treatment. However, some ECs (such as Sulfamethoxazole, Trimethoprim, Ketoprofen, Diclofenac, Metoprolol, and Naproxen) showed high uncertainties in their fate, probably due to degradation in soil and influential crop parameters.DiscussionThe results of this study contribute to the argument that the reuse of treated wastewater for irrigation, if properly monitored, can be a safe approach in agriculture and can support policymakers in developing future legislative frameworks for sustainable water management.

IntroductionThe use of treated municipal wastewater (TWW) represents a relevant opportunity for irrigation of agricultural crops in semi-arid regions to counter the increasing water scarcity. Pharmaceutically active compounds (PhACs) are often detected in treated wastewater, posing a risk to humans and the environment. PhACs can accumulate in soils and translocate into different plant tissues, reaching, in some cases, edible organs and entering the food chain.MethodsThis study evaluated the uptake and translocation processes of 10 PhACs by olive trees irrigated with TWW, investigating their accumulation in different plant organs. The experiment was conducted in southern Italy, in 2-year-old plants irrigated with three different types of water: freshwater (FW), TWW spiked with 10 PhACs at a concentration of 200 µg L−1 (1× TWW), and at a triple dose (3× TWW), from July to October 2021. The concentration of PhACs in soil and plant organs was assessed, collecting samples of root, stem, shoot, leaf, fruit, and kernel at 0 (T0), 50 (T1), and 107 (T2) days of irrigation. PhACs extraction from soil and plant organs was carried out using the QuEChERS method, and their concentrations were determined by high-resolution mass spectrometry coupled with liquid chromatography.ResultsResults of uptake factors (UF) showed a different behavior between compounds according to their physicochemical properties, highlighting PhACs accumulation and translocation in different plant organs (also edible part) in 1× TWW and 3× TWW compared to FW. Two PhACs, carbamazepine and fluconazole, showed interactions with the soil–plant system, translocating also in the aerial part of the plant, with a translocation factor (TF) greater than 1, which indicates high root-to-leaf translocation.DiscussionFindings highlight that only few PhACs among the selected compounds can be uptaken by woody plants and accumulated in edible parts at low concentration. No effects of PhACs exposure on plant growth have been detected. Despite the attention to be paid to the few compounds that translocate into edible organs, these results are promising for adapting wastewater irrigation in crops. Increasing knowledge about PhACs behavior in woody plants can be important for developing optimized wastewater irrigation and soil management strategies to reduce PhACs accumulation and translocation in plants.

Nano-biochar is a source of blackish carbonaceous material, a prerequisite for sustainable crop productivity. By using a variety of feedstock materials, nanobiochar synthesis can be employed via pyrolysis. Therefore, a project was initiated to explore the morpho-physio-biochemical alteration at the vegetative stage of wheat crops after the foliar application of nanobiochar suspension (NBS). This investigation was conducted at the Botanical Research Area of the University of Lahore in a randomized complete block design (RCBD) arrangement, with four treatments (0, 1, 3, and 5% NBS) by maintaining three replications for each treatment using the wheat variety “Zincol”. Nano biochar suspension in above mentioned concentrations were foliarly applied at the end of tillering/beginning of leaf sheath elongation of wheat seedlings to assess the morphological changes (root length, shoot length, number of leaves, fresh biomass/plant, dry biomass/plant), physio-biochemical alterations (total free amino acids, total sugars, chlorophyll content, protein, phenols, flavonoids), and nutrient uptake (Na, K, Ca, Mg, N, P contents. Our findings indicate that the foliar application of 3% NBS yielded the most favorable results across all measured attributes. Furthermore, Treatment-4 (5% NBS) specifically improved certain traits, including leaf area, total soluble proteins, and leaf calcium content. Finally, all NBS resulted in a decrease in carotenoid and sodium content in wheat seedlings.

The use of reclaimed wastewater for irrigation could result in the release of pharmaceutically active compounds (PhACs) and their metabolites into the agroecosystem. In this study, we investigated the fate of carbamazepine (CBZ) and its metabolites, with the aim of clarifying their behavior in a soil–plant system in a greenhouse experiment. The research was carried out using irrigation water especially fortified with high doses of CBZ (200 or 600 ppb) in order to evaluate the dynamics of CBZ and its metabolites in the soil and basil organs. The results of the study showed that CBZ is easily absorbed by the aerial part of the basil plant. The soil contained two metabolites of CBZ, namely acridine and carbamazepine-10,11-epoxide, as revealed by high-resolution mass spectrometry analyses. In addition, acridine was found in the aerial parts of basil plants. Furthermore, the greater presence of CBZ and its metabolites in bulk soil indicated a positive role of the basil rhizosphere in the degradation of such compounds or a positive role of the plant in the removal of the contaminant by uptake. Considering the observed morphological parameters and the mean CBZ content in wastewater, significantly lower than that used in the experiment, basil can be considered resistant to the application of irrigation water contaminated with CBZ.

Abstract Background A modified version of the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method has been tested for quantifying six active compounds of pharmaceuticals (PhACs), i.e., two different antibiotics, two anti-inflammatories, one antifungal, and one anti-depressant, extracted from roots, leaves and stems, pulp, pits, and oil obtained from olive trees. The different matrices have been polluted with all contaminants at 25, 50, and 250 µg L−1 and the recoveries were determined by liquid chromatography tandem–mass spectrometry. The validation of the method has been carried out by determining linearity, recovery, precision, limits of detection (LODs), and limits of quantification (LOQs) values. A matrix-matched calibration for each matrix has been adopted in order to avoid the matrix effect at the aforementioned levels of fortification. Results The recoveries of PhACs from the different matrices were always above 70% and the relative standard deviation (RSD) always ≤ 20%, conditions required for the validation of the method. The LOD and LOQ values were always lower than 25 µg L−1, i.e., always lower than the minimum concentration used in the experiment; therefore, the method can be validated at 25, 50, and 250 µg L−1. Conclusions This method can represent a valid alternative to the traditional extraction methods to quantify pharmaceuticals extracted also from fatty matrices. Graphical Abstract

Research on nanoparticles (NPs) is gaining great attention in modulating abiotic stress tolerance and improving crop productivity. Therefore, this investigation was carried out to evaluate the effects of copper oxide nanoparticles (CuO-NPs) on growth and biochemical characteristics in two maize hybrids (YH-5427 and FH-1046) grown under normal conditions or subjected to saline stress. A pot-culture experiment was carried out in the Botanical Research Area of “the University of Lahore”, Lahore, Pakistan, in a completely randomized design. At two phenological stages, both maize hybrids were irrigated with the same amount of distilled water or NaCl solution (EC = 5 dS m−1) and subjected or not to foliar treatment with a suspension of CuO-NPs. The salt stress significantly reduced the photosynthetic parameters (photosynthetic rate, transpiration, stomatal conductance), while the sodium content in the shoot and root increased. The foliar spray with CuO-NPs improved the growth and photosynthetic attributes, along with the N, P, K, Ca, and Mg content in the roots and shoots. However, the maize hybrid YH-5427 responded better than the other hybrid to the saline stress when sprayed with CuO-NPs. Overall, the findings of the current investigation demonstrated that CuO-NPs can help to reduce the adverse effects of salinity stress on maize plants by improving growth and physio-biochemical attributes.

Abstract Soil degradation resulting from deforestation contributes to a dramatic decline in soil quality whose restoration must go through reforestation with pioneer species. We investigated the effects of cypress and black locust, pioneer but exotic species, on soil chemical properties and microbial and enzymatic activities of two marginal soils. The sampling sites were Lama Giulia and Locone lake in the Murge plateau of the Apulia Region, Italy. The soils at Lama Giulia presented a silty loam texture, while at Locone Lake site were sandy, and most likely due to the different texture, the former exhibited higher organic C, N, P and micronutrients contents than Locone Lake under black locust reforestation, despite the latter was reforested earlier. In addition, the higher microbial entropy and turnover of Locone Lake’s soils suggested a less conservative soil state than Lama Giulia’s soils. The effects of black locust reforestation at Lama Giulia on almost all soil parameters considered did not differ from those of the corresponding pasture, confirming the more conservative soil state in that site and suggesting that the time of reforestation was not enough to get differences between the reforested and not reforested soil. The soils reforested with cypress showed the significantly highest SOC, N, dissolved organic C and microbial biomass C content. In addition, it presented also the numerically largest dehydrogenase, phosphatase and β-glucosidase activities, soluble carbohydrates, and phenolic compounds content. These results may be ascribed to the longer litter deposition occurred in cypress soils.

The reuse of treated wastewater for crop irrigation is vital in water-scarce semi-arid regions. However, concerns arise regarding emerging contaminants (ECs) that persist in treated wastewater and may accumulate in irrigated crops, potentially entering the food chain and the environment. This pilot-scale study conducted in southern Italy focused on tomato plants (Solanum lycopersicum L. cv Taylor F1) irrigated with treated wastewater to investigate EC uptake, accumulation, and translocation processes. The experiment spanned from June to September 2021 and involved three irrigation strategies: conventional water (FW), treated wastewater spiked with 10 target contaminants at the European average dose (TWWx1), and tertiary WWTP effluent spiked with the target contaminants at a triple dose (TWWx3). The results showed distinct behavior and distribution of ECs between the TWWx1 and TWWx3 strategies. In the TWWx3 strategy, clarithromycin, carbamazepine, metoprolol, fluconazole, and climbazole exhibited interactions with the soil-plant system, with varying degradation rates, soil accumulation rates, and plant accumulation rates. In contrast, naproxen, ketoprofen, diclofenac, sulfamethoxazole, and trimethoprim showed degradation. These findings imply that some ECs may be actively taken up by plants, potentially introducing them into the food chain and raising concerns for humans and the environment.

Magnetic chitosan nanoparticles, synthesized by in situ precipitation, have been used as adsorbents to remove sulfamethoxazole (SMX), a sulfonamide antibiotic dangerous due to its capacity to enter ecosystems. The adsorption of SMX has been carried out in the presence of tertiary wastewaters from a depuration plant to obtain more realistic results. The effect of pH on the adsorption capacity significantly changed when carrying out the experiments in the presence of wastewater. This change has been explained while taking into account the charge properties of both the antibiotic and the magnetic chitosan. The composition of wastewaters has been characterized and discussed as regards its effect on the adsorption capacity of the magnetic chitosan. The models of Elovich and Freundlich have been selected to describe the adsorption kinetics and the adsorption isotherms, respectively. The analysis of these models has suggested that the adsorption mechanism is based on strong chemical interactions between the SMX and the magnetic chitosan, leading to the formation of an SMX multilayer.

Abstract Background The quick, easy, cheap, effective, rugged, and safe (QuEChERS) method can be employed for multi-residue analyses instead of traditional extraction methods due to its advantages in terms of extraction time and required equipment. A modified version of the QuEChERS method has been developed for quantifying eight pharmaceuticals belonging to different classes in three real soils with different chemical properties. Firstly, the soils have been polluted with all contaminants and the recoveries were determined by liquid chromatography tandem–mass spectrometry. Due to similar recoveries from the three soils, the validation of the method has been carried out only on a soil by determining linearity, recovery, precision, limit of detection (LOD) and limit of quantification (LOQ) values. A matrix-matched calibration for the soil has been adopted in order to avoid the matrix effect and three levels of fortification (50, 100 and 500 µg L−1) were used. Results The recovery of all pharmaceuticals, with the exception of tetracycline, from any soil was between 72 and 113%. In the validation procedure, recoveries of fortified samples ranged from 80 to 99%, the relative standard deviations ranged between 1.2 and 11.8%, and the LOQ between 20 and 36.9 μg kg−1. Conclusion The results of the present study confirmed the validity of the modified QuEChERS method for the extraction of pharmaceuticals from soils in the range 50–500 μg kg−1. Graphical Abstract

Abstract Background The irrigation with treated wastewaters can be a way for the introduction of organic contaminants in soils. However, their adsorption onto soils can allow a control of their bioavailability and leaching. The adsorption is influenced by properties of contaminants (water solubility, chemical structure) and soils (organic matter content, pH, mineralogy). This study aimed to investigate the effect of mineralogical composition, organic matter content and others parameters of soils on the adsorption of sulfamethoxazole (SMX) and diclofenac (DCF), two contaminants of emerging concerns (CECs), in real cases (Altamura, Sibari and Noci soils). Results The isotherms data showed that the adsorption of the two CECs closely matched the Freundlich model, even if the DCF could also fit the linear one. The only exception was the adsorption of SMX on the soil of Sibari, for which Langmuir's model fitted better. In all cases, the K d values were the highest for Altamura soil according mainly to its content of organic carbon. Positive correlations were found between K d value of DCF and the soil organic carbon and Al oxyhydroxides content, suggesting their roles in its adsorption, while SMX showed only a slight positive correlation with the soil organic carbon content. Finally, between the two CECs studied, DCF was more adsorbed than SMX also because of the lower water solubility of the former. Conclusions The good interaction between DCF and soil organic carbon suggests the organic amendment of soils before the application of treated watewaters. The low adsorption of SMX onto soils suggests greater leaching of this compound which is, therefore, potentially more dangerous than DCF. For this reason, the application of a filtration system with appropriate adsorbent materials before the application of wastewater to soils should be expected. Graphical Abstract

IntroductionThe use of novel soil amendments and the exploitation of plant growth-promoting microorganisms are considered promising tools for developing a more sustainable agriculture in times when ensuring high-yield productions with limited resources is essential.MethodsIn this study, the potential of brewers' spent grain (BSG), the major by-product of the brewing industry, as organic soil amendment, was investigated. Bioprocessed BSG, obtained by an enzymatic treatment coupled with fermentation, together with native BSG, were used as amendments in a pot-trial. An integrated analytical approach aimed at assessing the modification of the physicochemical properties of a typical Mediterranean alkaline agricultural soil, and the plant growth-promoting effect on escarole (Cichorium endivia var. Cuartana), was carried out.ResultsThe use of biomasses led to soil organic content and total nitrogen content up to 72 and 42% higher, compared to the unamended soils. Moreover, the lower pH and the higher organic acids content doubled phosphorus availability. Although the number of leaves per plant in escaroles from pots amended with native and bioprocessed BSG did not show any difference compared to plants cultivated on unamended pots, the average fresh weight per escarole head, was higher in pots amended with bioprocessed BSG.DiscussionHence, the results collected so far encourage BSG application for agricultural purpose, while solving the problem of disposing of such abundant side stream.

To investigate the toxic effects of lead (Pb) on key metabolic activities essential for proper germination and seedling growth of maize seeds, experiments were carried out with different levels of Pb (0 to 120 mg of Pb L−1 as PbCl2) applied through growth medium to two maize hybrids H-3310S and H-6724. The research findings indicated that growth and metabolic activities were adversely affected by increased Pb contamination in growth medium; however, a slow increase in these parameters was recorded with increasing time from 0 to 120 h. Protease activity decreased with an increase in the level of Pb contamination but increased with time; consequently, a reduction in seed proteins and an increase in total free amino acids were observed with time. Similarly, α-amylase activity decreased with an increase in Pb concentration in growth medium while it increased with increasing time from 0 to 120 h; consequently, reducing and non-reducing sugars increased with time but decreased with exposure to lead. The roots of both maize hybrids had higher Pb contents than those of the shoot, which decreased the uptake of nitrogen, phosphorus, and potassium. All these nutrients are essential for optimal plant growth; therefore, the reduction in growth and biomass of maize seedlings could be due to Pb toxicity that altered metabolic processes, as sugar and amino acids are necessary for the synthesis of metabolic compounds, rapid cell division, and proper functioning of enzymes in the growing embryo, but all were dramatically reduced due to suppression of protease and α-amylase by toxicity of Pb. In general, hybrid H-3310S performed better in Pb-contaminated growth medium than H-6724.

Pharmaceuticals (PhACs) are chemical substances that, after their use, can reach wastewater treatment plants, but the resulting treated wastewater (TWW) can still contain these contaminants. If TWWs are used for irrigation, PhACs can contaminate crops and also hinder their growth. The aim of this work was to evaluate the effects of 12 PhACs and their mixture at different doses on basil germination and early growth and on its photosynthetic pigment content. The germination percentage was not affected by PhACs even when applied at the highest doses. The results showed that the germination speed cannot be considered as an index of vigor of future seedlings as not all seeds that germinated first developed the best. PhACs between 25 and 100 ppb did not show negative effects on early growth and photosynthetic pigments of basil; in fact, in some cases the seeds even benefitted from their application as if it were a chemical treatment developed for the seeds. The highest assessed dose of PhACs always caused a reduction in growth parameters and the photosynthetic pigment content of basil, especially with climbazole, naproxen, triclosan, and the mixture of PhACs. In general, basil can be considered a species tolerant to PhACs after taking into account their average content in wastewater; however, more studies are needed to evaluate the long-term effects of PhACs and their translocation to edible parts.

Nutrient deficiency negatively affects the yield and quality of citrus fruit. The present experiment was carried out to investigate the improvement in fruit yield and juice quality of Kinnow (Citrus reticulata L.) by foliar application of nano-biochar suspension (NBS). The experiment was carried out in a citrus farmer’s orchard with a history of low fruit yield, using a randomized complete block design. Four NBS treatments, i.e., 0% (control), 1, 3, and 5%, were applied through foliar application at the flowering stage. Foliar application of NBS at 5% and 3% significantly (p < 0.05) improved flowering, fruit retention, fruit set, fruit size, length, weight, diameter, juice volume levels, and minimized fruit dropping. The electrical conductivity of the juice was significantly decreased by increases in NBS concentration. Total dissolved solids increased slightly with treatments as compared to control. However, NBS foliar application did not show significant effects on nitrogen (N), potassium (K), and sodium (Na) leaf contents, but had some effect on phosphorus (P) content. Principal component analysis and a correlation matrix revealed significant (p < 0.05) positive and negative associations among the studied traits. The results of the current experiment showed that all parameters were significantly improved with the application of NBS at 3 and 5%, except that N, K, and Na levels were unaffected. The most encouraging results were achieved at a concentration of 5% NBS. In conclusions, the foliar application of NBS had a significant positive impact on fruit yield and juice quality.

The current social context requires an increase in food production, improvement of its quality characteristics and greater environmental sustainability in the management of agricultural systems. Technological innovation plays a great role in making agriculture more efficient and sustainable. One of the main aims of precision farming (PF) is optimizing yield and its quality, while minimizing environmental impacts and improving the efficient use of resources. Variable rate techniques (VRT) are amongst the main management options for PF, and they require spatial information. This work incorporates maps of soil properties from low induction electromagnetic measurements into nitrogen (N) balance calculations for a field application of VRT nitrogen fertilization of (Triticum durum Desf., var. Tirex). The trial was conducted in 2018-19 at Genzano di Lucania (PZ, Italy) geologically located on the clayey hillsides of the Bradanica pit and the Sant'Arcangelo basin. Three soil homogeneous areas were detected through low induction electromagnetic measurements and used as uniform management zones. The amount of nitrogen fertilizer to be applied by VRT was calculated on the base of estimated crop nitrogen uptake and soil characteristics of each homogeneous area. Crop response to VRT was compared to uniform nitrogen application (UA) on the whole field. The application of VRT resulted in a reduction of 25% nitrogen fertilizer with the same level of yield respect to UA. Grain protein content, as well as gluten content and N content, were significantly higher in VRT than in UA. As a consequence of lower nitrogen input and higher levels of N removal, VRT reached a higher nitrogen use efficiency than UA, and this indicates a lower environmental impact and a higher economic profitability.

Pleurotus ostreatus is one of the most cultivated mushrooms worldwide. It is a lignocellulolytic fungus cultivated on different substrates, whose more common raw material is straw. The present study investigated the biological efficiency of Pleurotus ostreatus as affected by the different age of straw and the growing media preparation process in four production cycles. The content of organic carbon significantly decreased during the growing media preparation, while the content of total nitrogen, moisture, and ash, as well asthe pH value, showed an opposite trend. The first production cycle was characterized by the highest total and soluble sugar content. A dramatic reduction in soluble sugars was recorded at the end of the preparation of the growing media, regardless of the production cycle, while the total sugars were slightly reduced during the production cycle. The microbial population was significantly influenced by the growing media preparation, while only bacteria were slightly influenced by the straw’s age. In contrast, cellulase activity significantly increased in the old straw, while an opposite trend was observed for pectinase activity. The β-glucosidase activity was influenced only by the growing media preparation. As expected, cluster analysis showed that the microbial community changed in each phase of growing media preparation. Finally, the biological efficiency of Pleurotus ostreatus decreased from 26.28% to 15.49% with increasing age of the straw, which may presumably be ascribed to the higher content of sugars in fresh straw compared to the older ones. Therefore, fresh straw should be used to prepare the growing media of Pleurotus ostreatus in order to increase its biological efficiency.

The changes in soil organic matter composition induced by anthropogenic factors is a topic of great interest for the soil scientists. The objective of this work was to identify possible structural changes in humic molecules caused by a 2-year rotation of durum wheat with faba bean, lasted for a decade, and conducted with different agricultural practices in a Mediterranean soil. Humic acids (HA) were extracted at three depths (0-30, 30-60 and 60-90 cm) from a Mediterranean soil subjected to different tillage (no tillage, minimum tillage and conventional tillage), crops (faba bean and wheat), and fertilization. The changes in HA quality were assessed by several chemical (ash, yield and elemental analysis) and spectroscopic techniques (solid-state 13C nuclear magnetic resonance, Fourier transform infrared and fluorescence). The results suggest that the different agronomic practices strongly affected the quality of HA. Smaller but more aromatic molecules were observed with depth, while the fertilization induced the formation of simpler and less aromatic molecules due to the enhanced decomposition processes. Under no tillage, more stable humic molecules were observed due to the less soil aeration, while under conventional tillage larger and more aromatic molecules were obtained. Compared to wheat, more aromatic and more oxidized but less complex molecules were observed after faba bean crop. The inorganic fertilization accelerates the decomposition of organic substances rather than their stabilization. At the end of each crop cycle, humic matter of different quality was isolated and this confirms the importance of the rotation practice to guarantee a diversification of the soil organic matter with time. Finally, no tillage induces the formation of more stable humic matter.

The interaction of organic carbon (OC) with clay minerals and amorphous iron and aluminum oxides, especially in the finest soil fractions (

The interaction of organic matter with the finest soil fractions (250 μm) is highest in the upper soil layer, while the finest fraction is in the deepest one. The greatest OC content is observed in the topsoil layer and in the finest soil fraction. DRIFT analysis suggests that organic components are more present in the finest fraction, calcite is mainly localized in the coarse fraction, quartz is in micro-aggregates and 53–20 μm fraction, and clay minerals are in the finest fraction.