Impacts of cattle management and agricultural practices on water quality through different approaches: physicochemical and ecotoxicological parameters.

The intensification of livestock farming can pose risks to the environment due to the increased use of veterinary products and the generation of waste in confined areas. The quality of water bodies near livestock establishments (Areco River (A) and Doblado stream (D), San Antonio de Areco, Buenos Aires, Argentina) was studied by physicochemical parameters, metals, pesticides, emerging contaminants, and lethal and sublethal toxicity (neurotoxicity and oxidative stress) in larvae of the native amphibian Rhinella arenarum. Six sites were selected: upstream (S1A and S1D), at the level (S2A and S2D), and downstream (S3A and S3D) from the establishments. A low concentration of dissolved oxygen was observed in Doblado stream (< 2.34 mg/L). Cu, Mn, V, and Zn exceeded the limits for the protection of aquatic life at various sites. Between 24 and 34 pesticides were detected in all sites, with 2,4-D, atrazine, and metolachlor being the most recurrent. In water and sediment, the concentrations of ivermectin (S2A, 1.32 µg/L and 58.18 µg/kg; S2D, 0.8 µg/L and 85.22 µg/kg) and oxytetracycline (S2A, < 1 mg/L and < 1 mg/kg; S2D, 11.8 mg/L and 39 mg/kg) were higher at sites near the establishments. All sites caused between 30 and 38.3% of lethality and produced neurotoxicity and alterations in the reduced glutathione content. Moreover, larvae exposed to samples from all sites incorporated ivermectin. These results demonstrate the degradation of the studied sites in relation to the agricultural activities of the area, highlighting the need to take measures to protect and preserve aquatic ecosystems.

Assessing the transformation products and fate of Oxytetracycline by simulated aerobic degradation tests.

Oxytetracycline (OTC) is a widely used broad-spectrum antibiotic, whose presence in water and sediments was reported in various regions of the world. The effects of OTC and other tetracyclines on the environment have been intensively studied although many of their transformation products (TPs) formed in the environment and their impact have not been yet fully characterized. Abiotic and biotic degradation tests under aerobic conditions at two pH values were carried out using OTC in artificial water/sediment systems to assess the effect of these variables on the environmental fate of the pollutant. HPLC-MSn was employed to detect and identify the main degradation products and pathways. Several transformations involved in the process were identified including alcohol oxidation, decarbonylation and hydroxylation. Differences in TPs and kinetics were found among degradation conditions, remarking a faster degradation of both OTC and TPs in the presence of microorganisms and at lower pH values. In summary, a total of 44 TPs were detected and structures were proposed for 20 of them, none of them having been previously reported. Furthermore, OTC degradation generated 24 TPs which remained in either solution or sediment, although none of them displayed higher algae toxicity than OTC. These results might be useful for planning future remediation and monitoring strategies.

Metals, pesticides, and emerging contaminants on water bodies from agricultural areas and the effects on a native amphibian.

In the Paraná River lower basin, an important agro-productive area of Argentina, crop fields and cattle breeding activities are common and may affect water quality. So, the aim of this study was to analyze the impacts of cattle breeding and agricultural activities on a stream from Buenos Aires, through physicochemical parameters (metals, pesticides, and emerging contaminants) and ecotoxicological parameters with Rhinella arenarum larvae, a native amphibian species. Three sites were selected on an ordinary plain stream that goes through agricultural fields and a cattle breeding establishment (upstream -S1-, near -S2- and downstream -S3- the establishment). Physicochemical parameters were measured in situ (in water) and in laboratory (in water and sediment samples: metals, pesticides, ivermectin and oxytetracycline). A semi-static chronic toxicity bioassay (504 h) was performed with water samples, and neurotoxicity, oxidative stress and genotoxicity biomarkers were measured after acute exposure (96 h). According to the index, a degradation in the water quality was observed in all sites. Ivermectin (8.03 mg/kg) and oxytetracycline (1.9 mg/kg) were detected in sediment samples from S2. Pesticides were detected in all sites, mainly in water samples: S1 presented the highest variability (7 residues) and in S3 AMPA, glyphosate and acetochlor concentrations were higher (10.3, 22.4 and 23.8 µg/L). Also, all sites significantly produced lethality at chronic exposure. Lethality at 504h was 40% for S1, 56.66% for S2 and 93.33% for S3. At acute exposure, the oxidative stress biomarkers were altered on R. arenarum larvae exposed to all sites and the neurotoxicity biomarkers were altered on larvae exposed to S1 and S3. Water quality was severely degraded by the surrounding agricultural and cattle breeding activities, which may represent a threat to the ecosystems.

Effect of TiO2 Nanoparticles and Extrusion Process on the Physicochemical Properties of Biodegradable and Active Cassava Starch Nanocomposites.

Biodegradable polymers have been strongly recognized as an alternative to replace traditional petrochemical plastics, which have become a global problem due to their long persistence in the environment. In this work, the effect of the addition of titanium dioxide nanoparticles (TiO2NP) on the morphology, physicochemical properties and biodegradation under industrial composting conditions of cassava starch-based nanocomposites obtained by extrusion at different screw speeds (80 and 120 rpm) were investigated. Films performed at 120 rpm (S120 and S120-TiO2NP) showed completely processed starch and homogeneously distributed nanoparticles, leading to much more flexible nanocomposites than those obtained at 80 rpm. The incorporation of TiO2NP led to an increase in storage modulus of all films and, in the case of S120-TiO2NP, to higher strain at break values. From the Kohlrausch-Williams-Watts theoretical model (KWW), an increase in the relaxation time of the nanocomposites was observed due to a decrease in the number of polymer chains involved in the relaxation process. Additionally, S120-TiO2NP showed effective protection against UV light, greater hydrophobicity and faster biodegradation in compost, resulting in a promising material for food packaging applications.

Effects of the geometry of reinforcement on physical properties of sodium caseinate/TiO2 nanocomposite films for applications in food packaging.

Plastic materials for food packaging are being replaced by biodegradable films based on biopolymers due to the adverse effects they have had on animal life and the environment. In this study, nanocomposite films containing 2.5 wt% sodium caseinate and 2 wt% glycerol were reinforced with 0.1 or 0.2 wt% nano TiO2 prepared in two forms: spheres (P25) and tubes. The effects of nanoreinforcement geometry on mechanical, tensile, barrier, thermogravimetric, and optical properties, and distribution of nanoparticles were described. The interactions among film components were analyzed by Fourier transform infrared spectroscopy (FTIR). Addition of nanotubes significantly increased E' (341 wt%) and E" (395 wt%) moduli, the Young modulus E (660 wt%), the residual mass at 500°C (38 wt%), and color change (6.78) compared to control film. The compositional mapping studies showed that P25 nanoparticles were homogeneously distributed between the surfaces of the film while nanotubes were found on the bottom surface. The changes in position of the FTIR spectra signals as compared to pure protein signals indicated strong matrix/reinforcement interactions. In addition, the changes in intensity in 1100, 1033, and 1638 cm-1 FTIR signals suggested formation of a protein/Tween 20 ester. The geometry of reinforcement was highly relevant regarding physical properties, showing nanotubes as being very successful for enhancing tensile properties.

Nanoreinforcement as a strategy to improve physical properties of biodegradable composite films based on biopolymers.

Food packaging is evolving from inert plastic to renewable biopolymer film that acts as barrier against gases, light radiation, and microorganisms, reducing food waste without environmental damage. Distinct starting systems were selected to prepare films: single polymer matrix, blend of polymers, cross-linked polymers, and emulsion-based matrix. The blend of polymers was one of the best approaches to improve mechanical and barrier properties of films, especially when one of the polymers was pectin, gelatin or xanthan gum. These polymers can form a gel and increase the viscosity of the starting systems leading to a more elastic matrix. Although some of these films showed potential to replace plastic materials, their physical properties were poor compared to plastics. Thus, several strategies were used to strengthen matrix building block connections or interactions between nanoreiforcement and matrix compounds with the aim of improving physical properties. Among metal oxides, TiO2, ZnO, CaO, and MgO were the most studied, alone or in combinations with other reinforcements. Natural fillers, like chitosan and cellulose nanofibers were also added to improve the biopolymer's performance. Several of these systems successfully extended the shelf life of food systems by retarding spoilage, showing great potential to improve food quality and reduce waste. However, most of the studies were carried out on a laboratory scale and it would be necessary to explore the feasibility of producing these films on an industrial scale.

Metal-Pseudomonas veronii 2E Interactions as Strategies for Innovative Process Developments in Environmental Biotechnology.

The increase of industrial discharges is the first cause of the contamination of water bodies. The bacterial survival strategies contribute to the equilibrium restoration of ecosystems being useful tools for the development of innovative environmental biotechnologies. The aim of this work was to study the Cu(II) and Cd(II) biosensing, removal and recovery, mediated by whole cells, exopolymeric substances (EPS) and biosurfactants of the indigenous and non-pathogenic Pseudomonas veronii 2E to be applied in the development of wastewater biotreatments. An electrochemical biosensor was developed using P. veronii 2E biosorption mechanism mediated by the cell surface associated to bound exopolymeric substances. A Carbon Paste Electrode modified with P. veronii 2E (CPEM) was built using mineral oil, pre-washed graphite power and 24 h-dried cells. For Cd(II) quantification the CPEM was immersed in Cd(II) (1-25 µM), detected by Square Wave Voltammetry. A similar procedure was used for 1-50 µM Cu(II). Regarding Cd(II), removal mediated by immobilized EPS was tested in a 50 ml bioreactor with 0.13 mM Cd(II), pH 7.5. A 54% metal retention by EPS was achieved after 7 h of continuous operation, while a 40% was removed by a control resin. In addition, surfactants produced by P. veronii 2E were studied for recovery of Cd(II) adsorbed on diatomite, obtaining a 36% desorption efficiency at pH 6.5. Cu(II) adsorption from a 1 mM solution was tested using P. veronii 2E purified soluble EPS in 50 mL- batch reactors (pH = 5.5, 32°C). An 80% of the initial Cu(II) was retained using 1.04 g immobilized EPS. Focusing on metal recovery, Cu nanoparticles (NPs) biosynthesis by P. veronii 2E was carried out in Cu(II)-PYG Broth at 25°C for 5 days. Extracellular CuNPs were characterized by UV-Vis spectral analysis while both extracellular and intracellular NPs were analyzed by SEM and TEM techniques. Responses of P. veronii 2E and its products as biosurfactants, bound and soluble EPS allowed Cu(II) and Cd(II) removal, recovery and biosensing resulting in a multiple and versatile tool for sustainable wastewater biotreatments.

Arsenate removal from aqueous solution by montmorillonite and organo-montmorillonite magnetic materials.

Magnetic-clay (MtMag) and magnetic-organoclay (O100MtMag) nanocomposites were synthesized, characterized and evaluated for arsenic adsorption. Batch arsenic adsorption experiments were performed varying pH conditions and initial As(V) concentration, while successive adsorption cycles were made in order to evaluate the materials reuse. The highest As(V) removal efficiency (9 ± 1 mg g-1 and 7.8 ± 0.8 mg g-1 for MtMag and O100MtMag, respectively) was found at pH 4.0, decreasing at neutral and alkaline conditions. From As(V) adsorption isotherm, two adsorption processes or two different surface sites were distinguished. Nanocomposites resulted composed by montmorillonite or organo-montmorillonite and magnetite as the principal iron oxide, with saturation magnetization of 8.5 ± 0.5 Am2 Kg-1 (MtMag) and 20.3 ± 0.5 Am2 Kg-1 (O100MtMag). Thus, both materials could be separated and recovered from aqueous solutions using external magnetic fields. Both materials allowed achieving arsenic concentrations lower than the World Health Organization (WHO) recommended concentration limit after two consecutive adsorption cycles (2.25 and 4.5 µg L-1 for MtMag and O100MtMag, respectively).

Structural characterization of nanoemulsions stabilized with sodium caseinate and of the hydrogels prepared from them by acid-induced gelation.

Hydrogels obtained by acidification with glucono-δ-lactone (GDL), starting from nanoemulsions formulated with different concentrations of sodium caseinate (1-4 wt%) or 4 wt% sodium caseinate and sucrose (2-8 wt%), were prepared with the aim of quantifying structural parameters of both, initial nanoemulsions and hydrogels after 2.5 h of GDL addition, using the Guinier-Porod (GP) or the generalized GP models. Gelation process was followed by performing in situ temperature-controlled X-ray small angle scattering experiments (SAXS) using synchrotron radiation. In nanoemulsions, the calculated radius of gyration for oil nanodroplets (Rg oil ) decreased with increasing protein concentration and for the 4 wt% protein nanoemulsion, with increasing sucrose content. Calculated values of Rg oil were validated correlating them with experimental Z-average values as measured by dynamic light scattering (DLS). For hydrogels, radii of gyration for the sphere equivalent to the hydrogel scattering object (R gsph ) were close to 3 nm while correlation distances among building blocks (R g2 ) were dependent on formulation. They increased with increasing contents of sodium caseinate and sucrose. R g2 parameter linearly correlated with hydrogel strength (G' ∞ ): a more connected nanostructure led to a stronger hydrogel.

TiO2 and N-TiO2-photocatalytic degradation of salicylic acid in water: characterization of transformation products by mass spectrometry.

The aim of this work is to study the byproducts formed as a result of the photocatalytic process under different conditions of light wavelength and photocatalyst doping, rendering valuable information about the fate of pollutants for water treatment applications. Salicylic acid was selected as a model emerging pollutant and powders of nitrogen-doped titanium dioxide (N-TiO2) and TiO2 were prepared by the sol-gel process, using TiO2 P-25 Degussa as benchmark. Two light sources, UVA fluorescent tubes (372 nm) and blue LEDs (462 nm), were employed for photolysis and photocatalysis experiments. Transformation products formed during the process were studied by high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS). Major differences were found in the amount and identity of the transformation products due to the different light sources, detecting similar transformation products among the studied catalysts. Under UVA light, hydroxylated and carbonylated byproducts were the first intermediates to reach maximum abundances whereas presumed ring opening products were the last ones. On the other hand, under blue LED illumination byproducts accumulated with decreased mineralization. Photocatalytic degradation pathways were proposed based on the findings.

Performance of semi-continuous anaerobic co-digestion of poultry manure with fruit and vegetable waste and analysis of digestate quality: A bench scale study.

Poultry manure (PM) can contain ammonium and ammonia nitrogen, which may inhibit the anaerobic process. The aim of this work was to evaluate the performance of anaerobic digestion of PM co-digested with fruit and vegetable waste. Two semi-continuous bench scale (19L) stirred tank reactors were used. The operating conditions were: 34.5 °C, 2 gVS/L.d (organic load rate), 28 d of hydraulic retention time and 100 revolutions per m (1 h × 3 times by day) for the agitation. The reactors were fed PM and a mixture of PM and fruit and vegetable waste (FVW) at equal proportions (based on wet weight). The performance of the anaerobic process was assessed through biogas and methane yields, reduction of organic matter, release of nitrogen compounds and the monitoring of stability indicators (pH, volatile fatty acids (VFA), total (TA) and partial (PA) alkalinity). Moreover, the digestate quality was evaluated to determine potential risk and benefits from its application as biofertilizer. Toxicity was assessed using Daphnia magna immobilization tests. Results showed that biogas and methane yields from PM-FVW were 31% and 32% higher than PM alone, respectively. Values of organic matter, pH, alpha (PA/TA) and VFA revealed that stability was approached in PM and PM-FVW. The co-digestion of PM with FVW led to the highest methane and biogas yields, lower FAN and TAN concentrations, and a better digestate quality compared to mono-digestion of this manure.

Relationship between nano/micro structure and physical properties of TiO2-sodium caseinate composite films.

Films obtained by casting, starting from conventional emulsions (CE), nanoemulsions (NE) or their gels, which led to different structures, with the aim of explore the relationship between structure and physical properties, were prepared. Sodium caseinate was used as the matrix, glycerol as plasticizer, glucono-delta-lactone as acidulant to form the gels, and TiO2 nanoparticles as reinforcement to improve physical behavior. Structural characterization was performed by SAXS and WAXS (Small and Wide Angle X-ray Scattering, respectively), combined with confocal and scanning electron microscopy. The results demonstrate that the incorporation of the lipid phase does not notably modify the mechanical properties of the films compared to solution films. Films from NE were more stable against oil release than those from CE. Incorporation of TiO2 improved mechanical properties as measured by dynamical mechanical analysis (DMA) and uniaxial tensile tests. TiO2 macroscopic spatial distribution homogeneity and the nanostructure character of NE films were confirmed by mapping the q-dependent scattering intensity in scanning SAXS experiments. SAXS microscopies indicated a higher intrinsic homogeneity of NE films compared to CE films, independently of the TiO2 load. NE-films containing structures with smaller and more homogeneously distributed building blocks showed greater potential for food applications than the films prepared from sodium caseinate solutions, which are the best known films.

Degradation alternatives for a commercial fungicide in water: biological, photo-Fenton, and coupled biological photo-Fenton processes.

Imazalil (IMZ) is a widely used fungicide for the post-harvest treatment of citrus, classified as "likely to be carcinogenic in humans" for EPA, that can be only partially removed by conventional biological treatment. Consequently, specific or combined processes should be applied to prevent its release to the environment. Biological treatment with adapted microorganism consortium, photo-Fenton, and coupled biological photo-Fenton processes were tested as alternatives for the purification of water containing high concentration of the fungicide and the coadjutants present in the commercial formulation. IMZ-resistant consortium with the capacity to degrade IMZ in the presence of a C-rich co-substrate was isolated from sludge coming from a fruit packaging company wastewater treatment plant. This consortium was adapted to resist and degrade the organics present in photo-Fenton-oxidized IMZ water solution. Bacteria colonies from the consortia were isolated and identified. The effect of H2O2 initial concentration and dosage on IMZ degradation rate, average oxidation state (AOS), organic acid concentration, oxidation, and mineralization percentage after photo-Fenton process was determined. The application of biological treatment to the oxidized solutions notably decreased the total organic carbon (TOC) in solution. The effect of the oxidation degree, limited by H2O2 concentration and dosage, on the percentage of mineralization obtained after the biological treatment was determined and explained in terms of changes in AOS. The concentration of H2O2 necessary to eliminate IMZ by photo-Fenton and to reduce TOC and chemical oxygen demand (COD) by biological treatment, in order to allow the release of the effluents to rivers with different flows, was estimated.

Metal bioleaching from anaerobic sediments from Reconquista River basin (Argentina) as a potential remediation strategy.

Anaerobic sediments of urban watercourses are subjected to industrial pollution and frequently tend to accumulate heavy metals. The biocatalyzed oxidation and reduction of sulphur compounds that occur within the sediment are key reactions that determine mobility of metals such as that occurred in mine acidic drainage reactions. The aim of this work was to study the application of these processes using heap leaching technology for the remediation of anaerobic contaminated sediments from Reconquista River basin. The bioleaching potentiality for remediation was demonstrated through batch tests in shake flasks with different pulp densities of anaerobic sediment containing 338 mg kg-1 of Zn and 117 mg kg-1 of Cu. Subsequently, bioleaching heap systems were compiled into columns of 12-cm height and 6-cm diameter, fitted with perlite to improve drainage. In order to assess the effect of elementary sulphur over the mobility of metals from the bioheap to the aqueous solution, increasing concentrations of elementary sulphur (1, 2, 5 % w/w) were added. After 3 months of acidification generated by periodic watering, the extraction of 70 % of the initial Zn and 43 % of the initial Cu was achieved. Polluted sediments from waterways as Reconquista River should not be indiscriminately manipulated if acid drainage is possible. Remediation by a simple and economically viable strategy like heap leaching is feasible.

New insights about flocculation process in sodium caseinate-stabilized emulsions.

Flocculation process was studied in emulsions formulated with 10wt.% sunflower oil, 2, 5 or 7.5wt.% NaCas, and with or without addition of sucrose (0, 5, 10, 15, 20 or 30wt.%). Two different processing conditions were used to prepare emulsions: ultraturrax homogenization or further homogenization by ultrasound. Emulsions with droplets with diameters above (coarse) or below (fine) 1µm were obtained. Emulsions were analyzed for droplet size distribution by static light scattering (SLS), stability by Turbiscan, and structure by confocal laser scanning microscopy (CLSM) and small angle X-ray scattering (SAXS). SAXS data were fitted by a theoretical model that considered a system composed of poly dispersed spheres with repulsive interaction and presence of aggregates. Flocculation behavior was caused by the self-assembly properties of NaCas, but the process was more closely related to interfacial protein content than micelles concentration in the aqueous phase. The results indicated that casein aggregation was strongly affected by disaccharide addition, hydrophobic interaction of the emulsion droplets, and interactions among interfacial protein molecules. The structural changes detected in the protein micelles in different environments allowed understanding the macroscopic physical behavior observed in concentrated NaCas emulsions.

Improving the physical properties of starch using a new kind of water dispersible nano-hybrid reinforcement.

Plasticized cassava starch matrix composites reinforced by a multi-wall carbon nanotube (MWCNT)-hercynite (FeAl2O4) nanomaterial were developed. The hybrid nanomaterial consists of FeAl2O4 nanoparticles anchored strongly to the surface of the MWCNT. This nano-hybrid filler shows an irregular geometry, which provides a strong mechanical interlocking with the matrix, and excellent stability in water, ensuring a good dispersion in the starch matrix. The composite containing 0.04wt.% of the nano-hybrid filler displays increments of 370% in the Young's modulus, 138% in tensile strength and 350% in tensile toughness and a 70% decrease in water vapor permeability relative to the matrix material. All of these significant improvements are explained in terms of the nano-hybrid filler homogenous dispersion and its high affinity with both plasticizers, glycerol and water, which induces crystallization without deterioration of the tensile toughness.

Synthesis, characterization and photocatalytic activity of 1D TiO2 nanostructures.

Nanowire/nanorod TiO(2) structures of approximately 8 nm in diameter and around 1,000 nm long were synthesized by alkaline hydrothermal treatment of two different TiO(2) nanopowders. The first precursor was TiO(2) obtained by the sol-gel process (SG-TiO(2)); the second was the well-known commercial TiO(2) P-25 (P25-TiO(2)). Anatase-like 1D TiO(2) nanostructures were obtained in both cases. The one-dimensional (1D) nanostructures synthesized from SG-TiO(2) powders turned into rod-like nanostructures after annealing at 400 °C for 2 h. Conversely, the nanostructures synthesized from P25-TiO(2) preserved the tubular structure after annealing, displaying a higher Brunauer-Emmett-Teller surface area than the first system (279 and 97 m²/g, respectively). Despite the higher surface area shown by the 1D nanostructures, in both cases the photocatalytic activity was lower than for the P25-TiO(2) powder. However, the rod-like nanostructures obtained from SG-TiO(2) displayed slightly higher efficiency than the sol-gel prepared powders. The lower photocatalytic activity of the nanostructures with respect to P-25 can be associated with the lower crystallinity of 1D TiO(2) in both materials.

In situ synchrotron radiation X-ray scattering study on the effect of a stearic sucrose ester on polymorphic behavior of a new sunflower oil variety.

The effect of the stearic sucrose ester (SE) S-170 on crystallization behavior and polymorphism of two stearins obtained from a new variety of high stearic high oleic sunflower oil was studied by pulsed nuclear magnetic resonance (p-NMR), small (SAXS) and wide (WAXS) angle X-ray scattering using synchrotron light and differential scanning calorimetry (DSC). p-NMR studies showed that there is always a crystallization temperature below which SE S-170 accelerated crystallization and above which SE S-170 delayed nucleation and growth. The effect of SE S-170 strongly depended on supercooling. It was efficient as a seed for high supercooling (low crystallization temperatures) but this efficiency diminished at low supercooling (temperatures close to the melting point) when few crystals were formed. SAXS and WAXS results demonstrated that depending on crystallization temperature SE S-170 promoted crystallization of α and ß forms with more polymorphic similarity and inhibited occurrence of ß' forms especially the ß'2 polymorph. However, in some conditions SE S-170 favored crystallization of ß'1 polymorph. DSC experiments showed that SE S-170 significantly diminished total melting enthalpies when the effect was a delay in crystallization. For other conditions no significant differences were found in melting temperatures or total melting enthalpies. When stearins were stored at 25°C, crystallization in the ß2 form was promoted. Depending on crystallization temperature, polymorphic forms ß'1 and ß2 may be obtained as the main polymorphic forms. This is very relevant from the technological point of view. Depending on the application, SE S-170 may help obtain the required polymorphic form: ß'1 form for spreads and ß2 polymorph for chocolate production.