Efficient dissipation of acetamiprid, metalaxyl, S-metolachlor and terbuthylazine in a full-scale free water surface constructed wetland in Bologna province, Italy: A kinetic modeling study.

The study investigated the dissipation ability of a vegetated free water surface (FWS) constructed wetland (CW) in treating pesticides-contaminated agricultural runoff/drainage water in a rural area belonging to Bologna province (Italy). The experiment simulated a 0.1% pesticide agricultural water runoff/drainage event from a 12.5-ha farm by dissolving acetamiprid, metalaxyl, S-metolachlor, and terbuthylazine in 1000 L of water and pumping it into the CW. Water and sediment samples from the CW were collected for 4 months at different time intervals to determine pesticide concentrations by multiresidue extraction and chromatography-mass spectrometry analyses. In parallel, no active compounds were detected in the CW sediments during the experimental period. Pesticides dissipation in the wetland water compartment was modeled according to best data practices by fitting the data to Single First Order (SFO), First Order Multi-Compartment (FOMC) and Double First Order in Parallel (DFOP) kinetic models. SFO (except for metalaxyl), FOMC and DFOP kinetic models adequately predicted the dissipation for the four investigated molecules, with the DFOP kinetic model that better fitted the observed data. The modeled distribution of each pesticide between biomass and water in the CW highly correlated with environmental indexes as Kow and bioconcentration factor. Computed DT50 by DFOP model were 2.169, 8.019, 1.551 and 2.047 days for acetamiprid, metalaxyl, S-metolachlor, and terbuthylazine, respectively. Although the exact degradation mechanisms of each pesticide require further study, the FWS CW was found to be effective in treating pesticides-contaminated agricultural runoff/drainage water within an acceptable time. Therefore, this technology proved to be a valuable tool for mitigating pesticides runoff occurring after intense rain events.

Silica Monolith for the Removal of Pollutants from Gas and Aqueous Phases.

This study focused on the application of mesoporous silica monoliths for the removal of organic pollutants. The physico-chemical textural and surface properties of the monoliths were investigated. The homogeneity of the textural properties along the entire length of the monoliths was assessed, as well as the reproducibility of the synthesis method. The adsorption properties of the monoliths for gaseous toluene, as a model of Volatile Organic Compounds (VOCs), were evaluated and compared to those of a reference meso-structured silica powder (MCM-41) of commercial origin. Silica monoliths adsorbed comparable amounts of toluene with respect to MCM-41, with better performances at low pressure. Finally, considering their potential application in water phase, the adsorption properties of monoliths toward Rhodamine B, selected as a model molecule of water soluble pollutants, were studied together with their stability in water. After 24 h of contact, the silica monoliths were able to adsorb up to the 70% of 1.5 × 10-2 mM Rhodamine B in water solution.

Combined solid-state NMR, FT-IR and computational studies on layered and porous materials.

Understanding the structure-property relationship of solids is of utmost relevance for efficient chemical processes and technological applications in industries. This contribution reviews the concept of coupling three well-known characterization techniques (solid-state NMR, FT-IR and computational methods) for the study of solid state materials which possess 2D and 3D architectures and discusses the way it will benefit the scientific communities. It highlights the most fundamental and applied aspects of the proactive combined approach strategies to gather information at a molecular level. The integrated approach involving multiple spectroscopic and computational methods allows achieving an in-depth understanding of the surface, interfacial and confined space processes that are beneficial for the establishment of structure-property relationships. The role of ssNMR/FT-IR spectroscopic properties of probe molecules in monitoring the strength and distribution of catalytic active sites and their accessibility at the porous/layered surface is discussed. Both experimental and theoretical aspects will be considered by reporting relevant examples. This review also identifies and discusses the progress, challenges and future prospects in the field of synthesis and applications of layered and porous solids.

Experimental Determination of the Molar Absorption Coefficient of n-Hexane Adsorbed on High-Silica Zeolites.

Determination of the molar absorption coefficients of the CH3 bending mode at ν˜ =1380 cm-1 (ϵ1380 ) of n-hexane adsorbed from the gas phase on two different dealuminated zeolites is derived by a combination of IR spectroscopy and microgravimetric analysis. High-silica zeolite Y (HSZ-Y) and zeolite ZSM-5 (with SiO2 /Al2 O3 ratios of 200 and 280, respectively) with different textural and surface features are selected to evaluate the effect of the pore structure and architecture on the value of ϵ1380 of the adsorbed n-hexane. Experimental data indicate that the molecule experiences a different adsorption environment inside zeolites; thus resulting in a significant change of the dipole moment and very different ϵ1380 values: (0.278±0.018) cm µmol-1 for HSZ-Y and (0.491±0.032) cm µmol-1 for ZSM-5. Experimental data are also supported by computational modeling, which confirms the effect of different matrices on the IR absorption intensity. This study reveals that the use of probe molecules for quantitative measurements of surface sites has to be judiciously adopted, especially if adsorption occurs in the restricted spaces of microporous materials.

Potential Applications and Limitations of Electronic Nose Devices for Plant Disease Diagnosis.

Electronic nose technology has recently been applied to the detection of several plant diseases and pests, with promising results. However, in spite of its numerous advantages, including operational simplicity, non-destructivity, and bulk sampling, drawbacks include a low sensitivity and specificity in comparison with microbiological and molecular methods. A critical review of the use of an electronic nose for plant disease diagnosis and pest detection is presented, describing the instrumental and procedural advances of sensorial analysis, for the improvement of discrimination between healthy and infected or infested plants. In conclusion, the use of electronic nose technology is suggested to assist, direct, and optimise traditionally adopted diagnostic techniques.

Pot experimental trial for assessing the role of different composts on decontamination and reclamation of a polluted soil from an illegal dump site in Southern Italy using Brassica juncea and Sorghum bicolor.

A pot experiment was carried out to evaluate the remediation potential of Brassica juncea and Sorghum bicolor in the decontamination of soil polluted with heavy metals such as copper, lead, tin, and zinc along with polychlorinated biphenyls, polycyclic aromatic hydrocarbons, and heavy hydrocarbons. Two composts obtained from different composting processes were tested as biostimulating agents. At the end of the trial, the effect of plant/compost combinations on soil microbial composition, contaminant removal, biochemical indicators, and plant biomass production was determined. The results highlighted that compost addition improved plant biomass despite slowing down plants' removal of organic and inorganic contaminants. In addition, compost partially enhanced the soil biochemical indicators and modified the relative abundance of the rhizosphere microorganisms. Sorghum showed better mitigation performance than Brassica due to its higher growth. The soil fertility level, the choice of plant species, and microbial richness were found fundamental to perform soil remediation. In contrast, compost was relevant for a higher crop biomass yield.

Removal and fate of pesticides in a farm constructed wetland for agricultural drainage water treatment under Mediterranean conditions (Italy).

A non-waterproofed surface flow constructed wetland (SFCW), treating agricultural drainage water in Northern Italy, was investigated to gain information on the potential ability for effective pesticide abatement. A mixture of insecticide imidacloprid, fungicide dimethomorph, and herbicide glyphosate was applied, by simulating a single rain event, into 470-m-long water course of the SFCW meanders. The pesticides were monitored in the wetland water and soil for about 2 months after treatment. Even though the distribution of pesticides in the wetland was not uniform, for each of them, a mean dissipation of 50% of the applied amount was already observed at ≤7 days. The dissipation trend in the water phase of the wetland fitted (r2 ≥ 0.8166) the first-order model with calculated DT50 of 20.6, 12.0, 5.8, and 36.7 days for imidacloprid, dimethomorph, glyphosate, and the glyphosate metabolite AMPA, respectively. The pesticide behavior was interpreted based on the chemical and physical characteristics of both the substances and the water-soil system. Despite the fast abatement of glyphosate, traces were detected in the water until the end of the trial. The formation of soluble 1:1 complex between glyphosate and calcium, the most representative cation in the wetland water, was highlighted by infrared analyses. Such a soluble complex was supposed to keep traces of the herbicide in solution.

Effect of bioactive compounds released from Brassicaceae defatted seed meals on bacterial load in pig manure.

Animal manure application to soils is considered to be one of the main cause of antibiotic and bacterial pathogen spread in the environment. Pig livestock, which is the source of one of the most used fertilizer for cultivated land, is also a hotspot for antibiotics and antibiotic-resistant bacteria. Besides harsh chemical and physical sanitization treatments for the abatement of antibiotics and bacterial load in livestock waste, more sustainable and environmentally friendly strategies need to be considered. In this context, the use of natural substances which are proved useful for pest and disease control is currently under exploration for their role in the reduction of bacterial pathogen population. Among these, plants and derived products from the Brassicaceae family, characterized by the presence of a defensive glucosinolate-myrosinase enzymatic system, have been successfully exploited for years in agriculture using the so-called biofumigation technique against crop diseases. Although the application of biofumigation to suppress a range of soil borne pests has been well documented, no studies have been examined to reduce bacterial population in animal waste. In the present study, the release and the antibacterial activity of bioactive compounds deriving from different Brassicaceae defatted seed meals against pathogens and bacterial population in pig manure is addressed. Rapistrum rugosum and Brassica nigra defatted seed meals were found to be the most active products against tested pathogens and able to significantly reduce the bacterial load in the manure.

Sulfonamide antibiotics embedded in high silica zeolite Y: a combined experimental and theoretical study of host-guest and guest-guest interactions.

A combined experimental and computational study of the interactions of three sulfonamides--sulfadiazine, sulfamethazine, and sulfachloropyridazine--embedded into the cages of high silica zeolite Y is here proposed. For all host-guest systems, the close vicinity of aromatic rings with zeolite framework was evidenced by multidimensional and multinuclear ((1)H, (13)C, (29)Si) SS-NMR measurements. Host-guest and guest-guest interactions were also elucidated by in situ FTIR spectroscopy and confirmed by ab initio computational modeling. Single molecules of sulfamethazine and sulfachloropyridazine were stabilized inside the zeolite cage by the vicinity of methyl and amino groups, respectively. Sulfadiazine is present in both monomeric and dimeric forms. Multiple weak H-bonds and van der Waals type interactions between organic molecules and zeolite are responsible for the irreversible extraction from water of all the examined sulfa drugs.

Exploring the Animal Waste Resistome: The Spread of Antimicrobial Resistance Genes Through the Use of Livestock Manure.

Antibiotic resistance is a public health problem of growing concern. Animal manure application to soil is considered to be a main cause of the propagation and dissemination of antibiotic residues, antibiotic-resistant bacteria (ARB), and antibiotic resistance genes (ARGs) in the soil-water system. In recent decades, studies on the impact of antibiotic-contaminated manure on soil microbiomes have increased exponentially, in particular for taxonomical diversity and ARGs' diffusion. Antibiotic resistance genes are often located on mobile genetic elements (MGEs). Horizontal transfer of MGEs toward a broad range of bacteria (pathogens and human commensals included) has been identified as the main cause for their persistence and dissemination. Chemical and bio-sanitizing treatments reduce the antibiotic load and ARB. Nevertheless, effects of these treatments on the persistence of resistance genes must be carefully considered. This review analyzed the most recent research on antibiotic and ARG environmental dissemination conveyed by livestock waste. Strategies to control ARG dissemination and antibiotic persistence were reviewed with the aim to identify methods for monitoring DNA transferability and environmental conditions promoting such diffusion.

Toluene Adsorption by Mesoporous Silicas with Different Textural Properties: A Model Study for VOCs Retention and Water Remediation.

In this work, different mesoporous silicas were studied as potential sorbents for toluene, selected as a model molecule of aromatic organic fuel-based pollutants. Three siliceous materials with different textural and surface properties (i.e., fumed silica and mesoporous Santa Barbara Amorphous (SBA)-15 and Mobil Composition of matter (MCM)-41 materials) were considered and the effect of their physico-chemical properties on the toluene adsorption process was studied. In particular, FT-IR spectroscopy was used to qualitatively study the interactions between the toluene molecule and the surface of silicas, while volumetric adsorption analysis allowed the quantitative determination of the toluene adsorption capacity. The combined use of these techniques revealed that textural properties of the sorbents, primarily porosity, are the driving forces that control the adsorption process. Considering that, under real conditions of usage, the sorbents are soaked in water, their hydrothermal stability was also investigated and toluene adsorption by both the gas and aqueous phase on hydrothermally pre-treated samples was studied. The presence of ordered porosity, together with the different pore size distribution and the amount of silanol groups, strongly affected the adsorption process. In toluene adsorption from water, SBA-15 performed better than MCM-41.

Resource use efficiency of indoor lettuce (Lactuca sativa L.) cultivation as affected by red:blue ratio provided by LED lighting.

LED lighting in indoor farming systems allows to modulate the spectrum to fit plant needs. Red (R) and blue (B) lights are often used, being highly active for photosynthesis. The effect of R and B spectral components on lettuce plant physiology and biochemistry and resource use efficiency were studied. Five red:blue (RB) ratios (0.5-1-2-3-4) supplied by LED and a fluorescent control (RB = 1) were tested in six experiments in controlled conditions (PPFD = 215 µmol m-2 s-1, daylength 16 h). LED lighting increased yield (1.6 folds) and energy use efficiency (2.8 folds) as compared with fluorescent lamps. Adoption of RB = 3 maximised yield (by 2 folds as compared with RB = 0.5), also increasing leaf chlorophyll and flavonoids concentrations and the uptake of nitrogen, phosphorus, potassium and magnesium. As the red portion of the spectrum increased, photosystem II quantum efficiency decreased but transpiration decreased more rapidly, resulting in increased water use efficiency up to RB = 3 (75 g FW L-1 H2O). The transpiration decrease was accompanied by lower stomatal conductance, which was associated to lower stomatal density, despite an increased stomatal size. Both energy and land surface use efficiency were highest at RB ≥ 3. We hereby suggest a RB ratio of 3 for sustainable indoor lettuce cultivation.

Unraveling the Role of Red:Blue LED Lights on Resource Use Efficiency and Nutritional Properties of Indoor Grown Sweet Basil.

Indoor plant cultivation can result in significantly improved resource use efficiency (surface, water, and nutrients) as compared to traditional growing systems, but illumination costs are still high. LEDs (light emitting diodes) are gaining attention for indoor cultivation because of their ability to provide light of different spectra. In the light spectrum, red and blue regions are often considered the major plants' energy sources for photosynthetic CO2 assimilation. This study aims at identifying the role played by red:blue (R:B) ratio on the resource use efficiency of indoor basil cultivation, linking the physiological response to light to changes in yield and nutritional properties. Basil plants were cultivated in growth chambers under five LED light regimens characterized by different R:B ratios ranging from 0.5 to 4 (respectively, RB0.5, RB1, RB2, RB3, and RB4), using fluorescent lamps as control (CK1). A photosynthetic photon flux density of 215 µmol m-2 s-1 was provided for 16 h per day. The greatest biomass production was associated with LED lighting as compared with fluorescent lamp. Despite a reduction in both stomatal conductance and PSII quantum efficiency, adoption of RB3 resulted in higher yield and chlorophyll content, leading to improved use efficiency for water and energy. Antioxidant activity followed a spectral-response function, with optimum associated with RB3. A low RB ratio (0.5) reduced the relative content of several volatiles, as compared to CK1 and RB ≥ 2. Moreover, mineral leaf concentration (g g-1 DW) and total content in plant (g plant-1) were influences by light quality, resulting in greater N, P, K, Ca, Mg, and Fe accumulation in plants cultivated with RB3. Contrarily, nutrient use efficiency was increased in RB ≤ 1. From this study it can be concluded that a RB ratio of 3 provides optimal growing conditions for indoor cultivation of basil, fostering improved performances in terms of growth, physiological and metabolic functions, and resources use efficiency.

Effect of undesalted dissolved organic matter from composts on persistence, adsorption, and mobility of cyhalofop herbicide in soils.

The effect of undesalted dissolved organic matter (DOM) extracted from composts on the degradation, adsorption, and mobility of cyhalofop herbicide in soils was studied. A paddy-field sediment poor in organic matter (OM), an OM-rich forest soil, and DOM from agroindustrial or municipal waste compost were used. DOM increased the cyhalofop-acid but not the cyhalofop-butyl solubility in water. The degradation of cyhalofop-butyl in the sediment was slow, giving cyhalofop-acid as the only metabolite, whereas in forest soil, the process was faster, and three byproducts were detected. Soil pretreatment with DOM did not modify the degradation pattern but only reduced the adsorption of cyhalofop-butyl by soil, whereas it increased the adsorption of cyhalofop-acid. Among the cationic components of DOM solutions, the potassium ion seems to be related to the increased adsorption of the cyhalofop-acid in both OM-poor and OM-rich soils, yielding reversible complexes with the former and favoring hydrophobic interactions with the latter.

Lethal effects of Cr(III) alone and in combination with propiconazole and clothianidin in honey bees.

Several anthropogenic contaminants, including pesticides and heavy metals, can affect honey bee health. The effects of mixtures of heavy metals and pesticides are rarely studied in bees, even though bees are likely to be exposed to these contaminants in both agricultural and urban environments. In this study, the lethal toxicity of Cr alone and in combination with the neonicotinoid insecticide clothianidin and the ergosterol-biosynthesis-inhibiting fungicide propiconazole was assessed in Apis mellifera adults. The LD50 and lowest benchmark dose of Cr as Cr(NO3)3, revealed a low acute oral toxicity on honey bee foragers (2049 and 379 mg L-1, respectively) and the Cr retention (i.e. bee ability to retain the heavy metal in the body) was generally low compared to other metals. A modified method based on the binomial proportion test was developed to analyse synergistic and antagonistic interactions between the three tested contaminants. The combination of an ecologically-relevant field concentration of chromium with clothianidin and propiconazole did not increase bee mortality. On the contrary, the presence of Cr in mixture with propiconazole elicited a slight antagonistic effect.

Effect of humic monomers on the adsorption of sulfamethoxazole sulfonamide antibiotic into a high silica zeolite Y: An interdisciplinary study.

The adsorption efficiency of a high silica zeolite Y towards sulfamethoxazole, a sulfonamide antibiotic, was evaluated in the presence of two humic monomers, vanillin and caffeic acid, representative of phenolic compounds usually occurring in water bodies, owing their dimension comparable to those of the zeolite microporosity. In the entire range of investigated pH (5-8), adsorption of vanillin, as a single component, was reversible whereas it was irreversible for sulfamethoxazole. In equimolar ternary mixtures, vanillin coadsorbed with sulfamethoxazole, conversely to what observed for caffeic acid, accordingly to their adsorption kinetics and pKa values. Lower and higher adsorptions were observed for sulfamethoxazole and vanillin, respectively, than what it was observed as single components, clearly revealing guest-guest interactions. An adduct formed through H-bonding between the carbonyl oxygen of vanillin and the heterocycle NH of sulfamethoxazole in amide form was observed in the zeolite pore by combined FTIR and Rietveld analysis, in agreement with Density Functional Theory calculations of the adduct stabilization energies. The formation of similar adducts, able to stabilize other naturally occurring phenolic compounds in the microporosities of hydrophobic sorbents, was proposed.

Adsorption and desorption of triasulfuron by soil.

The adsorption and desorption of the herbicide triasulfuron [2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide] by three soils, soil organic matter (H(+) and Ca(2+)-saturated), and an amorphous iron oxide were studied. Adsorption isotherms conformed to the Freundlich equation. It was found that pH is the main factor influencing the adsorption in all of the systems. Indeed, the adsorption on soils was negatively correlated with pH. The highest level of adsorption was measured on soils with low pH and high organic carbon content. Moreover, it was found that humic acid is more effective in the adsorption compared with calcium humate (the pH values of the suspensions being 3.5 and 6, respectively). Experiments on amorphous iron oxide confirmed the pH dependence. Desorption was hysteretic on soils having high organic carbon content.

Identification of volatile markers in potato brown rot and ring rot by combined GC-MS and PTR-MS techniques: study on in vitro and in vivo samples.

Ralstonia solanacearum (Rs) and Clavibacter michiganensis subsp. sepedonicus (Cms) are the bacterial causal agents of potato brown and ring rot, respectively, and are included in the A2 list of quarantine pathogens in Europe. Identification by GC-MS analysis of volatile organic compounds from Rs or Cms cultured on different nutrient media was performed. GC-MS and PTR-MS analysis were carried out also on unwounded potato tubers infected with the same pathogens. Infected tubers were produced by experimental inoculations of the plants. In in vitro experiments, Rs or Cms emitted volatile compounds, part of which were specific disease markers of potato (2-propanol and 3-methylbutanoic acid), mainly originating from bacterial metabolism (i.e., amino acid degradation, carbohydrate and fatty acid oxidation). In potato tubers, pathogen metabolism modified the volatile compound pattern emitted from healthy samples. Both bacteria seem to accelerate metabolic processes ongoing in potatoes and, in the case of Rs, disease markers (1-hepten-3-ol, 3,6-dimethyl-3-octanone, 3-ethyl-3-methylpentane, 1-chloroctane, and benzothiazole) were identified.

Removal of sulfamethoxazole sulfonamide antibiotic from water by high silica zeolites: a study of the involved host-guest interactions by a combined structural, spectroscopic, and computational approach.

Sulfonamide antibiotics are persistent pollutants present in surface and subsurface waters in both agricultural and urban environments. Sulfonamides are of particular concern in the environment because they are known to induce high levels of bacterial resistance. Adsorption of sulfamethoxazole sulfonamide antibiotic into three high silica zeolites (Y, mordenite, and ZSM-5) with pore opening sizes comparable to sulfamethoxazole dimensions is reported. Sulfamethoxazole was almost completely removed from water by zeolite Y and MOR in a few minutes. Adsorption onto ZSM-5 showed an increased kinetics with increasing temperature. Antibiotic sorption was largely irreversible with little antibiotic desorbed. Sulfamethoxazole incorporation and localization into the pore of each zeolite system was defined along with medium-weak and cooperative host-guest interactions in which water molecules play a certain role only in zeolite Y and mordenite.

Removal of sulfonamide antibiotics from water: Evidence of adsorption into an organophilic zeolite Y by its structural modifications.

Sulfonamide antibiotics are persistent pollutants of aquatic bodies, known to induce high levels of bacterial resistance. We investigated the adsorption of sulfadiazine, sulfamethazine, and sulfachloropyridazine sulfonamides into a highly dealuminated faujasite zeolite (Y) with cage window sizes comparable to sulfonamide dimensions. At maximal solubility the antibiotics were almost completely (>90%) and quickly (t<1min) removed from the water by zeolite. The maximal amount of sulfonamides adsorbed was 18-26% DW of dry zeolite weight, as evidenced by thermogravimetric analyses and accounted for about one antibiotic molecule per zeolitic cage. The presence of this organic inside the cage was revealed by unit cell parameter variations and structural deformations obtained by X-ray structure analyses carried out using the Rietveld method on exhausted zeolite. The most evident deformation effects were the lowering of the Fd-3m real symmetry in the parent zeolite to Fd-3 and the remarkable deformations which occurred in the 12-membered ring cage window after sulfadiazine or sulfachloropyridazine adsorption. After sulfamethazine adsorption, zeolite deformation caused a lowering in symmetry up to the monoclinic P2/m space group. The effective and irreversible adsorption of sulfonamides into organophylic Y zeolite makes this cheap and environmentally friendly material a suitable candidate for removing sulfonamides from water.