Caracterización y modelización teórica de nuevos agentes quelantes análogos al EDDHE para su uso como fertilizantes

Tesis Doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento Química Agrícola, Geología y Geoquímica, Fecha de lectura 18-07-200

Modeling arsenic in European topsoils with a coupled semiparametric (GAMLSS-RF) model for censored data

Arsenic (As) is a versatile heavy metalloid trace element extensively used in industrial applications. As is carcinogen, poses health risks through both inhalation and ingestion, and is associated with an increased risk of liver, kidney, lung, and bladder tumors. In the agricultural context, the repeated application of arsenical products leads to elevated soil concentrations, which are also affected by environmental and management variables. Since exposure to As poses risks, effective assessment tools to support environmental and health policies are needed. However, the most comprehensive soil As data available, the Land Use/Cover Area frame statistical Survey (LUCAS) database, contains severe limitations due to high detection limits. Although within International Or- ganization for Standardization standards, the detection limits preclude the adoption of standard methodologies for data analysis. The present work focused on developing a new method to model As contamination in European soils using LUCAS soil samples. We introduce the GAMLSS-RF model, a novel approach that couples Random Forests with Generalized Additive Models for Location, Scale, and Shape. The semiparametric model can capture non-linear interactions among input variables while accommodating censored and non-censored observations and can be calibrated to include information from other campaign databases. After fitting and validating a spatial model, we produced European-scale As concentration maps at a 250 m spatial resolution and evaluated the patterns against reference values (i.e., two action levels and a background concentration). We found a significant variability of As concentration across the continent, with lower concentrations in Northern countries and higher concentrations in Portugal, Spain, Austria, France and Belgium. By overcoming limitations in existing databases and methodologies, the present approach provides an alternative way to handle highly censored data. The model also consists of a valuable probabilistic tool for assessing As contamination risks in soils, contributing to informed policy-making for environmental and health protection

Synthesis and characterization of nano Fe and Mn (hydr)oxides to be used as natural sorbents and micronutrient fertilizers

Fe and Mn (hydr)oxides are widely used as contaminant sorbents in water/wastewater systems but their potential use as micronutrient fertilizers is still poorly known. In this research, four nano-metal (hydr)oxides (amorphous Mn oxide (AMO), Fe-Mn binary oxide (FMBO), two-line ferrihydrite (2L-Fh) and goethite) were successfully synthesized and completely characterized (infrared and Mössbauer spectroscopy, X-ray diffraction particle size, specific surface area, point of zero charge). AMO, FMBO and 2L-Fh were introduced to interact with AgNO3 (20.0 µM) and TlNO3 (100.0 µM) diluted solutions for three days to check their potential capability as potential Ag+ and Tl+ adsorbents. AMO and FMBO (4% w/w) were tested as nanofertilizers by arranging a hydroponic bioassay for 35 days on white lupin culture as a Mn-hyperaccumulator plant model. AMO structure was identified as an amorphous mixture of Mn oxides while FMBO was an Fe dopped birnessite. Both materials were efficient in extracting Ag+ and Tl+ although large Mn concentration was released from FMBO to the solutions. AMO and FMBO promoted Fe and Mn nutrition in plants. Synthetic iron chelate (Fe-EDDHA), present in the nutrient dissolution, could be adsorbed onto AMO surface by producing Fe and Mn accumulation in roots and increasing Mn uptake rate without toxicity symptoms. Therefore, AMO and FMBO not only demonstrated their efficiency as adsorbents, but also displayed they would be promising nanomaterials as micronutrient fertilizer

Evaluation of the sorption potential of mineral materials using tetracycline as a model pollutant

Tetracycline (TC) is among the most used antibiotics in animal feedstock in the EU. Antibiotics’ persistence as emerging pollutants in the environment is evidenced by their long half-life in residual organic-mineral sediments and waters. The risk associated with this persistence favours antibiotic-resistant microbiota, affecting human health and ecosystems. The purpose of the present work is to assess the adsorption of TC into natural clay minerals, synthetic iron hydroxides and calcined sewage sludge. TC adsorption isotherms were performed in three replicated batch tests at three di erent pH values (4, 6, 8) and TC concentrations (33–1176 mg.L−1). X-Ray di raction (XRD) mineralogy, cation exchange capacity (CEC), Brunauer, Emmett and Teller specific surface area (BET-SSA) and point of zero charge salt effect (PZSE) were determined for the characterization of materials. Sorption was analysed by means of fitting Langmuir and Freundlich adsorption models, which showed good fitting parameters for the studied materials. Low-charge montmorillonite (LC Mnt) is displays the best sorption capacity for TC at maximum TC concentration (350–300 mgTC.g−1) in the whole range of pH (4–8). Sepiolite and smectites adsorbed 200–250 mgTC.g−1, while illite, calcined sludge or iron hydroxides present the lowest adsorption capacity (<100 mgTC.g−1). Nevertheless, illite, sepiolite and ferrihydrite display high adsorption intensities at low to medium TC concentrations (<300 mg.L−1), even at pH 8, as is expected in wastewater environmental conditionsThis work has been economically supported by the Ministry of Economy and Competitiveness of Spain (CTM2013-47874-C2-2-R and AGL2016-78490-R)

Stevensite-based geofilter for the retention of tetracycline from water

The antibiotic tetracycline, is considered a contaminant of emerging concern due to its presence in wastewater effluents, surface waters and groundwaters. Adsorption of tetracycline on soils and clays has been extensively studied to remove the contaminant from the water. A decreasing adsorption as the pH increases is normally reported in the pH range 3–9. However, adsorption isotherms performed on a commercial stevensite presented increasing adsorption with the increasing pH, in the pH range 2–8. This is very interesting since the pH in natural and wasterwaters are normally in the range 6–8. A laboratory design of a geofilter using a mixture of sand and stevensite was tested against an inflow solution of tetracycline 1 g/L, NaNO3 0.1 M and pH = 7 in an advective transport cell experiment. The number of tetracycline molecules exceed by >3 times the number exchangeable positions in the stevensite geofilter. Under these conditions, the TC adsorption on the geofilter reaches 590 mg/g, surpassing the retention capacity of most adsorbents found in literature. Besides, the tetracycline is completely desorbed by the inflow of a saline solution (Mg(NO3)2 0.5 M, at pH = 2) with capacity to replace the exchangeable positions, thus, recovering the geofilter and the tetracyclineThis work has been financially supported by the Spanish Ministry of Economy and Competitiveness through the AGL2016-78490-R projec

Modeling arsenic in European topsoils with a coupled semiparametric (GAMLSS-RF) model for censored data

International audienc