RESSALVA Atendendo solicitação da autora, o texto completo desta tese será disponibilizado somente a partir de 13/09/2021. UNIVERSIDADE ESTADUAL PAULISTA “JÚLIO DE MESQUITA FILHO” INSTITUTO DE PESQUISA EM BIOENERGIA unesp PROGRAMA INTEGRADO (UNESP, USP E UNICAMP) DE PÓS-GRADUAÇÃO EM BIOENERGIA Green stabilization of nanoscale zero valent iron (nZVI) with rhamnolipids produced by agro-industrial waste: application on nitrate reduction Cinthia Cristine de Moura Tese apresentada ao Instituto de Pesquisa em Bioenergia de Rio Claro, Universidade Estadual Paulista, como parte dos requisitos para obtenção do título de Doutor em Ciências. Orientador(a): Jonas Contiero Setembro - 2019 Green stabilization of nanoscale zero-valent iron (nZVI) with rhamnolipids produced by agro-industrial waste: application on nitrate reduction CINTHIA CRISTINE DE MOURA Rio Claro 2019 Tese apresentada ao Instituto de Pesquisa em Bioenergia de Rio Claro, Universidade Estadual Paulista, como parte dos requisitos para obtenção do título de Doutor em Ciências. Orientador(a): Jonas Contiero M929g Moura, Cinthia Cristine de Green stabilization of nanoscale zero valent iron (nZVI) with rhamnolipids produced by agro-industrial waste : application on nitrate reduction / Cinthia Cristine de Moura. -- Rio Claro, 2019 137 f. : il., tabs. Tese (doutorado) - Universidade Estadual Paulista (Unesp), Instituto de Pesquisa em Bioenergia - IPBEN, Rio Claro Orientador: Jonas Contiero 1. Biossurfactantes. 2. Nanopartículas de ferro zero valente. 3. Resíduos agrícolas. 4. Remediação Ambiental. 5. Design experimental. I. Título. Sistema de geração automática de fichas catalográficas da Unesp. Biblioteca do Instituto de Biociências, Rio Claro. Dados fornecidos pelo autor(a). Essa ficha não pode ser modificada. User Máquina de escrever Título alterado para "Green stabilization of nanoscale zero-valent iron (nZVI) with rhamnolipids produced by agro-industrial waste: application on nitrate reduction" “A lei da mente é implacável. O que você pensa, você cria; O que você sente, você atrai; O que você acredita Torna-se realidade”. Buda AGRADECIMENTOS Primeiramente gostaria de agradecer a Universidade Estadual Paulista “Júlio de Mesquita Filho” e ao Instituto de Pesquisa em Bioenergia, bem como aos coordenadores e professores. À Capes pela bolsa de auxílio financeiro. O presente trabalho foi realizado com apoio da Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Código de Financiamento 001. Agradeço ao Prof. Dr. Jonas Contiero pela sua sabedoria e paciência, que me ensinaram muito. Ao Prof. Dr. Miguel Jafelicci e ao Prof. Dr. Rodrigo Marques por gentilmente cederem o laboratório no Instituto de Química da Unesp de Araraquara para realização dos testes com as nanopartículas. Aos meus pais Júlio e Sandra por sempre incentivarem a continuidade deste trabalho, por me ouvirem e por sempre estarem ao meu lado nos momentos difíceis. Ao meu irmão Douglas, a minha cunhada Mariana e meu sobrinho Diogo, por trazerem alegria nos poucos momentos que estávamos juntos. Aos amigos do LMI, pelo convívio diário, pelos papos na hora do café, por me ensinarem, por me ouvirem, aconselharam, e por terem sido minha família nesses 4 anos. Ao Rodolfo e Caio que me ensinaram e ajudaram na síntese das nanopartículas e nas discussões dos resultados. A Ana Maria, que foi minha chefe, minha estagiária, minha mãe, minha irmã, minha filha e em todas as situações: minha amiga. Nada disso teria sido possível sem você ao meu lado. A Thalita Moura e Yaliana Tafurt, mesmo longe nunca deixaram de me apoiar. A Cristhian Lao, que me apoiou, ouviu e ajudou durante todo o doutorado. Obrigada por sempre estar ao meu lado, por não desistir de mim e nem me deixar desistir. As minhas primas, que considero como irmãs: Flávia Nunes e Nathália Giovanni. Ao meu tio Fernando que me deu várias caronas, os longos papos no transito faziam as viagens mais divertidas. Aos meu pais, tia Elaine, tia Rosana, tio Fernando, primas Rafaela e Nathália, obrigada por terem vindo na defesa, obrigada por encararem as longas horas de viagem e por fazerem parte desse momento tão especial! E agradeço a todos aqueles que de alguma forma contribuíram para o andamento do trabalho realizado durante esta etapa da minha formação profissional. Resumo A contaminação ambiental causada por compostos orgânicos é um importante problema que afeta solos e água superficiais. Para reduzir ou remover esses poluentes, os locais contaminados são geralmente tratados com métodos físicos e químicos. No entanto, a maioria dessas técnicas de remediação é custosa e geralmente leva à remoção incompleta e à produção de resíduos secundários. A nanotecnologia consiste na produção e aplicação de estruturas extremamente pequenas, cujas dimensões estão na faixa de 1 a 100 nm, neste cenário a nanopartícula de ferro zero valente representa uma nova geração de tecnologias de remediação ambiental. É não tóxica, abundante, barata, fácil de produzir, e seu processo de produção é simples. No entanto, a fim de diminuir a tendência de agregação, a nanopartícula de ferro zero é frequentemente revestida com surfactantes. A maioria dos surfactantes é quimicamente sintetizado a partir de fontes petroquímicas, eles são persistentes ou parcialmente biodegradáveis, enquanto oferecem baixos riscos à saúde humana, esses compostos podem prejudicar plantas e animais. Para diminuir o uso de métodos químicos, a síntese e estabilização verde de nanomateriais metálicos apresentam-se como uma opção menos perigosa ao meio ambiente. Os biossurfactantes podem potencialmente substituir qualquer surfactante sintético, eles são compostos extracelulares produzidos por microrganismos, como bactérias, e cultivados em diferentes fontes de carbono, podendo ser substratoshidrofílicos. Os biossurfactantes possuem uma grande variedade de estruturas químicas e propriedadesde superfície e entre eles estão os ramnolipídios que já foram intensamente investigados e estudados. Os ramnolipídios podem ser produzidos pela Pseudomonas aeruginosa em diferentes substratos, incluindo o glicerol. Uma produção bem-sucedida de biossurfactantes depende do uso de materiais renováveis e de baixo custo. O glicerol bruto, principal subproduto do processo de transesterificação em uma usina de biodiesel, é um substrato amplamente utilizado para a produção de ramnolipídios. A fim de obter a melhor temperatura e concentração inicial de glicerol, o design rotacional composto central e o método de superfície de resposta foram empregados para delimitar as melhores condições para aumentar a produção de ramnolipídeos e diminuir o glicerol remanescente no meio. Com o auxílio do Método de Superfície e Resposta foi possível verificar a viabilidade do uso do glicerol bruto livre de sal, atingindo uma produção de 2,63 g/L de ramnolipidios e depleção total da fonte de carbono, no meio otimizado contendo 25 g/L de fonte inicial de carbono a 32 ° C. Em seguida, as nanopartículas de ferro zero foram sintetizadas utilizando a redução química com borohidreto de sódio. Foram testadas duas metodologias: (i) adição de ramnolipídios durante a síntese química e (ii) adição após a síntese. As nanopartículas foram subsequentemente testadas quanto à eficiência na redução de nitrato em água subterrânea simulada sob condições anaeróbias em pH 4. A nanopartícula de ferro zero sintetizada adicionando ramnolipídios após a síntese, mostrou a melhor eficiência com uma taxa de remoção de cerca de 78% de remoção de nitrato e concentração inicial de nitrato de 25. mg/L. O método para preparar nanopartícula de ferro zero, usando ramnolipídios como agente estabilizador, mostrou-se uma alternativa promissora para a funcionalização de superfície da nanopartícula, em substituição a surfactantes sintéticos e tóxicos Palavras chave: Biossurfactantes. Química verde. Design experimental. Glicerol. Nanopartícula de ferro zero valente. Águas subterrâneas. Abstract Environmental contamination caused by organic compounds is the most important challenge that affects a huge number of soils and water surfaces. To reduce or remove these pollutants, contaminated sites are usually treated using physical and chemical methods. However, most of these remediation techniques are expensive and commonly lead to incomplete removal and to the production of secondary wastes. Nanotechnology is the production and application of extremely small structures, whose dimensions are in the range of 1 to 100 nm and Nanoscale zero-valent iron represents a new generation of environmental remediation technologies, is non-toxic, abundant, cheap, easy to produce, and its reduction process requires little maintenance. Nonetheless, in order to diminish the tendency of aggregation, nanoscale zero-valent iron is often coated with surfactants. Most surfactants are chemically synthesized from petrochemical sources, they are slowly or partially biodegradable, while offer low harm to humans, such compounds can influence plants and animals. To decrease the use of chemical methods green synthesis and stabilization of metallic nanomaterials viable option. Biosurfactants can potentially replace virtually any synthetic they are extracellular compounds produced by microbes such as by bacteria and grown on different carbon sources containing hydrophobic/hydrophilic substrates. The biosurfactants have a wide variety of chemical structures and surface properties and among them is the rhamnolipids which have been intensively investigated and extensively reviewed, they can be produced by Pseudomonas aeruginosa from different substrates, including glycerol. Successful production of biosurfactants depends on the use of renewable materials and low cost. Crude glycerol is the primary byproduct of the transesterification process in a biodiesel plant and it is a widely used substrate for rhamnolipid production. To provide the best temperature and initial concentration of glycerol the central composite rotational design and response surface method were employed to increase rhamnolipids yield and lower the glycerol remaining in the medium. The response surface method methodology indicated the viability of the use of crude glycerol, reaching a production of 2.63 g/L of biosurfactant and total depletion of carbon source, at the optimized medium containing 25 g/L of initial carbon source at 32 °C. Then, the iron nanoparticles were synthesized using the chemical reduction of ferric ions with sodium borohydride. Were tested two methodologies: (i) adding rhamnolipids during the chemical synthesis and (ii) adding after the synthesis. The nanoparticles were subsequently tested for their efficiency in nitrate reduction in simulated groundwater under anaerobic conditions at pH 4. The nanoscale zero-valent iron synthetized adding rhamnolipids after the synthesis showed the best efficiency with a removal rate about 78% and initial nitrate concentration of 25 mg/L. The method for preparing nanoscale zero-valent iron using rhamnolipids biosurfactants as stabilizer was found as a promising alternative for the synthesis and surface functionalization of iron nanoparticles, in replacement to toxic synthetic surfactants Key words: Biosurfactants. Green chemistry. Experimental design. Glycerol. Nanoscale zero-valent iron. Groundwater. Lista de Figuras Figure 1.1 Illustration of the top-down and bottom-up approaches _______________ 19 Figure 1.2 Typical production of biosurfactants during growth __________________ 23 Figure 1.3 The relationship between biosurfactant concentration, surface tension, and formation of micelles. __________________________________________________ 24 Figure 1.4 Structure of the four main counterparts of rhamnolipids ______________ 28 Figure 1.5 Transesterification reaction of a triacylglycerol with an alcohol. ________ 33 Figure 2. 1 Schematic illustration of (a) surface modification and (b) network stabilization 52 Figure 2. 2 Molecular structure of the surfactants Sodium Dodecyl Sulfate (SDS), Alkylphenol polyethoxylate (Triton X-100), Polyvinylpyrrolidone (PVP), Polyethylene glycol (PEG) 54 Figure 2. 3 Molecular structure of the main biosurfactants (a) Sophorolipids, (b) Mannosylerythritol Lipids (MEL) (c) Emulsan (d) Surfactin (e) Rhamnolipids 63 Figure 2. 4 Application of nZVI for in situ remediation. 68 Figure 2. 5 The core consists of principally zero-valent iron and supplies force for the reducing reactions with pollutants. The shell is mostly iron oxides/hydroxides created by the oxidation of zero-valent iron and it supplies sites for chemical reduction reaction.⠀ 70 Figure 3. 1 Experimental rhamnolipids concentration plotted against rhamnolipids concentration predicted by the fitted model _________________________________ 98 Figure 3. 2 Experimental glycerol remaining concentration plotted against glycerol remaining concentration predicted by the fitted ______________________________ 99 Figure 3. 3 Response surface curve of interaction of initial glycerol and temperature (a) rhamnolipids; (b) glycerol remaining _____________________________________ 100 Figure 4. 1 FTIR spectra of rhamnolipids _________________________________ 112 Figure 4. 2X-ray diffraction peaks associated with nZVI particles after the synthesis (e) bare nZVI, (c) nZVI-A (a) nZVI-S. and associated with nZVI particles 1 month after the synthesis (f) bare-nZVI(d) nZVI-A and (b) nZVI-S _________________________ 113 Figure 4. 3 Zeta potential and pzc of nZVI ________________________________ 114 Figure 4. 4 Average particle diameter size distribution of nZVI particles. ________ 115 Figure 4. 5 FEGSEM images (magnitude 30.0 k) of (a) bare-nZVI (b) nZVI-A (c) nZVI- S _________________________________________________________________ 116 Figure 4. 6 TGA and DTA curves for (a) bare-nZVI, (b) nZVI-A and (c) nZVI-S. _ 117 Figure 4. 7 Effect of time and initial nitrates concentration on nitrates reduction using nZVI at pH 4 (a) 25 mg/L NO3-N (b) 50 mg/L NO3-N (c) 100 mg/L NO3-N and effect of time and initial nitrates concentration on ammonia concentration using nZVI at pH 4 (d) 25 mg/L NO3-N (e) 50 mg/L NO3-N (f) 100 mg/L NO3-N ________________ 121 Figure A. 1 Results of tests using P. aeruginosa strains in different temperatures using 25 g/L of glycerin regarding to (a) rhamnolipids production by P. aeruginosa PAO1, (b) rhamnolipids production by P. aeruginosa LBI (c) rhamnolipids production by P. aeruginosa __________________________________________________________ 133 Lista de Tabelas Table 1.1 Type and microbial origin of biosurfactants ________________________ 25 Table 1.2 P. aeruginosa strain in various carbon source._______________________ 27 Table 1.3 Production of Rhamnolipids by Pseudomonas strains using Glycerol _____ 35 Table 2. 1 Production of biosurfactants using different strains and carbon sources ...... 59 Table 2. 2 Remediation applications for most common pollutants 69 Table 3. 1 Real and coded values of independents variables for the central composite rotational design. _____________________________________________________ 95 Table 3. 2 Planning matrix for central composite rotational design and experimental results ______________________________________________________________ 96 Table 3. 3 Analysis of variance for response surface quadratic model regarding rhamnolipids. ________________________________________________________ 97 Table 3. 4 Analysis of variance for response surface quadratic model regarding glycerol remaining ___________________________________________________________ 99 Table 3. 5 Planning matrix for validation of optmization design and experimental results __________________________________________________________________ 101 Table 4. 1 Stabilization methodology of nZVI ______________________________ 110 Table 4. 2 Regions of mass loss and gain (%) of nZVI-A and nZVI-S samples. ____ 118 Table 4. 3 Observed pseudo first-order rate coefficient of nitrate reduction with nZVI __________________________________________________________________ 120 Table A. 1 Matrix of pre-test analysis with P. aeruginosa strains in different conditions. __________________________________________________________________ 130 Table A. 2 Pre-tests results for different pH, temperaturature and initicial concentration of glycerol pro-analysis _______________________________________________ 132 Table A. 3 Yield coefficients regarding to biomass yield on substrat (YX/S), rhamnolipid yield on substrat (YP/S) and rhamnolipid yield on biomass (YP/X). 134 Sumário 1. INTRODUCTION 13 1.1. NANOTECHNOLOGY 15 1.1.1. NANOTECHNOLOGY APLICATIONS 15 1.1.2. TYPES AND APPLICATIONS OF NANOPARTICLES: 16 1.1.3. PHYSICOCHEMICAL OF NANOTECHNOLOGY APPLIED TO THE STABILIZATION PROCESS 17 1.1.3.1. Superparamagnectic Nanoparticles 17 1.2. NANOSCALE ZERO-VALENT IRON (NZVI) 18 1.3. SYNTHESIS OF NON-STABILIZED NZVI PARTICLES 18 1.3.1. TOP-DOWN APPROACHES 18 1.3.2. BOTTOM-UP APPROACHES 19 1.3.2.1. Chemical Reduction 19 1.3.2.3. Electrochemical method 20 1.3.2.4. Pulsed Plasma: 20 1.3.2.5. Sonochemical Method 21 1.3.2.6. Biosynthesis of nzvi 21 1.4. SURFACTANTS 22 1.5. BIOSURFACTANT 23 1.6. PRODUCTION OF RHAMNOLIPIDS 26 1.7. PROCESS OF BIOREMEDIATION 29 1.8. RHAMNOLIPIDS IN BIOREMEDIATION 30 1.9. CRUDE GLYCEROL 32 2. Background and project relevance 35 3. Objectives 36 GENERAL 36 References 36 2. BIOSURFACTANTS AS GREEN CHEMICAL STABILIZERS FOR NANOSCALE ZERO VALENT IRON 48 Abstract 48 1. Introduction 48 2. Methods 50 3. Nanoscale zero-valent iron 50 3.1. AGGLOMERATION STABILIZATION 50 3.1.1. PRE-AGGLOMERATION STABILIZATION 51 3.2. STABILIZATION OF NANOSCALE ZERO-VALENT IRON 51 3.2.1. NETWORK STABILIZATION (OR VISCOUS STABILIZATION) 52 3.2.2. SURFACE MODIFICATION 52 Electrostatic repulsion 52 Steric stabilization 52 Electrosteric stabilization 53 3.3. CHEMICAL STABILIZATION AND ITS DISADVANTAGES 53 3.4. GREEN STABILIZATION AND ITS ADVANTAGES 56 4. Green stabilization allies: biosurfactants 58 4.1. HIGH MOLECULAR WEIGHT POLYMERIC BIOSURFACTANTS 60 4.1.1. EMULSAN 60 4.1.2. LIPOSAN 61 4.1.3. ALASAN 61 4.1.4. MANNOPROTEIN 61 4.2. LOW MOLECULAR WEIGHT BIOSURFACTANTS 62 4.2.1. FATTY ACIDS AND PHOSPHOLIPIDS 62 4.2.2. LIPOPEPTIDES 62 4.2.3. GLYCOLIPIDS 62 Rhamnolipids 63 Sophorolipids 64 Trehalose lipids 64 Mannosylerythritol lipids (mel) 64 4.3. GREEN CHEMISTRY ALLIES: BIOSURFACTANTS 65 4.3.1. TOXICITY 66 5. Nanoscale zero-valent iron in remediation 67 5.1. FE TOXICITY 70 6. Biosurfactants and nanoscale zero-valent iron: state of art 71 7. Future research needs 72 8. Conclusion 73 9. References 74 3. EXPERIMENTAL DESIGN TO IMPROVE CRUDE GLYCEROL CONSUMPTION AND RHAMNOLIPIDS PRODUCTION 91 Abstract 91 1. Introduction 91 2. Materials and methods 93 2.1. MATERIALS 93 2.2. RAW MATERIAL 93 2.3. MICROORGANISMS 93 2.4. MEDIA 93 2.5. PREPARATION OF PRODUCTION MEDIUM 94 2.6. SAMPLE AND PROCESSING 94 2.7. EXPERIMENTAL DESIGN THROUGH CENTRAL COMPOSITE ROTATABLE DESIGN (CCRD) 94 2.8. STATISTICAL ANALYSIS 95 2.9. VERIFICATION EXPERIMENTS 95 3. Results and discussion 95 3.1. CENTRAL COMPOSITE ROTATABLE DESIGN 95 3.2. REGRESSION MODEL FOR RHAMNOLIPIDS (Y1) 96 3.3. REGRESSION MODEL FOR INITIAL GLYCEROL (Y2) 98 3.4. SURFACE RESPONSE METHOD (RSM) FOR RHAMNOLIPIDS (X1) AND INITIAL GLYCEROL (X2) CONCENTRATIONS 99 3.5. VALIDATION TESTS 101 4. Conclusion 102 References 103 4. RHAMNOLIPIDS AS GREEN STABILIZER OF NZVI AND ITS APPLICATION ON NITRATE REMOVAL IN SIMULATED GROUNDWATER 106 ABSTRACT 106 1. Introduction 106 2. Materials and methods 108 2.1. MATERIALS 108 2.1. PRODUCTION AND EXTRACTION OF RHAMNOLIPIDS 108 2.2. SURFACE ACTIVITY MEASUREMENTS AND STRUCTURAL CHARACTERIZATION OF RHAMNOLIPIDS 109 2.3. SYNTHESIS AND GREEN STABILIZATION OF NZVI 109 2.4. NANOPARTICLE CHARACTERIZATION 110 2.5. NITRATE REDUCTION TESTS 110 3. Results and discussion 111 3.1. RHAMNOLIPIDS PRODUCTION AND CHARACTERIZATION 111 3.2. NZVI CHARACTERIZATION 112 3.3. NITRATE REDUCTION BY NZVI IN LOW PH CONDITIONS 119 4. Conclusion 121 References 122 General conclusions 128 A. ANNEX 129 1. Selection of the Pseudomonas aeruginosa strain 129 1.1. MATERIALS AND METHODS 129 1.1.1. MICROORGANISM 129 1.1.2. GROWING CONDITIONS 129 1.1.2.1. Preparation of the inoculum 129 1.1.2.2. Flask experiments 129 1.1.3. EXPERIMENTS 130 2. Results and discussion 130 3. Conclusion 134 References 134 13 1. Introduction Nanotechnology is the production and application of extremely small structures, at the level of atoms, molecules, and supramolecular structures, whose dimensions are in the range of 1 to 100 nm (ISO, 2009; NSET, 2003). Is an innovative alternative that can be used for the remediation of contaminated sites, it has the potential to significantly affect environmental protection, because it has the property to remove the finest contaminants from water supplies and air and mitigate pollutants in the environment (NSET, 2003). Environmental pollution by organic contaminants is a major problem today. Recently, there have been many reports of soil and surface water locations contaminated with organic pollutants (CETESB, 2016; EPA, 2002; EUROPEAN COMMISSION DG; ALERT; SERVICE, 2013), with a great impact on soil and groundwater. Nanoscale zero-valent iron (nZVI) represents a new generation of environmental remediation technologies, because nZVI is non-toxic, abundant, cheap, easy to produce, and its reduction process requires little maintenance (FU; DIONYSIOU; LIU, 2014). To reduce problems with aggregation, nZVI is often coated with surfactants (CRANE; SCOTT, 2012; NSET, 2003). Surfactants play major roles improving the particle mobility (DUTRA, 2015) and lowering the interfacial tension, they also prevent coalescence of newly formed drops (MORSY, 2014). Most of the commercially available surfactants are chemically synthetized , produced based on petrochemical sources (BANAT; MAKKAR; CAMEOTRA, 2000; GAUTAM; TYAGI, 2006; VAN BOGAERT et al., 2007). Furthermore, some of the surfactants are only slowly or partially biodegradable (KUMAR, 2019) contributing to environmental impact (HAUSMANN; SYLDATK, 2015). Thus, the rapid advances in biotechnology and increased environmental awareness, the chemically surfactants have increasingly been replaced by biologically synthetized surfactants (BANAT; MAKKAR; CAMEOTRA, 2000; GAUTAM; TYAGI, 2006). Surfactants present low toxicity to humans but can affect plants and animals, i.e. ethoxylated alcohols, found in laundry detergents are toxic to fish (MULLIGAN; YONG; GIBBS, 2001a). Biosurfactants are an alternative, they can potentially replace the synthetic surfactant (REIS et al., 2013; SÁENZ-MARTA et al., 2015). Biosurfactants can be applied in bioremediation field, to clean the contaminated soil and water (THAVASI, 2011), they present advantages in microbial enhance oil recovery (MEOR) , when 14 compared to the synthetic surfactants (BANAT et al., 2010). They have low toxicity and high biodegradability and biocompatibility, additionally, present functionality under extreme conditions of temperature, pH, salinity; with possibility of production from renewable sources (BANAT et al., 2010; COOPER, 1986; DESAI; BANAT, 1997a) and the in situ application (WANG et al., 2016) Pseudomonas aeruginosa has the ability to synthesize a glycolipid-type biosurfactant, rhamnolipids this was first reported in 1949 by Jarvis et al., appud (MAIER; SOBERÓN-CHÁVEZ, 2000). It can produce rhamnolipids from substrates including C11 and C12 alkanes, succinate, pyruvate, citrate, fructose, glycerol, olive oil, glucose and mannitol (ROBERT et al., 1989). They have been intensively investigated and extensively reviewed (MAIER; SOBERÓN-CHÁVEZ, 2000; NITSCHKE; COSTA; CONTIERO, 2005; OCHSNER; HEMBACH; FIECHTER, 1996). The application of biosurfactants in the bioremediation has become one of the methods used in the remediation of contaminated sites. They can be used to clean the contaminated soil and water (THAVASI, 2011). The use of a raw material of agro-based wastes, low-cost renewable substrates and the new research about rhamnolipids applications on biodegradation and toxicity are worth further investigation and may make biosurfactants a versatile sustainable molecule. The industrial conversion of renewable resources into useful compounds has been receiving much attention; the use of crude glycerol is becoming very important from the environmental point of view (MORITA et al.; 2007; EASTERLING et al., 2009). It is a widely used substrate for rhamnolipid production (SYLDATK et al. 1985) since a wide variety of microorganisms, as Pseudomonas aeruginosa, can utilize glycerol as a source of carbon and it is often formed as an intermediate in both the aerobic and anaerobic catabolism of lipids and glucose. (JOHNSON, TACONI, 2007; HAUSMANN; SYLDATK, 2015). The hypothesis of this work lies in the fact that the rhamnolipids produced by Pseudomonas aeruginosa strain, using glycerol as a substrate may significantly increase the stabilization of nanoparticles of zero valent iron. It can become a novel application for biosurfactants allied to a consequently reduction on the costs of the process due to the use of a renewable substrate. 36 3. Objectives General Stabilization of de nanoscale zero-valent iron (nZVI) aiming the biosurfactant produced by Pseudomonas aeruginosa using glycerol as a carbon source. Specific 1. A bibliographic survey about the state of the art of nZVI and biosurfactants; 2. Optimization of temperature and initial carbon source for the production of rhamnolipids and glycerol consumption using Pseudomonas aeruginosa LBI 2A1; 3. Production, stabilization and characterization of nZVI using rhamnolipids as capping agent; 4. Study the performance of bare nZVI and stabilized nZVI in nitrate removal. 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