Bianca Ferreira da Silva

1. NATIONAL INSTITUTE FOR ALTERNATIVE TECHNOLOGIES OF DETECTION, TOXICOLOGICAL EVALUATION AND REMOVAL OF MICROPOLLUTANTS AND RADIOATICVES (INCT-DATREM) Comite gestor:

2. Bianca Ferreira da Silva Nelson R. Stradiotto

4. Objective • - to achieve progress on holistic knowledge on emerging and radioactive contaminants of environmental and • human health point of view by cooperative production between active researchers in interdisciplinary fields of • Chemistry, Engineering, Geology, Physics, Biology and Toxicology. • -new technologies for risk assessment, detection, quantification and emerging contaminants • and their by-products reduction will be developed, contributing to environment and human health protection, • regulatory legislation and barriers reduction of trade markets. • -to obtain diagnosis on industrial effluents, wastewater and contamination levels of surface water, • collecting water and water supplied to population. • -to evaluate toxicological and/or mutagenic potential concerning some emerging contaminants • and their derivatives for a better understanding of their transportation processes, bioaccumulation, persistence • and biotransformation in environment or human metabolism. • -to map the radioactivity of these waters • - to develop alternative processes of low cost and efficiency for emerging contaminants removal in complexes matrices. • The goal is to contribute to human resource formation and improvement of post-graduation degree • by collaboration between consolidated, emerging and in consolidation courses • - to contribute to actual legislation and environmental control of micropollutants and their by-products

5. GOALS AND PROJECT INDICATORS • Form a net of research groups all over Brazil and outside the country to answer the challenge: • 1: sample collection and preparation aiming suitability for chromatographic analysis of dyes, pharmaceuticals, • flame retardants in water samples and importation and exportation products at recommended levels by CONAMA, • ANVISA, INMETRO and other legislation and control agencies. • 2: To develop and validate methods for pollutants determination employing HPLC technique coupled to different detectors • 3: Water samples will be collected from selected rivers according to CETESB-SP protocol. • 5: Establish analytical protocols from sample preparation to identification and quantification of target species • employing extraction and/or pre-concentration steps for complex matrices with low levels of constituents. • 6: Formation of human resources capable of collecting, sample treatment and application of analytical methods • for emerging pollutant analysis in complex samples as well as development of other modern, fast and efficient methods. • 7: Electrochemical sensors development aiming simplicity and low cost of analytical methods applicable • to detection and quantification of emerging contaminants in complex matrices. Redox electrochemical processes of dyes • will be followed by spectroelectrochemical techniques as well as their interaction with DNA modified electrodes • and nitrogenous bases. • 8: Constructionandcharacterizationofglassycarbonelectrodes, goldwithcarbonnanotubesfilms, • titaniumnanotubes/chitosan, graphemeandnanoimprintedpolymersand self-assembledmonolayers • and self-assembledmonolayerselectrodesaimingelectrochemicalsensors.

6. Goal 9: Construction of biomimetic sensors based on redox catalysts which mimetizes important enzymatic reactions of human metabolism. For this purpose, lacasse, tirosinase, glutathione, transferase and beta-lactamase will be used as active site model for mimetizing P450. 10: Construction of sensors based on transduction principle. Optical sensors will be based on MIP directly synthesized onto optical fibers surfaces. Magnetosensors will be based on supermagnetic nanoparticles modified by MIPcore-shell. These new sensor analysis aims alternative in loco analysis of high selectivity and detectability for potential commercialization of formed product. 11: Development of sensing systems based on Lateral Flow Assay aiming multiples detections of emerging pollutants and their metabolites by using interaction with magnetic nanoparticles modified by MIP. 12: Automation of the control response of the sensors developed for analysis "in situ" system. 13: Investigation and identification of by-products formed after chlorination step, solar simulator irradiation, singlet oxygen, ultraviolet irradiation, metabolic oxidation and reduction with enzymes and others reactions mimeting aquatic biota by analytical methods and by-products toxicity/mutagenicity evaluation. 14: Coupling information on main toxic components in effluents, sewage and sediments by chemical analysis of target compounds for screening the contribution of each compound on final toxicity of samples. 15: Risk exposure evaluation of contaminants as well as products of chlorination and other processes during treatment of industrial effluents. For this purpose, different assays will be applied to different classes of contaminants aiming efficiency evaluation of proposed degradation processes after different treatment methodologies. 16: Development of new advanced oxidation processes as photo-Fenton and photoelectrofenton for efficient degradation of target contaminants. The final products will be monitored by LC-MS technique as well as the intermediates generated during treatment to understanding the biological compatibility or tocxicity/genotoxicity of treated effluents and propose degradation pathways. 17: Enhancement of TiO2 or WO3 electrodes performance for photoelectrochemical purposes on organic compounds degradation under solar and visible irradiation.

7. 18: Investigation of other strategies for improving electrochemical efficiency process. 19: Reactors development for electrochemical oxidation, photoelectrochemical and photocatalytic measurements for developing treatment systems suitable for industrial conditions. After reactor, electrodes and general system performance evaluation, a pilot scale system will be developed for meeting the requirements of more economic and functional effluent treatment. 20: Quality evaluation of food produced in different Brazilian regions, development of more suitable technologies for mapping food quality concerning micropollutants concentration banned in foreign trade. 21: Develop suitable analytical methods for emerging contaminants quantification for control agencies. 22: Purchase and use training of portable equipment’s for dissolved radon determination which will be installed in the following universities: Universidade de Santa Cecília (Santos, SP), Universidade de Brasília (Brasília, DF), Universidade Federal do Ceará (Fortaleza, CE), Universidade Federal de Rondônia (Porto Velho, RO) and Universidade Federal do Amapá (Macapá, AP). 23: Contacting potable water supplier agencies in the cities of Santos, Brasília, Fortaleza, Porto Velho and Macapá at São Paulo, Minas Gerais, Paraná and MatoGrosso do Sul states, for establishing water sampling logistic. 24: In loco dissolved Radon analysis performance and analytical analysis of alpha and beta radioactivity by Isotopes and Hydrochemistry Laboratory (LABIDRO) located at IGCE-UNESP-Rio Claro for installation of new methodologies. 25: Evaluation of radioactivity levels and mapping of interest areas in which values are detected above limits allowed by Brazilian legislation. 26: Identification of radionuclides contents in rocks and soil for determination of main minerals responsible for water transfer due to water-soil/rock interaction processes.

8. 27: Evaluation of primary DNA damages (chain cleavage and oxidative damage in purine and pyrimidine bases) from in vitro and in vivo tests which could be identified by comet assay, chromosomal aberrations, micronuclide assay and those related to genic expression pattern, evaluated especially by PCR (Polymerase Chain Reaction) techniques. 28: Evaluation of emerging contaminants effect on somatic cells for investigation of possible toxic-reproductive effects in germinal mice cells 29: Identification of mechanisms responsible for mutagenic and carcinogenic potential of emerging pollutants and, as a result, propose of strategies for minimizing or eliminating such effects. 30: Report obtained results to responsible sectors, for alerting on needed actions, including suggestion of mitigation initiatives.

9. ANALITOS • micropollutants” and some considered as “emerging contaminants”: compounds even at low concentrations are potential chemicals of causing adverse ecological effect and harmful to human health. • -pharmaceutical products (antibiotics, anti-inflammatory, psychoactive, hormones) and their metabolites • -personal care products (surfactants, brightness, sunscreen) • pesticides • microcystins • desreguladoresendócrinos – bisphenol • -flame retardants (polibromated and other halogenated compounds) • Insecticides • biocides • dyes • aromatic amines • plastifying agents • biological metabolites, toxins and their by-products • some radioactive materials

10. 1. Separation Methods • development of analytical methods for detection, extraction and pre-concentration • of these pollutants in complex matrices, such as effluent, sewage, surface waters and others. • Técnicas • -Liquid chromatography methods coupled with photometric detectors (UV-visible and diode array), • -Fluorescence, refractive index, electrochemistry (DE) • -Liquid Chromatography coupled with mass spectrometry (LC-MS-MS) • -Application of mass spectrometry coupled with inductively coupled plasma (ICP-MS) • hyphenated separations techniques such as HPLC and GC (HPLC-ICP-MS) • -Development of molecular imprinted polymer (MIP) • -Combination of stationary phases for HPLC-ED systems • 6-Electrochemical Detectors coupled to HPLC

11. 2. Chemical Sensors • to develop analytics systems with excellent analytical performance, fast and economical for application in the determination of emerging pollutants, • in order to become alternative tools • to analysis methods already existing, rationalizing waste of chemicals and maximizing the potential of human resources. • Development of nanostructured materials: Preparation, characterization and study of the properties and applications of new • materials based on mixed oxides of silica gel and modification of materials described above with enzymes, antibodies, nucleic acids • and compounds biomimetic, with the aim of developing more versatile sensors useful in the determination of emerging contaminants. • 2. Synthesis and characterization of supermagneticas nanoparticles coated microslides. todevelopsensors based on magnetic pre-concentration • of analyte modified by these nanoparticles. • 3. Synthesis, optimization and characterization of molecularly printed polymers. synthesis an application of molecular imprinted polymer (MIP) • 4. Biosensors: biosensors are based on cholinesterase enzymes, peroxidase and oligonucleotides, aimed at implementing the detection of • anticholinesterases agents and emerging Eco-toxicological agents.

12. 2.Chemical Sensors 5. Sensors biomimetic: RI detectors sensors based on redox catalysts that mimic enzyme reactions important in human metabolism. 6. Construction of sensors with optical and magnetic transduction: exploration of transduction systems alternative in the development of sensors, aimed at carrying out analyzes in situ and with high selectivity and detectability. In such a way, that the sensors obtained can be transformed into marketable products. 6.1.Optical Sensors: emerging pollutants has optical properties such as fluorescence (hormones and quinolones) and color (dyes), this line of research aims the development of optical sensors, which will be constructed by immobilizing molecularly imprinted polymers (MIP) directly on the surface of optical fibers. In this case, the synthesis of MIP should be previously optimized. 6.2. Construction of magnetossensores: magnetic nanoparticles will be modified by antibodies or DNA and used in the detection of the analyte of interest through of sandwich-type tests, competitive or by hybridization, according to each case. 7.Analysis Systems in lateral flux: This line of research aims to develop methods of multiple detection for proposed environmental pollutants, inspired by the diagnostic systems POC (point-of-care) extending its recognized application

13. 3.Radionuclides evaluation in environmental studies • Establishment of a radiometric laboratorial net: sampling of waters and preliminary analyses of radioactivity • due to the dissolved radon. • 2) Methodological refinement: the technique for measuring the alpha and beta total radioactivity in waters • will be refined by the use of high resolution gamma rays spectrometry • 3) Radiometric mapping: the generation of gross-alpha and gross-beta activity data in waters will permit to perform • the mapping of “hot spot” areas characterized by values above the maximum established by the brazilian legislation • 4) Thermochronology/cosmogenic radionuclides: a) to evaluate the insertion rate of the principal rivers of • selected hydrographic basins (inclusive with discussions of related uplift, tectonic and climatic mechanisms) • b) to determine the shape and direction of the relief evolution (relief downgrade vertical vs.scarps lateral retraction) • taking into account the comparison of denudation rates in several topographic sectors (scarps, summits, and valleys).

14. Orçamento FAPESP: 2014/50945-4 Processo CNPq: 465571/2014-0 Valor: R$ 6.695.376,354 Vigência: 01/2017 -2022 ( 6 anos) CNPq: Custeio: 1.251.672,27 – liberado 147.585,00 Capital : 1.593.037,42 – liberado 138.714,00 CAPES Bolsas: R$ 458.542,38 FAPESP : R$ 3.347.688,18 Reserva técnica Institucional: 669.537,64 Infraestrutura direta do projeto: 535.630,11 Benefício complementar (gestores) : 12.000 x 8 = 576.000,00 Valor disponível material permanente: 1.566.520,00 – tarifa importação (15%)

15. EQUIPE FAPESP

17. fapesp