INCT-ACQUA by Editora Cubo

INCT-ACQUA ACTIVITY REPORT - Expedient Editors

Ana Cláudia Q. Ladeira – CDTN Angela Mello Ferreira – CEFET-MG Claudia L. Caldeira – EE/UFMG Francisco A. R. Barbosa – ICB/UFMG Helio A. Duarte – ICEx/UFMG Índila Ribeiro – INCT-Acqua Jaime W. V. Mello – UFV José G. Tundisi – IIEGA Virginia S. T. Ciminelli – EE/UFMG

Production Management Credits

Editora Cubo Rafael Mozeto and Larissa Orlandi FUNDEP intervention in a photograph by Marcus Desimoni/Agência Nitro (Publication background) / FUNDEP intervention in a photograph from SXC (Science Highlights - Research Topic  background) / Mateus Baranowisk (Science Highlights - Research Topic  - Part  background) / Center of Microscopy/UFMG (National and International Partnerships - Project Highlights from Brazil-Australia Collaboration - background) / Hana Lanky, st award winner of the photograph contest sponsored by “Geopark Quadrilátero Ferrífero (“Calçada” Mountain Range, Minas Gerais, Brazil - cover picture) / Michele Elmes (Educational and Outreach Activities background) / Other images (Image bank)

The editors express their gratitude to the INCT-ACQUA colleagues who contributed to this edition. This document was prepared as an account of work done by INCT-ACQUA users and staff. Whilst the document is believed to contain correct information, neither INCT-ACQUA nor any of its employees make any warranty, express, imply or assume any legal responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed within. As well, the use of this material does not infringe any privately owned copyrights. Instituto Nacional de Ciência e Tecnologia em Recursos Minerais, Água e Biodiversidade Headquarters Universidade Federal de Minas Gerais – UFMG Escola de Engenharia – Bloco II Departamento de Engenharia Metalúrgica e de Materiais Av. Antonio Carlos,  – - Belo Horizonte – MG, Brazil Telephone + () - E-mail inct.acqua@demet.ufmg.br Home Page www.acqua-inct.org Management Committee Director Vice-Director Vice-Director

Virginia S.T. Ciminelli – DEMET/UFMG Francisco Antônio R. Barbosa – ICB/UFMG José Galizia Tundisi – IIEGA/SP Angela Mello Ferreira – CEFET/MG Ana Claudia Q. Ladeira – CDTN Jaime Wilson V. Mello – UFV Hélio Anderson Duarte – ICEx/UFMG Cataloguing Card

National Institute of Science and Technology on Mineral Resources, Water and Biodiversity Activity Report / National Institute of Science and Technology on Mineral Resources, Water and Biodiversity = Instituto Nacional de Ciência e Tecnologia em Recursos Minerais, Água e Biodiversidade (INCT-ACQUA). – –. – Belo Horizonte : INCT-ACQUA, –.  p. ISSN - . Mineral resources. . Water. . Biodiversity. I. Título.

Summary 4

Introduction

10 Facts and Figures 12 National and International Partnerships 22 Educational and Outreach Activities 33 Science Highlights 108 Publications 114 Contacts

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

Introduction National Institute of Science and Technology on Mineral Resources, Water and Biodiversity – INCT-Acqua Instituto Nacional de Ciência e Tecnologia em Recursos Minerais, Água e Biodiversidade

Introduction

INTRODUCTION

A program launched by the Brazilian Ministry of Science, Technology, and Innovation (MCTI) established the National Institute of Science and Technology on Minerals Resources, Water, and Biodiversity (INCTAcqua) in 2009. By combining and integrating Mineral Resources, Water, and Biodiversity, INCT-Acqua adopts the paradigm in which water is the common denominator of the initiatives focused on innovation and scientific, social, and sustainable regional development. The activities of the Institute encompass two major areas: (i) the assessment of the impact of mining activities on the quality of water, soil, and air, together with the conservation of biodiversity and (ii) adding value and environmental performance to mineral-based products and processes. There have been a number of scientific, technological, and outreach achievements over the past four years that are worth highlighting in this report. Of environmental relevance is the identification of a nanoscale mechanism underlying the long-term arsenic fixation in the environment. The mechanism involves arsenic sorption onto aluminum-iron (hydr)oxide nanoparticles occurring in soils, followed by aggregation in a process to produce nanosized aluminum-hematite. Such a stable arsenic form is reflected in the low bioaccessibility of geogenic materials of both natural and anthropogenic origin. The fixation process is fast (days to weeks) and can be applied to treat water contaminated with uranium and rare-earth elements. A uranium mining area contaminated by acid mine drainage was investigated by using sulfur isotope fractionation. The results showed that the bio-reduction reactions that take place in lake sediments play an important role in the natural attenuation phenomena and could be an option for the remediation of this environment. The use of bacteria, including cyanobacteria, and microcrustaceans as potential biological indicators of water quality conditions has been consolidated. A powerful strategy to assess both the functional and taxonomic bacterial diversity is the metagenomic approach. The effect of the presence of metals in waters on the hatching of resting stages of Daphnia species was also evaluated. The use of manganese concentrations that were 50-fold higher than that allowed under Brazilian law did not inhibit the hatching rate but negativelly affect the organims reproduction. Furthermore, the role of cyanobacteria in the absorption and adsorption of specific contaminants was investigated, aimed at the possibility of using these organisms as bioacumulators/ biotransformers of metals and metalloids, thus enhancing the participation of the bioremediation approach. The use of synchrotron radiation has also been tested as an alternative to identifying loci for arsenic chemical species within cells, as well as arsenic complexation with glutathione, in an attempt to broaden the role played by these organisms in the absorption process. The synthesis of magnetic nanomaterials/nanocomposites under milder and more environmentally friendly conditions is worth highlighting. The nanocomposites were shown to effectively oxidize and remove inorganic/ organic compounds from aqueous systems. Magnetic nanomaterials are attractive, as they facilitate the solidliquid separation in the treatment of large volumes of water. In an innovative application, functionalized magnetic nanoparticles, called ferrofluids, improved the speed and efficiency of phase disengagement during solvent extraction. The chemical reactivity of sulfide minerals involved in the acid mining drainage at the molecular level was investigated in detail by computer simulations. Insights about the preferential cleavage surfaces and the structural and electronic properties of chalcopyrite, covellite, bornite, pyrite, and arsenopyrite are provided. The reaction mechanism of pyrite and arsenopyrite oxidation in the presence of water and oxygen was elucidated at a molecular level, unveiling the role of the water in this process and supporting the interpretation of experimental data. Solvent extraction conditions for the separation of a number of relevant metals have been established. One example is the recovery of europium and yttrium from expended computer monitors, which offers economic and environmental benefits due to the high value of rare-earth elements and other metals. Also highlighted in this report is an original approach to improving electrowinning performance, in which a device was developed to predict the mechanical behavior of metal deposits, thereby assisting industry to optimize processes and increase productivity. There are outstanding examples of effective INCT-Acqua – industry collaboration that have resulted in clear benefits for the industrial sector and significant gains in capacity building. In the AMIRA project – Electrowinning of Base Metals – global companies provided funds in a consortium mode to groups from United States, Australia, and Brazil. The research by INCT-Acqua resulted in operational improvements that ranked zinc production in the Votorantim unit in Três Marias, Brazil, as the most efficient worldwide and led to an annual savings of US$3.3 million dollars, as stated by Dr. Adelson de Souza, Technologies General Manager at Votorantim Metais. INCT-Acqua played a key role in an issue that received considerable media coverage worldwide - arsenic contamination in Paracatu. This seven-year research project, funded by Kinross Brasil Mineração, involved a multidisciplinary group from Brazil and abroad. Extensive investigation of soil, dust, water, and food clearly showed that the health risks from arsenic exposure for the general population in Paracatu are low and

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

comparable to the normal dietary intake of arsenic throughout Brazil. This work also involved an extensive program of scientific communication to clarify the science concerning arsenic and to inform residents about the true risks. “The project can be considered a landmark in the mineral industry for its broad scope and the employed scientific and technical tools. The outcomes were essential to maintaining the high reputation of the company and a respectful relationship with key stakeholders, without which we could not ensure the continuity of our operations”, remarked Alessandro Nepomuceno, Sustainability and Permitting Director at Kinross Gold Corporation. The partnership with Indústrias Nucleares do Brasil (INB) culminated in the development of an ionexchange process to recover uranium from acid mine drainage and the operation of a pilot plant in the INB unit in Caldas, MG to treat 150m3/h of effluent with a production capacity of 15 t/year of U3O8. One of the main commitments of the INCT program is to convey the scientific and technological content to society in general. The Center for Reference and Qualification on Sustainability of the Alto Paraopeba Region (CESUP) was established by INCT-Acqua in the town of Conselheiro Lafayette in 2012. Embracing the main pillars of Geopark Quadrilátero Ferrífero for the territory – Innovation, Education, Sustainable Family Farming, and Economic Diversification with Social Inclusion – CESUP has contributed to capacity building at all levels, from elementary schools to rural communities, with a focus on the development of the mining territory, as shown in this report. It is important to note the widespread connection with the international community with a very productive collaboration in research projects, which complements and expands local expertise, as well as an active exchange of students and faculty members. After seven years of the creation of INCT-Acqua, the central question remains fresh: “How to harmonize industrial growth with the conservation of water resources, biodiversity, and cultural heritage?” The long cycles of economic development and prosperity are triggered by technological innovations that permeate all sectors of the economy, according to the well-known Kondratieff model. It is believed that the next sixth cycle will depend on increasing productivity of natural resources. This increase implies a more efficient use of the mineral deposit itself, as well as of water, energy, and other inputs. In this context, a deep understanding of the social, cultural, and ecological values of water, including the ecosystem services and the existing biodiversity, is needed. Further pressure will come from the competition for increasingly scarce natural resources that are unevenly distributed worldwide, as well as from climate change. Breakthroughs will come from truly interdisciplinary approaches supported by a broad agreement involving the private sector, government, and society. This has been the vision of INCT-Acqua since its creation in 2009, and the Institute is ready to face these upcoming and increasingly complex challenges. Virginia Ciminelli, Francisco Barbosa and José Galizia Tundisi September 2016

Premises Mineral resources, water and biodiversity are competitive advantages and should guide initiatives focused on capacity building, innovation, and scientific, economic and social development.

Water is a transformation agent to promote innovation, to increase industrial competitiveness, social approval and a regional sustainable development.

Scope Provide a comprehensive evaluation of the environmental impact of the mineral industry on water, sediments, air and on aquatic biodiversity. Re-design industrial processes with the aim of minimizing the consumption of natural resources and the production of wastes. Develop innovative and integrative approaches for the diagnosis and remediation of impacted mining areas. Focus on capacity building, with new perspectives of sustainability and business diversity. Assist stakeholders in shaping the future of mining territories.

INTRODUCTION

MANAGEMENT COMMITTEE Virginia S. T. Ciminelli – UFMG (Director INCT-Acqua) José Galizia Tundisi – IIEGA (Vice-Director INCT-Acqua) Francisco Antônio Rodrigues Barbosa – UFMG (Vice-Director INCT-Acqua) Ana Claudia Queiroz Ladeira – CNEN-CDTN Angela de Mello Ferreira – CEFET-MG Hélio Anderson Duarte – UFMG Jaime Wilson Vargas de Mello – UFV ADVISORY COUNCIL Renato Ciminelli (President of Geopark Quadrilátero Ferrífero), President Carlos Nogueira Costa Junior (Secretary of Geology, Mining and Mineral Processing, MME) Evando Mirra de Paula e Silva (Emeritus Professor, UFMG) Francisco Alves (Editorial Director, Brasil Mineral Magazine) Leonardo Santana Dias (Geotechinal Manager, Coffey Mining) Silvio Crestana (Researcher and Former President of Embrapa) LEADING INSTITUTIONS UFMG (Universidade Federal de Minas Gerais) IIEGA (Instituto Internacional de Ecologia e Gerenciamento Ambiental) CDTN (Centro de Desenvolvimento da Tecnologia Nuclear) CEFET-MG (Centro Federal de Educação Tecnológica de Minas Gerais) UFV (Universidade Federal de Viçosa) NATIONAL COLLABORATION FASAR (Faculdade Santa Rita) UFC (Universidade Federal do Ceará) UFJF (Universidade Federal de Juiz de Fora) UFSJ (Universidade Federal de São João Del-Rei) UFVJM (Universidade Federal dos Vales do Jequitinhonha e Mucuri) PROGRAMS AND PROJECTS ON TERRITORIAL DEVELOPMENT PROJECTS CODAP (Public Consortium for the Development of Alto Paraopeba) GEOPARK Quadrilátero Ferrífero COLLABORATION IN SPECIFIC PROJECTS AMIRA International CENPES/PETROBRÁS (Petróleo do Brasil S.A.) CNEN/LAPOC (Laboratório Poços de Caldas) GOLDER Associates IGAM (Instituto Mineiro de Gestão das Águas) INB Caldas (Indústrias Nucleares do Brasil) KINROSS Brasil Mineração SANAP (South American Network for Acid Prevention) VM (Votorantim Metais) INTERNATIONAL COLLABORATION CNEA (Centro Atómico Constituintes, Comisión Nacional de Energía Atómica), Argentina Helmholtz Centre for Environmental Research, Germany Jacobs University, Germany KIT (Karlsruhe Institute of Technology), Germany Murdoch University, Australia Ohio University, United States of America Stockholm University, Sweden Technical University of Kosice, Slovakia The Pennsylvania State University, United States of America The University of Queensland, Australia University of Aarhus, Denmark University of Guelph, Canada

inct-acqua â–ª activity RepoRt 2013-2016

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INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

Facts and Figures

facts and figures

FACTS AND FIGURES

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

National and International Partnership

national and international partnership

NATIONAL AND INTERNATIONAL PARTNERSHIP

Alessandro Nepomuceno – Sustainability and Permitting Director at Kinross Gold Corporation “The assessment of arsenic exposure of the population of Paracatu* due to the mineralogy of Morro do Ouro (Minas Gerais, Brazil) played a pivotal role in demystifying the theme of arsenic and addressing the legitimate fears expressed by the local community. The research investigation also demonstrates that mining companies should be proactive in order to assure the sustainability of their operations. The project can be considered a landmark in the mining industry due to its broad scope and expertise, as well as the advanced scientific and technical tools that have been employed. The outcomes were also essential to maintaining the high reputation of the company and the respectful relationship with key stakeholders (community, environmental agencies, City Hall, and the public attorney’s office), without which we could not ensure the continuity of our operations.” *see next page

Dr. Adelson de Souza – Technologies General Manager at Votorantim Metais The Votorantim Metais - INCT Acqua partnership, as part of the AMIRA project P705C*, was of great importance in improving the performance of the Três Marias (TM) unit. The project provided a diagnosis of the effect of organic impurities in Zinc Electrowinning. As a result of the investigations, the electrical current efficiency increased from 90.1 to 92.5 - 93.5% while the energy consumption decreased from 3.303 kWh/t zinc to approximately 3.072-3.132kWh/t zinc. The improvements represent approximately US$3.3 million per year in energy savings and have increased productivity. With the achieved indexes, the TM Metallurgical Unit was raised to a leading position worldwide in Zinc production costs.

(1) Jack Ng – The University of Queensland, Australia. (2) Michael Moats – Missouri University of Science and Technology, USA. (3) Dina Lopez – Ohio University, USA. (4) Kwadwo Osseo-Asare – The Pensylvania State University, USA. (5) Gordon Brown – Stanford University, USA. (6) Susan Glasauer – University of Guelph, Canada. (7) Thomas Heine – Jacobs University, Germany. (8) Kay Knöller – Helmholtz Centre for Environmental Research, Germany. (9) Jim A. Field – The University of Arizona, USA. (10) Massimo Gasparon – The University of Queensland, Australia. (11) Joe Dinz da Costa – The University of Queensland, Australia. (12) Supapan Seraphin – Arizona State Univesity, USA. (13) Michael Nicol – Murdoch University, Australia. (14) Gianluca Timò – Ricerca su Istema Energetico, Italy. (15) Tomas Hávlik – Technical University of Kosice, Slovakia. (16) Peter G. Weidler – KIT (Kalsruhe Institute of Technology), Germany. (17) Marta Litter – CNEA (Centro Atómico Constituintes), Argentina. (18) Lars G. M. Pettersson – Stockholm University, Sweden. (19) Yves Dhau Decuypere – International Consultant for Territorial Development, France.

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

Project Highlights from Brazil-Australia Collaboration

Assessment of arsenic exposure for the population of Paracatu, Minas Gerais

Water availability in the Alto Paraopeba basin of Brazil: implications for one of the world’s largest iron ore mining districts

INCT-Acqua was a key player in an issue that received considerable media coverage worldwide - arsenic contamination in Paracatu. This seven-year research project, funded by Kinross Brasil Mineração-KBM, involved a multidisciplinary group from Brazil and abroad (Dr. Massimo Gasparon and Dr. Jack Ng, University of Queensland). Extensive investigation of soil, dust, water, and food clearly showed that the health risks from arsenic exposure for the general population in Paracatu are low and comparable to the normal dietary intake of arsenic throughout Brazil. The work also involved an extensive program of science communication implemented to clarify the science concerning arsenic and to inform residents about the true risks. One significant scientific finding from this work was the identification of a nanoscale mechanism underlying the long-term As fixation in the environment. The mechanism involves arsenic sorption onto Al-Fe (hydr)oxide nanoparticles occurring in soils, followed by aggregation in a process to produce nanosized Al-hematite. Such a stable arsenic form is reflected in the very low bioaccessibility of geogenic materials of both natural and anthropogenic origin, and explains the low level of exposure in a region where natural arsenic concentration is very high.

A sub-catchment of the Paraopeba River was selected for this study. Trends in river discharge, rainfall, population, and water demand were calculated for this sub-catchment from existing Government records. Since 2012, the Alto Paraopeba region has been affected by drought, and this, combined with an increase in population and demand for water resources, has resulted in a significant decrease in measured river discharge. The value for 2014 in the sub-catchment of the Paraopeba River under investigation was 22% lower than that predicted from historical records. The reduction in rainfall, coupled with the increase in surface and groundwater use, is also causing a rapid depletion of groundwater resources. The net reduction in water availability raises the prospective of severe water shortages in a region that has never before been affected by water scarcity, with severe negative consequences for social and economic development, and environmental and human health.

NATIONAL AND INTERNATIONAL PARTNERSHIP

Dr. Massimo Gasparon (The University of Queensland, Australia) was granted a Special Visiting Professor fellowship from the Science without Borders program.

A new method to analyze single particles in air particulates

Capacity building

In partnership with the UFMG Center for Microscopy, we are in the final stages of the development of a new method for the collection and analysis of single particles in airborne dust, using the Mineral Liberation Analysis (MLA). This method can be applied to trace the source of most elements in air particulate matter (with an analytical throughput of over 10,000 particles per hour), which can therefore be used to identify and manage sources responsible for the release of potentially toxic elements into the atmosphere.

The collaboration with Dr. Gasparon included co-supervision/co-tutelle of 6 Ph.D. students (from UFV, CDTN and UFMG) and 3 Post-Doc fellows. Exchange/training programs involved 3 undergraduate students, 1 M.Sc. student, 1 visiting researcher, and 1 visiting professor (from Brazil); and 2 Ph.D. students (from Australia).

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

Organization of Events and Seminars

“IX Week of Science and Technology-Renewable Energy and Advanced Solar Cells Technology”, Seminar, Department of Chemistry, CEFET-MG. October 16, 2014. Gianluca Timò (Ricerca su Sistema Energetico, Italy)

“Production Trends and Research Opportunities in Copper Electrorefining”, Seminar, School of Engineering, UFMG. June 21, 2016. Michael Moats (Missouri University of Science and Technology, USA)

“5th International Congress on Water Management in Mining”, Santiago, Chile. May 18-20, 2016. (INCT-Acqua, Co-Organizer) “Surface pH Measurements: Enabling New Insights into Dissolution and Precipitation Kinetics”, Seminar, School of Engineering, UFMG. May 10, 2016. Kwadwo Osseo-Asare (The Pennsylvania State University, USA)

“Arsenic Remediation by Formation of Arsenic Sulfide Minerals in a Continuous Anaerobic Bioreactor”, Seminar, School of Engineering, UFMG. April 07, 2016. Jim A. Field (University of Arizona, USA)

“INCT-Acqua Workshop on Alto Paraopeba Mining Territory”, Workshop, School of Engineering, UFMG. May 18, 2015. “Arsenic Speciation in Water and Sediment”, Symposium, School of Engineering, UFMG. May 11, 2015. “Computer Simulation and Synchrotron Radiation in Environmental Chemistry and Geochemistry”, Workshop, Department of Chemistry, UFMG. March 16-18, 2015. Lars G. M. Pettersson (Stockholm University, Sweden), Gordon Brown (Stanford University, USA)

“Materials Processing and Separation Processes in Aqueous Systems: Solids, Solutions and Interfaces”, Seminar, Department of Chemistry, UFMG. June 25, 2015. Kwadwo Osseo-Asare (The Pennsylvania State University, EUA)

“Ultrafast Observation of Formation and Breaking of Chemical Bonds in Heterogeneous”, Seminar, Department of Chemistry, UFMG. March 17, 2015. Lars G. M. Pettersson (Stockholm University, Sweden)

“Recycling Electronic Wastes by Using Hydrometallurgical Methods”, Seminar, School of Engineering, UFMG. October 20, 2014. Martina Petranikova (Chalmers University of Technology, Sweden)

“Project Sun on Clean - Materials Science Contribution for Solar Energy-Project: Seventh Framework Programme. Marie Curie Actions. International Research Staff Exchange Scheme”, Workshop, Department of Chemistry, CEFET-MG. October 17, 2014. Gianluca Timò (Ricerca su Sistema Energetico, Italy)

“X- Ray Diffraction: Principle and Application”, Seminar, Department of Chemistry, CEFET-MG. October 2, 2014. Peter G. Weidler (Karlsruhe Institute of Technology-KIT, Germany)

“Ultrafst Observation of Formation and Breaking of Chemical Bonds in Heterogeneous Catalysis”, Seminar, Department of Chemistry, UFMG. August 22, 2014. Lars G. M. Pettersson (Stockholm University, Sweden)

“Theoretical Modeling of X-ray Spectroscopies”, Seminar, Department of Chemistry, UFMG. August 20, 2014. Lars G. M. Pettersson (Stockholm University, Sweden)

“Environmental, Landscape & Urban Planning Concepts & Cases Applied to Mining Regions and Local Communities Engagement”, Seminar, School of Engineering, UFMG. October 18, 2013. Silvia Serrao-Neumann and Darryl Low Choy (Griffith University, Australia)

“New Challenges in the Exploration of Chalcopyrite”, Workshop, Brazilian Synchrotron Light Laboratory, Campinas - SP, Brazil. September 30, 2013. LNLS, UFMG, UFC, UNESPE

“Analysis of Carbon Nanotubes Using TEM and SEM Interfaced with Raman Spectrometer”, Seminar, Institute of Exact Sciences, UFMG. May 24, 2013. Supapan Seraphin (Arizona State Univesity, USA)

NATIONAL AND INTERNATIONAL PARTNERSHIP

Invited Lectures (from a total of 52) 6th International Congress on Arsenic in the Environment (As2016). “New Insights in the Mechanisms of Arsenic Association With Iron Oxides in the Environment”. Stockholm, Sweden. June, 19-23, 2016. Virginia S.T. Ciminelli

5th International Congress on Water Management in Mining. “Water Scarcity in Mining Areas: Why We Can no Longer Go with the Flow”. Santiago, Chile. May 20, 2016. Massimo Gasparon and Virginia S.T. Ciminelli

Water JPI Conference. “Why International Research Cooperation is Necessary for Solving Water Challenges? How to cooperate?”. Rome, Italy. May 19, 2016. Francisco A. R. Barbosa

International CECAM-Workshop in Development of Next Generation Accurate Approximate DFTB Methods. “Clay Mineral Nanotubes – a SCC-DFTB Study”. Bremen, Germany. October 11-15, 2015. Hélio A. Duarte

The Inter-American Network of Academies of Sciences & UNESCO International Hydrological (IANAS-UNESCO-IHP)Workshop Water Quality in the Americas. “The Quality of Surface and Groundwater Resources”. Orange Country, California. USA. September 3-5, 2015. José Galizia Tundisi

XV Demon Developers Workshop. “Inner Surface Modified Imogolite Nanotubes – A SCC-DFTB Study”. Sofia, Bulgaria. May 28-31, 2015. Hélio A. Duarte

International Workshop - Computer Simulation and Synchrotron Radiation in Environmental Chemistry and Geochemistry. “ACID MINE DRAINAGE: Concepts, Assessment and Case Study”. Belo Horizonte-MG, Brazil. March 16-18, 2015. Ana Claudia Q. Ladeira

10th Congress of the World Association of the Theoretical and Computational Chemists – WATOC2014. “Reactivity of the Sulfide Mineral Surfaces – A DFT Study”. Casa Piedra - Santiago, Chile. October 5-10, 2014. Hélio A. Duarte

5th International Congress on Arsenic in the Environment (As2014). “Arsenic in Mining: Sources and Stability”. Buenos Aires, Argentina. May 11-16, 2014. Virginia S. T. Ciminelli

SUN ON CLEAN - Ricerca Sul Sistema Energetico SPA- SER. “Functionalization of Surface and Development of Advanced Materials for Environmental Application”. Milan, Italy. April 3, 2014. Angela de Mello Ferreira

XXXIV Brazilian Congress of Soil Science Symposium. “Role of Soil Mineralogy in Environmental Contamination Processes for Trace Elements.”. Florianópolis - SC, Brazil. July 28-August 02, 2013. Jaime W. V. de Mello

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

Scientific Missions Michael Moats – Missouri University of Science and Technology, USA. Seminar. UFMG, Belo Horizonte, Brazil. June 20-22, 2016; Technical Visit and Lecture. Votorantim Metais Zinco, Juiz de Fora, Brazil. June 22-24, 2016.

Kwadwo Osseo-Asare – The Pennsylvania State University, USA. Visiting Professor. UFMG, Belo Horizonte, Brazil. May – July, 2015; Elected Foreign Member of the Brazilian Academy of Sciences. Rio de Janeiro, Brazil. May, 03-06, 2016; Seminar and Meeting. UFMG, Belo Horizonte, Brazil. May 07-11, 2016.

Peter M. Fleming – CDTN/CNEN, Brazil Training. Helmholtz Centre of Environmental Research – UFZ, Leipzig, Germany. September-November, 2013; Wismut GmbH, Ronneburg, Germany. October, 2013.

Jaime W. V. de Mello – UFV, Brazil Work Mission. The University of Queensland, Queensland, Australia. July, 2012- March, 2013; The University of Queensland. Brisbane, Australia. September, 2013.

Students Exchange Ifeyiwa Obuekwe – University of Benin, Nigeria (Post Doc). UFV, Viçosa, Brazil. March, 2015 - April, 2016.

Massimo Gasparon – The University of Queensland, Australia. Special Visiting Professor. UFMG, Belo Horizonte, Brazil. February, April, and June, 2013; February, May, November, 2014 and 2015; February and October 2016.

Virginia S. T. Ciminelli – UFMG, Brazil Seminar and Worshop. Developing a Pan American Hub for Environmentally and Socially Compatible Mining. Lima, Peru. March 7-9, 2016. Project Meeting AMIRA International LTD (AMIRA Project P705-C). Victoria, Canada. June, 2014. Seminar. Brazil/US Women Scientists and Engineers. Boston, USA. February, 2013.

Daniel Majuste – UFMG, Brazil Project Meeting AMIRA International LTD (AMIRA Project P705-C) - Sepon Mine Site, Laos, March 2016; Rustenburg, South Africa, January, 2015; Rolla, USA. July 2015; Victoria, Canada. June, 2014;

The University of Queensland, Australia. April, 2015 - March, 2016.

Michele Elmes – The University of Queensland, Australia (PhD). UFMG, Belo Horizonte, Brazil. May - August, 2015.

Andy Alan Mella Orellana – Universidad de Chile, Chile. UFMG, Belo Horizonte, Brazil. March - July, 2015.

Juliana Cecília de Mendonça Silva – UFMG, Brazil. Jacobs University, Bremen, Germany. August, 2014 - July, 2015.

Antonio Lenito Soares Junior – UFMG, Brazil. Jacobs University, Bremen, Germany. August, 2014 - July, 2015.

Angel Moraes – Universidad Complutense de Madrid, Spain. UFMG, Belo Horizonte, Brazil. April - October, 2014.

Magnum Augusto Moraes Lopes de Jesus – CEFET-MG, Brazil.

Participant of the V Dutch Visitors Programme (DVP) - High Tech Systems and Material. Amsterdam, The Netherlands. November 4, 2014.

Materials for Energy and Environment division TECNALIA, San Sebastián – Spain. July - September, 2014.

Angela de Mello Ferreira – CEFET-MG, Brazil

The University of Queensland, Brisbane, Australia. March, 2013 February, 2014.

Work Mission. Ricerca su Sistema Energetico, Milan, Italy. May, 2013; March, 2014; January, 2015.

Hélio A. Duarte – UFMG, Brazil Work Mission. University of Calgary, Alberta, Canadá. April 11-18, 2013; Work Mission. Jacobs University, Bremen, Germany. June 16-27 , 2014.

Rodinei Augusti – UFMG, Brazil Work Mission. University of Wageningen, Wageningen, Netherlands, July, 2013 - July, 2014.

Claudia Lima Caldeira – UFMG, Brazil Training. Soil and Earth Sciences- The University of Queensland, Brisbane, Australia. July - August, 2014.

Erico Tadeu Fraga Freitas – UFMG, Brazil (PhD).

Alysson Martins Almeida Silva – UFMG, Brazil.

Sebastien Amaya Roncancio – Universidad Nacional de San Luis, Argentina. UFMG, Belo Horizonte, Brazil. Jan - April, 2014.

NATIONAL AND INTERNATIONAL PARTNERSHIP

Interaction with other projects and INCT’s INCT-ADAPTA (Adaptations of Amazonian Aquatic Biota)

CNPq/CT MINERAL – CDTN

V Workshop INCT-ADAPTA and INCT’s meeting - The main purpose

Development of technologies for the recovery of rare earths from secondary sources, microchemistry/mineralogical characterization and applications in the production chain (2013-2017).

was checking overlaps, interfaces and mainly points to enhance cooperation between the INCT’s. This meeting was an initiative of INCT-ADAPTA (CNPq / FAPEAM).

INCT-INAMI (National Institute of Science and Technology on Nanotechnology for Integrated Markers)

CNPq/CT MINERAL – DEMET-UFMG Purification of sulphuric liquors of nickel using synergistic solvent extraction (2011-2015).

Scientific collaboration and co-supervision for doctoral student.

CNPq – ICB-UFMG

Project BRA 9057 - IAEA (International Atomic Energy

Metagenomic analysis of prokariots in sediment from Córrego da Mina, Iron Quadrangle-Minas Gerais (2012-2015).

Agency) Strengthening the regulatory system to ensure alignment of the safety

CNPq/CT MINERAL – CDTN

of nuclear fuel cycle facilities to the best international practices. (CDTN)2014-2016.

Characterization and Mitigation of Environmental Impacts Arising from Acid Mine Drainage (2011-2014).

FP7/ IRSES

FAPEMIG – ICB-UFMG

Exchange Program of the EUROPEAN COMMISSION, Study of soiling

Metagenom of sediment from stream rich in heavy metal, Iron Quadrangle (2014-2016). Diversity of prokariot and of gens resistant to arsenic in sediments from pristine and historically impacted by mining activities (2012-2015).

effect and glass surface modification of concentrating photovoltaic (CPV) modules: Climate influence and comparative testing - Sun on Clean project, involving the following countries: Italy (leader), Spain, Russian and Brazil. (Angela de Mello Ferreira- coordinator in Brazil) 2012-2014.

FP7/IRSES Exchange Program of the EUROPEAN COMMISSION, Computer Simulations of Thermally Excited Molecules and Materials by First Principles. involving the following countries: Germany (leader),

FAPEMIG – ICB-UFMG/CEFET-MG/FIOCRUZ/MHN-JB/UFMG Diversity and functional characteristics of yeasts associated with bromeliads in areas of campos rupestres of the Serra da Piedade, Minas Gerais, through the metagenomic and transcriptomic approach, and cultivation (2016-2017).

Spain, Italy, France, Mexico, Canada, Japan and Brazil. (Hélio A

FAPEMIG – BELAS ARTES-UFMG

.Duarte- coordinator in Brazil) 2012-2015.

Stability versus instability in the digital art (2014-2016). Using 3D cameras in Character cut-out animation (2014-2016). The Digital Game-Book Goes to School: Development of interactive narratives and technologies for hypermedia, web and mobile devices as support for paradidactic books (2014-2015).

J.A. RENGIFO-HERRERA/CINDECA - Universidade de La Plata (UNLP) TiO2 photocatalysis, “Synthesis and characterization of materials (TiO2) sensitive to visible light “and” Fenton process and the photoFenton water disinfection. (Research Center of Applied Science of

FAPEMIG (PRONEM) – DEMET-UFMG

JJ Husky-CINDECA, University of La Plata, UNLP (Argentina); Brazil.

Study of the removal of manganese contained in industrial effluents and acid waters from acid mine drainages using distinct hydrometallurgical methods (2012-2015).

(Andréa R. Marques Guimarães). 2013-2015

Tecnalia Research & Innovation/Spain Surface modification process based on sol-gel thin film deposition technology. (Tecnalia Research & Innovation - Spain, Department of Materials for Energy and Environment, San Sebastián-Spain; Brazil. (Angela de Mello Ferreira - CEFET-MG- main researcher) 2014.

FAPEMIG/FUNDAÇÃO MUNICIPAL DE CULTURA (FMC) – BELAS ARTES-UFMG Preservation and memory of the art front volatility (2013-2015).

FAPEMIG/THE UNIVERSITY OF QUEENSLAND, AUSTRALIA – UFV

Additional Funding

Fe and Al hydroxides as geochemical barrier: acid drainage mitigation and processing phases (2011 - 2014).

AMIRA INTERNATIONAL/VOTORANTIM METAIS –

FAPEMIG/THE UNIVERSITY OF QUEENSLAND, AUSTRALIA – CDTN

DEMET-UFMG/ MURDOCH UNIVERSITY Electrowinning of Base Metals. Partners: 4 Universities and 8 global companies (2011-2017).

Study of the hydrogeology and geochemistry of a uranium mine waste rock dump: alternatives for remediation or further exploitation (2011-2015).

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

FAPEMIG/PRONEX PROJECT – MICROSCOPY CENTER (UFMG) - CEFET-MG/DEMET-UFMG Multidisciplinary Center for High Resolution Microscopy and Microanalysis (2010-2015)

FAPEMIG/VALE – CDTN/UFOP Project for Excellence in Manganese (2010 – 2016).

FINEP – CDTN Development of a process to produce zirconium sponge and zirconium alloy tubes (2010-2015).

FINEP – IIEGA Monitoring of rural and urban watersheds. Integrated analysis of water quality (2010-2015).

FINEP – IIEGA Real time monitoring of the six reservoirs of the waterway (Hidrovia) Tietê River, São Paulo State (2010-2014).

ISOHIDRO – CDTN Isotope hydrology of formation and production waters ( 2012-2015).

KINROSS Brasil Mineração – DEMET-UFMG/UFV (BRAZIL)/ UNIVERSITY OF QUEENSLAND/ENTOX (AUSTRALIA) Assessment exposure assement for the population of Paracatu, Brazil. Stages 1-4 (2011-2017).

MCT/CNPq - PELD – ICB-UFMG Long-term Program on Ecological Research – Phase II- Ecological processes and the conservation of biological diversity of th Atlantic Forest in the middle Rio Doce watershed, Minas gerais (2012-2015).

PETRÓLEO BRASILEIRO S/A – DEMET-UFMG CO2 capture and separation applied to natural gas from the pre-salt scenario: Synthesis, structural characterization and performance evaluation of multifunctional advanced ceramic membranes and new adsorbents (2009-2016).

SWEDISH RESEARCH COUNCIL – ICEX (Department of Chemistry)-UFMG Surface Reactivity of Sulfide Minerals – Connection to acid mine drainage. Brazil-Swedish cooperation program. Swedish research council (2014-2017).

VALE – DEMET-UFMG/R.LAWRENCE (Canada) Assessment of the potential of Acid Mine Drainage Generation in Base Metal Deposits (2011-2013).

VOTORANTIM METAIS – IIEGA Limnology, physical, chemical and biological condition of the São Francisco River (40 km).Evaluation of sediment contamination, impact of zinc in the survival of fishes, management of contaminated sediment (2005-2014).

VOTORANTIM METAIS – DEMET-UFMG Effects of organic impurities and additives on the current efficiency of zinc electrowinning ando n the product quality (2013-2017).

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

Educational and

Outreach Activities

educational and outReach activities

Graduate Courses

“Advanced Oxidation Processes Used in the Elimination of Chemical and Microbiological Contamination of Water”.

Graduate Degree in Watershed Management – ICB/UFMG

educational and outreach activities

Francisco A. R. Barbosa (chair).

Graduate Program in Metallurgical, Materials and Mining Engineering – UFMG

Andrea R. Marques Guimarães (CEFET-MG - Organizer). Julian Andrés Regifo-Herrera (J.J Ronco CINDECA - Universidad de La Plata - UNLP - Argentina - Lecturer). CEFET-MG, Brazil. August 20-26, 2013.

“Energy Systems in Sustainable Development”, 16 h. Joe Diniz da Costa, The University of Queensland – Australia. November 16-26, 2015. “Membrane Science &Technology”, 20 h. Joe Diniz da Costa, The University of Queensland – Australia. September 15-26, 2014.

Lectures and Workshops Knowlodge Transfer to Society, Elementary and Secondary Schools

“Gold Hydrometallurgical Processing”, 15h. Juan F. Schwarzen, Universidad de Chile. September 23 and 30, 2013.

Francisco A. R. Barbosa

Graduate Program in Materials Engineering (CEFET-MG) Graduate Program in Metallurgical, Materials and Mining Engineering (UFMG)

“Environmental Conditions and Impacts of Mining Activities: The

“Application of the Rietveld Method for Mineral Samples”, 15h. Peter

Horizonte-MG, Brazil. October 21, 2015.

George Weidler, Karlsruhe Institute of Technology – Germany, October 6-10, 2014.

INCT-Acqua Initiative”. Week Knowledge UFMG 2015 - Meeting of Science, Education and Culture of the ICB/UFMG. Belo

“Water Governance in Brazil: Challenges and Perspectives”. Minas Gerais and Spain: Dialogue For Innovation In Water Resources

Short Courses

Management. Belo Horizonte-MG, Brazil. June 23, 2015. “Services of Aquatic Ecosystems“. Symposium Water Resources In the Southeast: Water Security, Risks, Impacts and Solutions.

“Density Functional Theory – Formalism and Methodology”.

organized by the Brazilian Academy of Sciences. São Paulo-SP, Brazil.

Hélio A. Duarte (UFMG-Lecturer). Universidad Nacional de San Luis,

November 20-21, 2014.

Argentina. April 08-13, 2015.

“ICPOES” – Inductively Coupled Plasma Optical Emission Spectroscopy. Virginia S.T. Ciminelli (UFMG-Organizer), Júlio César José da Silva

Hélio A. Duarte “Mineral Resources, Water and Biodiversity – Química Nova (Thematic Issue)”. Week of Science and Technology - CEFET-MG.

(UFJF-Lecturer). UFMG, Brazil. December 15-16, 2014.

Belo Horizonte-MG, Brazil. October 22, 2015.

“Density Functional Theory – Formalism and Methodology”.

“Mineral Resources, Water and Biodiversity – Química Nova

Hélio A Duarte (UFMG-Lecture). FFCLRP – USP, Ribeirão Preto,

(Thematic Issue)”. Symposium of Professionals Chemistry Teaching

Brazil. September 1-5, 2014.

– SIMPEQ, UNICAMP. Campinas-SP, Brazil. October 31, 2014.

“Computational Modeling of Chemical Speciation in Aqueous Solution. Native Defects in Solids and Chemical Surface Reactivity”. Hélio A. Duarte (UFMG-Lecture). Jacobs University – Bremen,

Paulina Maia-Barbosa “Ecology Accessible to All”. Workshop: Participatory Monitoring Watershed. Belo Horizonte, MG, Brazil. November 21-22, 2013.

Germany. June 16-17, 2014.

Virginia S. T. Ciminelli

“Surface Engineering: Thin Film Deposition Technology”.

“Water, Mining, Biodiversity: Competing Uses, Drought Impacts,

Angela de Mello Ferreira (CEFET-MG – Organizer). Iñigo Braceras

Prospects. “Symposium Water Resources In the Southeast: Water

(Tecnalia Research & Innovation - Spain - Lecturer). CEFET-MG,

Security, Risks, Impacts and Solutions”. organized by the Brazilian

Brazil. April 23-24, 2014.

Academy of Sciences. São Paulo-SP, Brazil. November 20-21, 2014.

“Treatment of Industrial Wastewater: Conventional and Advanced Methods”.

“Scientific Knowledge In Environmental Impact Assessment and

Angela de Mello Ferreira (CEFET-MG - Organizer - Lecturer). CEFET-MG,

Approach”. Transdisciplinarity in Science, organized by the Brazilian

Brazil. October 22-23, 2013.

Academy of Sciences. Belo Horizonte-MG,Brazil. April 10, 2013.

Human Health In Mining Regions: A Systemic And Multidisciplinary

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

“Assessment of arsenic exposure for the population of Paracatu, Minas Gerais, Brazil”.

Gabriela Cordeiro Silva

The results of this Kinross/UFMG research project have been

in Metallurgical, Mining and Materiais Engineering of UFMG, Brazil.

presented in a series of seminars held in:

October, 2013.

UFMG Thesis Award: Best Thesis in 2013 from the Graduate Program

Advisor: Virginia S. T. Ciminelli Belo Horizonte-MG, Brazil Opinion leaders and Press - February 2, 2016. Public Ministry and CETEM - July 1, 2015.

Co-Advisor: Angela de Mello Ferreira

Guilherme Ferreira de Lima UFMG Thesis Grand Award – Wide Area of Exact Sciences and Engineering, Brazil. October 2014.

Paracatu-MG, Brazil Opinion leaders and Press - January 27, 2016. Kinross company employees - June 29-30, 2015.

Honorable Mention – Chemistry, Capes Thesis Award, Brazil. December, 2014. UFMG Thesis Award – Chemistry, Brazil. December, 2014.

Directors, Supervisors and Teachers of State and City Schools -

Advisor: Hélio A. Duarte

November 9 and 13, 2013.

Co-Advisor: Heitor Avelino de Abreu

City Council. Kinross - November 20, 2013.

José Galizia Tundisi

Faculty members and students of FINOM (Faculdade do Noroeste de Minas), IFTM (Instituto Federal do Triângulo Mineiro) and Tecsoma Faculty - November 20 and 27, 2013. Rotarys Club and Masonic homes - November 20 and 27, 2013. Commercial and Industrial Association of Paracatu, The Agency for Social Economic Development of Paracatu, Trade Union and Accountants - November 2, 2013.

Awards and Distinctions

IANAS-UNESCO-IHP – Outstanding Leadership as co-chair of the Water Program, USA. September, 2015.

Virginia S. T. Ciminelli Slawomir Dominic Piatinik Award, Brazil. For lifetime achievement highlighted by scientific production and capacity to train skilled professionals. October, 2015. Elected Foreign Member of the National Academy of Engineering, USA. September, 2014. Admitted to the National Order of Scientific Merit, Brazil. October, 2013. Elected Member of the National Academy of Engineering, Brazil.

Daniel Majuste CETEM Award for Mineral Technology. October, 2013. Co-authors: Virginia S. T. Ciminelli, Maria Sylvia Silva Dantas, Rogério Magalhães-Paniago and Kwadwo Osseo-Asare

October, 2013.

EDUCATIONAL AND OUTREACH ACTIVITIES

Products and Educational Materials

Website Videos

www.acqua-inct.org Youtube Channel – INCT-Acqua “Impacts of Metals in Aquatic Biota and their Removal Through Bioremediation”. Professor: Francisco A. R. Barbosa, 2016. LINK: https://www.youtube.com/watch?v=XZp86Hkvp6U “The Use of Bacteria as Bio-Indicators of Impacts Caused by Mining”. Professor: Francisco A. R. Barbosa, 2016. LINK: https://www.youtube.com/watch?v=EGuWoxvsxi4 “INCT-Acqua in the School: Water School”. CESUP, 2016. LINK: https://youtu.be/kBTTmyoM0Ok “Game Water Drop”. Professor: Francisco Marinho, 2016. LINK: https://www.youtube.com/watch?v=8ndJ8aDgeHU “Process Optimization and Development of Base Metal Electrowinning”. Professor: Daniel Majuste, 2015. LINK: https://www.youtube.com/watch?v=0izPN1VYWtw “Selection and Development of Functional Materials for Liquid Effluents Decontamination”. Professor: Angela de Mello Ferreira, 2015. LINK: https://www.youtube.com/watch?v=mTYiYZKHcHA “The Aquatic Biodiversity in Mining Areas”. Professor: Francisco A. R. Barbosa, 2015. LINK: https://www.youtube.com/watch?v=hmJ_Wq6Gihs “Toxic Contaminant Immobilization”. Professor: Virginia S.T. Ciminelli, 2015. LINK: https://www.youtube.com/watch?v=RitQS55DFbM

Printed media, digital games and installations

Química Nova na Escola Magazine (Thematic Issue) – Mineral Resources, Water and Environment. Editors: Duarte, H.A.; Rossi, A.V.; Giordan, M. SBQ, ISSN 0104-8899, 2014. 46 pages. Game Water Drop

News for radio broadcast, magazines, TV and websites

This project involved the development of an educational digital game. The avatar is a drop of water, which must follow the paths of a catchment area from the source to the mouth of a large river without being contaminated or affected by environmental degradation of various types. The goal is for the drop of water to reach the mouth of the river in the cleanest way possible. Along the way, the player comes across both enemies (polluters) and friends (decontamination agents and treatment). Magazines and Newspapers: 15 Newsletter: 2 TV: 7 Websites: 5 Newsletter INCT-Acqua: 7

INCT-ACQUA ▪ ACTIVITY REPORT 2013-2016

Community Empowerment and Capacity Building in Mining Territories The Alto Paraopeba Region (MG) is the most important iron ore - steel production hub in Brazil. “Environmental Education and Family Farming” was the selected topic for a pilot-project aimed at developing methodologies; mobilizing, engaging, and empowering rural communities in mining territories; and diversifying the region’s economy. Cooperative and capacity building projects were coordinated by the Center for Reference on Education and Sustainability in the Alto Paraopeba Region (CESUP). CESUP was created by INCT-Acqua in 2012 to become an outpost of the Institute in the region. Codap (Public Consortium for Development of the Alto Paraopeba Region), Geopark Iron Quadrangle, Embrapa (Brazilian Agriculture Research Corporation, Corn and Sorghum Center), and the Ministry of the Environment were engaged in these initiatives. The findings described here are to be replicated in other mining areas.

Program on Agriculture in Mining Territories and the Center of Reference for Agriculture in Mining Territories The INCT-Acqua initiatives were launched during the Seminar: Agriculture in Mining Territories, held on May 23, 2014. Two important outcomes of this Seminar were the creation of the Embrapa R&D Program on Agriculture in Mining Territories and the Center of Reference for Agriculture in Mining Territories, installed in the town of Ouro Branco in August 2016.

EDUCATIONAL AND OUTREACH ACTIVITIES

Environmental Education Program in Family Agriculture (PEAAF) PEAAF is a Brazilian governmental program with the focus on agroecology, environmental regulations, and solutions of rural environmental problems, with emphasis on water resources. Deliverables: • A “Pedagogical Political Plan for Family Agriculture in the Alto Paraopeba Region,” built with the participation of institutional and agriculture community leaders. • Local farm production is being prepared to become a major supplier of Industrial restaurants in the region. This initiative is supported by SEBRAE-MG and EMBRAPA, which provide marketing services, production planning, and expertise to the farmers.

Forum on Economic and Social Development of the Alto Paraopeba Region, April 2014.

Distance Learning for Environmental Education in Family Farming - PEAAF (INCT-Acqua/Geopark in Partnership with the Ministry of Environment) 105 participants (regional leaders, students of the School of Regional Family Agriculture, farmers and representatives of Farmers Association) in a 120 h course, administered in two editions: 2014 and 2016.

inct-acqua ▪ activity RepoRt 2013-2016

INCT-Acqua in the School: Pedagogical Garden Project: “Creating Sustainable Space in School” focused on the garden as a space for a multidisciplinary, hands-on teaching and learning methods. More than 150 students were enrolled (Nossa Senhora do Carmo City School and Raimundo Campos City School, Ouro Branco, MG).

INCT-Acqua in the School: Photography Workshops focusing on water and the environment 175 students were enrolled in two workshops provided by the photographer Matthew Baranowski, held at Sr. Odorico Martinho da Silva City School (Congonhas, MG in September 2015) and at the Oswaldo Cruz City School (Ouro Branco, MG in May 2016). This project included a photo exhibition and an awards ceremony for the best works.

educational and outReach activities

INCT-Acqua in the School: Water School 60 students were enrolled in activities, such as role-play games, chats, and expeditions to water springs to improve understanding of water quality and to produce possible solutions for local environmental problems (City School Oswaldo Cruz, Ouro Branco, MG, March 2016).

Workshop Environmental Monitoring System with the use of free software and hardware 25 participants were trained (April-May 2016) to become multipliers in the Arduino platform, a tool to develop devices for real time monitoring of environmental parameters and making them available to the comunity through mobile devices. In addition to improving knowledge on environmental education, this approach also empowers the local population in information technology.

inct-acqua ▪ activity RepoRt 2013-2016

Testimonies Maria Nazaria da Paixão Santos Cidiclei Ivonei dos Santos – Family Farmers It is a great honor to live in Ouro Branco. With this message, we intend to tell a little of our story as farmers. We were born on a farm, and all our food used to come from our crops and livestock. With the project “Agents for Environmental Education in Family Agriculture” and the support of INCT-ACQUA, we feel that we are recognized and honored Family Farmers. The dignity of our work on the farm has been restored.

Silvaní de Fátima Vieira – Principal of the Oswaldo Cruz City School – Water and Photography Workshop The partnership with INCT-Acqua was essential for broadening our student’s knowledge and practices regarding the rational use of water and the conservation of the riparian forest close to the springs.

Paulo Cezar Lopes Corrêa - President of CODAP Partnerships provide new opportunities. CESUP, with the support of INCT-Acqua, has leveraged projects focused on regional development that are important for the territory. These initiatives are important to guaranteeing a future with sustainable social and economic diversity.

Mateus Baranowiski – Volunteer Photographer in the Photography Workshop Projects I appreciate the opportunity to share my knowledge with the children, raising awareness and contributing to the preservation of our environment. I also see a great opportunity to show the children a different activity from their daily lives, and perhaps, from photography workshops, a new professional will appear in the future.

Maria de Lourdes de Almeida – Local Coordinator of Cesup CESUP has the mission to convey scientific knowledge to the community. One example of CESUP’s accomplishments was the training of agents for environmental education in family agriculture. This was done in partnership with the Ministry of the Environment, enabling agents to disseminate knowledge on environmental issues among the local farmers.

Pablo Daniel Cupertino Dias – Student at Oswaldo Cruz Ctiy School It’s very important to take care of the water. It’s not only the City Hall’s responsibility; each one of us has to do our part to avoid a shortage of water.

Renato Ciminelli – President of the Geopark Quadrilatero Ferrifero Steering Committee Through a number of cooperative projects, INCT-Acqua provided the fundamental partnership for the installation and consolidation of the Geopark Quadrilatero Ferrifero (GQF). The scientific and financial support, together with the staff from INCT-Acqua made it feasible to construct the four GQF pillars: (i) a Territory of Innovation and Education, (ii) a Territory of Sustainable Family Farming, (iii) a Forefront Territory for Sustainability, and (iv) a Territory of Economic Diversification and Social Inclusion. Geopark Quadrilátero Ferrifero is now in full operation and entitled, according to UNESCO´s guidelines, to apply for accreditation as a Global Geopark.

educational and outReach activities

Knowledge Transfer to Society, Elementary and Secondary Schools in Alto Paraopeba 2016 Workshop “Sustainable House, Association of Homeless of Conselheiro Lafaiete – ASTCOL.” Conselheiro Lafaiete-MG, Brazil. April 30, 2016. INCT Acqua/Cesup/Geopark/CODAP Inaugural Lecture of “Training in Environmental Education Agents in Family Agriculture” in partnership with the Ministry of Environmental. Conselheiro Lafaiete-MG, Brazil. May 7, 2016. INCT Acqua/Cesup/Geopark/CODAP

2015 Seminar “Education in the Rural Zone”. Conselheiro Lafaiete-MG, Brazil. April 27, 2015. INCT-Acqua/CESUP/Geopark/CODAP Workshop “Business Visions and Development for Small Mining. Belo Horizonte-MG, Brazil. August 19, 2015. INCT-Acqua/CESUP/Geopark/SEBRAE-MG/ Sindiextra

2014 Alto Paraopeba Shipping or Journey: Paths to Sustainability. Conselheiro Lafaiete, Congonhas, Ouro Branco, Cristiano Otoni, Caranaíba-MG, Brazil. April, 7- 8, 2014. INCT-Acqua/CESUP/Geopark/CODAP Seminar “Alto Paraopeba Sustainable Development”. Congonhas-MG, Brazil. April 9, 2014. INCT-Acqua/CESUP/ Geopark/Embrapa/CODAP Seminar “Minas Gerais and Queensland at the forefront of Mining and Innovation Practices”. Belo Horizonte-MG, Brazil. April 25, 2014. INCT-Acqua/CESUP/ Geopark/The University of Queensland Seminar “Agenda 21”. Ouro Branco-MG, Brazil. May 9, 2014. INCT-Acqua/CESUP/Geopark/CODAP

Training on Environmental Education in Family Farming for CODAP Council. Sete Lagoas-MG, Brazil. May 19, 2014. INCT-Acqua/CESUP/ Geopark/CODAP/Embrapa Seminar “Agriculture in Mining Territories”. Sete Lagoas-MG, Brazil. May 23, 2014. INCT-Acqua/CESUP/ Geopark/CODAP/Embrapa II Workshop “Management Plan Ouro Branco Mountain State Park”. Ouro Branco-MG, Brazil. June 17, 2014. INCT-Acqua/CESUP/Geopark/CODAP CSIRO Mission - International Research: List of Major Mining Projects with Communities. Congonhas-MG, Brazil. September 2, 2014. INCT-Acqua/CESUP/Geopark/CSIRO I Workshop “Environmental Education Territorial in Family Agriculture”. Ouro Branco-MG, Brazil. November 26, 2014. INCT-Acqua/CESUP/Geopark/CODAP/Embrapa/ Ministry of the Environment

2013 Seminar “Management in Sport and Legacy of Major Sporting Events – Challenges of Minas Gerais and Brazil”. Belo Horizonte-MG, Brazil. March 12, 2013. INCT-Acqua/CESUP/ Griffith University/ Geopark Lecture Cycle Chemistry in Agriculture. Conselheiro Lafaiete-MG, Brazil. April 29, 2013. INCT-Acqua/CESUP/Geopark/CODAP International Seminar: ““Mining as Anchor for Territorial Development - CSIRO Case”. Ouro Branco-MG, Brazil. June 13, 2013. INCT-Acqua/CESUP/Geopark/CODAP/CSIRO Workshop “Program in Environmental Education on Family Agriculture”. Ouro Branco-MG, Brazil. November 26-27, 2013. INCT-Acqua/CESUP/Geopark/CODAP/Embrapa/ Ministry of the Environment

Science

Highlights 34

Research Topic 1

Assessment of Water and Enviromental Quality, and Aquatic Biodiversity 63

Research Topic 2

Natural and Synthetic Materials for Enviromental and Technological Applications 80

Research Topic 3

Advances in Hydrometallurgical Processes 93

Research Topic 4

Acid Rock Drainage 33

INCT-ACQUA â–Ş ACTIVITY REPORT 2013-2016

Research Topic 1 PART 1 Assessment of Water and Enviromental Quality, and Aquatic Biodiversity 35

Water availability, water quality water governance: the future ahead

The SĂŁo Francisco river research development: Basic science for river recovery of metal contamination

Water quality and phyto-zooplankton communities from mining areas in the upper Paraopeba watershed, Minas Gerais, Brazil

Taxonomic and functional investigation of a microbial community inhabiting a metal-rich tropical stream sediment

Water availability, water quality water governance: the future ahead J.G. Tundisi1,*, T.M. Tundisi2, V.S.T. Ciminelli3, F.A.R. Barbosa4 International Institute of Ecology, University of FEEVALE. São Carlos - São Paulo, Brazil. International Institute of Ecology. São Carlos - São Paulo, Brazil. 3 Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG. Brazil. 4 Department of General Biology, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG. Brazil. *Corresponding author: tundisi@iee.com.br 1 2

Keywords: Water availability, water quality, pollution, water security.

Water availability, water quality and water governance are, today, at the center of the discussion on Water Security. Four interrelated issues are dominating in water security: water availability, human vulnerability to hazards and disasters, human needs (especially food security) and sustainability (Cook and Bakker, 2012). Before the presence of Homo sapiens on Planet Earth, water was available for the ecosystems to maintain biogeochemical cycles and biodiversity. When mankind expanded, occupying the whole globe and diversifying its activities, so the multiple uses and water demands increased and also diversified. Today, 70% of the water available is used for food production. Hydroelectricity, navigation, public supply, and recreation, are all human activities that use most of the remaining freshwater resources of Planet Earth. But as the human demands for water expanded and diversified, so did the contamination and degradation of the water resources and the inland water ecosystems: lakes, rivers, creeks and reservoirs. Agricultural fertilizers, untreated human sewage, industrial effluents, pesticides and herbicides are polluting the freshwater ecosystems at an alarming rate. In this paper we will attempt to show how the integration of water availability, water quality and water governance can be fundamental for the water security of human populations and ecosystem functioning. Water Availability - Water is a renewable resource. The hydrological cycle has maintained and will maintain for millennia, the cycle of life on the planet, the biogeochemical cycles of nutrients that are the source of life such as phosphorus, nitrogen, amino acids, proteins and sugars.

The availability of water resources, surface and groundwater in different continents shows areas of abundance and scarcity, and significant variations within continental scales. Information on supply/demand of water for continents, regions and watersheds still needs to be improved. A strong and well-designed database for each individual watershed with a high degree of reliability is fundamental for advanced water governance. Since water also supports the functioning of ecosystems this indirect support should be taken into account in the data for the availability of water. The role of water in the biogeochemical cycles, water as a source/sink for gases and ions, and its dilution capacity have to be considered in the statistics for water availability. It is necessary to balance ecosystems and human needs of water in a true effort to evaluate the amount of water necessary for each region, continent or watersheds. Also, continental or regional changes of hydrological cycles as a consequence of climatic changes (excess rainfall or longer dry periods) have to be included in the future accounting of the water balance for each region, continent or watershed. Water shortage, water scarcity and water stress have to be considered as the context of water availability and water demands (Rogers 2006). Shiklomanov (1999) predicts an increase of 26% in water uses for agriculture, 61% in water uses for urban areas, 13% in water uses for industry and an overall increase in 29% of world water demand from to 2000 to 2050. According to Shikolomanov there will be a 49% of increase in the human population during the same period. Water security for human population uses has to be considered with the same value as water security to maintain the ecosystems and the functioning of

INCT-ACQUA â–Ş ACTIVITY REPORT 2013-2016

Table 1. Water balance by continent (km3/year) (Shikolomanov, 1993).

Continent

Precipitation

Evaporation

Drainage*

8 290

5 320

2 970

Asia

32 200

18 100

14 100

Africa

22 300

17 700

4 600

North America

18 300

10 100

8 180

South America

28 400

16 200

12 200

Australia/Oceania

7 080

4 570

2 510

Antarctic

2 310

118 880

71 990

46 870

Europe

Total

*Includes drainage into the groundwater basins and continental ice flows in Antarctica

the ecosystems. Table 1 shows the water balance by continent. Water quality - Water quality is important and relevant for water security. The history of degradation of water quality shows a continuous deterioration with increasing complexity mainly in the 20th century and with cumulative impacts on human health. Pollution can impair water availability in many regions, increasing the vulnerability of human populations; the economic impact of degradation of water quality can be accounted as the increase in the costs of treatment, or the impact on human health or loss of biodiversity. The human caused threats to water quality, such as eutrophication, acidification, sedimentation of surface water, degradation of underground sources and the POPS (persistent

organic pollutants), have cumulative effects, increase the costs of water treatment for producing potable water and can lead to several problems of human health and economic losses. Determination of water quality shows increasing complexity as the organic and inorganic components are introduced by air, soil and effluents inputs (Fig. 1). One key component for the protection of water quality is the mosaic of vegetation, riparian forests and wetlands in watersheds. Protected water sources can produce water of good quality almost free of contaminants with the cost of treatment for potability between US$2 and US$5 per 1000 m3. Degraded water sources that are unprotected by vegetation produce water of bad quality (high concentration of suspended material, contaminants). The cost of

Figure 1. Trends in water quality in the evolution of water quality problems in industrialized countries. In emerging economies the sequence is more complex. Modified from Chapman (1992).

SCIENCE HIGHLIGHTS

treatment for potability of these waters can be as high as US$100 per 1000m3 (Tundisi and MatsumuraTundisi, 2010,2012). The economic connections of water quality deterioration, human health degradation and loss of ecosystem services have to be quantified. Figure 2 shows the overall causes of water quality deterioration. Climatic changes can affect water quality as well as water quantity, resulting in scarcity. The synergistic effect of soil uses, non-point sources of contamination and climatic changes are not known and there is still insufficient scientific information (Cisneros and Tundisi, 2012). Water governance - An integrated watershed management is a key initiative to overcome the problems caused by water availability, water demand and water quality. The economy of the watersheds and their sustainable development will depend on a basin society (a basin committee and a water agency) that will control the supply/ demand, and provide opportunities for the collective participation on governance with the water as the focus, and in implementing planning and actions. The sustainable development of a watershed (a biogeophysiographical boundary) will depend on this integration of water availability, water uses and water users, control of pollution, soil uses and regulation of agricultural, industry and sewage discharge (Rogers 2006). In order to develop a policy for management, a scientific database is fundamental and a cadre of trained scientists and managers with a systemic and interdisciplinary background. The governance of water can be improved by introducing modelling and predictive approaches using biogeophysical, economic and social data at a watershed level. Ecohydrological technologies to improve management will be fundamental for advances (Zalewski 2014). It is fundamental also to reduce current water demand rather than to increase water supply for one service (agriculture for example) at the expense of another service (e.g. environmental) (Curmi et al. 2013). Research Needs - In order to follow up water quality problems it is necessary to keep track of

Figure 2. Main causes of degradation of water quality. Based on a survey of 600 lakes and reservoirs in all continents. Source: ILEC 2011.

all material flows (in the air water and soils) and their cycles at organic and inorganic compartments. The interaction of water quality and human health should be followed by permanent research activities, epidemiological statistics and experimental research. Equally important is to understand the relationship between the persistent organic pollutants and their impact on human health and on biodiversity (Jorgensen, Tundisi and Matsumura-Tundisi 2012). Research on resistant pathogens is another fundamental topic for future developments. Also the impact of land/soil use on the water quality, is another need for research at the watershed level. Finally the implementation of networks of competence around the world â€“ integrating laboratories is another need. Risk analysis and vulnerability of human populations to both scarcity and water quality deterioration is a field of research and management that needs to be improved. Education and capacity building with a systemic and interdisciplinary approach is a need in research and management. There is a need also to improve our capacity of understanding the impacts of climatic changes on the water quality with research directed to this problem in all continents and regions.

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References ADAPTED FROM HYDROLOGICAL SCIENCES AND WATER SECURITY: PAST, PRESENT AND FUTURE. 2014, June. In: Proceedings of the 11th Kovacs Colloquium. Paris, France: IAHS. 366 pp.

ROGERS, P. 2006. Water governance, water security, water sustainability. In: Rogers, P., Lhamas, M.R., MartinezCortina, L. (eds). Waters crisis: myth or reality? London: Taylor & Francis. 331 pp.

CHAPMAN, D. (ed). 1992. Water quality assessments. UNEP, UNESCO, WHO.

SHIKLOMANOV, I.A. 1993. World water resources. In: Gleick, P.H (ed). Water in crisis: a guide to the world´s freshwater resources. Pacific Institute for studies in Development, Environment and Security, Stockholm Environmental Institute.

CISNEROS, B.J., TUNDISI, J.G. (eds). 2014. Water for the Americas. Inter American Network of Academies of Science. COOK, C., BAKKER, K. 2010. Water security: debating an emerging paradigm. Global Environmental Change 22: 94-102.

SHIKLOMANOV, I.A. 1999. WORLD WATER RESOURCES AND WATER USE, PRESENT ASSESSMENT AND OUTLOOK FOR 2050. St. Petersburg, Russia: State Hydrological Institute.

CURMI, E. et al. 2013. An integrated representation of services provided by global water resources. J. Environ. Management. 129: 456-462.

TUNDISI, J.G., MATSUMURA-TUNDISI, T. 2010. Impactos potenciais das alterações do Código Florestal nos recursos hidricos. Biota Neotropica 10 (4): 67-76.

ILEC. 2011. Development of ILBM Platform Process. Research Center for Sustainability and Environment, Shiga University.

TUNDISI, J.G., MATSUMURA-TUNDISI, T. 2012. Limnology. Taylor & Francis, CRC Press. 832 pp.

JORGENSEN, S.E., TUNDISI, J.G., MATSUMURA-TUNDISI, T. 2012. Handbook of inland waters ecosystem management. CRC Press.

ZALEWSKI, M. 2014. Ecohydrology, biotechnology, and engineering for cost efficiency in reaching the sustainability of the biosphere. Ecohydrology and Hydrobiology 14: 14-20.

The São Francisco river research development: Basic science for river recovery of metal contamination J.G. Tundisi1,*, T.M. Tundisi2, J.E.M. Tundisi2, D. Abe2, T. Bere3, F. Blanco2, V.T. Silva2, F.S. Soares2 International Institute of Ecology, University of FEEVALE . São Carlos - São Paulo, Brazil. International Institute of Ecology. São Carlos - São Paulo, Brazil. 3 Chinhoyi University of Technology, Chinhoyi, Zimbabwe. *Corresponding author: tundisi@iee.com.br 1 2

Keywors: Water monitoring, hydrodynamics, sediments, effluent discharge.

The São Francisco river in its middle region between the Três Marias reservoir (Lat 18o12’26”; Long 45o15’32”) up to the confluence of Abaeté River (Lat 18o02’12” Long 45o11’15’) receives the discharge of zinc processing industrial plant. The sediments of this river have high metal concentrations of cadmium and zinc. With the aim to prepare a diagnosis of the river ecological situation and provide a scientific background for recovery of this ecosystem, research on limnological dynamics, hydrodynamics and the biological communities of water and sediment were carried out in the last 7 years. Figure 1 shows the region of study and the stations where sediment was collected. Water quality variables were temperature, dissolved oxygen, conductivity, pH, redox potential, turbidity (Chapman, 1992). The collected sediments were dried and metals were extracted and measured with Atomic Absorption equipment Varian AA 250 FS Model. Ecotoxicological studies were carried out by using aquatic organisms such as Chironomus xantus, Danio rerio and Hyallela azteca submitted to elutriate of interstitial sediment water. Peryphytic diatoms were submitted to experimental conditions and ecotoxicological tests were performed with this component of the biota. Hydrodynamic conditions of the river and the sediments dynamics were measured at 10 transversal stations in the river with the use of a 3 D WAVE / current meter. The variables measured were current velocity, direction, pressure. A batymetric chart was prepared and digitalized.

The values of the water discharge from the São Francisco River varied from an average of 848 49 m3/s during the rainy period to a minimum of 536 m3/s during the dry period. The intensity of the water flux and their relationships with the mechanical transport of the sediments coupled with the metal concentration measured demonstrated the areas of concentration of contaminated sediments in the river stretch studied. Due to the water flux of the river either in dry or wet period, erosion and transport of the sediments are common. A large amount of sediment is removed and transported along, the river course. Hidromares (2008). However there are hot spots concentrated at specific regions due to the river morphological characteristics, and lower current velocity. The results of the water quality of the river and the contaminated sediments, the current velocity and its directions and the responses of the organisms to the contaminated conditions show that the environmental factors are favorable to a lessened impact on the organisms: the concentrations of dissolved yellow substances in the water (gelbstoff); high concentration of calcium in the water; pH higher than 7. For example the biodiversity of the benthic organisms at two sites, one more contaminated (SF6) and other less contaminated (SF8) did not show great difference in species richness (23 taxa for SF6 and 26 taxa for SF8). Thus the contamination caused by heavy metals is not sufficient to cause adverse effects on benthic invertebrates. Peryphyton community showed high capacity of metal accumulation. This depends upon metal concentration, exposure duration (continuous or intermittent) and light intensity.

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Figure 1. Sampling stations in the São Francisco Region.

Shift in species composition of peryphyton were observed with different metal concentrations (Bere et al, 2010, 2013); shifts in species composition occurs when water and contaminated sediments interact with aquatic biota selecting species and communities. The interaction of field and laboratory experiments applied to the study of this stretch of the São Francisco River is a useful combination to evaluate the degree of contamination of metals and its impact on the aquatic biota. The results obtained show that despite the contamination of the sediments in the hot spots due to river morphology and the current the environmental conditions prevent a high impact on the biological community. The information accumulated in this study is extremely important as a basis for the recovery of the

São Francisco River in this region. A first and obvious measure is to cease the impact of discharged and contaminated effluents of the zinc industrial plant. A second action is to provide technical approaches to the sediment recovery specially the contaminated hot spots (Jorgensen, Tundisi and Matsumura-Tundisi, 2013). One possibility is to remove the first meter of the contaminated hot spot with special equipment that pumps the sediments. Other possible technical approach is in situ oxidation of the hot spots of contaminated sediment. This will remove probably the sediment downstream and the high water current combined with favorable environmental conditions will disperse it downstream the river diluting the metal concentration.

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Continuous monitoring of the environmental conditions, hydrodynamics of the river and sediments contamination is another long term action that is an important follow up after the zero metal effluent discharge (Jorgensen et al, 2005).

Acknowledgments CNPq and CAPES. Votorantim Metais has partially funded this work.

References BERE, T., TUNDISI, J.G. 2010. Brazilian Journal Biology 70 (3): 493-502. BERE, T., TUNDISI, J.G., MATSUMURA-TUNDISI, T., BLANCO F.P., SILVA, V.T. 2013. Diatom assemblages as indications of water quality in lotic systems: new approaches for river management. In: IAQUA-Report. pp. 58-59. CHAPMAN, D. (ed). 1992. Water Quality Assessments. UNESCO, WHO, UNEP. 585 pp.

HIDROMARES, IIE. 2008. Estudo das condições hidrodinâmicas e dispersivas para os sedimentos do Rio São Francisco – Trecho entre Três Marias e Rio Abaeté (MG). 46 pp. Relatório final. JORGENSEN, J.E., LOFLER RAST, W., STRASKRABA, M. 2005. Lake and reservoir management. Elsevier. 502 pp. JORGENSEN, J.E., TUNDISI, J.G., MATSUMURA-TUNDISI, T. 2013. Handbook of inland aquatic ecosystems management. Taylor & Francis B. 422 pp.

Water quality and phyto-zooplankton communities from mining areas in the upper Paraopeba watershed, Minas Gerais, Brazil C. Lizieri1, T.A.S.V. Paes1, K.A.F. Moura1, M.W. Franco1, R.M. Menendez1, P.M. Maia-Barbosa1, F.A.R. Barbosa1,* Laboratory of Limnology, Ecotoxicology and Aquatic Ecology-LIMNEA, Department of General Biology/ICB, Universidade Federal de Minas Gerais (UFMG). Belo Horzionte - MG, Brazil. *Correponding author: barbosa@icb.ufmg.br

Keywords: Water quality, phytoplankton, zooplankton, mining areas, Upper Paraopeba Watershed.

The Alto Paraopeba region in Minas Gerais State, comprising municipalities of Congonhas, Jeceaba, Belo Vale, Ouro Branco, among others, is one of the largest iron producer areas in Brazil. This area has been intensely exploited in terms of mining activities, what can become a potential source of heavy metal contamination to the water bodies surrounding the mine areas. The presence of heavy metals in aquatic ecosystems may cause negative impacts not only on biological communities, but also on the human population health due to the bio-magnification through the food chain and its toxic effects.

To provide insights into this issue, characteristics of water condition and description of phyto- and zooplankton communities from streams around the mining areas in the Upper Paraopeba watershed (Iron Quadrangle) have been examined in this work. Water samples were taken to quantify the concentrations of metals (total and dissolved) and nutrients (nitrogen and phosphate) and to describe the phyto- and zooplankton communities present. The location and names of each site are showed in Figure 1. Mãe d´Água was considered the reference area. The nutrients results showed a high concentration of total

Figure 1. Image taken from google earth showing the location of the nine field sites (yellow) and the major surrounding municipalities (red).

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Tabela 1. Nutrients concentrations in streams form the Alto Paraopeba.

Sampling sites

Total-N mg/L

Nitrite mg/L

Nitrate mg/L

Ammonium mg/L

Total-P mg/L

Phosphate mg/L

Mãe d’água

0.11

0.0001

0.0042

0.0672

<BLD

Maria José

1.1

0.0005

0.0031

0.0281

0.2443

0.0027

Luis Ventura

28.43

0.0058

0.0034

2.3104

2.6723

0.4484

Bananeiras

16.87

0.0592

0.0128

2.3104

1.345,6

0.3412

Maranhão

9.23

0.1110

0.1086

2.3681

0.2807

0.1250

Gurita

14.41

0.0060

0.0066

0.6330

0.6188

0.3262

Soledade

8.93

0.0105

0.0043

0.4529

0.5266

0.2082

Ponciana

0.59

0.0007

0.0029

0.0389

0.0172

0.0013

Paraopeba

1.76

0.0011

0.0030

0.1326

0.0753

0.0108

*<BLD = Below detection limit.

nitrogen in five sampling sites (Table 1). However, the concentrations of nitrate and nitrite were very low. These results suggest that the main contributor to the total nitrogen comes from organic material (untreated sewage). Additionally, the concentrations of total phosphate exceeded 0.15 mg/L reference value by legislation CONAMA Res. 0357 for waters of class 3 (human consumption after conventional treatment) in six sites. The total and dissolved metal concentrations (Al, As, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Si and Zn) did not exceed the established limits except for manganese and aluminium which concentrations are showed in Figure 2.

The diversity of phyto- and zooplankton communities is considered low, although these results are the ones expected for lotic and impacted environments. Some representative members of phytoplankton community are showed in Figure 3. We have recorded in the field samples more than 30 morphologically distinct phytoplankton strains. In the zooplankton community 16 taxa were recorded (Table 2) with dominance of Rotifers and Protozoa. Rotifers have been reported as a common group in freshwater ecosystems since they are quantitatively more abundant among the three principal zooplankton groups. According to Sarma et al., (2007) they are opportunistic, with short life cycle

    Aluminium



Manganese

     

Mãe d'água

Maria José Luiz Ventura Bananeiras D

Maranhão

Gurita

Soledade

Ponciana

Paraopeba

Figure 2. Aluminium and manganese concentrations in streams from the Upper Paraopeba watershed. T= total; D = Dissolved. Sampling date: July/August 2014. Limits of these metals according to the CONAMA to water class 3= 0.2 and 0.5 mg.L-1 respectively.

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Figure 3. Photomicrographs of representative morphotypes of the phytoplankton community recorded in streams from Upper Paraopeba watershed. A-L: morphotypes of cyanobacteria; M-R: morphotypes of eukaryotic microalgae group.

Table 2. Zooplankton community from the Upper Paraopeba watershed.

Zooplankton Community

Protozoa

Rotifera

Arcela sp. Arcela hemisphaerica Arcela rotundata Centropyxis discoides Cyphoderia ampulla Difflugia sp. Epistylis spp. Vorticella sp. Ciliophora NI

Asplanchna sp. Bdeloidea Brachionus angularis Brachionus calyciflorus Lepadella patella Chironomidae Nematoda

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and able to utilize a wide variety of food resources. Brachionus, often found in the samples, and several species of Bdelloidea class are also considered tolerating gross pollution and recognized as indicators of environments rich in organic matter (Sladecek, 1983) as well as Chironomidae (Marques et al., 1999). Conversely, the Protozoa testate amoebae (Arcela sp., Centropyxis sp., Cyphoderia sp., Difflugia sp.) are unable to survive in highly variable environments. Taken together our results demonstrate that mining activities are not the only potential source

to water bodies contamination. Instead, the lack of sewage treatment is the major contributor to water pollution in the Upper Paraopeba watershed. Understanding the factors that disturb the natural dynamic of these water bodies is crucial for predicting future threats as well as understanding how they can affect the health of human population. Despite preliminary this work provides results that can help to design positive measures for preserving aquatic ecosystems, including living resources in mining areas.

References CONSELHO NACIONAL DO MEIO AMBIENTE – CONAMA. 2005. Resolução nº 357, de 17 de março de 2005.

SARMA, S.S.S., AZURA-GARCIA, R., NANDINI, S. 2007. Aquatic Ecol. 41: 631-638.

MARQUES, M.M.G.S.M., BARBOSA, F.A.R., CALLISTO, M. 1999. Brazil. Rev. Bras. Biol. 59.

SLADECEK, V. 1983. Hydrobiologia 100: 169-171.

Taxonomic and functional investigation of a microbial community inhabiting a metal-rich tropical stream sediment P.S. Costa1, M.P. Reis1, E. Chartone-Souza1, A.M.A. Nascimento1,* Laboratory of Genetics of Microorganisms, Department of General Biology, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Correponding author: amaral@ufmg.br

Keywords: Metagenome, prokaryote, metal, sediment.

The Iron Quadrangle (Minas Gerais, Brazil) is one of the world’s largest mining regions, being historically exploited for over 300 years. Since then, many toxic metals and metalloids were released into the environment, leading to the contamination of water bodies (Reis et al. 2013). Prokaryote species exhibit broad distribution, having been researched across a wide range of natural environments such as soil, marine, freshwater, plant, and animal, including human. Many have revealed to be important members for the health and/or ecological balance of various environments (Kasting and Siefert 2002). Prokaryotic community was investigated since it influences the bioavailability of toxic metals and metalloids and is important in the ecological balance of various environments (Earth Microbiome Project). The study focused on the taxonomic and functional diversity in the microbiome from Mina Stream, historically metal-contaminated. The sediment was collected from Mina Stream which is located in the Iron Quadrangle (Brazil). Environmental DNA was extracted and was sequenced using next-generation platform. The data generated were submitted to bioinformatics analysis (Costa et al. 2015). MSS microbiome resulted in 273,710 high quality reads with the average read length of 450 bp. Bacteria were by far the most abundant prokaryotic domain comprising 98.2% (30,738 OTUs), whereas archaeal reads showed a relative paucity (1.8%, 240 OTUs). Bacterial and archaeal phyla diversity are shown in Figure 1. A taxonomic profile that was obtained by comparison to the Greengenes database revealed a complex microbial community. A total of 30,738 OTUs were assigned to 52 known bacterial phyla. Nevertheless, most OTUs were

affiliated with four phyla: Proteobacteria (45%), Bacteroidetes (18%) and an equal proportion (4%) of Acidobacteria and OD1. The group “other bacteria” comprised minor bacterial phyla such as Gemmatimonadetes, Cyanobacteria, OP3, OP11, Spirochaetes, TM7 among others, representing 8% of the OTUs. Furthermore, 2,157 OTUs were considered to be unclassified at the phylum level and thus may represent new bacterial taxa. Contigs were recruited by bacterial and archaeal genomes, especially Candidatus Nitrospira defluvi and Nitrosopumilus maritimus, and their presence suggests the process of N cycling in Mina Stream sediment (MSS) (Costa et al. 2015). The top species from CSS as well as the highest coverage of a reference genome were observed for neutrophilic iron-oxidizing bacteria, likely reflecting the elevated concentrations of iron (Fe) (21 g/Kg). A comparison between the CSS and MSS microbiota revealed an overrepresentation of some genera, such as Geobacter, Gallionella, Crenothrix and Mariprofundus (Reis et al. data not published). Twenty-eight functional subsystems characterized by biochemical pathways and gene clusters that work together or that are somehow related were identified in the MSS metagenome. Protein metabolism, clustering-based subsystems, miscellaneous, carbohydrates, and RNA metabolism presented the largest number of annotated contigs. Other subsystems were related to mobile elements (phages, transposons, integrons, plasmids, and pathogenicity islands, 4%) and stress response (3%), both responsible for the fast response and adaptation of the microbial community to changes in the environment. Functional reconstruction revealed a large, diverse set of genes for ammonium assimilation and ammonification.

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Figure 1. Taxonomic composition of bacterial (A) and archaeal (B) taxa from MSS microbiome based on the Greengenes database. Other bacteria: Gemmatimonadetes, Cyanobacteria, OP3, OP11, Spirochaetes, TM7, Chlorobi, WS3, Elusimicrobia, GN04, TM6, GN02, Tenericutes, Armatimonadetes, BRC1, NC10, WPS-2, Fibrobacteres, Fusobacteria, H-178, FCPU426, Kazan-3B-28, WS5, NKB19, Thermi, AC1, TPD-58, WS6, Synergistetes, OP8, WS2, ZB3, SC4, OP1, SBR1093, SR1, Lentisphaerae, GAL15, PAUC34f, LCP-89 and MVS-104. (Reproduced from Costa et al. 2015).

These processes have been implicated in the maintenance of the N cycle and the health of the sediment. SEED subsystems functional annotation unveiled a high degree of diversity of metal resistance genes, suggesting that the prokaryotic community is adapted to metal contamination (Costa et al. 2015). This study provides important insights into the structure of the prokaryotic community of a tropical freshwater sediment, indicating its possible role

in the N and C cycles and in the transformation of Fe and As. Functional annotation unveiled a high diversity of several metal resistance genes, indicating that this microbial community is well adapted to metal contamination. Finally, the results reported herein may contribute to expand the current knowledge of the microbial taxonomic and functional composition of tropical metalcontaminated freshwater sediments.

References COSTA, P.S., REIS, M.P., ÁVILA, M.P., LEITE, L.R., ARAÚJO, F.M., SALIM, A.C., OLIVEIRA, G., BARBOSA, F.A., CHARTONE-SOUZA, E., NASCIMENTO, A.M.A. PloS One 10 (3): e0119465-e0119465.

KASTING, J.F., SIEFERT, J.L. 2002. Science 296: 1066-68. REIS, M.P., BARBOSA, F.A., CHARTONE-SOUZA, E., NASCIMENTO, A.M.A. 2013. Extremophiles 17: 301-19.

EARTH MICROBIOME PROJECT. Available: http://www. earthmicrobiome.org.

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Research Topic 1 PART 2 Assessment of Water and Enviromental Quality, and Aquatic Biodiversity 49

Environmental impact evaluation of metals in sediments from the Doce River Basin, Brazil

Risk assessment of manganese contamination in cyanobacteria and zooplankton resting eggs

Potential of Synechococcus sp. (Cyanobacteria) for arsenic biotransformation: evidences from culture experiments

A XAFS study on Arsenic and GSH molecular interactions

Determination of mercury biosorption by Microcystis novacekii (Cyanobacteria) biomass

Îą

Environmental impact evaluation of metals in sediments from the Doce River Basin, Brazil C.V.A. Santolin1, V.S.T. Ciminelli2, C.C. Nascentes1, C.C. WindmĂśller1,* Department of Chemistry, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: claucw@netuno.lcc.ufmg.br

1 2

Keywords: Sediments; metals; Rio Doce Basin.

The Doce River Basin (DRB) is located in the southeastern region of Brazil, and is home to the largest steel complex in Latin America, including

the largest open pit mining industry in the world. Several economic activities are performed along the DRB, including mining, agriculture and food

Figure 1. Doce River Basin map and collection sites.

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industry activities. The mining activities involve the exploration of a range of minerals and gold on a smaller scale. The quality of water in the basin has been monitored since 1997 by the state agency for environmental control; however, there are no reports about metals in sediments of the basin. There is insufficient information for an assessment of metal distribution in the DRB, especially for the most toxic metals, such as mercury. We have quantified Al, Cr, Co, Cu, Fe, Hg, Mn, Pb and Zn levels and the physicochemical parameters in sediment from the basin and statistically analyzed these variables. The results have also been discussed using the geoaccumulation index (Igeo) and enrichment factor (EF), which contributes to the knowledge of the metal geochemistry in this basin. Sediment samples were collected from 19 sites selected in the basin in October 2011 by the State Institute of Water Management (IGAM), as shown in Figure 1. The points were chosen because of their classification as having poor water quality according to water monitoring report from IGAM. The concentrations of total metals were performed employing a fast sequential flame atomic absorption spectrometer (FS-FAAS) Varian AA240FS, with the conditions specified for each element. Cobalt and lead were quantified by inductively coupled plasma optical emission spectrometry (ICP-OES), using a Perkin Elmer Optima 8000 instrument and the determination of total Hg was performed using a direct mercury analyzer (DMA-80, Milestone).

Geoaccumulation Index (Igeo) The Igeo index was established as a ratio between the local metal concentrations in sediments and a reference value taken as the standard or a background value: log2 Cm Equation 1 I geo = 1.5xC bg where: Cm= measured concentration of metal M in the sediment; Cbg= concentration taken as background (values from Costa et al., 2003) to the metal M; 1.5 = factor that minimizes the possible variations of the background values determined for the metal in the environment, as well as small anthropogenic influences. Seven classes make up the Igeo, ranging from unpolluted to extremely polluted, which corresponds

to a 100-fold enrichment relative to the value of the postulated background.

Enrichment Factor (EF) The EF is the element concentration ratio in the sediment and its natural background concentration (Equation 2). In the case of EF, a reference element concentration, treated as the normalizer (element whose source must be natural and whose concentration should not vary greatly) is inserted in the calculation to balance the mineralogical variations in sediment (Qi et al., 2010). EF=(Msed/Rsed)/(Mbg/Rbg) Equation 2 where Msed = measured concentration of metal M in the sediment; Rsed= concentration of R normalizing element, which is one whose source must be natural and whose concentration should not vary greatly in the sediment; Mbg = concentration taken as background to the metal M; Rbg = background concentration assumed as the R normalizing element. The normalization technique is used to distinguish the natural variability of metals from the variability associated with the accumulation in the sediments due to anthropogenic activities. Normalization of sediment for trace metals can use the concentration of elements such as Al, Fe, Li, and Y, among others, in addition to parameters such as organic matter and particle size. The sediment analyses revealed that 15% of DRB samples were above the Canadian Sediment Quality Guidelines (CCME, 1999) TEL for Hg, 100% for Cr, 53% for Cu, 21% for Zn and 21% for Pb. Together, these results are equivalent to a total violation of 41%, related to the SQG, for the DRB sediments. The classification using geochemical standards of quality of the collection points of the DRB as to the origin of the metals analyzed revealed that sites RD001, RD009, RD025, RD029, RD031, RD034 and RD035 were considered contaminated because of their Igeo and EF values. When compared to the results obtained by analyzing the SQG, it can be concluded that these sites are the most impacted in the DRB, probably because of anthropogenic activity. The results indicated that it is important a quality monitoring program of sediments, and also studies of speciation

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Figure 2. Histogram Geoaccumulation Index.

Figure 3. Enrichment factor histogram.

and mobility of these metals in this basin in order to better understand the geochemistry of possible contaminants and also propose mitigation ways when necessary.

Acknowledgements This study was supported by CNPq, FAPEMIG (project APQ 03861-09).

References CCME. 1999. Canadian Sediment Quality Guidelines for the Protection of Aquatic Life. Canadian Environmental Quality Guideline. Winnipeg: Canadian Council of Ministers of the Environment.

SANTOLIN, C.V.A., CIMINELLI, V.S.T., NASCENTES, C.C., WINDMÃ–LLER, C.C. 2015. Environmental Earth Sciences 74: 1235-1248.

QI, S., LEIPE, T., RUECKERT, P., DI, Z., HARFF, J. 2010. Journal of Marine Systems 82: S28-S42.

Risk assessment of manganese contamination in cyanobacteria and zooplankton resting eggs C. Lizieri1, T.A.S.V. Paes1, G.K.V. Pereira1, K.A.F. Moura1, M.W. Franco1, F.A.R. Barbosa1,*, P.M. Maia-Barbosa1 Laboratory of Limnology, Ecotoxicology and Aquatic Ecology-LIMNEA, Department of General Biology/ICB, Universidade Federal de Minas Gerais (UFMG). Belo Horzionte - MG, Brazil. *Correponding author: barbosa@icb.ufmg.br

Keywords: Manganese toxicity, resting eggs, cyanobacteria.

Manganese is an essential micronutrient to the normal growth and development of both vegetables and animals. However, high concentration of this element can become highly toxic to the organism (Pittman, 2005). A stress agent alters the homeostatic state of the organism which responds in order to restore it. Such responses can be used as a tool to evaluate the environment quality, giving subsidy to biomonitoring technique From the growing interaction between the miningindustrial sector and the scientific community, research have concentrated their efforts to provide knowledge and technology to assist the recovering, mitigation and monitoring of the negative impacts caused by exploitative activities of natural resources, including the mining sector. In this work we evaluate responses of aquatic microorganisms (cyanobacteria strains and resting eggs of zooplankton) exposed to low and supraoptimal supply of manganese. The effects of Mn were evaluated based on cyanobacteria growth and hatching rate of resting eggs of zooplankton. Two distinct strains of cyanobacteria were used as test organisms- Synechococcus sp. and Nostoc sp while for zooplankton resting eggs of Daphnia ambigua were used. All cyanobacteria cultures were placed in Erlenmeyer containing 150 mL of BG-11 culture medium added of increasing doses of Mn (0.5, 1.0, 5.0, 15.0 and 50.0 mg L- 1) as MnCl24H2O. The control groups were cultivated in BG-11 medium without the addition of Mn. The pH of each solution was kept in 6.0 by using MES buffer. The cultures growth were evaluated by reading absorbance in spectrophotometer every day of exposure for 96 hours. After the period of exposure the cultures

were centrifuged and washed in MES-EDTA (20mM and 10mM) and then subsamples were taken to chlorophyll analysis and determination of accumulated Mn content in the cells. The resting eggs were isolated from sediments by using the sugar flotation method (Onbé, 1978) and decapsulated with hypochlorite solution (Paes, et al., 2016). The isolated eggs were exposed to the same Mn concentrations of the cyanobacteria experiment above mentioned. The experiment was carried out in incubator with a photoperiod of 12 h and temperature of 20°C, adequate condition to hatching resting eggs of D. ambigua. Synechococcus sp. and Nostoc sp. showed different responses under stress conditions of Mn. The growth of Synechococcus was highly affected under high concentrations of Mn and a small reduction (17 %) in lower concentration after 72 hr of exposure (Figure1). On the other hand, Nostoc growth only showed a small reduction (16%) in higher concentration of Mn and after 72hr of exposure. The excess of Mn in solution decreased the chlorophyll content in Synechococcus cultures. These decline occurred differently among the treatments. Nevertheless, the content of Mn in dry biomass of Synechococcus exposed to Mn did not differ compared to control group. This finding shows that Synechococcus did not accumulate Mn into the cells. However, the growth reduction in parallel to decreased chlorophyll content suggests that Mn affects negatively the metabolism of Synechococcus even at low levels (0.5 mg/L after 96 hr). The experiment using resting eggs did not show significantly effect of Mn on the hatching rate (F(5, 24)= 0.79; p=0,57) (Fig. 2). However, under concentration of 50 mg.L-1 of Mn the individuals did

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Figure 1. (A) Synechococcus cells (white arrow). (B) Growth behavior of Synechococcus subjected to different concentrations of Mn. OD = Optical density

Figure 2. Hatching of Daphnia ambigua resting eggs (%) exposed to different concentrations of manganese (n = 120 eggs/treatment). Vertical bars denote 0.95 confidence intervals.

not survive, thus demonstrating a highly toxic effect of the Mn at high concentration. Analysis of responses at high Mn concentrations are important to establish the tolerance level and selectivity of the species, besides guiding further bioindication and bioremediation studies focusing in contaminated environments at high levels of Mn. The present work allows to conclude that toxic effects of Mn differ among species and time of exposure which might be very dangerous for some organisms even at low concentration while others it will depend of long-term exposure. The factors that are involved in toxic effect of Mn are still unknown and these are our challenges for future work.

Reference ONBĂ‰, T. 1978. Bull Jpn. Soc. Sci. Fish. 44: 1141.

PITTMAN, J.K. 2005. New Phytologist 167: 733-742.

PAES, T.A.S.V., RIETZLER, A.C., PUJONI, D.G.F., BARBOSA, P.M. 2016. Anais da Academia Brasileira de CiĂŞncias 88 (1): 179-186.

Potential of Synechococcus sp. (Cyanobacteria) for arsenic biotransformation: evidences from culture experiments M.W. Franco1,*, F.A. Guedes1, I.F. Vasconcelos2, B.L. Batista3, D.G.F. Pujoni1, S.M.S. Magalhães4, F. Barbosa Jr5, F.A.R. Barbosa1 Laboratory of Limnology, Ecotoxicology and Aquatic Ecology-LIMNEA, Department of General Biology/ICB, Universidade Federal de Minas Gerais (UFMG). Belo Horzionte - MG, Brazil. 2 Department of Metallurgical and Materials Engineering, Universidade Federal do Ceará (UFC). Fortaleza - CE, Brazil. 3 Center of Natural Sciences and Humanities, Universidade Federal do ABC (UFAB). Santo André - SP, Brazil. 4 Department of Social Pharmacy, Universidade Federal de Minas Gerais(UFMG). Belo Horizonte - MG, Brazil. 5 Laboratory of Toxicology and Essentiality of Metals, Faculty of Pharmaceutical Sciences of Ribeirão Preto, Universidade de São Paulo (USP). Ribeirão Preto - SP, Brazil. *Corresponding author: maionewf@hotmail.com 1

Keywords: Cyanobacteria, arsenic, speciation, Synechococcus.

The biogeochemistry of As is complex and involves transformation into various chemical species with different levels of toxicity. In lakes, phytoplankton blooms activity has a strong influence on As availability and speciation (Hellweger and Lall 2004). The possibility of using microorganisms in clean technologies for environmental decontamination has spurred the search for resistant organisms that are capable of biotransforming toxic elements such as As. Cyanobacteria are of interest because of their dominant position in aquatic environments impacted by different types of pollutants. The detoxification mechanisms of arsenate [As(V)] by microorganisms include absorption, reduction and efflux in arsenite [As(III)] or methylated forms (MMA/DMA) (Rosen 2002). Molecules containing cysteine residues such as the tripeptide glutathione ( -L-glutamyl-Lcysteinylglycine, GSH) are critical in this process because of the high As(III) affinity for sulfhydryl groups. Arsenic metabolism by cyanobacteria has mainly been studied in water-bloom-forming species from eutrophic lakes. Based on the hypothesis that cyanobacterial strains obtained from contaminated environments are more likely to possess efficient mechanisms of As biotransformation, in this study we analyzed the As compounds formed by Synechococcus sp., a non-toxic and non-bloomforming cyanobacterial strain obtained from a stream

in a mining area contaminated with As (average 0.06 mg L-1). The aim of this study was to evaluate the biotransformation of As by Synechococcus sp. Cyanobacteria cultures (1500 mL) were cultivated in BG-11 medium in Erlenmeyer flasks. For inoculation the cultures were centrifuged and added to the media to yield a final concentration of 7 x 107 cells mL-1. Freshly prepared solutions of sodium arsenate or sodium arsenite were added to obtain a final concentration of 400 mg L-1 As(V) or 6 mg L-1 As(III). As speciation was performed by high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) and X-ray absorption fine structure spectroscopy (XAFS) at Laboratório Nacional de Luz Syncrotron. The intracellular levels (60.0 mg g-1) of As were the same after 30 days of exposure to As(V) and As(III). After As(V) exposure the most abundant As species were As(V) > As(III) > Organic As, whereas after As(III) exposure were As(V) > Organic As > As(III) (Table 1). Among the organic As species observed, one exhibited the same retention time of arsenobetaine (AsB) (C5H11AsO2), a zwitterion with a positive charge on the As atom and a negative charge on the carboxyl group (Figure 1). Arsenobetaine is considered to be non-toxic containing a single arsenic atom in the +5 oxidation state bound to three methyl groups and one acetic

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Figure 1. Speciation analysis of Synechococcus sp. biomass exposed to As(III). An expansion of the As species observed at a retention time of 3 to 4.5 min is shown.

acid group. This As compound is the main As excretion product in zooplankton and fish, also found in macroalgae (Caumette et al., 2012). However, this As chemical species has not previously been detected in cyanobacteria. More specific techniques are required for the identification of AsB. As(V) intracellular dominance, followed by As(III) and biomethylated species in minor quantities (less than 5%) were also demonstrated in studies with other

cyanobacteria species (Wang et al., 2013, Yin et al., 2011), in Synechococcus sp. production of organic species occurred in higher proportions, notably after As(III) exposure (Table 1), probably because As(III) can be readily methylated and presents affinity to protein sulfhydryl groups. Arsenic K-edge XANES spectra were obtained from aqueous standards of different compounds of As (As(V), As(III), As(III)+GHS and DMA) (Figure 2A) and compared to the spectra obtained from biomass samples exposed to As(V). It was found that oxygen and sulfur are the possible components of the intracellular As coordination. A linear combination of As(III) and As(V) standards was fitted to the XANES spectrum of lyophilized cells exposed to As(V) and the fit revealed that 34% of the intracellular As was reduced to As(III) and 66% remained As(V) (Figure 2b). These results were consistent with the proportions of the chemical species determined by HPLC-ICP-MS. However, the determination of the coordination by XAFS has limitations including a high limit of detection and energy intensity of the light beam from

Table 1. Proportions of As chemical species as percentages of the total extract.

As added As(III)

Extracted fraction intracellular

As(III)

12.11 ± 2.84

6.28 ± 1.79

3.49 ± 0.62 1.01 ± 0.13 0.86 ± 0.15

76.21 ± 4.83

0.14 ± 0.01 0.42 ± 0.08 0.38 ± 0.24

98.82 ± 0.14

supernatant 0.14 ± 0.01 As(V)

intracellular supernatant

2.62 ± 0.35 34.97 ± 1.99 -

DMA

MMA

UiS* species

AsB

As(V)

2.20 ± 0.05

60 ± 2.28

0.13± 0.06

99.86 ± 0.06

Values are given in average ± SE. *UiS unidentified As species.

Figure 2. (A) XANES spectra of the As K-edge obtained from intracellular As (biomass) and the As(III), As(V), DMA and As(III)+GSH patterns for As(V)-O, As(III)-O, As-C and As-S bonds, respectively. (B) The linear combination of As(V) and As(III) spectra indicated contributions of 66% and 34% respectively to the As K-edge spectrum of intracellular As.

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Table 2. Comparison of As species (i%) in cells of distinct cyanobacteria species after exposure to As oxyanions.

Cyanobacteria species Synechococcus sp. Synechocystis sp. Microcystis sp. Nostoc sp.

M. aeruginosa

As exposed: Time DMA + As(V) As(III) species/concentration (days) MMA

AsB

As(III) 6 mg L-1

6.2

4.5

12.1

As(V) 400 mg L-1

34.9

2.2

2.5

As(III) 7.5 mg L-1

80* 96* 89*

16* 2* 7*

3* 1* 3*

As(III) 3.75 mg L-1**

81*

< 1*

As(V) 7.5 mg L **

77*

11*

< 1*

-1

Reference

This work Yin et al. 2011

Wang et al. 2013

*Concentrations estimated according to the values presented in results. **Maximum concentration exposed.

the synchrotron radiation source. Even with a large number of scans at low temperatures the low signalto-noise ratio obtained precluded the determination of the coordination of As. Changes in the redox state and methylation are the major mechanisms of As detoxification found in cyanobacteria (Table 2). The use of XANES and HPLC-ICP-MS allowed the unambiguous identification of the As redox states and biotransformation properties of Synechococcus sp. These data provide a foundation for future studies of this biological model under environmentally relevant conditions to evaluate the effects of As on

the metabolism of Synechococcus sp., to understand the role of cyanobacteria in the biogeochemical cycle of As and finally to use this promising potential of As biotransformation for remediation of As in environmental contamination.

Acknowledgements Authors are grateful to financial and logistic support provided by the Laboratรณrio Nacional de Luz Syncrotron for XAFS measurements.

References CAUMETTE, G., KOCH, I., REIMER, K.J. 2012. J. Environ. Monit. 14: 2841-53.

WANG, Z., LUO, Z., YAN, C. 2013. Environ. Sci. Pollut. Res. 20: 7286-95.

HELLWEGER, F.L., LALL, U. 2004. Environ. Sci. Technol. 38: 6716-23.

YIN, X-X., CHEN, J., QIN, J. et al. 2011. Plant Physiol. 156: 1631-8.

ROSEN, B.P. 2002. FEBS Lett. 529: 86-92.

A XAFS study on Arsenic and GSH molecular interactions M.W. Franco1, I.F. Vasconcelos2, L.V. Modolo3, F.A.R. Barbosa1,* Laboratory of Limnology, Ecotoxicology and Aquatic Ecology-LIMNEA, Department of General Biology/ICB, Universidade Federal de Minas Gerais (UFMG). Belo Horzionte - MG, Brazil. 2 Department of Metallurgical and Materials Engineering, Universidade Federal do Ceará (UFC). Fortaleza - CE, Brazil. 3 Department of Botany, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: barbosa@icb.ufmg.br 1

Keywords: Glutathione, arsenic, X-ray Absorption Spectroscopy, arsenic, sulfhydryl groups.

The chemical reactions between organic compounds and inorganic arsenic (As) have been investigated in an attempt to better understand the mechanisms by which arsenic may be immobilized by living organisms. The tripeptide glutathione ( -glutamilcisteinilglicina; GSH) plays a critical role in the cell homeostasis as the most abundant reducing agents in various biochemical pathways (Monostori et al., 2009). This tripeptide has been used as a model molecule to study As binding to reduced sulfhydryl groups. X-ray Absorption Spectroscopy (XAFS) provides data in atomic scale, is element specific and allows to discriminate the oxidation state of a target atom in combination with its local structure (coordination). In this study we investigated the chemical reactions between As(III) or As(V) with GSH using X-ray absorption spectroscopy (XAFS). XAFS measurements were performed in freshly prepared solutions in the molar ratios of 1: 0.5, 1: 1, 1: 2, 1: 4 As(III)+GSH and 1: 0.5 ; 1: 2, 1: 4, 1: 6 As(V)+GSH. The measurements were performed at the National Synchrotron Light Laboratory (LNLS) in Campinas, Brazil. The data were analyzed by using software (Athena, Artemis and FEFF 6.0) (Ravel and Newville, 2005). The passive electrons reduction factor (S02) of 0.87 ± 0.05 was obtained from a fit to a crystalline standard (NaAsO2) and used in all fits to the data. The XANES spectra for As(III)+GSH showed a clear shift in absorption edge towards lower energy values as the As:GSH ratio changes from 1:0 (aqueous As(III)) to 1:4 (Fig. 1A), the reduction in the energy absorption edge is remarkable in As(V)+GSH samples (Figure 1B). A saturation is observed (in green) in the higher proportion of GSH regardless of the initial As oxidation state (Fig. 1 A and B). This phenomena

Figure 1. (A) Normalized As K-edge XANES spectra for As(III)+GSH and (B) As(V)+GSH at increasing As: GSH molar ratios. (C) EXAFS oscillations (multiplied by k3) extracted from As(V)+GSH XAFS spectra.

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is a result of changes in electron density of As atom which was initially coordinated by oxygen and became coordinated by the less electronegative sulfur atom in the reaction product: the complex As(GS)3. The fit of the Extended X-Ray Absorption Fine Structure (EXAFS) spectra showed a phase shift due to differences in As coordination (Figure 1C). The magnitude of the Fourier transform of the EXAFS data (Figure 2) shows evident changes in the As coordination with increasing proportions of GSH as indicated by arrows, the signal provided by the As-O bond gradually decreases accompanied by a gradual increase in the signal provided by the As-S bond which became evident in the 1:2 proportion. This is consistent with the consumption of GSH in the As(V) to As(III) reduction process as a precondition for the complex formation. Best fit results to EXAFS data (Table 1) shows the gradual substitution of As-O bonds in the coordination of As(III) or As(V) formed respectively by approximately 3 or 4 oxygen atoms, towards the formation of the three As-S bonds in the GSH complex. This previous reduction of As(V) to As(III) before complexation with GSH was also demonstrated in prepared solutions using proton and 13C NMR (Delnomdedieu et al., 1994). EXAFS specially provides information on atomic environment. In the present study, the higher 2 was obtained for the intermediate proportions of As(V)+GSH, indicating more disorder in the local atomic environment

Figure 2. Magnitude of Fourier- EXAFS data for As(V)+GSH at increasing As: GSH molar ratios.

Table 1. Best fit results to EXAFS data.

Samples

As-O N

R (Å)

As(III) aqueous

3.1±0.1

1.791±0.007

As(III)+GSH 1:0.5

2.4±0.1

As(III)+GSH 1:1

2.0±0.1

As(III)+GSH 1:2

R (Å)

2.1±0.4

1.789±0.002

2.9±0.2

0.3±0.1

2.282±0.011

2.3±1.2

1.785±0.004

1.7±0.4

0.7±0.1

2.272±0.007

2.2±0.9

0.8±0.1

1.790±0.012

1.5±0.9

1.9±0.2

2.266±0.008

2.7±0.8

As(III)+GSH 1:4

3.1±0.2

2.254±0.007

2.8±0.7

As(V) aqueous

4.2±0.3

1.691±0.006

3.4±0.7

As(V)+GSH 1:0.5

3.9±0.3

1.695±0.005

3.6±0.8

As(V)+GSH 1:2

3.3±0.2

1.713±0.006

6.0±0.8

1.2±0.2

2.244±0.009

4.4±1.3

As(V)+GSH 1:4

1.4±0.2

1.728±0.010

4.9±1.5

2.1±0.2

2.258±0.005

3.1±0.6

As(V)+GSH 1:6

3.2±0.2

2.254±0.006

3.1±0.7

N = coordination number; R = bond length; values in brackets.

As-S

(10-3 Å2)

= Debye-Waller factor; relative misfit (R-factor) of at most 0.7% for all fits. Uncertainty

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that may be a consequence of the reaction steps, in which the intermediary As(III) is formed before complexation. As-S bond lengths do not significantly changed between samples confirming the robustness of the fits. The complexation behavior of As(III) and As(V) with GSH was analyzed by XAFS point of view. After

the reduction of As(V) to As(III) in freshly prepared solutions, the compound As(GS)3 is formed with a higher electron density around As atom compared with the oxyanions of As(III) and As(V). Information about the molecular mechanisms of As biological immobilization can help to clarify the complex biochemistry of As.

References DELNOMDEDIEU, M., BASTI, M.M., OTVOS, J.D., THOMAS, D.J. 1994. Chem. Biol. Interact. 90: 139-55.

RAVEL, B., NEWVILLE, M.J. 2005. Synchrotron Radiat. 12: 537-4i.

MONOSTORI, P., WITTMANN, G., KARG, E., TÃšRI, S. 2009. J. Chromatogr. B 877: 3331-46.

Determination of mercury biosorption by Microcystis novacekii (Cyanobacteria) biomass M.W. Franco1,*, L.A. Mendes2, C.C. Windmöller2, M.S. Dumont1, F.A.R. Barbosa1 Laboratory of Limnology, Ecotoxicology and Aquatic Ecology-LIMNEA, Department of General Biology/ICB, Universidade Federal de Minas Gerais (UFMG). Belo Horzionte - MG, Brazil. 2 Laboratory of Mercury Analysis, Chemistry Department, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: maionewf@hotmail.com 1

Keywords: Mercury, bio-sorption, cyanobacteria, Microcystis novacekii, biomass.

Bio-sorption is the process of removal of heavy metals by the passive binding to non-living biomass from an aqueous solution (Davis et al., 2003). The adsorption of toxic metals in biomass of various organisms has been studied in order to develop inexpensive and efficient processes for the removal of metals from wastewater. Production and cost of biomass for metal removal systems have been tested utilizing diverse sources of biomass (Bailey et al., 1999). Microorganisms are target in biosorption studies for their high surface-to-volume ratio, providing important surface area where the bio-sorption processes take place. Microcystis novacekii (Cyanobacteria) was isolated from lake Dom Helvécio (Rio Doce Park, southeast Brazil) and has been maintained under culture conditions in the Laboratory of Limnology, Ecotoxicology and Aquatic Ecology (LIMNEA). This strain has been used in studies of toxic elements bioaccumulation such as lead and arsenic. The aim of this study was to determine the capacity of M. novacekii biomass to remove mercury íons (Hg+2) in distinct physical and chemical conditions. M. novacekii cultures (4L) were cultivated in BG-11 medium in Erlenmeyer flasks under constant light (27µmol.cm-2), temperature (20± 1°C) and aeration with filtered air (45µm). After 30 days the biomass was collected by centrifugation (7700 rpm), lyophilized and stored (-20°C). For bio-sorption experiments some variables were standardized in previous tests: adsorption equilibrium time (10 h), proportion of lyophilized biomass used (1 mg/ml) and pH of aqueous solution maintained at 6 using MES buffer [2-(N-morpholino) ethanesulfonic

acid]. After exposure to Hg concentrations of 2 to 200 mg/L (Figure1). The maximum bio-sorption was determined according to the models of Langmuir and Freundlich isotherms (Figure 2). To evaluate the influence of the solution pH on the mercury adsorption process biomass samples were exposed to Hg solutions of 50 mg/L at pH values from 3 to 8. To evaluate the influence of co-ions in the adsorption solutions of Hg2+ (0.25 mM) were prepared with the addition of Fe+2, Fe+3 or Mn+2 at concentrations of 0.125; 0.25 and 0.5 mM. The maximum quantity of Hg adsorbed (Qe) according to the isotherms of Langmuir (44.84 mg/g, Figure 1A) and Freundlich (39.28 mg/g, Figure 1B) was comparable to Spirogyra hyaline (Zygnematophyceae) that presented a maximum bio-sorption capacity of 35.71 mg/g Hg (Kumar and Oommen, 2012). The maximum efficiency of bio-sorption was 93.0 ± 4.4% in the concentration of 50 mg/L (Figure 1), was used in the subsequent experiments.

Figure 1. Hg adsorbed (mg g -1) as function of Hg concentration (mg L-1).

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Figure 2. Freundlich (A) and Langmuir (B) isotherms. Qe: Hg adsorbed in the biomass. Ce: Hg concentration in the aqueous phase.

Figure 3. Hg+2 removed (%) by the biomass from aqueous solution as function of the pH in the concentration of 50 mg/L.

As a function of the pH in solution the maximum removal efficiency was found in pH 7 (97.2%). Phosphate and hydroxyl groups in cell wall are deprotonated in neutral conditions favoring chemical interactions (Sujoy et al., 2007). Spherical amorphous extracellular deposits of Hg+2 were found as the main process of bio-sorption in bacteria lyophilized biomass exposed to HgCl2 (Franรงois et al., 2012). The Hg removal efficiency was greater than 94.71% for all concentrations of co-ions tested) in constant concentration of Hg (Figure 4). The presence of co-ions in solution is not considered an issue for using M. novacekii biomass in processes of water decontamination with Hg ions. All the properties of M. novacekii biomass analyzed here are favorable to the application of this cyanobacteria strain in processes of waste water decontamination in distinct conditions, mostly when Hg is present in high concentration. For this reason, the use of M. novacekii biomass is indicated for the development of techniques used in wastewater treatment.

Figure 4. Hg+2 removed by the biomass from aqueous solution (%) as function of co-ions (Fe+3, Fe+2 and Mn+2). Concentrations in mM.

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References BAILEY, S. E., OLIN, T.J., BRICKA, R.M., ADRIAN, D.D. 1999. Wat. Res. 33: 2469-2479. DAVIS, A.T., VOLESKY, B., MUCCI, A. 2003. Water Research 37: 4311-4330.

FRANÇOIS, F., LOMBARD, C., GUIGNER, J.M., SOREAU, P., BRIAN-JAISSON, F., MARTINO, G., VANDERVENNET, M., GARCIA, D., MOLINIER, A., PIGNOL, D., PEDUZZI, J., ZIRAH, S., REBUFFAT, S. 2012, February. Appl. Environ. Microbiol. 78 (4): 1097-1106. KUMAR, J.I.N., OOMMEN, C. 2012. Environ. Biol. 33: 27-31.

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Research Topic 2 Natural and Synthetic Materials for Enviromental and Technological Applications 64

Role of Al - Fe (hydr)oxides on mobility and bioavailability of contaminants. Part 1: mechanism of arsenic fixation

Role of Al - Fe (hydr)oxides on mobility and bioavailability of contaminants. Part 2: Arsenic, Uranium and some REE

Structure and property of Covellite and Arsenopyrite and their cleavage surfaces

Magnetically separable nano-sized Mn3O4 composite for cadmium and arsenic adsorption

TiO2 and TiO2/SiO2 photocatalyst films for water treatment application

Role of Al - Fe (hydr)oxides on mobility and bioavailability of contaminants. Part 1: mechanism of arsenic fixation E.T.F. Freitas1, L.A. Montoro2, J.W.V. de Mello3, M. Gasparon4, V.S.T. Ciminelli5,* Centre of Microscopy and Post Graduate Program on Metallurgical, Materials and Mining Engineering. Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. 2 Department of Chemistry, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. 3 Department of Soils, Universidade Federal de Viçosa (UFV).Viçosa - MG, Brazil. 4 School of Earth Sciences, The University of Queensland. St. Lucia - QLD, Australia. 5 Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: ciminelli@demet.ufmg.br 1

Keywords: Arsenic fixation, oriented-attachment, nanocrystalline Al-hematite.

A mechanism responsible for long-term As fixation in the environment is described here for the first time. Arsenic (1.6±0.5 wt%) was unambiguously identified in mesocrystals of Al-hematite with an As/Fe molar ratio of 0.026±0.006 in environmental samples. The As-bearing Al-hematite is interpreted as a secondary phase formed from iron (hydr)oxides. Experimental evidence supports a mechanism whereby arsenic adsorption onto Al-ferrihydrite nanoparticles (NPs) is followed by Al-ferrihydrite aggregation in a process of self-assembly oriented attachment (OA) to produce nanosized Al-hematite mesocrystals, with goethite as a possible intermediate phase. Arsenic species are incorporated and thus irreversibly trapped in the aggregates. Structural Al was identified in all the As-bearing iron (hydr)oxides. The key role of iron or aluminum (hydr)oxides on the mobility and bioavailability of As in the environment is well established. However, the detailed ageing/recrystallization mechanisms taking place following the initial adsorption/coprecipitation of As, and the role of Al in these processes remain to be fully understood. The structural characterization of As-bearing phases in environmental samples is not trivial due to particles heterogeneity, small grain size and low concentrations. Synchrotron-based analytical techniques combined with theoretical molecular modeling or with other spectroscopic techniques

have been increasingly applied to investigate As distribution, speciation, and bonding characteristics. The spatial resolution limit of the aforementioned techniques, however, can be overcome by transmission electron microscopy (TEM). This method allows the characterization of solid phases at the nanoscale, with better spatial resolution than any other technique. The combined spectroscopy and X-ray diffraction (for bulk analysis) with high resolution TEM (for phase characterization at nanoscale) were applied to investigate As-bearing phases in environmental samples (Freitas et al., 2015). New insights into the mechanism of As incorporation in the structure of Al-Fe-(hydr)oxides such as Al- substituted goethite and hematite are provided.

Arsenic fixation in enriched Al and Fe oxisols Enriched Fe-Al-enriched oxisols exposed to As-sulfide tailings from hydrometallurgical processing plant in a gold mine in Minas Gerais State were investigated. After more than a decade of disposal the impoundments were removed and the oxisol liner samples were recovered for analyses. A sample from the local oxisol, representing the material before exposure to the As-sulfide tailings,

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Figure 1. (A) STEM image of an aggregate of crystalline hematite NPs. (B) High resolution STEM image of the area inside square in (A) showing the oriented aggregated NPs. (C) Electron diffraction pattern performed in the aggregate in (A) confirming the hematite phase. (D-F) EDS maps of Fe, Al and As of the aggregate shown in (A).

was also investigated. The main constituents of the samples were identified as quartz, kaolinite, muscovite, siderite, albite, gibbsite, hematite and goethite by XRD analysis (Freitas et al. 2015). The As content was 12±7 mg.kg-1 in the natural oxisol (NOX) and ranged from 1,886 mg.kg-1 to 6,375 mg.kg -1 in the oxisol liners (OXL). TEM analysis showed the presence of ferrihydrite, goethite and hematite. Most arsenic (60-69 wt%) in the OXL samples was found in association with crystalline nanoparticle aggregates of Fe-Al-(hydr)oxides. Structural Al was identified in all As-bearing phases by EDS analysis. Arsenic was homogeneously distributed in the structure of nanocrystals of Al-substituted hematite (α-(Fe,Al)2O3) (Figure 1) and

goethite (α-(Fe,Al)OOH). The arsenic content found in Al-hematite ranged from 0.90 to 3.23 wt%, (e.g. from 9,000 to 32,300 mg.kg-1). In Al-goethite, the As content ranged from 1.20 to 2.40 wt% (12,000 to 24,000 mg.kg-1). As hematite and goethite are the most stable phases among Fe-(hydr)oxides, the large amount of As incorporated in crystal structure of such phases is therefore less mobile in the environment. A mechanism is proposed for the incorporation of As into hematite in which Al-ferrihydrite nanoparticles (NPs) act as a template. According to this mechanism (Figure 2), As is adsorbed onto existing or newlyformed Al-ferrihydrite, thus modifying its surface properties. The Al-ferrihydrite NPs then aggregate through a self-assembling oriented attachment

Figure 2. Schematic model illustrating the formation of mesocrystals of hematite and the process of As incorporation in its structure.

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(OA) process, ultimately resulting in hematite mesocrystals by ageing. The formation of goethite in an intermediate step cannot be excluded. It is known that Al in the system increases the surface area of ferrihydrite, thus improving its adsorption capacity, slowing down phase transformation into hematite, and giving more stability to these phases (Schwertmann et al., 1979; Violante et al., 2009, Adra et al., 2015). The presence of Al might have hindered the growth of the newly formed Fe-(hydr)oxides NPs so that the OA-based crystal growth was favoured, and therefore the amount of As immobilized in the OA upon attachment of the Al-Fe-(hydr)oxide nanoparticles. Then, arsenic primarily sorbed on the

NPs is irreversibly incorporated in the Al-hematite phase.

Acknowledgements The authors are grateful to CNPq, Fapemig and CAPES PROEX for financial support and for the PVE (Science Without Borders) fellowship to M. Gasparon. Kinross Brasil Mineração is gratefully acknowledged for supplying the samples. The Brazilian Nanotechnology National Laboratory (LNNano/LNSL) and the Center for Microscopy (CM-UFMG) are also acknowledged for the infrastructure used to carry out the experiments.

References ADRA, A., MORIN, G., ONA-NGUEMA, G., BREST, J. 2016. Arsenate and arsenite adsorption onto Al-containing ferrihydrites. Implications for arsenic immobilization after neutralization of acid mine drainage. Applied Geochemistry 64: 2-9. FREITAS, E.T.F., MONTORO, L.A., GASPARON, M., CIMINELLI, V.S.T. 2015. Natural attenuation of arsenic in the environment by immobilization in nanostructured hematite. Chemosphere 138: 340-347.

SCHWERTMANN, U., FITZPATRICK, R.W., TAYLOR, R.M., LEWIS, D.G. 1979. The influence of aluminum on iron oxides. Part II. Preparation and properties of Al-substituted hematites. Clays and Clay Minerals 27 (2): 105-112. VIOLANTE, A., PIGNA, M., DEL GAUDIO, S., COZZOLINO, V., BANERJEE, D. 2009. Coprecipitation of arsenate with metal oxides. 3. Nature, mineralogy and reactivity of iron(II)-aluminum precipitates. Environmental Science & Technology 43: 1515-1521.

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Role of Al - Fe (hydr)oxides on mobility and bioavailability of contaminants. Part 2: Arsenic, Uranium and some REE J.W.V. de Mello1,*, V.S.T. Ciminelli2, M. Gasparon3, E.T. Freitas4, L.P. Cardoso5, G. Barcelos5, R.W. Veloso5 Department of Soils, Universidade Federal de Viรงosa (UFV).Viรงosa - MG, Brazil. Department of Metallurgical and Materials Engineering, Universidade Federal de Minhas Gerais (UFMG). Belo Horizonte - MG, Brazil. 3 School of Earth Sciences, The University of Queensland. St. Lucia - QLD, Australia. 4 Centre of Microscopy and Post Graduate Program on Metallurgical, Materials and Mining Engineering. Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. 5 Post graduate program on Soil Science, Universidade Federal de Viรงosa (UFV). Viรงosa - MG, Brazil. *Corresponding author: jwvmello@ufv.br 1 2

Keywords: As, U, La, Ce, Al-goethites, gelglocs, environmental stability.

The low mobility and bioacessibility of arsenic associated with Fe (hydr)oxides in geogenic materials from natural (soils, sediments and fallout dust) and from anthopogenic origin has been demonstrated by different investigations. The high affinity between Fe and As is well known and has a key role in controlling arsenic mobility in the environment and in treatment of contaminated water. What is not fully established is the role of Al in arsenic fixation by Fe (hydr) oxides. Indirect benefits have been observed in previous investigations. The presence of aluminum was shown to increase the specific surface area and the stability of the iron phases, and to favor arsenic adsorption and fixation (Silva et al., 2010; Ladeira and Ciminelli, 2004). Goethites with structural Al were shown to combine high adsorption capacity and stability under a wide range of environmental conditions, including reducing conditions (dissimilatory reductive dissolution by Shewanella putrefascians), relative to other Fe (hydr)oxides (Silva et al., 2010). The role of Fe (hydr)oxides, mainly the poorly crystalline ones, in the mobility of As was also confirmed in creeks close to gold mining areas in Minas Gerais State. Such (hydr)oxides associated to gelflocs containing microorganisms, algae, and clay minerals (Figure 1) have proved very efficient to retain As in the area under mining influence

(Veloso et al., submitted). Pictures of these gelflocs in water streams (Figure 1a) as well as microscopic features and their chemical composition (Figure 1b) are shown. Not only the mobility, but also the toxicity of As is attenuated by association with Fe (hydr)oxides. This has been suggested by experiments for assessment of As ecotoxicity with plants (Figure 2) and worms in soils. The higher the maximum adsorption capacity (MAC) of the soil sample, the greater is the As lethal doses (LD50). It is worth of note that the As MAC is directly related to the contents of Al and Fe (hydr) oxides in soils. Such experiments also show that the As ecotoxicity is attenuated by ageing (Figure 2), probably because the association of As with Fe (hydr) oxides becomes more stable over time. (Moraes et al., submitted). Arsenic association with Al-Fe (hydr)oxides has also a determinant role on As bioavailability, which is the amount of contaminant or nutrient absorbed by the body after ingestion, inhalation or dermal contact. Arsenic in soil, dust and mineral forms is a lot less than 100% bioavailable. Arsenic bioaccessibility (the fraction that is soluble in the gastrointestinal tract and hence may be bioavailable for uptake) in soil and dust from a gold mining area (Paracatu) is typically less than 10% and more likely to be only a few percent in the samples we collected and tested. The low bioavailability of arsenic in the soil and

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Figure 1. (A) Iron (hydr)oxides gel flocs in water streams close to gold mining area; (B) TEM micrograph and chemical composition of gel flocs.

Figure 2. Sorghum plants growth in the presence of increasing doses of arsenic, one day and six weeks after soil contamination.

dust in Paracatu has been confirmed by others (Ono et al., 2012). Preliminary results suggest that Al and Fe (hydr) oxides precipitation is also efficient to treat water contaminated with Uranium and REE (La and Ce). But co-precipitation of U with Al-Fe (hydr)oxides seems to be limited to low amounts of the actinide. Investigations of As precipitation in the presence of Fe and Al indicated that the presence of Al can delay the arsenic removal process at high pH, as

well as decrease the stability of the slimes (Mello et al., submitted)

Acknowledgements Authors are grateful to CNPq, Fapemig and CAPES for financial support and for the fellowships to M. Gasparon (PVE - Science Without Borders Program) and J. Mello (Sabbatical leave - CAPES).

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References MELLO, J.W.V., GASPARON, M., SILVA, J. 2016. Submitted. MORAES, M.L.B., MELLO, J.W.V., ABRAHÃO, W.A.P., MELO, M.C. 2016. Submitted. ONO, F.B., GUILHERME , L .R.G., PENIDO, E .S., CARVALHO, G.S., HALE, B., TOUJAGUEZ, R., BUNDSCHUH, J. 2012. Environmental Geochemistry and Health 34: 457-465.

SILVA, J., MELLO, J.W.V., GASPARON, M., ABRAHÃO, W.A.P., CIMINELLI, V.S.T., JONG, T. 2010. Water Research 44: 5684-5692. VELOSO, R.W., MELLO, J.W.V., GLASAUER, S., ABRAHÃO, W.A.P. 2016. Submitted.

Structure and property of Covellite and Arsenopyrite and their cleavage surfaces A.L. Soares Jr1, J.C.M. Silva1, H.A. de Abreu1, H.A. Duarte1,* Department of Chemistry, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: duarteh@ufmg.br

Keywords: Mineral sulfides, covellite, arsenopyrite, DFT.

The sulfide minerals are natural crystalline, or synthetic binary or ternary analogues, sulfur compounds. The former are considered the most important source of base metals, such as copper, zinc, nickel, among others (Bader, 1991; Becke and Edgecombe, 1980). For example, chalcopyrite (CuFeS 2), bornite (Cu 5FeS 4), chalcocite (Cu 2S) and covellite (CuS) are typical copper minerals. Iron sulfides, such as pyrite (FeS) and arsenopyrite (FeAsS), are commonly found in association with the metal sulfides of economic interest and are the most common gold-bearing sulfides. Mining tailings generated in the extraction of metal sulfides may be hazardous to the environment due to the generation of acid rock drainage (ARD). The society’s demand for more sustainable, efficient and secure metal extraction processes is pivotal to the feasibility of mining operations. We have pursued important efforts to investigate the reactivity of the sulfide mineral surfaces. This is a crucial step for understanding the leaching process for metal extraction and ARD mechanisms at a molecular level (Oliveira et al., 2012, Morales-García et al., 2014, Silva et al., 2015, Lima et al., 2011). There is consensus that for improving the leaching process for metal extraction and the mitigation of the ARD it is necessary to investigate the structural, electronic and chemical properties of the sulfide minerals and their surfaces. Covellite is commonly found in copper deposits as a product of secondary enrichment or of alteration of other sulfide minerals, such as chalcopyrite (Majuste et al., 2013). Chalcopyrite is the main source of copper and in recent years has received increased attention from the scientific community, both experimentally (Majuste et al., 2013) and theoretically (Oliveira et al., 2012; Lima et al., 2011). Arsenopyrite contributes to the ARD, and furthermore it is the main source

of toxic arsenic compounds, which can be released into the environment under the ARD process. The covellite and arsenopyrite minerals and their surfaces were investigated by means of Density Functional (DFT)/plane waves calculations aiming to contribute to the understanding of their oxidation mechanism at a molecular level.

CuS Theoretical studies of the CuS bulk (Figure 1a) were performed and reported in the literature (Morales-García et al., 2014). Unit cell parameters, structural and geometry are overestimated, with deviations in the bond size up to 2% compared with experimental data (Evans and Konnert, 1976). The generalized gradient approximation for the exchange/correlation functional including the empirical Hubbard parameter (GGA+U) has been used to improve the electron correlation description and structural estimates. The results shown in the Table 1 indicate that U=5 is the most appropriate to describe covellite. Band structure and density of states (DOS) confirm that this material is nonmagnetic and conductive (Figure 2a). The projected density of states (PDOS) reveal higher contribution near the Fermi level from d and p orbitals localized on the copper and sulfur atoms, respectively. Moreover, there is anisotropy in the electrical conductivity with electronic states confined along the crystallographic plane ab (Figure 2b) wherein the conduction occurs preferentially through the trigonal arrangement plane of copper and sulfur atoms. The analysis of the electron localization function (ELF) (Becke and Edgecombe, 1990) suggests that the disulfide bond has strong covalent character,

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Figure 1. (A) CuS bulk, hexagonal unit cell. (B) Five supercell (2x2) cleavages that occurs along the crystallographic plane (001).

Table 1. Experimental and optimized lattice parameters of the covellite unit cell with GGA and GGA+U exchange-correlation functional.

Experimental

PAW + PBE

a=b (Ă…)

3.7938(5)

c (Ă…)

16.341(1)

US + PAW+U U3

3.826

3.791

16.596

16.589 16.400 16.402

Figure 2. (A) Covellite: band structure and density of states, US+PBE. The Fermi level was shifted to 0 eV. (B) Projected density of states in the atomic orbitals: px, py sulfur atoms and the dxy e dx2-y2 copper atoms.

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while the other interactions have an ionic character. The Bader’s analysis (QTAIM - Quantum Theory of Atoms in Molecules) (Bader, 1991) confirms the covalent character of the S-S bond. The Cu-S bonds are classified as ionic bonds because of the positive Laplacian in Bader’s analysis. It is known that preferential cleavage of the CuS happens along the c axis crystallographic (001) and lower energy is required to break ionic bond. These facts suggest that Cu–S bond cleavage occur in the surface reconstruction. This proposal was confirmed in the surface cleavage study. Furthermore Bader’s analysis indicates that sulfur atoms occupy 60% in the volume cell. Bulk modulus value is 79.47 GPa. In the surface investigation (Figure 1b) the equivalent C and D surfaces are the most favored. The energy surface of A and B (or E) surfaces are at least 16.3 meV Å-2 (0.26 J m-2) and 53.0 meV Å-2 (0.85 J m-2) larger, respectively. On the other words, the Cutet–Stri bond is preferentially broken in the cleavage process. The structural properties show greater reconstructions in the B and E surfaces, wherein there are formations of new bonds. C and D surfaces just have relaxation of the surface atoms. In the A surface reconstruction, there is a detachment of a planar monolayer, with molecular formula CuS, and the atoms on the new surface are only relaxed. The electronic behavior of all surfaces classify it as a conductor material, in which the orbitals d and p from copper and sulfur atoms, respectively, contribute mainly to the conduction band as in bulk material. Only in the A surface, the number of occupied states have increased above Fermi level when compared with bulk, justified by planar monolayer formation. The QTAIM topological analysis and ELF information show that S–S and Cu–S bonds maintain the covalent and the ionic character, respectively. Together with the Bader’s charge analysis, the interpretation of the density in BCP and PDOS results show different charge distributions in the reconstructed surfaces, in which the sulfur atoms are the most electronegative centers. These results will guide subsequent reactivity studies, wherein interaction sites of the leaching and oxidation agents applied in hydrometallurgical processes will be investigated.

arsenic and sulfur dianions (As-S) coordinated to the iron atom in an octahedral shape. The results (Silva et al., 2015) show that there are chemical bonds between Fe–As and Fe–S atoms and a covalent As–S bond (Figure 3a) which is confirmed by the ELF (Figure 4). This is the strongest bond in the system and it is not expected to break in the cleavage of FeAsS. No Fe–Fe bond was found between these atoms because there is only a ring critical point in this position, as shown in Figure 3b. About the cleavage plane, the literature data are not in agreement among planes (100), (110) and (101). Models of the surfaces (001), (010), (100), (011), (101), (110), (111) and (210) were calculated and their cleavage energies compared. The results (Silva et al., 2015) show that the surfaces (001), (010) and (100) have similar energies and could be considered as the preferential cleavage surface, but the surface (001) had the lowest surface energy of the

Figure 3. (A) Bond critical points and (B) Ring critical points in FeAsS. Yellow atoms are sulfur, purple are arsenic and red are iron.

FeAsS Arsenopyrite is the most common arsenic mineral in nature, and it can be found in many ore deposits. It has monoclinic unit cell with space group P21/c with 4 FeAsS formulas per unit cell. Its structure contains

Figure 4. ELF of arsenopyrite As-S bond. Red is iron, purple is arsenic and yellow is sulfur.

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a c

Arsenopyrite Bulk Cleavage

Acknowledgements

b b

three (1.05 Jm-2) and its structure is shown in Figure 5. These surfaces are formed without breaking any As-S bond, which is the strongest bond in the periodic solid. The DOS analysis of the surfaces shows that the Fe atom is the preferred adsorption site, which means that it is the place where the oxidation reaction causing ARD can start. In these works, the structures of covellite and arsenopyrite were described in order to investigate the cleavage surfaces, which will be used in the studies about the reaction of these surfaces with leaching agents.

() Surface

Figure 5. ELF of arsenopyrite As-S bond. Red is iron, purple is arsenic and yellow is sulfur.

The authors are grateful to the Brazilian government agencies: CAPES, FAPEMIG and CNPq.

References BADER, R.F.W. 1991. A quantum theory of molecular structure and its applications. Chemical Reviews 91: 893-928. BECKE, A.D., EDGECOMBE, K.E. 1990. A Simple Measure of Electron Localization in Atomic and MolecularSystems. Journal of Chemical Physics 92: 5397-5403.

MORALES-GARCÍA, A., SOARES, A.L., SANTOS, E.C., ABREU, H.A., DUARTE, H.A. 2014. First-Principles Calculations and Electron Density Topological Analysis of Covellite (CuS). The Journal of Physical Chemistry A 188: 5823-5831.

EVANS, H.T., KONNERT, J.A. 1976. Crystal-Structure Refinement of Covellite. American Mineralogist 61: 996-1000.

OLIVEIRA, C., LIMA, G.F., ABREU, H.A., DUARTE, H.A. 2012. Reconstruction of the Chalcopyrite Surfaces – a DFT Study. The Journal of Physical Chemistry C 116: 6357-6366.

LIMA , G.F., OLIVEIRA, C.U., ABREU, H.A., DUARTE, H.L.A. 2011. Water Adsorption on the Reconstructed (001) Chalcopyrite Surfaces. The Journal of Physical Chemistry C 115: 10709-10717.

SIILVA, J.C.M., ABREU, H.A., DUARTE, H.A. 2015. Electronic and structural properties of bulk arsenopyrite and its cleavage surfaces – a DFT study. RSC Advances 5: 2013-2023.

MAJU STE, D., CIMINELLI, V.S.T., ENG, P.J., OSSEOASARE, K. 2013. Applications of in situ synchrotron XRD in hydrometallurgy: literature review and investigation of chalcopyrite dissolution. Hydrometallurgy 131: 54-663.

Magnetically separable nano-sized Mn3O4 composite for cadmium and arsenic adsorption A.M. Ferreira1,*, G.C. Silva2, A.P. Heitmann2, R.R. Cunha2, P. R.P. Paiva2, V.S.T. Ciminelli3 Department of Chemistry, Centro Federal de Educação Tecnológica de Minas Gerais (CEFET-MG). Belo Horizonte - MG, Brazil. 2 Department of Materials Engineering, Centro Federal de Educação Tecnológica de Minas Gerais (CEFET-MG). Belo Horizonte - MG, Brazil. 3 Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: angelamello@des.cefetmg.br 1

Keywords: Adsorption, cadmium, arsenic, magnetic nano-adsorbent.

Composites with magnetic properties have been successfully synthesized by a novel and environmentally friendly route, which precipitates manganese oxide (Mn3O4) onto magnetite particles by using O2 (an eco-friendly oxidant). This material presents high affinity and load capacity for arsenic, and also for cadmium ions in aqueous media. Magnetic separation is an effective technique for separating magnetic particles and has been used for several applications in areas such as biochemistry, analytical chemistry, mining and environmental engineering. It has the advantage of being rapid, easily applied in large-scale operations and easily automated. The challenge of separating powder adsorbents with high specific surface area from aqueous solution can be addressed with the use of magnetic composites. The composites can be conveniently recovered by magnetic separation, avoiding the filtration steps, which may represent a barrier to the application of high performance advanced materials in the treatment of large volumes of aqueous solutions.Our research group has been working on magnetic composites synthesis aiming at developing new functional materials to be used as effective adsorbents in removing trace metal contaminants, such as cadmium and arsenic from aqueous systems. The adsorption capacity of these materials is associated with the microporous structure, surface area and OH functional groups capable of reacting with different chemical species. Hausmannite (Mn 3O4) is one of the most stable manganese oxides in soils that have been shown to be

capable of sorbing large amounts of trace metal ions (Backes et al. 1995; Olmos et al. 2005). Silva et al. (2012) have synthesized Mn3O4 magnetic composites to remove As(III) from solutions and have shown that the magnetic composite presents high affinity for arsenic (Figure 1). The adsorption isotherm for As(III) is fitted by the Langmuir-Freundlich model and the estimated maximum As(III) adsorption capacity at pH 5 was 0.36±0.02 mgAs.m-2 (or q=15mg. g-1), b=2L.mg-1. The composite prepared with synthesized, commercial and ball-milled magnetite and the pure Mn3O4 samples have shown high and similar affinity for As(III). X-ray absorption near edge structure -XANES of the As-loaded composites showed that As(III) is successfully oxidized by Mn3O4. Also, Raman and Infrared (IR) spectroscopy have been used to understand the arsenic complexation by a magnetic Mn3O4 composite (Silva et al. 2013) and the results suggest monodentate and bidentate mononuclear complexation models. Cadmium adsorption in this Mn3O4/Fe3O4 magnetic composite was also investigated at pH 6 and pH 7 (Heitmann et al., 2014). The adsorption isotherm is fitted using the Langmuir-Freundlich model (Figure 1). The estimated maximum adsorption capacities of Cd(II) at pH 6 and 7 are similar, 0.28±0.02 and 0.31±0.02 mg.m-2, respectively. The kinetic studies of cadmium adsorption showed that the adsorption follows the pseudo-second-order model. In the Raman spectra of the loaded Mn3O4 magnetic composite samples, Cd presence modifies the bands related to hausmannite vibrations and causes the

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Figure 1. Arsenic adsorption on to composites (Mn3O4/Fe3O4) prepared with synthesized, commercial and ball-milled magnetite (a) and cadmium adsorption on to composite prepared with commercial magnetite (b).

appearance of a band related to Cd-O. The results indicate that cadmium is being adsorbed in a specific way by the manganese oxide in the composite. Figure 2 shows the magnetic solid-liquid separation and TEM image of the composite particles. The predominance of octahedral morphology is observed. The size of nanoparticles is estimated around 25-30 nm. The adsorption experiments have demonstrated that magnetic micro-sorbents present a good

immobilization capacity towards As(III) and Cd(II) from aqueous solutions. The magnetic property of magnetite, which is attached to the active Mn3O4, allows an easy removal of the sorbent particles from the solution. The present work simplifies the synthesis of a manganese oxide composite to be applied in environmental systems with a combined role of oxidant and adsorbent.

Figure 2. TEM image of composite crystal (25-30nm) and magnetic separation (Heitmann et al., 2016).

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References BACKES, C.A., MCLAREN, R.G., RATE, A.W., SWIFT, R.S. 1995. Soil Sci. Soc. Am. J. 59: 778-785.

PRADEEP, T., MALIYEKKAL, S.M., LISHA, K.P. 2010. Chem. Eng. J. 160: 432-439.

BARKA, N., OUZAOUIT, K., ABDENNOURI, M., EL MAKHFOUK, M., QOURZAL, S., ASSABBANE, A., AIT-ICHOU, Y., NOUNAH, A. 2012. Desali. Water Treat. 43: 8-16.

QIN, Q., WANG, Q., FU, D., MA, J. 2011. Chem. Eng. J. 172: 68-74.

HEITMANN, A. P., SILVA, G.C., PAIVA, P.R.P., DANTAS, M.S.S., CIMINELLI, V.S.T., DINOLA, I.C.S., FERREIRA, A.M. Water Sci &Technology, doi: 10.2166/wst.2016.446.

SILVA, G.C., FERREIRA, A. M., ALMEIDA, F. S., DANTAS, M.S.S., CIMINELLI, V.S.T. 2013. Spectroch. Acta. Part A, Molecular and Biomolecular Spectr. 100: 161-165.

HEITMANN, A.P., SILVA, G.C., PAIVA, P.R.P., FERREIRA, A.M. 2014. Cerâmica, São Paulo 60 (355): 429-435. OLMOS, A.V., REDÓN, R., GATTORNO, G.R., ZAMORA, M.E.M., LEAL, F.M., OSORIO, A.L.F., SANIGER, J.M. 2005. J. Colloid Interface Sci. 291: 175-180.

SILVA, G.C., ALMEIDA, F.S., FERREIRA, A.M., CIMINELLI, V.S.T. 2012. Mater. Res. 15: 403-408.

TiO2 and TiO2/SiO2 photocatalyst films for water treatment application M.A.M.L. Jesus1, M.S.S. Dantas2, A.M. Ferreira1* Department of Chemistry, Centro Federal de Educação Tecnológica de Minas Gerais (CEFET-MG). Belo Horizonte - MG, Brazil. 2 Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: angelamello@des.cefetmg.br 1

Keywords: TiO2, TiO2/SiO2, thin film, sol-gel, photocatalysis.

In this work we proposed a thin film of composites containing a mixture of TiO2 and SiO2 with enhanced photocatalytic activity compared to the pure TiO2. All these thin films were immobilized on borosilicate glass systems by sol-gel technology and were successfully tested for the photocatalytic degradation of methylene blue dyes under UV/visible light irradiation. Photocatalytic water treatment using nanocrystalline titanium dioxide is a well-known advanced oxidation process (AOP) for environmental remediation (Naghibi et al.,2015). With the in situ generation of electron-hole pairs upon irradiation with light, AOP can mineralize a wide range of organic compounds into harmless final products such as carbon dioxide, water, and inorganic ions, Fig 1. Up to this moment, TiO2 has been widely used due to its photocatalytic activity and photo-induced superhydrophilicity. Substantial efforts have been made to develop and improve new and effective water decontamination methods, mainly related to the

photocatalysts (Naghibi et al.,2015; Goei and Lim, 2014). The field of application for photocatalysis is extensive and has contributed to the development of new ways to prevent and remove organic contaminants (Gutiérrez et al., 2013). Among all the semiconductors photocatalysts, titanium dioxide (mainly anatase) is widely used at environmental applications because of desirable factors, such as relatively low cost, availability, biologically and chemically inert, and good photoactivity compared to other semiconductors (Nakata and Fujishima, 2012). Normally dispersed nanoparticle is use as a photocatalyst for water decontamination and our research group has been working on improving the photocatalytic activity of TiO2 by obtaining a thin film of TiO2/SiO2 mixed oxides on substrates by sol-gel method. In this work, pure TiO2 and TiO2/ SiO2 composite films containing 14%Ti (Si86Ti14) and 60%Ti (Si 40Ti 60) have been deposited over glass substrates by sol-gel dip-coating method

Figure 1. Schematic diagram of the photocatalytic degradation of the pollutant (Goei and Lim, 2014).

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Figure 2. Raman spectra of pure TiO2 (a) and TiO2/SiO2 (b) composite films treated at different temperatures (Jesus et al., 2015).

aiming at obtaining super hydrophilic, adherent and photocatalytic surface. The influence of the titanium content and the calcination temperature have been evaluated. The obtained TiO2/SiO2 thin films have presented high transmittance, low water contact angle and good mechanical properties. Raman spectroscopy was used to characterize the phase transformation of titania at TiO2 and TiO2/SiO2 films. Figure 2 shows the Raman spectra of TiO 2 (Fig 2a) and TiO2/SiO2 films (Fig 2b) heat-treated at different temperatures. TiO2 films have clearly showed anatase phase, presenting the main peaks at 143, 396, and 639 cm-. In this case, no rutile peaks were identified. Regarding the composite, only the Si40Ti60 exhibited anatase phase (Fig 2b) with the peaks shifted, because of the presence of SiO2 that can affect anatase crystallization (Jesus et al., 2015). The composite with low Ti content (Si86Ti14) did not show anatase/rutile peaks (Fig 2b), probably, due to high Si/Ti molar rate. Photocalyst test suggests that both composite samples exhibited photocalytic effect

under UV light. The Si40Ti60 composite film presented the best photocatalytic activity, followed by TiO2 and finally Si86Ti14 composite. After a 2-hour-long test, Si 40Ti 60 composite has decomposed about 80% of the dye, followed by pure TiO2 (75%), and finally Si86Ti14 (67%). The photocatalytic activity of TiO2/SiO2 mixed oxides is enhanced by larger surface area, porosity, dispersed TiO2 phase and the formation of peculiar catalytic active sites such as Ti-O-Si and Si-O-O bridging bonds at the TiO2/SiO2 interface (Jesus et al., 2015). The presence of SiO2 creates new active sites due to interaction between TiO 2 and SiO 2. The results of the present work showed that TiO2/SiO2 composite films obtained by sol-gel process are promising for water treatment application (degradation of dyes) due to the great photocatalytic activity, associated to low cost, high thermal stability, high wear resistance, and superhydrophilic properties. The main advantage with glass substrate is the transparency of the system even after the

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immobilization. This can allow the penetration of light, which can result in improved photocatalysis (Lazar, Varghese and Nair , 2012). This technique can allow the development of wisely designed photocatalytic reactors with decreased energy consumption or can avoid post-separation stages in photocatalytic water treatment processes, Fig 3. Reactor design is an intense focus for photocatalytic water treatment. Photocatalytic water treatment by this technique is a highlight topic of environmental research and a versatile technique for pollutant degradation.

Figure 3. Reactor design for photocatalytic water treatment.

References GOEI, R., LIM, T. 2014. Water Research 59: 207-218. GUTIÉRREZ, D.J.R., MATHEWS, N.R., MARTÍNEZ, S.S. 2013. Journal of Photochemistry and Photobiology A: Chemistry 262: 57-63. JESUS, M.A.M.L., NETO, J.T.S., TIMÒ, G., PAIVA, P.R.P., DANTAS, M.S.S., FERREIRA, A.M. 2015. Applied Adhesion Science 3: 1-5.

NAGHIBI, S., VAHED, S., TORABI, O., JAMSHIDI, A., GOLABGIR, M.H. 2015. Applied Surface Science 327: 371-378. NAKATA, K., FUJISHIMA, A. 2012. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 13: 169- 189.

LAZAR, M.A., VARGHESE, S., NAIR, S.S. 2012. Catalysts 2: 572-601.

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Research Topic 3 Advances in Hydrometallurgical Processes 81

Enhancing phases disengagement of solvent extraction processes using magnetic nanoparticles

Mechanical testing: a new approach to evaluate electrowinning performance

Development of hydrometallurgical processes aiming the recovery of REE, U, Th, Zr and Si from different sources

Removal of Ca and Mg from nickel electrowinning solutions

Enhancing phases disengagement of solvent extraction processes using magnetic nanoparticles N.C.C. Lobato1, A.M. Ferreira2, M.B. Mansur1* Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. 2 Department of Chemistry, Centro Federal de Educação Tecnológica de Minas Gerais (CEFET-MG). Belo Horizonte - MG, Brazil. *Corresponding author: marcelo.mansur@metalmat.ufrj.br 1

Keywords: Solvent extraction, magnetic nanoparticles, hydrometallurgy.

Solvent extraction, also known as liquidliquid extraction, has become an important step in hydrometallurgy for the separation, purification, and concentration of metal ions from aqueous solutions by using an immiscible organic phase. The industrial operation normally occurs in mixer-settler units. In the mixer, the mixture of the aqueous and organic phases takes place, while the phase disengagement occurs in the settler. Since the phase disengagement occurs by gravity sedimentation, such a process can be sufficiently slow and sometimes ineffective. As a result, larger areas for sedimentation are required, increasing investment costs. To accelerate and increase efficiency in the settler, a magnetic organic solution was developed so that the disengagement between the organic and

aqueous phases could be aided by a magnetic field. The magnetic organic phase was obtained by mixing the extractant Cyanex 272 (bis-2,4,4-trimethylpenthyl phosphinic acid) with a magnetic liquid containing superparamagnetic nanoparticles, comprised of magnetite (Fe3O4) and maghemite Fe2O3), with dimensions between 6 and 16 nm. The nanoparticles were coated by oleic acid in order to make them hydrophobic and thus efficiently dispersed in the organic medium, as shown in Figure 1. With the use of this magnetic organic phase, the phase disengagement rate was 3 to 5 times faster when compared to the traditional system. In fact, the results shown in Figure 2 reveal that both phases, in the absence of nanoparticles, separated completely within 55±3 s. In the presence of the nanoparticles

Figure 1. Transmission electronic microscopy images of bare nanoparticles (A) and nanoparticles coated by oleic acid (B).

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Figure 2. Variation of sedimentation and coalescence interface heights with time at changing concentrations of magnetic nanoparticles ([nanoparticles] = 0, 10, 20, and 30 g L-1).[Co] = 1 g L-1; [Cyanex 272] = 10% v/v; A/O volume ratio = 1; T = 25 °C; pH = 4).

Figure 3. Evolution of phase disengagement in the absence (left or blue) and with 30 g/l (right or black) of magnetic nanoparticles ([nanoparticles] = 0 and 30 g/l; [Co] = 1 g/L; [Cyanex 272] = 10% v/v; A/O volume ratio = 1; T = 25 °C; pH = 4).

this separation took 17±9 s, 17±8 s, and 11±3 s when the concentration of magnetite was 10, 20, and 30 g L-1, respectively. A comparison of the evolution of the phase disengagement of a system without nanoparticles and with a concentration of 30 g L-1 nanoparticles can be seen in Figure 3. The time at which the emulsion is completely poured into the glass graduated cylinder was considered the initial time (t = 0 s). It can be noted in the magnetic system phase disengagement was almost fully completed

during the first 3 seconds of the process, reaching the complete phase separation at t = 11 s. In the absence of nanoparticles, phase separation was completed at t = 51 s. Additionally, the presence of nanoparticles in the organic fluid up to 30 g L-1 did not affect the extraction of cobalt with Cyanex 272, under the investigated operating conditions. In fact, the same behavior on the extraction of cobalt was obtained when no magnetic particle was used. An obtained

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S-shaped curve on the metal extraction with pH revealed that Cyanex 272 behaves as a typically cationic extractant, and the extraction of Co2+ involves an ion-exchange mechanism with the donor H+ ion present in the molecule of the extractant. Stripping tests using 1 mol/l of H2SO4 (A/O = 1, T = 25 ºC) revealed that cobalt was quantitatively stripped out of the organic phase (stripping = 97±2%) in one single

contact, regardless of the concentration of magnetic nanoparticles. Chemical stability tests revealed that nanoparticles coated with oleic acid are not resistant when in contact with aqueous solutions at pH 2. To broaden the method’s application range, nanoparticles containing protective coating for acidic solutions are being currently investigated.

References LOBATO, N.C.C., FERREIRA, A.M., MANSUR, M.B. 2016. Evaluation of magnetic nanoparticles coated by oleic acid applied to solvent extraction processes. Separation and Purification Technology 168: 93-100.

VATTA, L.L., SANDERSON, R.D., KOCH, K.R. 2006. Magnetic nanoparticles: properties and potential applications. Pure Applied Chemistry 78: 1793-1801.

PALYSKA, W., CHMIELEWSKI, A.G. 1993. Solvent extraction and emulsion separation in magnetic fields. Separation Science and Technology 28: 127-138.

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Mechanical testing: a new approach to evaluate electrowinning performance D. Majuste1,*, V.S.T. Ciminelli1 Department of Materials and Metallurgical Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: daniel.majuste@demet.ufmg.br

Keywords: Zinc, nickel, electrowinning, energy, impurities.

The energy costs for producing electrolytic base metals, such as zinc and nickel, account for a significant part of their selling price. Therefore, industry faces a continuing pressure to improve this process efficiency. Previous works have described the effects of impurities on the energy efficiency of the electrowinning processes and on the morphology and crystal structure of the metallic product only. What has not been clearly established yet is how the morphology and texture of the electrodeposit will affect its mechanical properties and, thus, the effectiveness of the stripping and cutting stages. As the Zn and Ni deposits are bent during stripping by an applied load to the extremity of the deposit, the resulting deformation may lead to the fracture of the material and to the disruption of the stripping process, with the consequent implications in the electrowinning performance. As the Ni deposit is normally cut to be sold as small sheets or as coins, deposits with high hardness may cause a decrease in the deposit ductility, affecting both efficiency of the stripping stage and performance of the cutting machines. Then, a better understanding of the effect of contaminants on mechanical properties of metal deposits allows a more detailed assessment of product quality. Metallic impurities and some organic compounds may contaminate the feed electrolyte solution and affect the current efficiency of the electrowinning processes and the quality of the metals deposited on the corresponding cathodes. Due to a trend of metal extraction from low-grade ores, a gradual rise of the organic concentration in the electrolytes may be expected, particularly when oxide ores (e.g., zinc silicate) are treated. In this context, our group has investigated the effects of residual organic compounds on the electrowinning of Zn (Majuste et al., 2014; Majuste et al., 2015) and Ni (Freire et al.,

2015), by an approach that combines electrochemical techniques with product analysis by microscopy and mechanical testing. The bending behavior is assessed with a customized device (Fig. 1a) and correlated to the main features of the deposit. In the case of the Ni deposits, the nanohardness of this material is also of relevance. The selected organic compounds, which are used in industrial operations, include: flocculant, flotation collectors and lubricating oil (for Zn); and extractant, diluent, flocculant, acid mist suppressant and lubricating oil (for Ni). The mechanisms by which the molecules, analyzed by Fourier transform infrared spectroscopy and gas chromatography, may affect the kinetics of metal reduction and hydrogen evolution reactions under practical conditions are evaluated. The morphology and crystallographic texture of the metal deposit, which determine its mechanical properties, are discussed based on the degree of organic adsorption on the electrode surface and interactions with water molecules and electroactive species (Majuste et al., 2015).

Figure 1. Photograph of the device used in the bending tests of the metal deposits.

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Figure 2. Effect of organics on Zn electrowinning using a continuous-flow cell with Al cathodes and Pb-0.5% Ag anodes. Conditions: 62 g.L-1 Zn2+; 162 g.L-1 H2SO4; 38 ยบC; 530 A.m-2; 6 h. Legend: lubricating oil (black line), collector for impurities (blue line), flocculant (green line) and collector for zinc (red line).

Figure 3. Moment versus angle curves for samples produced from organic-free electrolyte (red line) and solution containing 50 mg.L-1 of collector for impurities (black line). Inset shows micrographs of Zn deposits.

The effect of impurities on mechanical properties of the metal deposit were evaluated after identifying the main contaminants of the Zn electrolyte, according to the corresponding effects on current efficiency (Figure 2) and, consequently, on energy consumption. Bending tests were carried out up to an angle of 50ยบ. The measurements revealed that the organics affect the mechanical properties of the Zn deposit differently. The properties were found to be strongly correlated to the porosity of the metal deposit, grain size and preferred orientation (texture) of the Zn hexagonal platelets (Majuste et

al., 2016). Highly porous deposits exhibited low ductility, which in turn caused the fracture of the sample at small bending angles (Fig. 3), impeding effective stripping. With regard to the effect of organic compounds on Ni electrowinning, the results indicated that only the flocculant and the acid mist suppressant exhibit relevant negative effects on current efficiency and energy consumption. At higher concentrations (50-100 mg.L-1) in the sulfate solution (80 g.L-1 Ni2+; 50 g.L-1 Na+; pH 2.8), the effect of the suppressant also includes the cracking of the Ni deposit during

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the process (60 ºC; 300 A.m-2; 6 h), which is likely related to observed reduction of grain size. Only the addition of flocculant or acid mist suppressant to the electrolyte has increased the nanohardness of the Ni deposit, which may affect the performance of the stripping and cutting stages after electrowinning. Our approach, which provides a prediction for the behavior of different deposits during the stripping operation, allows a better assessment of the effect of organic impurities, and also metallic impurities and additives, on the quality of electrodeposits, thereby

assisting industry to optimize conditions and increase productivity.

Acknowledgements This work has been developed within the scope of AMIRA Project (P705B/P705C – Electrowinning of base metals), which is currently sponsored by 8 global companies and has the CNPq, Fapemig and Capes as the research providers.

References FREIRE, N.H.J., MAJUSTE, D., CIMINELLI, V.S.T. 2015. In: 26º Encontro Nacional de Tratamento de Minérios e Metalurgia Extrativa – ENTMME. Poços de Caldas, MG, vol. 2, pp. 222-231. MAJUSTE, D., CIMINELLI, V.S.T., MARTINS, E.L.C., SOUZA, A.D., NICOL, M.J. 2014. In: 7th International Symposium on Hydrometallurgy (Hydro 2014). Victoria, BC, Canada, vol. 2, pp. 153-162.

MAJUSTE, D., MARTINS, E.L.C., SOUZA, A.D., NICOL, M.J., CIMINELLI, V.S.T. 2015. Hydrometallurgy 152: 190-198. MAJUSTE, D., BUBANI, F.C., BOLMARO, R.E., MARTINS, E.L .C., CETLIN, P.R., CIMINELLI, V.S.T. 2016. Hydrometallurgy. Submitted.

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Development of hydrometallurgical processes aiming the recovery of REE, U, Th, Zr and Si from different sources C.A. Morais1,*, J.C.B.S. Amaral1, L.V. Resende1, R.D. Abreu1, C.A. Ferreira1, T.S. Formiga1 1 Center for Development of Nuclear Technology (CDTN/CNEN). Belo Horizonte - MG, Brazil. *Corresponding author: cmorais@cdtn.br

Keywords: Zirconium, solvent extraction, leaching, thorium, rare earth elements, uranium.

Generally, the extractive metallurgy consists in a variety of procedures used to process minerals containing metallic elements and to convert them into metals of required purity for specific applications. The required purity often depends on the preceding steps used during the processing; some are used only for producing relatively pure metals while others are quite efficient in producing metals of high purity (HavlĂk, 2008). In this review, processes used in the hydrometallurgical separation of different elements such, zirconium and hafnium; rare earth elements (REE), uranium, thorium, and silica are reported. Solvent extraction was the most suitable process to separate heavy REE; to separate terbium and dysprosium from other REE as well as to recover Europium and Yttrium from computer monitors. Acid leaching was used to recover REE, thorium and uranium from industrial residue as well as to dissolve zirconium and SiO2 from zircon ore.

Separation of heavy rare earth elements by solvent extraction Studies of solvent extraction of individual REE have been extensively carried out with the use of various extractants in different medium. However, only few of the studies take into account industrial application. R. D. Abreu and Morais (2014) studied the separation of rare earth elements (REE) from heavy REE concentrate through solvent extraction, in which seven extractants were investigated: three organophosphorus acids (DEHPA, IONQUEST 801 and CYANEX 272), a mixture of DEHPA/TOPO and three amines (ALAMINE 336, ALIQUAT 336

Figure 1. Laboratory of solvent Extraction.

and PRIMENE JM-T). The organophosphorus extractants were investigated in hydrochloric and sulphuric medium whereas the amines performance was assessed in a sulphuric acid medium. In the extraction step, the best separation factors for the adjacent elements were obtained with DEHPA and IONQUEST 801. For 1.0 mol L -1 DEHPA in an initial acidity of 0.3 mol L-1 H+, the separation factor was 2.5 Tb/Dy, 2.1Dy/Ho, 1.9 Ho/Er, 2.0 Ho/Y and 1.1 Y/Er. For 1.0 mol L -1 IONQUEST 801 in 0.3 mol L -1of H + it was 2.7 Tb/Dy, 2.4 Dy/Ho, 2.1 Ho/Er, 2.1 Ho/Y e 1.5 Y/Er. The study concluded that IONQUEST 801 is the most indicated for the separation of heavy REE since it has lower affinity with the REE compared to the affinity of DEPHA/ REE, which makes the stripping of the REE from IONQUEST 801 easier than from DEHPA. Moreover, the number of stages necessary for the stripping of the REE from IONQUEST 801 was much smaller than that observed when DEPHA was employed.

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Figure 2. Profile of the REE in aqueous phase – Extraction and scrubbing steps of Tb separation circuit.

Separation of terbium and dysprosium from others REE by solvent extraction Abreu and Morais (2014) studied the fractionating of terbium and dysprosium from heavy REE concentrate by using solvent extraction circuit in a counter-current system. As the efficiency of the REE extraction with acid extractants rises with the increase of the atomic number of the element, the aim of this work was to extract the elements with higher atomic number maintaining Tb and Dy in the aqueous phase. Thus, terbium was separated first with subsequent separation of dysprosium. The experiments were carried out by using IONQUEST 801 as the extractant and a REE hydrochloric acid liquor as feed solution. Using a mixer-settlers counter current circuit composed of 10 extraction stages, 15 scrubbing stages, 10 stripping and 2 stages to remove the free-solvent acidity, it was obtained a Tb product of 95% purity, with a recovery of 90%. For Dy, the yield was 99.6% and the purity of the product was 98.5% using 12 extraction stages, 15 scrubbing stages, 10 stripping and 2 solvent regeneration stages.

Recovery of europium and yttrium from computer monitors screens This study describes the development of a process for the recovery of Eu and Y from cathode ray tubes (CRTs) of discarded computer monitors with the

proposition to obtain a flow diagram for the metals dissolution. Amongst other elements, europium and yttrium are present in the CRTs in quantities – 0.73 wt% of Eu and 13.4 of Y wt % – that make their recovery worthwhile. The process developed comprises the acid digestion of the sample with concentrated sulphuric acid followed by water dynamic leaching at room temperature. After 15 min of acid digestion and 1.0 h of water leaching, a pregnant sulphuric liquor containing 17gL-1 Y and 0.71gL-1 Eu was obtained indicating a yield of Eu and Y of 96% and 98%, respectively. Both steps, acid digestion and water leaching, could be performed at room temperature (Resende & Morais, 2015).

Recovery of rare earths, Th and U from industrial residue generated by monazite alkaline treatment Monazite is a rare earth phosphate ore that contains thorium and uranium as associated metals. In the alkaline treatment of monazite, a residue, containing thorium, uranium and some amount of REE is generated. The aim of this study is the recovery of thorium, uranium and rare earths from this residue, which was produced in Brazil from the mid-50s until the year of 1992. The variables investigated in the leaching step were: leaching agent type and concentration, percentage of solids, temperature and leaching time. The results indicated that the leaching of the industrial residue was most effective when performed with sulfuric acid 2 molL-1

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and a residue with 85% ZrO2 and 10 % SiO2. In this case, a SiO2 of 99% was obtained. In the direct acid leaching of the molten mass using HNO3 as leaching agent, dissolution of approximately 97% ZrO2 and a residue containing 92% SiO2 were obtained, with a mass reduction of approximately 80%.

Separation of zirconium and hafnium by solvent extraction Figure 3. Laboratory of Leaching.

in 2 hours of mechanical stirring at room temperature and with 10% of solids. In these conditions, a recovery of 79.3% of rare earths, 99.8% of Th and 99.8% of U was obtained from an original sample containing 34.9% of Th, 1.14% of U and 8.48% of Rare Earths.

Zircon ore processing aiming the recovery of zirconium and silica Ferreira, Formiga and Morais (2015) described the influence of some variables in the leaching of zirconium and in the recovery of silica present in the product of the zircon alkaline fusion. The silica and zirconium dissolution were investigated through two routes: the traditional one that consists of an alkaline fusion followed by acid leaching and a new route using just direct acid leaching. In the alkaline fusion step, a reaction time of 45 min and a NaOH/sample ratio of 1.3 were sufficient to achieve a complete fusion reaction. The leaching experiments showed that the direct acid leaching (new route) was able to obtain a good zirconium and silica separation. The alkaline leaching of the molten mass of zircon containing 31.8% ZrO2, 14.1% SiO2, 47.8% Na2O and 5 % humidity produced a liquor containing about 20 gL-1 silica (dissolution of approximately 73% Si)

Hafnium occurs in all zirconium ores in the range 2 to 3%, but the use of zirconium in the nuclear industry requires concentrations less than 100 mg kg-1 of hafnium (nuclear purity) (Shariati & Yamini, 2006). In order to produce high pure zirconium, Amaral, Rocha and Morais (2014) studied the separation of these two elements present in nitric liquor by using the solvent extraction technique. Acid extractants (DEHPA, IONQUEST 801 and CYANEX 272), solvating extractants (TBP, CYANEX 923 and a mixture of TBP and CYANEX 923) were investigated. Aqueous phase solutions prepared from the liquor generated by the dissolution of the product of the zircon alkaline fusion were used. The content of Zr and Hf in these solutions was around 20 g L-1 and 0.4 g L-1, respectively. The content of NO3varied between 3 and 12 mol L-1 while de acidity content varied from 1.0 to 10 mol L-1 H+. In the acid extractant experiments, a high extraction of the metals was observed even at high acidities, however, with no selectivity for DEHPA and IONQUEST801 but with some selectivity for CIANEX 272. The use of CIANEX 272 in the separation of Zr and Hf was unfeasible due to the metal stripping difficulties. Among the extractants investigated, TBP showed the best separation of Zr/Hf. The extracted zirconium and hafnium in the TBP organic phase was efficiently stripped using water as the stripping agent. The best results were obtained with an acidity of 7.0 molL-1 H+ and nitrate concentration around 8.0 molL-1 NO3-.

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References ABREU, R.D., MORAIS, C.A. 2014. In: Proceedings of the 53rd Annual Conference of Metallurgists - COM. Vancouver, vol. 1, pp. 86-91.

HAVLÍK, T. 2008. Hydrometallurgy - Principles and applications. 1. ed. New York: Woodhead Publishing Limited.

ABREU, R.D., MORAIS, C.A. 2014, 19 March. Minerals Engineering 61: 82-87.

RESENDE, L.V., MORAIS, C.A. 2015, 24 September. Minerals Engineering 70: 217-221.

AMARAL, J.C.B.S., MORAIS, C.A. 2014. In: Proceedings of the International solvent Extraction Conference. Wurzburg, pp. 686-691.

SHARIATI, S., YAMINI, Y. 2006. Journal of Colloid and Interface Science 419-425.

FERREIRA, C.A., FORMIGA, T.S., MORAIS, C.A. 2015. In: Procedings of IMCET-2015. Turkey.

Removal of Ca and Mg from nickel electrowinning solutions A.S. Guimarães1, M.F.A. de Souza1, L.H. Santos1, G.D. Rodrigues2, M.B. Mansur1,* Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. 2 Department of Chemistry, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: marcelo.mansur@metalmat.ufrj.br 1

Keywords: Solvent extraction, aqueous two-phase systems, nickel purification.

Nickel is a widely demanded metal, being more than half of the world’s total production used in the manufacture of stainless steel. The hydrometallurgical production of high- grade, metallic nickel comes from leaching sulfide or lateritic ores. The latter involves a relatively complex extraction process. Metals present in the ores, such as calcium, cobalt, copper, iron, magnesium, manganese, among others, may be dissolved during leaching. These metals should be removed from solution prior to the recovery of metallic nickel by electrowinning. The purification of nickel sulfate leach solutions was evaluated using prepared multicomponent aqueous sulfuric acid solutions with metal ion concentrations similar to those typically found in High Pressure Acid Leaching (HPAL) industrial liquors, following the iron removal step. A prepurification step by solvent extraction using 20%v/v of Cyanex 272 (bis(2,4,4-trimethylpentyl) phosphinic acid) as extractant was found efficient to selectively separate zinc, cobalt, copper, and manganese at pH 4.5, as shown in Figure 1. This process is already done commercially. Calcium and magnesium, however, are not easily removed, and such removal may represent a technological contribution to the nickel extraction process. The presence of unextracted alkaline earth metals may seriously interfere in the successful operation of the electrolytic process used to produce Ni metal. In fact, the deposit of calcium on the diaphragms of electrowinning baths requires increasing voltages to overcome the increased electrical resistance of the diaphragm, with a subsequent increase in the voltage distribution within the cell and a disturbance of the necessary cathode potential for the deposit of a nickel metal from the catholyte.

Figure 1. Extraction of metals with Cyanex 272 (initial concentration in g L-1: [Ca] = 0.50; [Co] = 2.10; [Cu] = 0.25; [Mg] = 3.50; [Mn] = 0.55; [Ni] = 75.0; [Zn] = 0.06; T = 50ºC; A/O volumetric phase ratio = 1) (Guimarães et al., 2014).

Aiming to remove calcium and magnesium from nickel sulfate solutions, two distinct methods were evaluated: (i) Synergistic solvent extraction (SSX) with Cyanex 272 and mixtures with cationic extractants such as Versatic 10 (neodecanoic acid), D2EHPA (di-(2-ethylhexyl) phosphoric acid), MCA (mixture of carboxylic acids obtained from coconut oil) and naphthenic acid, and (ii) Aqueous Two-Phase Systems (ATPS). In the former method (SSX), potential extractants systems were identified: Versatic 10 (10%v/v), D2EHPA (5 and 10%v/v), MAC (5 and 10%v/v) and naphthenic acid (10%v/v), mixed with Cyanex 272 (20%v/v), which were found to be susceptible to promote the purification of nickel from calcium and magnesium (Guimarães, 2014). The mixture of D2EHPA (5%v/v) with Cyanex 272 (20%v/v), at pH 4.8, was found a promising and suitable synergistic system, resulting in high extraction levels of calcium ( 72%) and magnesium ( 60%) over

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nickel ( 2%), thus allowing to obtain a raffinate stream with about 96% of nickel that could be submitted directly to electrowinning step, as shown in Figure 2.

Figure 2. Extraction of calcium, magnesium and nickel by synergistic solvent extraction using 20%v/v of Cyanex 272 and 5% of D2EHPA (initial concentration in g L-1: [Ca] = 0.50; [Mg] = 3.50; [Mn] = 0.55; [Ni] = 75.0; T = 50ºC; A/O volumetric phase ratio = 1) (Guimarães, 2014).

Figure 3. Extraction of calcium, magnesium, and nickel using ATPS from the concentrate aqueous solution in a staged operation, in the absence of an extractant, and at pH = 2 (Santos et al., 2015).

The competition between calcium and nickel in the aqueous phase, and between Cyanex 272 and D2EHPA in the organic phase, were evaluated by Souza (2015) at equimolar conditions. The mixture Cyanex 272 + D2EHPA was found to be more selective for calcium to nickel (3.5 pH 5.0) compared to both extractants separately, reaching a maximum value at pH 4.5. In this pH, the separation factor for Ca/Ni obtained when using the mixture of extractants is about 17 times higher than that of D2EHPA and almost 800 times higher than that of Cyanex 272. This result is due to the synergism occurred between extractants and represents a significant contribution for this separation system. In the latter method (ATPS), the performance of some cationic extractants (Cyanex 272, 1N2N and PAN) at changing concentrations and the effect of the pH of the aqueous system (1, 6 and 11) were studied (Santos et al., 2015). In an attempt to evaluate the application range of this separation method, batch scale tests (bottom/top phase weight = 1) were carried out using aqueous solutions at two limiting metal ion concentration levels. In the concentrate condition, the bottom phase consisted of a solution containing [Ca] = 0.44 g/L, [Mg] = 1.42 g L-1 and [Ni] = 80.0 g L-1. In the dilute condition, the bottom phase consisted of a solution of sodium tartrate in which a given volume of the concentrate solution was added, resulting in a dilution of approximately 80 fold. ATPS were found highly selective to remove calcium from magnesium and nickel using no extractant and at low pH values (around 1-2) for both dilute and concentrate nickel solutions using 3 contacting stages (Figure 3). The results obtained so far reveal that calcium and magnesium could be removed by using solvent extraction and/or combination with ATPS. In fact, both methods were found technically viable to be applied in concentrated aqueous conditions.

References GUIMARÃES, A.S. 2014. Purificação de níquel a partir de soluções sulfúricas por extração por solventes utilizando-se Cyanex 272 e misturas de extratantes, MSc. Thesis, UFMG, 126 pp. GUIMARÃES, A.S., SILVA, P.S., MANSUR, M.B. 2014. Hydrometallurgy 150: 173-177.

SANTOS, L.H., CARVALHO, P.L.G., RODRIGUES, G.D., MANSUR, M.B. 2015. Hydrometallurgy 156: 259-263. SOUZA, M.F.A. 2015. Extração por solventes sinérgica aplicada à separação níquel/cálcio utilizando-se os extratantes Cyanex 272 e D2EHPA, MSc. Thesis, UFMG, 89 pp.

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Research Topic 4 Acid Rock Drainage 94

Assessment of sediments contamination caused by acid mine drainage: Stable isotopic and Sequential Extraction studies

Hydrochemical and isotopic evidences of discharge of acid effluents from a uranium mine in a river basin

101 Isotopic and gases analyses to characterize a uranium waste rock pile 104 Effect of carbonate mineralogy in the neutralization potential: Why different static tests lead to contradictory classification of ARD?

Assessment of sediments contamination caused by acid mine drainage: Stable isotopic and Sequential Extraction studies L.R. Souza1, K. Knöller2, A.C.Q. Ladeira1,* Center for Development of Nuclear Technology (CDTN/CNEN). Belo Horizonte - MG, Brazil. Department of Catchment Hydrology, UFZ Helmholtz Centre for Environmental Research. Halle, Germany. *Corresponding author: acql@cdtn.br 1 2

Keywords: Acid mine drainage, uranium, stable isotopes.

This study investigated the use of Sulphur Isotopic Fractionation ( 34S), and Sequential Extraction to determine and quantify the occurrence of bacterial reduction and the availability of contaminants present in superficial sediments from a reservoir and a river at Poços de Caldas Plateau (MG – Brazil). The area comprises a former uranium mine and its surroundings located in Caldas Municipality (Figure 1). Six sediment samples were taken along the Aguas Claras reservoir and the Antas river (S1 to

S6). The sequential extraction procedure was based on the modified BCR (Bureau Communautaire de Références) (Rauret et al. 1999) and Isotopic Fractionation analysis was according to Knöller et al., 2004. Sulphur isotopic fractionation is based on the fact that the sulphate from the Acid Mine Drainage can be reduced to sulphide due to bacterial action, where the sulphate with lighter sulfur isotopes ( 32S) is more readily metabolized because their bonds are weaker. As a consequence of this microbiological process, a distinct sulfur isotopic signature in sulphide

Figure 1. Overview of the study area showing the Águas Claras reservoir, the limits of the mining area, the Antas river and the sampling stations (indicated with stars).

SCIENCE HIGHLIGHTS

Figure 2. Isotope ratios in sulphate (SO4), acid volatile sulphide (AVS) and chromium reducible sulphur for the surface sediments.

is produced by depletion in 34S of up to 46‰. The analyses were carried out in three distinct sulfur compounds present in the sediments: (i) the sulphur present in the AVS (Acid Volatile Sulphide), (ii) the elemental and pyritic sulphur (CRS – Chromium Reducible Sulphur) and the (iii) water soluble sulphate. Figure 2 shows that the 34S signatures for the sulphate present slight variation throughout the reservoir and the river indicating that this anion derives from the same sulphur source in all sediments. The average 34S value for the sulphate for all samples is -3.03‰, and it is within the values reported for the pyrite from the Poços de Caldas Plateau region that ranges from +1.24 to -3.63‰. Thus, it may be concluded that the pyrite oxidation is the only source of sulphate. The AVS signatures were approx. – 37‰ for the sediments S1 and S3; the first and last sampling station inside the reservoir confirming the biological reduction. In addition, the lower 34S values for CRS inside the reservoir, ranging from -21‰ to -33‰, are lower than the values reported for the pyrite from the region and indicate the formation of neogenic pyrite originated from the FeS2 which is depleted in 34S due to the bacterial reduction processes. In contrast, the 34S value for CRS in the Antas river were more enriched and closer to the 34S value of -3,03‰ for the pyrite in the region. Therefore, bacterial sulphate reduction is a significant process inside Águas Claras reservoir and, consequently, the natural attenuation of contamination is expected, due to the precipitation of metallic sulphides followed by the formation of more stable phases such as neogenic pyrite.

Figure 3. Mn, Zn, U partitioning in the sediments, according to mBCR procedure. The metal concentrations in the original samples are displayed on the top of each column in mg/kg.

Sequential Extraction (Figure 3) showed that the high amounts of Mn, around 28 to 81%, were extracted in the labile fraction by using acetic acid; most likely due to its association with the carbonate phase (dolomite and calcite). The highest content of U in the labile fraction, approx. 60% was presented by sample S1. Minor amounts of U were extracted in the labile fraction in the other sediments, ranging

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from 2 to 23%. For these samples, U can be nonspecifically adsorbed on the surface of clays or on Fe and Mn oxyhydroxides. Despite the presence of the U in the labile fraction being extremely worrying, it is interesting to note that the U content in this fraction decreases downstream the reservoir from point S1 to S6, which indicated that the reservoir acts as a polishing pond. The mobility of Zn is evidenced by the high levels of extraction in the labile fraction (20 to 50%) indicating that it could be weakly adsorbed. Since metals in the labile fraction are considered readily and potentially bioavailable, the content of Zn associated to this fraction is especially concerning for the samples S1, S2 and S3, which contain high levels of zinc (5285 to 2417 mg/kg). Despite the evidences of natural attenuation, the presence of U, Zn and Mn in the labile fraction means that they can be easily available to the environment, and special

monitoring should be carried out to detect changes in pH and/or reduction potential in the reservoir. Remediation proposals for the Águas Claras reservoir are being assessed and the determination of the types of contaminants, as well as the metals availability and the form in which they are present may support the final remediation project. One remediation strategy can be the enhancement of the bacterial sulphate reduction (e.g. by adding appropriate electron donors), favoring the formation of zinc sulphide as well as the reduction of the highly soluble U(VI) to the less soluble and mobile U(IV).

Acknowledgements Authors are grateful to CNPq, Fapemig, CAPES and Indústrias Nucleares do Brasil.

References KNÖLLER, K., FAUVILLE, A., MAYER, B., et al. 2004. Chem. Geol. 204: 303-323.

RAURET, G., LÓPEZ-SÁNCHEZ, J.F., SAHUQUILLO, A., RUBIO, R., DAVIDSON, C., URE, A.M., QUEVAUVILLER, P. 1999. J. Environ. Monit. 1: 57-61.

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Hydrochemical and isotopic evidences of discharge of acid effluents from a uranium mine in a river basin C.A. de Carvalho Filho1,*, R.M. Moreira1, V.V.M. Ferreira1, P.H. Dutra1, A.F.G. Oliveira1, O.E.A. Branco2 Centre for Development of Nuclear Technology (CDTN/CNEN). Belo Horizonte - MG, Brazil. Universidade Federal de Juiz de Fora (UFJF).Juiz de Fora - MG, Brazil. *Corresponding author: cacf@cdtn.br 1 2

Keywords: Acid mine drainage, uranium, hydrochemistry, stable isotopes.

The uranium mining and milling facilities of Caldas, located at PoĂ§os the Caldas Plateau in southeastern Brazil, are in the process of decommissioning. The main environmental problem of this site is the generation of acid mine drainage (AMD) (Fernandes and Franklin, 2001). This work presents a hydrochemical and isotopic study

aiming at characterizing the AMD, originated at the tailings dam and at the waste rock pile 4, which ends reaching the drainage basin downstream the Caldas mining. This basin is formed by three small watercourses that belong to the Verde River watershed: Consulta Brook, Soberbo Creek and Taquari River (Figure 1).

Figure 1. Location of the study area: drainage basins and sampling stations.

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Twelve sampling stations were established in order to carry out the investigation (Figure 1). Two of them were located at effluent ponds: A2-25 at the exit of the settling pond, which receives the effluent from the tailing dam, and A1-75, inside the Nestor Figueiredo pond (BNF), which collects the acidic mine water. Sampling was in the rainy and dry seasons of 2010 and 2011. The Piper diagram in Figure 2 shows that the water at stations upstream the uranium mining and milling facilities (A1-2, A2-9, A3-5, and A3-1) are sodiumpotassium bicarbonate type, which corresponds to the natural or geogenic ionic composition of the respective watercourses. Stations A1-75 and A2-25 show an ionic composition corresponding to calciumsulfate waters type, which demonstrates the influence of the discharge of effluents. It can be seen in Figure 2 that the natural sodiumbicarbonate waters, upstream the facilities, are converted to the calcium-sulfate type immediately downstream the effluent discharge stations (A1-75 and A2-25). However, these waters are progressively restored to their former condition as they move away from the discharge stations, indicating a natural attenuation process.

Figure 2. Piper diagram of water samples.

Particularly in the Consulta Brook, the water analysis show contamination by F, Cd, U, Zn, Al, Mn and acidity (pH lower than 6), along with a pronounced increase in Ca, SO4, Mg, Pb, As, 238U, 226 Ra, 232Th and 228Ra. This was probably due to the discharges of the acid effluent from the BNF pond. For the Soberbo Creek the effluents from the settling pond (A2-25) caused enrichment in Ca, F, SO4 and Mo, downstream its point of discharging (A2-71). An example of the impact pattern due to some selected chemical species, F, U, As, SO4 and pH is shown in Figure 3. Figure 4 presents results related to stable isotopes, 18 O and 2H, in surface waters and in effluents collected in September-2011 (Carvalho Filho, 2014), together with historical local water isotopic data (Nordstrom et al., 1990). This figure indicates that: (1) the effluent from the BNF pond (A2-25) presents a typical isotopic composition of evaporated waters (plots below the GMWL); (2) the surface water samples have isotopic signatures similar to shallow groundwater. These samples are more enriched in the heavy isotopes (2H and 18O) than the deep groundwater of the Caldas mine and of the Morro do Ferro anomaly; (3) the effluent at station A1-75

SCIENCE HIGHLIGHTS

Figure 3. Spatial distribution of pH and selected chemical species (Carvalho Filho, 2014).

Figure 4. Stable isotopes ( 2H and 18O) composition of the water and effluent samples from the several sampling station (Left). 18O and 2H values along the watercourses (Right). VSMOW â€“ Vienna Standard Mean Ocean Water.

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presents an isotopic signature value between those of deep groundwater and surface water. Briefly, the variation of 18O and 2H values along the watercourses (Figure 4) mainly suggests that: i) discharges from the BNF pond (A1-75) promoted a depletion of 2H and 18O in the water downstream the discharge point (fromA1-2 to A1-76); ii) the effluent from the tailings pond (A2-25) has enriched the heavy isotope composition of the waters downstream its discharge, (as measured at station A2-71). The results showed some evidence that the acid effluents arising from the mining facilities caused interference in the composition of downstream waters, especially in the Consulta brook. Stable isotopes have proved to be effective as natural

tracers of effluent discharges from the ponds to the watercourses downstream. Further studies of the groundwater at the study area should be carried out in order to assess the need to improve the mitigating actions such as inserting liners or barriers downstream the discharges. Presently, the mining company is already undertaking some remediation actions.

Acknowledgments Authors are grateful to CNPq, Fapemig, Indústrias Nucleares do Brasil and the University of Queensland for isotopic analysis.

References

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CARVALHO FILHO, C.A. 2014. PhD. Thesis, CDTN/CNEN, Belo Horizonte.

FERNANDES, H.M., FRANKLIN, M.R. 2001. Journal of Environmental Radioactivity 54: 5-25.

COPAM/CERH. 2008. Deliberação normativa COPAM/ CERH nº 1 de maio de 2008. Minas Gerais, Belo Horizonte.

NORDSTRON, D.K., SMELLIE, J.A.T., WOLF, M. 1990. SKB Technical report. Stockholm.

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Isotopic and gases analyses to characterize a uranium waste rock pile P.M Fleming1,*, C.B. de Abreu2, P.C.R. Horta1, V.S.T. Ciminelli2, M.B. Mansur2, M. Gasparon3, R.L.R. Bortolini2, N.Y.C. Pereira2, R.M. Moreira1, V.M.F. Delage1, D.L. Lopez4, H.L.C. Alberti5 Center for the Development of Nuclear Technology (CDTN). Belo Horizonte - MG, Brazil. Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. 3 School of Earth Science, University of Queensland. St. Lucia - QLD, Australia. 4 Department of Geological Science, Ohio University. Ohio, USA. 5 Poรงos de Caldas Laboratory (LAPOC). Poรงos de Caldas - MG, Brazil. *Corresponding author: pmf@cdtn.br 1

Keywords: Waste rock pile, stable isotope, site characterization, gas analysis, uranium.

The process of accessing the ore body in conventional uranium mining involves the generation of large quantities of material that does not contain the target mineral, which are either piled on the surface or dumped in previously excavated slopes. Factors such as high material heterogeneity, segregation in the pile caused by the waste rock dumping procedure, presence of preferential flow paths and low saturation

level of the material in the pile may influence the generation of acid rock drainage (ARD). ARD is widely recognized as causing serious environmental hazards and it is a main concern in mining regulations and guidelines. Site characterization is a major step in the remediation and reclamation of uranium mining facilities. Data on site characteristics form the

Figure 1. The waste rock pile at uranium mine at Caldas/MG, showing its five platforms in different colors.

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Figure 2. Plot of D and 18O in water samples at the pile, regarding to the local water line – LWL, evaporation water line - EWL and the global meteoric water line - GMWL.

basis for environmental assessments, risk analyses, decommissioning plans, reclamation and monitoring programs. The characterization of the waste rock pile at a uranium mine in Caldas/MG – Brazil include, among other parameters, isotopic analysis of water and gases. The waste rock dump (21º 56’33.84”S; 46º 29’33.84”W) was built upon the course of the Consulta creek (Figure 1), has a volume of about 12.7x106 m3, an area of 56 ha and was distributed in five platforms (Fernandes and Scalvi, 2002). The internal configuration of the pile evolves over time due to physical and chemical weathering under the prevalent climatic conditions. This internal structure governs the hydrogeological behavior of the man-made earth structure. Knowing how gases and water behave within unconsolidated masses is mandatory when sustainable solutions are being developed for large-scale mining operations, where huge quantities of waste rock, with no economic value, are generated.

Isotopic Analysis of water The stable isotopes of water 2H (or D) and 18 O are very useful in providing information on hydrological processes, including groundwatersurface water interactions. Water samples for isotopic analysis were collected at 75 sampling stations in the vicinity of the waste rock, including samples from rain waters, streams, rivers and lakes, as well as watersheds nearby, wells and piezometers. The

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isotopic composition of rainwater, notwithstanding the limited amount of samples, has allowed the preliminary definition of a local meteoric water line LWL – by computing the linear relationship between the stable isotope deficits 18O and 2H (Figure 2). Samples that have lower deuterium excess values correspond to the evaporation water line – EWL, D‰ = 5,83 18O‰ - 3,24. These samples are characterized by intense evaporation such as lakes and tailing ponds. The results reflects a similarity of the isotopic identity between the groundwater and those waters that flow from the bottom of the waste rock dump. Groundwater can be assumed as the major contributor of water inside the waste rock dump, during the dry season.

Gas analysis Waste rock piles are a three-phase system where airflow is crucial for the dynamics of the geochemical processes (Abreu, 2013). The geochemistry reaction of sulphide oxidation is favored by the contact of the material with oxygen, whereas large volumes of water are not required for their occurrence. It was carried out a geochemical characterization of a waste rock pile, based on the distribution and concentration of gases within it, from the atmosphere and other gases produced in the sulphide oxidation process. Gas samples from the uranium waste rock pile were collected at 40cm depth and temperature measurements were taken at same depth.

SCIENCE HIGHLIGHTS

Figure 3. Oxygen concentration profile in waste rock pile; the white line delimits regions where ARD may occur.

Concentrations of O2, N2, CO2, H2 and Air were measured ex-situ via mass spectrometry. Gas analysis allowed identifying regions along the pile that are most susceptible to generate acid rock drainage, as shown in the Figure 3, for the O2 measurements. The western region of the heap, adjacent to the mine pit, preferably oxidizes and generates acid effluent while the eastern region does not. The study of the gases flow through the pile was supported by the studies of the solid and aqueous phases of the system. The methodology was proved to be efficient and economically viable for the characterization of sites

generating acid mine drainage. In addition, it can support decisions on the decommissioning process of waste rock piles and rehabilitation of areas degraded by mining activities.

Acknowledgements The authors are grateful to Indústrias Nucleares do Brasil, the Helmholtz Centre for Environmental Research - UFZ (Germany), Fapemig and CNPq.

References ABREU, C.B. 2013. Influência da fase gasosa como ferramenta auxiliar no diagnóstico do potencial de geração de drenagem ácida de rocha, PhD. Thesis, UFMG.

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Effect of carbonate mineralogy in the neutralization potential: Why different static tests lead to contradictory classification of ARD? C.L. Caldeira1,*, D.M.P. Ferreira, I.S. Batista1, M.S.S. Dantas1, V.S.T. Ciminelli1 Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais (UFMG). Belo Horizonte - MG, Brazil. *Corresponding author: claudia@demet.ufmg.br 1

Keywords: Acid rock drainage, siderite, static tests, neutralization potential.

Static tests are widely used to predict Acid Rock Drainage (ARD) from tailings containing sulfide minerals. These tests consist in measuring the neutralization and the acid potential of the waste, tailings and ores. The so-called Neutralization Potential (NP) and Acid Potential (AP) are defined differently according to the different static test protocols. These tests are relatively quick and inexpensive and are broadly applied during the first stages of environmental assessment (Plante et al., 2012; Capanema and Ciminelli, 2003; Lawrence and Wang, 1997). The AP values are calculated by the total sulfur or sulfur-sulfide content (Plante et al., 2012; Lawrence and Wang, 1997; Sobek et al., 1978). The NP values are measured through the addition of fixed amount of acid, that is consumed by the sample and the residual acidity is back titration with sodium hydroxide. Carbonate minerals and some silicates contribute to neutralization potential. However, it is observed that these contributions depend on the carbonate phases, silicate content, aluminium, iron and manganese content (oxidizable/hydrolysable elements) present in the sample. Calcite (CaCO3) has the highest neutralizing acid capability. Other minerals are dolomite (CaMg(CO3)2), magnesite (MgCO3), ankerite (Ca(Fe, Mg)(CO3)2), and siderite (FeCO3). Among these, the least effective neutralizer is siderite, because the neutralised acid is released again by Fe2+ oxidation/ hydrolysis, thus resulting in no net neutralization. In the present work, waste and tailings samples from gold ore mining were submitted to the

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following static tests: Modified-Sobek acid base accounting (MABA) (Lawrence and Wang, 1997), standard acid neutralization capacity (ANC), and ANC modified for siderite (ANC-SID) (Stewart et al., 2006). All these tests are based on the Sobek acid-base accounting (ABA) protocol (Sobek et al., 1978). The MABA test replaces acid attack at boiling temperature by acid attack at room temperature for longer times (24 h instead of 1-2h in the original ABA-Sobek). In addition, the final pH digestion should remain between 2 -2.5, and titration end-point pH of 8.3. Beyond that, staged addition of hydrochloric acid and different volumes defined by fizz ratings were proposed. Standard ANC and ANC-SID protocols are similar to original ABA-Sobek. The final pH digestion should be between 0.8-1.5 and the back titration runs up to pH 7; temperature is kept slightly lower (80-90oC); 2 drops of 30% H2O2 is added at pH 5 to oxidise and promote hydrolysis of any remaining dissolved Fe2+. The ANC-SID is a modified ANC test designed to account for the effects of siderite. The test involves larger amounts of H2O2 than those in the standard ANC method and titration of the filtered solution after digestion over a longer time period. Tests to determine NP were carried out in triplicate; one sample was submitted to back-titration with NaOH and the others were collected to analyse the solid residues. Total sulfur, sulfur-sulfide, total carbon and carbon-carbonate contents were determined by LECO and selective leaching. Residual total carbon contents were also analyzed.

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The results showed S-sulphide content varying from 0.66-3.45% and C-carbonate 0.68-8.1% (Table 1). Siderite and ankerite were the main carbonate phases identified by Raman spectroscopy; calcite appeared as a minor phase. The sulfide phases were mainly pyrite and pyrrhotite (not shown). Two criteria were used to evaluate the acidgenerating potential (Table 2): (i) NNP (NP – AP) expressed in kgCaCO 3/t and (ii) NP/AP ratio. Typically interpretation based on NNP parameter are: acid generation is uncertain for NNP values between -20 and 20 kgCaCO3/t, acid generation is likely for NNP values below -20kgCaCO3/t, and non

acid generation for NNP values above 20kgCaCO3/t. According to NP/AP criteria, the ARD classification as: acid generating if NP/AP < 1; non acid generating if NP/AP > 1; and uncertain, if 1< NP/AP < 2 (Plante et al., 2012). The NP results may vary significantly for a given sample, depending on the method employed in the NNP or NP/AP evaluation. Consequently, a high discrepancy in the parameters used to classify ARD potential can be observed. Except for AM2, classified as uncertain by NP/AP, NP-CO3 (calculated) criteria classified the samples as no acid generating (NPAG) (Table 2). The calculate neutralization potential

Table 1. Chemical and Raman analyses.

Samples

% S total

% S-sulfide

*% C Total

% **NP-CO3 C-carbonate (kgCaCO3/t)

Carbonate phases (relative amount)

AM1

0.94

0.86

0.93

0.68

Siderite » Calcite

AM2

1.53

2.14

0.99

Ankerite » Calcite

AM3

4.18

3.34

3.94

3.85

321

Ankerite » Siderite

AM4

3.67

3.45

9.32

8.07

673

Siderite » Ankerite

AM5

0.75

0.66

3.54

3.34

278

Calcite

Siderite

Ankerite

* C-organic matter - identified in all samples, except AM3. Expressive amount in AM2 around 50% ** NP-CO3 calculated based on C-carbonate content.

Figure 1. (A) neutralization potential (NP) values. (B) C-carbonate released (%) different static tests on the samples.

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Table 2. Static test results from different methods on the samples.

SAMPLES PARAMETERS

AM1

AM2

AM3

AM4

AM5

104

108

NP-MABA

187

116

119

NP-ANC-SID

195

173

194

NP-ANC

290

446

212

NP-CO3

321

673

278

NNP

-15

NP/AP

0.4

1.3

1.8

1.1

5.8

NNP

174

NP/AP

1.4

1.6

1.9

1.6

9.4

-1

186

338

191

1.0

1.6

2.8

4.1

10.3

NNP

216

565

258

NP/AP

2.1

1.7

3.1

6.2

13.5

NP-MABA AP

NP-ANC-SID AP

NP-ANC AP NNP NP/AP NP-CO3 AP

All units expressed as kgCaCO3/t, except NP/AP , unit-less. NPAG - no potential acid generation UNC - uncertainty potential zone PAG - potential acid generation

(NP-CO3) was estimated from C-Carbonate content, assuming that all C-carbonate content present in the sample is calcite (Table 1). The ARD classification assessed by MABA tests is more conservative. AM1 is classified as acid generating (PAG), AM2, AM3 and AM4 as uncertain and AM5 as no acid generating (NPAG). The question is: which method is more reliable? Comparison of the different NP values for each samples are presented in Fig. 1a. Except for AM2, for all the remaining samples, NP-CO3 values are higher than the other NP´s values. For AM2 all NP´s values are closer, which can be related to the absence of siderite. The difference between NP-CO3 and the other NP´s increases with increasing siderite content.

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The discrepancy of NP-ANC and NP-ANC-SID with NP-MABA is also attributed to the content of siderite. Stewart et al (2006) showed that for siderite content higher than 15%, the NP-ANC-SID values are lower than NP-ANC. The samples AM3 and AM4 presented NP-ANC-SID lower than NP-ANC whereas the samples AM1 and AM5 showed similar NP-ANC and NP-ANC-SID values. Ankerite, despite the presence of iron in its structure, exhibits a good neutralizing performance in the MABA tests, similarly to calcite. Samples containing predominantly ankerite (AM2 and AM3) showed an expressive C-carbonate dissolution during MABA tests (>90%) (Figure 1b) whereas partial C-carbonate dissolution (35-70%) was observed

SCIENCE HIGHLIGHTS

for the samples with siderite. Raman spectroscopy analyses confirmed reminiscent siderite in all MABA residues (not shown). Nearly total carbonate dissolution was achieved during ANC and ANC-SID tests - % C-released of 90-100%. This is expected considering the more aggressive conditions of ANCÂ´s tests. In conclusion, a misclassification of ARD generation potential can occur when the NP value is evaluated without mineralogy understanding. Higher discrepancies were observed when NP was based on C content (%). The NP-ANC-SID method accounts for the presence of siderite only for content higher

than 15%. NP-MABA presented the lowest values for all samples due to incomplete siderite dissolution, as shown by Raman and residual C-carbonate content. Hence, the siderite effect is low. The NP-MABA protocol was shown to be simpler and more realistic to predict ARD from a broader sample composition.

Acknowledgements The authors are grateful to the Brazilian government agencies: CAPES, FAPEMIG and CNPq, for financial support.

References CAPANEMA, L.X.L., CIMINELLI, V.S.T. 2003. REM: Revista Escola de Minas, Ouro Preto 56 (3): 206-211.

SOBEK, A.A., SCHULLER, W.A., FREEMAN, J.R., SMITH, R.M. 1978. EPA 600/2-78-054. pp. 47-50.

LAWRENCE, R.W., WANG, Y. 1997. In: Proc. 4th International Conference on Acid Rock Drainage. Vancouver, BC, pp. 449-464.

STEWART, W.A., MILLER, S.D., SMART, R. 2006. In: Proc. 7th International Conference on Acid Rock Drainage. St. Louis, Missouri, pp. 2098-2118.

PLANTE, B., BUSSIERE, B., BENZAAZOUA, M. 2012. Journal of Geochemical Exploration 114: 57-69.

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Publications

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PUBLICATIONS

Journals ABREU, L.B., AUGUSTI, R., SCHMIDT, L., DRESSLER, V.L., FLORES, E.M.D., NASCENTES, C.C. 2013. Analytical and Bioanalytical Chemistry 405 (24): 7643-7651. ABREU, R.D., MORAIS, C.A. 2014. Minerals Engineering 61: 82-87.

publications

ADEYEMO, A., MELLO, J.W.V., AGELE, S. 2015. International Journal of Plant & Soil Science 4 : 366-376. AGUIAR, A.O., DUARTE, R.A., LADEIRA, A.C.Q. 2013. Water, Air and Soil Pollution 224: 1-8. ALMEIDA, K.J., DUARTE, H.A., RAMALHO, T., NETO, J., SANTIAGO, R., FELICÍSSIMO, V. 2013. Organometallics 32 (4): 989-999. ALMEIDA, K.J., SILVA, T.C., NETO, J.L., ROCHA, M.V.J., RAMALHO, T.C., MIRANDA, M.N., DUARTE, H.A. 2016. Journal of Organometallic Chemistry 802 : 49-59. ALVES, J.O., BOTELHO, B.G., SENA, M.M., AUGUSTI, R. 2013. Journal of Mass Spectrometry 48 (10): 1109-1115. ALVES, J.O., SENA, M.M., AUGUSTI, R. 2014. Analytical Methods 6 (18): 7502-7509. AMAYA-RONCANCIO, S., LINARES, D.H., DUARTE, H.A., SAPAG, K. 2016. Journal of Physical Chemistry C 120 (20): 10830-10837. AMAYA-RONCANCIO, S., LINHARES, D.H., DUARTE, H.A., LENER, G., SPAG, K. 2015. American Journal of Analytical Chemistry 6: 38-46. ANDRADE, F.V., LIMA, G.M., AUGUSTI, R., SILVA, J.C.C., COELHO, M.G., PANIAGO, R., MACHADO, I.R. 2015. Journal of Water Process Engineering 7: 27-35. ANNONI, R., SOUZA, P.S., PETRÁNIKOVÁ, M., MISKUFOVA, A., HAVLÍK, T., MANSUR, M.B. 2013. Journal of Hazardous Materials 244-245: 335-341. AQUINO, F.J.T., AUGUSTI, R., ALVES, J.D., DINIZ, M.E.R., MORAIS, S.A.L., ALVES, B.H.P., NASCIMENTO, E.A., SABINO, A.A. 2014. Microchemical Journal 117: 127-132. ARANTES, L.A., VAREJÃO, E.V.V., PELIZZARO-ROCHA, K.J., CREDA, C.M.S., PAULA, E., LOURENÇO, M.P., DUARTE, H.A., FERNANDES, S.A. 2014. Chemical Biology & Drug Design 83: 550-559. AT H AY D E , D. D. , S O U Z A , D. F. , S I LVA , A . M . A . , VASCONCELOS, D., NUNES, E.H.M., COSTA, J.C.D., VASCONCELOS, W.L. 2016. Ceramics International 42: 6555-6571. BARBOSA, L.G., BARBOSA, F.A.R., ARAUJO, G.J.M., BICUDO, C.E.M. 2013. Limnética, Madrid 32: 71-86. BARBOSA, L.G., BARBOSA, F.A.R., BICUDO, C.E.M. 2013. Hydrobiologia, The Hague 710: 157-171. BARROS, C.F.A., SANTOS, A.M.M., BARBOSA, F.A.R. 2013. Acta Botanica Brasilica 27: 327-346. BELO, R.F.C., AUGUSTI, R., LOPES, P.S.N., JUNQUEIRA, R.G. 2013. Ciência e Tecnologia de Alimentos 33: 116-124. BITTENCOURT, L.M., LANA, D.A.P.D., PIMENTA, A.M.D., SANTOS, A.V., GONCALVES, A.P.F., AUGUSTI, R., COSTA, L.M. 2014. Journal of Brazilian Chemical Society 25 (2): 264-270. BRANDÃO, L.P.M., PUJONI, D., MAIA-BARBOSA, P.M. 2014. Brazilian Journal of Biology 74: 642-648. BRITO, S.L., MAIA-BARBOSA, P.M., COELHO, R.M.P. 2013. Brazilian Journal of Biology 73: 593-604.

CAMPOS, K.S., SILVA, G.F.B.L., NUNES, E.H.M., VASCONCELOS, W.L. 2014. Journal of Ceramic Processing Research 15: 403-407. CAMPOS, K.S., SILVA, G.F.B.L., NUNES, E.H.M., VASCONCELOS, W.L. 2014. Refractories and Industrial Ceramics 54: 407-412. CAMPOS, M.M.C., FARIA, V.H.F., TEODORO, T.S., BARBOSA, F.A.R., MAGALHÃES, S.M.S. 2013. Journal of Environmental Science and Health 48: 101-107. CAPANEMA, N.S.V., MANSUR, A.A.P., CARVALHO, S.M., SILVA, A.R.P., CIMINELLI, V.S., MANSUR, H.S. 2015. Materials 8: 4191-4209. C A R D I N A L I - R E Z E N D E , J. , R O J A S - O J E D A , P. , NASCIMENTO, A.M.A., SANZ, J.L. 2016. Chemosphere, Oxford 146: 519-525. CARVALHO FILHO, C.A., MOREIRA, R.M., GUIMARÃES, B.F., FERREIRA, V.V.M., AULER, L.M.L.A., PALMIERI, H.E.L., OLIVEIRA, A.F., DUTRA, P.H. 2016. Environmental Earth Sciences 75: 1-14. CARVALHO, T.C., TOSATO, F., SOUZA, L.M., SANTOS, H., MERLO, B.B., ORTIZ, R.S., RODRIGUES, R.R.T., FILGUEIRAS, P.R., FRANÇA, H.S., AUGUSTI, R., ROMÃO, W., VAZ, B.G. 2016. Forensic Science International 262: 56-65. CIMINELLI, V.S.T., BARBOSA, F.A.R., TUNDSI, J.G., DUARTE, H.A. 2014. Química Nova na Escola 8: 39-45. CIMINELLI, V.S.T., SOUZA, C., MAJUSTE, D., DANTAS, M.S.S. 2014. Hydrometallurgy 147-148: 188-195. CORREA, D.N., ZACCA, J.J., ROCHA, W.F.C., BORGES, R., SOUZA, W., AUGUSTI, R., EBERLIN, M.N., VENDRAMINI, P.H. 2016. Forensic Science International 260: 22-26. COSTA, P.S., REIS, M.P., ÁVILA, M.P., LEITE, L., ARAÚJO, F., SALIM, A., OLIVEIRA, G., BARBOSA, F., CHARTONESOUZA, E., NASCIMENTO, A.M.A. 2015. Plos One 10: e0119465. COSTA, P.S., SCHOLTE, L.L.S., REIS, M.P., CHAVES, A.V., OLIVEIRA, P.L., ITABAYANA, L.B., SUHADOLNIK, M.L.S., BARBOSA, F., CHARTONE-SOUZA, E., NASCIMENTO, A.M.A. 2014. Plos One 9: e95655. COSTA, P.S., TSCHOEKE, D., SILVA, B., THOMPSON, F., REIS, M. P., CHARTONE-SOUZA, E., NASCIMENTO, A.M.A. 2015. Genome Announcements 3 : e00122-15. DUARTE, H.A. 2014. Química Nova na Escola 8: 4-8. DUARTE, H.A., VANKOVA, N., FERREIRA, I.P., PANIAGO, E.B., HEINE, T. 2013. Journal of Physical Chemistry B 117 (39): 11670-11680. FELIPE, E.C.B., LADEIRA, A.C.Q. 2014. Holos, Natal 3: 291-298. FERREIRA, A.M., MARCHESIELLO, M., THIVEL, P.X. 2013. Separation and Purification Technology 107: 109-117. FERREIRA, A.M., SILVA, G.C., DUARTE, H.A. 2014. Química Nova na Escola 8: 30-38. FERREIRA, F.A.G., FRANCO, M.W., MAIA-BARBOSA, P., DRUMOND, M.A., BARBOSA, F.A.R. 2013. Pesquisa em Educação Ambiental 8: 51-61. FERREIRA , M.T.S., MAIA-BARB OSA , P.M. 2013. Biodiversidade Brasileira 2: 159-174. FRAGOSO-MOURA, E.N., BARBOSA, F.A.R., OPORTO, L.T., MAIA-BARBOSA, P.M. 2016. Brazilian Journal of Biology 76: 18-27.

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FRANCO, M.W., FERREIRA, F.A.G., VASCONCELOS, F.I., BATISTA, B.L., PUJONI, D.G.F., MAGALHÃES, S.M.S., BARBOSA JÚNIOR., F., BARBOSA, F.A.R. 2015. Environmental Science and Pollution Research International 22: 18607-18615. FREITAS, E.T.F., MONTORO, L.A., GASPARON, M., CIMINELLI, V.S.T. 2015. Chemosphere 138: 340-347. FREITAS, R.M., PERILLI, T.A.G., LADEIRA, A.C.Q. 2013. Journal of Chemistry 2013: 1-8. GOMES, F.C.O., SAFAR, S.V.B., MARQUES, A.R., MEDEIROS, A.O., SANTOS, A.R.O., CARVALHO, C., LACHANCE, M., SAMPAIO, J.P., ROSA, C.A. 2015. Antonie Van Leeuwenhoek, Dordrecht 107: 597-611. GUEDES, F.A., FRANCO, M.W., DRUMOND, M.A., MAIABARBOSA, P.M., BARBOSA, F.A.R. 2013. Pesquisa em Educação Ambiental 8: 51-61. GUIMARAES, A.S., MANSUR, M.B. 2016. World Academy of Science, Engineering and Technology 10: 467-470. GUIMARÃES, A.S., SILVA, P.S., MANSUR, M.B. 2014. Hydrometallurgy 150: 173-177. GUIMARÃES, L., NUNES, Y., LOURENÇO, M.P. 2013. Physical Chemistry Chemical Physics 15 (12): 4303-4309.

MAGALHAES, E.J., QUEIROZ, M.E.L.R., PENIDO, M.L.D., PAIVA, M.A.R., TEODORO, J.A.R., AUGUSTI, R., NASCENTES, C.C. 2013. Journal of Chromatography A 1309: 15-21. MAGALHÃES, S.M.S., BRÊTAS, C.M., BRÊTAS, J.M., PIANETTI, G.A., FRANCO, M.W., BARBOSA, F.A.R. 2014. Brazilian Journal of Biology 74 : S120-S124. MAIA-BARBOSA, P.M., MENENDEZ, R.M., PUJONI, D., BRITO, S.L., AOKI, A., BARBOSA, F.A.R. 2014. Biota Neotropica 14: 1-20. MAJUSTE, D., CIMINELLI, V.S.T., ENG, P.J., OSSEOASARE, K. 2013. Hydrometallurgy 131-132: 54-66. MAJUSTE, D., MARTINS, E.L.C., SOUZA, A.D., NICOL, M.J., CIMINELLI, V.S.T. 2015. Hydrometallurgy 152: 190-198. MARQUES, A.R., ATMAN, A.P.F., SILVEIRA, F.A.O., LEMOS-FILHO, J.P. 2014. Plant Ecology, Dordrecht 215: 517-529.

HEITMANN, A.P., SILVA, G.C., PAIVA, P.R.P., FERREIRA, A.M. 2014. Cerâmica, São Paulo 60: 429-435.

MARQUES, A.R., COSTA, C.F.A., ATMAN, A.P.F., GARCIA, Q.S. 2014. Weed Research 54: 576-583.

HOUMARD, M., NUNES, E.H.M., VASCONCELOS, D.C.L., BERTHOMÉ, G., JOUD, J.-C., LANGLET, M., VASCONCELOS, W.L. 2014. Applied Surface Science 289: 218-223.

MARQUES, A.R., GOMES, F.C.O., FONSECA, M.P.P., PARREIRAS, J.S., SANTOS, V.P. 2013. Solar Energy 87: 158-167.

HUETE-PEREZ, J.A., TUNDISI, J.G., ALVAREZ, P.J.J. 2013. Critical Reviews in Environmental Science and Technology 47: 13217-13219. JESUS, M.A.M.L., SILVA NETO, J.T., TIMÒ, G., PAIVA, P.R.P., DANTAS, M.S.S.; FERREIRA, A.M. 2015. Applied Adhesion Science 3: 5. JURISCH, M., AUGUSTI, R. 2016. Analytical Methods 8: 4543-4546. LADEIRA, A.C.Q., PANIAGO, E.B., DUARTE, H.A., CALDEIRA, C.L. 2014. Química Nova na Escola 8: 18-23. LEITE, C.M.C., CARDOSO, L.P., MELLO, J.W.V. 2013. Revista Brasileira de Ciência do Solo 37: 804-811. LIMA, G.F., MYRANDONAKIS, A., ABREU, H.A., DUARTE, H.A., HEINE, T. 2013. Journal of Physical Chemistry C 117 (8): 4124-4130. LOBATO, N.C.C., VILLEGAS, E.A., MANSUR, M.B. 2015. Resources, Conservation and Recycling 102: 49-57. LOBATO, N.C.C., FERREIRA, A.M., MANSUR, M.B. 2016. Separation and Purification Technology 168: 93-100. LOPES, R.M.F., FREITAS, V.L.O., MAIA-BARBOSA, P.M. 2013. Revista Monografias Ambientais 11: 2326-2359. LOPES, R.M.F., FREITAS, V.L.O., MAIA-BARBOSA, P.M. 2013. Árvore 37: 801-813. LOPES, R.P., AUGUSTI, D.V., SANTOS, F.A., VARGAS, E.A., AUGUSTI, R. 2013. Analytical Methods 5 (19): 5121-5127. LOURENÇO, M.P., GUIMARÃES, L., SILVA, M.C., OLIVEIRA, C., HEINE, T., DUARTE, H.A. 2014. Journal of Physical Chemistry C 118 (11): 5945-5953. MACEDO, A.L., FABRIS, J.D., PIRES, M.J.M., OLIVEIRA, W.L., ARDISSON, J.D., AUGUSTI, R., ARAGÓN, F.H., SANTOS, R.S., OLIVEIRA, L.C.A., PEREIRA, M.C. 2016. Journal of the Brazilian Chemical Society.

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MAGALHAES, E.J., NASCENTES, C.C., PEREIRA, L.S.A., GUEDES, M.L.O., LORDEIRO, R.A., AULER, L.M.L.A., AUGUSTI, R., QUEIROZ, M.E.L.R. 2013. Science and Justice 53 (4): 425-432.

MARQUES, A.R., PATRÍCIO, P.S.O., SANTOS, F.S., MONTEIRO, M.L., URASHIMA, D.C., RODRIGUES, C.S. 2014. Geotextiles and Geomembranes 42: 76-82. MARQUES, A.R., VIANNA, C.R., MONTEIRO, M.L., PIRES, B.O.S., URASHIMA, D.C., PONTES, P.P. 2016. Applied Soil Ecology. M A R Z A N O, I . M . , F R A N C O, M . S . , S I LVA , P. P. , AUGUSTI, R., SANTOS, G.C., FERNANDES, N.G., BUCCIARELLI-RODRIGUEZ, M., CHARTONE-SOUZA, E., PEREIRA-MAIA, E.C. 2013. Molecules 18 (2): 1464-1476. MELLO, J.W., DUARTE, H.A., LADEIRA, A.C.Q. 2014. Química Nova na Escola 8: 24-29. MIMURA, A.M.S., OLIVEIRA, M.A.L., SILVA, J.C.J., CIMINELLI, V.S.T. 2016. Journal of AOAC International: 252-259. MIRANDA JÚNIOR, R.A., MIMURA, A.M.S., DIVINO, A.C., SILVA, R.F., SILVA, J.C.J., CIMINELLI, V.S. 2014. Soil and Sediment Contamination 23 (3): 257-269. MORAIS C.A., ALBUQUERQUE, R.O., LADEIRA, A.C.Q. 2014. Química Nova na Escola 8: 9-17. MORAIS, C.A., MANSUR, M.B. 2014. Mineral Processing and Extractive Metallurgy 123: 61-66. MORALES-GARCIA, A., SOARES JÚNIOR, A.L., SANTOS, E.C., ABREU, H.A., DUARTE, H.A. 2014. The Journal of Physical Chemistry A 118 (31): 5823-5831. MOREIRA, R.P.L., AUGUSTI, D.V., SANTOS, F.A., VARGAS, E.A., AUGUSTI, R. 2013. Analytical Methods: 5121-5127. NUNES, E.H.M., LAMEIRAS, F.S., HOUMARD, M., VASCONCELOS, W.L. 2013. Radiation Physics and Chemistry 90: 79-86. OLIVEIRA, C., ABREU, H.A., SALAHUB, D.R., DUARTE, H.A. 2014. Journal of Physical Chemistry C 118 (44): 25517-25524.

PUBLICATIONS

OLIVEIRA, R.F., WINDMÖLLER, C.C., NETO, W.B., SOUZA, C.C., BEINNER, M.A., SILVA, J.B.B. 2013. Analytical Methods 5: 5746-5752. OLIVEIRA-PINTO, C., COSTA, P.S., REIS, M.P., CHARTONESOUZA, E., NASCIMENTO, A.M.A. 2016. Extremophiles, Tokyo 20: 283-289.

SAFAR, S.V.B., GOMES, F.C.O., MARQUES, A.R., LACHANCE, M., ROSA, C.A. 2013. International Journal of Systematic and Evolutionary Microbiology 63: 1165-1168. SANTOLIN, C.V.A., CIMINELLI, V.S.T., NASCENTES, C.C., WINDMÖLLER, C.C. 2015. Environmental Earth Sciences 74: 1235-1248.

OMETTO, J.P., CIMBLERIS, A.C.P., SANTOS, M.A., ROSA, L.P., ABE, D.S., TUNDISI, J.G., STECH, J.L., BARROS, N., ROLAND, F. 2013. Energy Policy 58: 109-116.

SANTOS, E.C., SILVA, J.C.M., DUARTE, H.A. 2016. Journal of Physical Chemistry C 120: 2760-2768.

PAES, T.A.S.V., RIETZLER, A.C., MAIA-BARBOSA, P.M. 2016. Anais da Academia Brasileira de Ciências 88: 179-186.

SANTOS, J.C.C., MANSUR, A.A.P., CIMINELLI, V.S.T., MANSUR, H.S. 2014. International Journal of Polymeric Materials and Polymeric Biomaterials 63 (4): 185-196.

PALMIERI, H.E.L., KNUPP, E.A.N., FERREIRA, C.A., WINDMÖLLER, C.C. 2013. BrJAC: Brazilian Journal of Analytical Chemistry 3: 451-459.

SANTOS, L.H., CARVALHO, P.L.G., RODRIGUES, G.D., MANSUR, M.B. 2015. Hydrometallurgy 156: 259-263.

PANTUZZO, F.L., SANTOS, L.R.G., CIMINELLI, V.S.T. 2014. Hydrometallurgy 144-145: 63-68. PAULA, C.C.A., VALADARES, A., JURISCH, M., PICCIN, E., AUGUSTI, R. 2016. RCM: Rapid Communications in Mass Spectrometry 30: 1176-1180. PAULA, C.C.A., YURISH, M., VALADARES, A., PICCIN, E., AUGUSTI, R. 2016. Forensic Science International 262: 56-65. PEREZ, J.M., FOSTIER, A.H., CARVALHO JÚNIOR, J.A., WINDMÖLLER, C.C., SANTOS, J.C., CARPI, A. 2014. Atmospheric Environment 6: 4537-4541. PERILLI, T.A.G., SICUPIRA, D.C., MANSUR, M.B., LADEIRA, A.C.Q. 2014. Holos 30: 264-271. PERIOTTO, N., TUNDISI, J.G. 2013. Brazilian Journal of Biology 73 (3): 471-482. PUJONI, D.G.F., MAIA-BARBOSA, P.M., BARBOSA, F.A.R., FRAGOSO JÚNIOR, C.R., VAN NES, E.H. 2016. Ecological Modelling 320: 358-365. QUEIROGA, J.A., CAMPOS, K.S., SILVA, G.F.B.L.E., SOUZA, D.F., NUNES, E.H.M., VASCONCELOS, W.L. 2013. Engineering Failure Analysis 34 : 290-299. REIS, M.P., AVILA, M.P., COSTA, P.S., BARBOSA, F., LAANBROEK, H.J., CHARTONE-SOUZA, E., NASCIMENTO, A.M.A. 2014. Frontiers in Microbiology 5: 630-638. REIS, M.P., ÁVILA, M.P., KEIJZER, R.M., BARBOSA, F., CHARTONE-SOUZA, E., NASCIMENTO, A.M.A., LAANBROEK, H.J. 2015. Frontiers in Microbiology 6: 11. REIS, M.P., BARBOSA, F., CHARTONE-SOUZA, E., NASCIMENTO, A.M.A. 2013. Extremophiles 17: 301-309. REIS, P.C.J., BARBOSA, F.A.R. 2014. Brazilian Journal of Biology 74: S113-S119. RESENDE, L.V., MORAIS, C.A. 2015. Minerals Engineering 70: 217-221. RESENDE, S.F., NUNES, E.H.M., HOUMARD, M., VASCONCELOS, W.L. 2014.Journal of Colloid and Interface Science 433: 211-217. REZENDE, P.S., COSTA, L.M., WINDMÖLLER, C.C. 2013. BrJAC: Brazilian Journal of Analytical Chemistry 10: 429-435. RIETZLER, A.C., MAIA-BARBOSA, P.M., RIBEIRO, M.M., MENENDEZ, R.M. 2014. Brazilian Journal of Biology 74: 518-520. RIGUEIRA, L.M.B., COSTA, L.M., LANA, D.A.P.D., AUGUSTI, R., PIMENTA, A.M.C., SANTOS, D.M. 2016. Food Chemistry 211:910-915.

SIAL, A.N., LACERDA, L.D., FERREIRA, V.P., FREI, R., MARQUILLAS, R.A., BARBOSA, J.A., GAUCHER, C., WINDMÖLLER, C.C., PEREIRA, N.S. 2013. Palaeogeography, Palaeoclimatology, Palaeoecology 387: 153-164. SICUPIRA, D., SILVA, T.T., LADEIRA, A.C.Q., MANSUR, M. 2015. Brazilian Journal of Chemical Engineering 32: 577-584. SICUPIRA, D.C., SILVA, T.T., LEÃO, V.A., MANSUR, M.B. 2014. Brazilian Journal of Chemistry Engineering 31: 195-204. SILVA, G.C., CIMINELLI, V.S.T., FERREIRA, A.M., ALMEIDA, F.S., PISSOLATI, N.C. 2014. Materials Research Bulletin 49: 544–551. SILVA, F.C., GUEDES, F.A.F., FRANCO, M.W., BARBOSA, F.A.R., MARRA, C.A., DUARTE, L.P., SILVA, G.D.F., VIEIRA-FILHO, S.A. 2013. Journal of Applied Phycology 25: 1723-1728. SILVA, G.C., FERREIRA, A.M., ALMEIDA, F.S., DANTAS, M.S.S., CIMINELLI, V.S.T. 2013. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 100: 161-165. SILVA, J.C.C., TEODORO, J.A.R., AFONSO, R.J.D.F., A Q U I N O, S . F. , A U G U S T I , R . 2 0 1 4 . R a p i d Communications in Mass Spectrometry 28 (9): 987-994. SILVA, J.C.M., ABREU, H.A., DUARTE, H.A. 2015. RSC Advances 5: 2013-2023. SILVA, J.C.M., ABREU, H.A., DUARTE, H.A. 2014. RSC Advances 5: 2013-2023. SILVA, M.C., LOURENÇO, M.P., SANTOS, E. C., DUARTE, H.A. 2013. Journal of Molecular Modeling 19 (5): 1995-2005. SILVA, M.C., SANTOS, E.C., LOURENCO, M.P., GOUVEA, M.P., DUARTE, H.A. 2015. Frontiers in Computational Materials Science 2 (16). SILVA, N.C., CHAGAS, E.G.L., ABREU, C.B., DIAS, D.C.S., LOPEZ, D., GUERREIRO, E.T.Z., ALBERTI, H.L.C., BRAZ, M.L., BRANCO, O., FLEMING, P. 2014. Radiation Protection Dosimetry 160: 74-77. SOARES JÚNIOR, A.L., SANTOS, E.C., MORELESGARCIA, A., DUARTE, H.A., ABREU, H.A. Chemistry Select. Accepted. SOUZA, A.G., CARDEAL, Z.L., AUGUSTI, R.J. 2013. Journal of Environmental Science and Health B 48 (3): 171-176. SOUZA, C., MAJUSTE, D., CIMINELLI, V.S.T. 2014. Hydrometallurgy 142: 1-11. SOUZA, C., MAJUSTE, D., DANTAS, M.S.S., CIMINELLI, V.S.T., 2014. Hydrometallurgy 147-148: 188-195.

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SOUZA , D.F., NUNES, E .H.M., PIMENTA , D.S., VASCONCELOS, D.C.L., NASCIMENTO, J.F., GRAVA, W., HOUMARD, M., VASCONCELOS, W.L. 2014. Materials Characterization 96: 183-195. SOUZA, J.J.L.L., ABRAHÃO, W.A.P., MELLO, J.W.V., SILVA, J.; COSTA, L.M.; OLIVEIRA, T.S. 2015. Science of the Total Environment 505: 338-349. SOUZA, L.R., KNÖLLER, K., LADEIRA, A.C.Q. 2016. Journal of Soils and Sediments 1 16(7): 1986-1994. SOUZA, L.R., LADEIRA, A.C.Q. 2013. Journal of Waste Management 2013: 1-7. SOUZA, P.P., RESENDE, A.M.M., AUGUSTI, D.V., BADOTTI, F., GOMES, F.D.O., CATHARINO, R.R., EBERLIN, M.N., AUGUSTI, R. 2014. Food Chemistry 143: 77-81. TEIXEIRA, L.S., VIEIRA, H.P., WINDMÖLLER, C.C., NASCENTES, C.C. 2014. Talanta, Oxford 119: 232-239. TUNDISI, J.G., MATSUMURA-TUNDISI, T. 2015. Revista USP 106: 23-30. TUNDISI, J.G. 2015. Revista USP 106: 8-10. TUNDISI, J.G., MATSUMURA-TUNDISI, T. 2014. Freshwater Reviews 6: 75-91. TUNDISI, J.G., MATSUMURA-TUNDISI, T., GOLDEMBERG, J., SARAIVA, A. 2014. Energy Policy 74: 703-708. TUNDISI, J.G., TUNDISI, T.M. 2016. Ecohydrology & Hydrobiology 16: 83-91. VASCONCELOS, D.C.L., NUNES, E.H.M., HOUMARD, M., MOTUZAS, J., NASCIMENTO, J.F., GRAVA, W., CIMINELLI, V.S.T., COSTA, J.C.D., VASCONCELOS, W.L. 2013. Journal of Non-Crystalline Solids 378: 1-6. VECCHIA, A.M.D., RODRIGUES, P.C.H., LADEIRA, A.C.Q., RIOS, F.R. 2015. Geonomos 22 (2): 77-90. VELOSO, T.C., PAIVA, P.R.P., SILVA C.A., LEÃO V.A. 2016. Metallurgical and Materials Transactions B 47 (3): 2005-2014. VIEIRA, H.P., NASCENTES, C.C., WINDMÖLLER, C.C. 2014. Journal of Food Composition and Analysis 34: 1-6. WINDMÖLLER, C.C., DURÃO JÚNIOR, W.A., OLIVEIRA, A., VALLE, C.M. 2015. Ecotoxicology and Environmental Safety 112: 201-211. YAN, X., AUGUSTI, R., LI, X., COOKS, R.G. 2013. Chempluschem 78 (9): 1142-1148.

Book Chapters BARBOSA, F.A.R. 2013. Uma breve história do Programa de Pesquisas Ecológicas de Longa Duração (PELD-CNPq) do Brasil: da semente ao fruto. In: PELD-CNPq: Dez Anos do Programa de Pesquisas Ecológicas de Longa Duração no Brasil: achados, lições e perspectivas. Recife: Ed. Universitária da UFPE, pp. 14-27. BARBOSA, F.A.R., LOVATO, M.B., NASCIMENTO, A.M., MAIA-BARBOSA, P.M., MONTE-MOR, R.L., PAGGLIA, A., STEHMANN, J.R. 2013. Dinâmica Biológica e Conservação da Biodiversidade da Mata Atlântica do Médio Rio Doce, MG (PELD/UFMG). In: PELD-CNPq: Dez anos do Programa de Pesquisas Ecológicas de Longa Duração do Brasil: achados, lições e perspectivas. Recife: Ed. Universitária da UFPE, pp. 115-146.

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BARBOSA, F.A.R., MAIA-BARBOSA, P.M., PUJONI, D.G.F., OPORTO, L.T. 2014. The Missing Piece in the Conservation Puzzle: Cohesion Among Environmental, Economic and Social Dimensions. In: The Global Water System in the Anthropocene. Springer International Publishing, pp. 215-227. CORTINA, J.L., LITTER, M., GIBERT, O., VALDERRAMA, C., SANCHA, A.M., CIMINELLI, V.S.T. 2016. Latin American experiences in arsenic removal from drinking water and mining effluents. In: Bryjak, M., Kabay, N., Rivas, B.L., Bundschuh, J. (orgs). Innovative Materials and Methods for Water Treatment: Solutions for Arsenic and Chromium Removal; Solutions for Arsenic and Chromium Removal. 1. ed. Londres: Taylor & Francis Group, Vol. 1, pp. 391-416. DUARTE, H.A. 2016. Molecular Simulation of Nanosized Tubular Clay Minerals. In: Yuan, P., Thill, A., Bergaya, F. (orgs). Nanosized tubular clay minerals. 1. ed. Amisterdam: Elsevier, Vol. 7, pp. 1-29. DUARTE, H.A. 2016. Molecular simulation of clay mineral nanotubes. In: Yang, P., Bergaya, F., Thill, A. (eds). Nanosized Clay Mineral Nanotubes. Elsevier. 778 pp. ISBN: 9780081002933. http://store.elsevier. com/Nanosized-Tubular-Clay-Minerals/ISBN9780081002933/. Release: 14/06/2016. LIMA, G.F., DE ABREU, H.A., DUARTE, H.A. 2014. Surface Reactivity of the Sulfide Minerals. In: Springborg, M., Joswig, J.O. (eds). Specialist Periodical Reports Chemical Modeling: Theory and Applications. London: The Royal Society of Chemistry, Vol. 10, pp. 153-182. GUEDES, F.A., FRANCO, M.W., OLIVEIRA, D., MAGALHÃES, S.M.S., BARBOSA, F.A.R. 2013. Cianobactérias como fonte de insumos biotecnológicos. In: Arruda, C., Carvalho, F. Inovações Ambientais - políticas públicas, tecnologias e oportunidades de negócios. Rio de Janeiro: Elsevier, pp. 167-189. MAGALHÃES, S.M.S., MOL, M.P.G. 2013. Medicamentos como Problema Ambiental. In: Medicamentos - Políticas, Assistência Farmacêutica, Farmacoepidemiologia e Farmacoeconomia. Belo Horizonte: COOPMED, pp. 291-319. TABARELLI, M., ROCHA, C.F.D., BARBOSA, F.A.R., HAY, J.D., ROMANOWSKI, H.P., ROCHA, O., LACERDA, L.D. 2013. Dez Anos de PELD: achados científicos e perspectivas. In: PELD-CNPq Dez Anos do Programa de Pesquisas Ecológicas de Longa Duração no Brasil: achados, lições e perspectivas. Recife: Ed. Universitária da UFPE, pp. 396-413. TUNDISI, J.G. 2013. A Governança da Água. In: Paula, J.A. (org). Água. 2. ed. Belo Horizonte: Editora da UFMG, Vol. 20, pp. 222-235. FERREIRA, V.V.M., CARVALHO FILHO, C.A., RODRIGUES, P.C.H., FLEMING, P.M., MEIRA-BELO, L.C. 2012. Radiometric Evaluation in a Uranium Mine under a Decommisioning Processs. Energy and Environment Research, Vol. 2, pp. 13-27.

Books BRAGA, B., TUNDISI, J.G., TUNDISI, T.M., CIMINELLI, V.S.T. (orgs). 2015. Águas Doces no Brasil. 4. ed. São Paulo: Escrituras Editora e Distribuidora de Livros Ltda. Vol. 1, 729 pp.

PUBLICATIONS

STRASKRABA, M., TUNDISI, J.G. 2013. Gerenciamento da qualidade da รกgua de represas. 3. ed. Sรฃo Paulo: Oficina de Textos. Vol. 500, 300 pp. HUPFFER, H.M., FIGUEIREDO, J.A.S., TUNDISI, J.G. 2013. Pagamento por Serviรงos Ambientais. 1. ed. Porto Alegre: ENTREmeios Editora. Vol. 500, 220 pp.

Patents CIMINELLI, V.S.T., SILVA, G.C., MELLO, A., SOUZA, C. 2013. Magnetic nanocomposites obtaining process from effluents and waste, products and use. Deposited in 03/13/2013. Protocol number: BR1020130059358. SOUZA, C., CIMINELLI, V.S.T. 2013. Process for recovery of cyanide by activated charcoal mixed circuits / ion exchange resin. Deposited in 12/27/2013. Protocol number: BR 1020130336246. COELHO, M.G., ANDRADE, F.V., LIMA, G.M., AUGUSTI, R., BELCHIOR, J.C., PEREIRA, G.V., OLIVEIRA, L.C.A. 2014. Use of iron oxide catalyst supported on autoclave cellular concrete to eradicate grub fly. Deposited in 25/03/2014. Protocol number: BR132014007098.

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contacts INCT-ACQUA MANAGEMENT COMMITTEE Virginia S. T. Ciminelli – UFMG, Director José Galizia Tundisi – IIEGA/SP, Vice-Director Francisco Antônio Rodrigues Barbosa – UFMG, Vice-Director Ana Claudia Q. Ladeira – CNEN-CDTN Angela de Mello Ferreira – CEFET-MG Jaime Wilson Vargas de Mello – UFV Hélio Anderson Duarte – UFMG

ADVISORY COUNCIL Renato Ciminelli, President Geopark Quadrilátero Ferrífero

presidencia@geoparkquadrilatero.org

Carlos Nogueira Costa Júnior Secretary of Geology, Mining and Mineral Processing – MME carlos.junior@mme.gov.br

Evando Mirra de Paula e Silva Emeritus Professor at UFMG evandomirra@gmail.com

Francisco Alves Editorial Director at Brasil Mineral Magazine franalves@signuseditora.com.br

Leonardo Santana Dias Geotechnical Manager – COFFEY Mining leonardo_santana@coffey.com

Silvio Crestana Researcher and Former President of Embrapa crestana@cnpdia.embrapa.br

EXECUTIVE OFFICE Dr. Claudia L. Caldeira – DEMET/UFMG Manager claudia@demet.ufmg.br

Christina Salvador – INCT-Acqua Secretary inct.acqua@demet.ufmg.br

Índila Ribeiro – INCT-Acqua Communication and Social Responsibility inctacqua@gmail.com

Gladstone Faria da Cruz Administrative Assistant novas@demet.ufmg.br

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CONTACTS

CESUP – CENTER OF REFERENCE AND QUALIFICATION FOR THE SUSTAINABILITY OF THE ALTO PARAOPEBA Renato Ciminelli Strategic & Institucional Coordinator presidencia@geoparkquadrilatero.org

Maria de Lourdes de Almeida Local Coodinator

cesup@altoparaopeba.mg.gov.br

FUNDEP – FUNDAÇÃO DE DESENVOLVIMENTO DA PESQUISA Camila dos Reis Cunha Project Analyst

camilacunha@fundep.ufmg.br

INSTITUTIONS AND CONTACTS UFMG – UNIVERSIDADE FEDERAL DE MINAS GERAIS Department of Metallurgical and Materials Engineering - School of Engineering Berenice Mendonça González gonzalez@demet.ufmg.br

Daniel Majuste

daniel.majuste@demet.ufmg.br

Marcelo Borges Mansur

marcelo.mansur@metalmat.ufrj.br

Virginia S. T. Ciminelli

ciminelli@demet.ufmg.br

Wander Luiz Vasconcelos wlv@demet.ufmg.br

Department of Mining Engineering - School of Engineering Evandro Moraes da Gama emgama@demin.ufmg.br

Sonia Denise Ferreira Rocha sdrocha@demin.ufmg.br

Department of Chemistry - Institute of Exact Sciences Cláudia Carvalhinho Windmoeller claucw@netuno.lcc.ufmg.br

Hélio Anderson Duarte duarteh@ufmg.br

Heitor Avelino de Abreu heitorabreu@ufmg.br

Rodnei Augusti

augusti@ufmg.br

Department of General Biology - Institute of Biological Sciences Andréa Maria A. Nascimento amaral@ufmg.br

Edmar Chartone de Souza echartone@yahoo.com.br

Francisco Antônio R. Barbosa

Paulina Maria Maia Barbosa maia@icb.ufmg.br

Pharmacy School Sérgia Maria Starling Magalhães sergiams@farmacia.ufmg.br

School of Architecture Flávio de Lemos Carsalade

flavio.carsalade@terra.com.br

School of Fine Arts Francisco Carlos de Carvalho Marinho chicomar.francisco@gmail.com

Wallace Lages

wallace.lages@gmail.com

AIIEGA – ASSOCIAÇÃO INSTITUTO INTERNACIONAL DE ECOLOGIA E GERENCIAMENTO AMBIENTAL Corina Verónica Sidagis Galli corina@iie.com.br

Donato Seiji Abe

donatoabe@iie.com.br

Felipe Cornachione Blanco principal@iie.com.br

Fernando de Paula Blanco fernando@iie.com.br

José Eduardo Matsumura Tundisi edu.iie@iie.com.br

José Galizia Tundisi tundisi@iie.com.br

Takako Matsumura Tundisi takako@iie.com.br

CNEN/CDTN – COMISSÃO NACIONAL DE ENERGIA NUCLEAR/ CENTRO DE DESENVOLVIMENTO DE TECNOLOGIA NUCLEAR Ana Cláudia Queiroz Ladeira ana.ladeira@cdtn.br

Carlos Antônio de Morais cmorais@cdtn.br

Carlos Alberto de Carvalho Filho cacf@cdtn.br

Paulo César Horta Rodrigues pchr@cdtn.br

Rubens Martins Moreira rubens@cdtn.br

UFV – UNIVERSIDADE FEDERAL DE VIÇOSA Igor Rodrigues de Assis igor.assis@ufv.br

Jaime Wilson V. de Mello jwvmello@ufv.br

Luiz Eduardo Dias ledias@ufv.br

Walter Antônio Pereira Abrahão wabrahao@ufv.br

barbosa@icb.ufmg.br

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CEFET-MG – CENTRO FEDERAL DE EDUCAÇÃO TECNOLÓGICA DE MINAS GERAIS Andréa Rodrigues Marques Guimarães andrearmg@gmail.com

Angela de Mello Ferreira

angelamello@des.cefetmg.br

Sidney Nicodemos da Silva sidney@des.cefetmg.br

Paulo Renato P. Paiva

paulorenato@gmail.com

FASAR – FACULDADE SANTA RITA Raphael de Vicq Ferreira da Costa

raphaelvicq@gmail.com

UFCE – UNIVERSIDADE FEDERAL DO CEARÁ Igor Frota de Vasconcelos ifvasco@ufc.br

UFJF – UNIVERSIDADE FEDERAL DE JUIZ DE FORA Júlio César José da Silva julio.silva@ufjf.edu.br

UFSJ – UNIVERSIDADE FEDERAL DE SÃO JOÃO DEL REI Luciana Guimarães

lucianaguimaraes@ufsj.edu.br

UFVJM – UNIVERSIDADE FEDERAL DOS VALES DO JEQUITINHONHA E MUCURI José Domingos Fabris jdfabris@gmail.com

INTERNATIONAL COLLABORATION Dina L. Lopez Ohio University, USA lopezd@ohio.edu

Jack Ng The University of Queensland, Australia j.ng@uq.edu.au

Joe Diniz da Costa The University of Queensland, Australia j.dacosta@eng.uq.edu.au

Kay Knöller Helmholtz Centre for Environmental Research, Germany kay.knoeller@ufz.de

Kwadwo Osseo-Asare The Pensylvania State University, USA ako1@psu.edu

Marta Litter CNEA, Argentina

marta.litter@gmail.com

Massimo Gasparon The University of Queensland, Australia m.gasparon@uq.edu.au

Michael Nicol Murdoch University, Australia m.nicol@murdoch.edu.au

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Peter Anton Staehr University of Aarhus, Denmark pst@bios.au.dk

Peter Georg Weidler Karlsruhe Institute of Technology, Germany peter.weidler@kit.edu

Susan Glasauer University of Guelph, Canada glasauer@uoguelph.ca

Thomas Heine Jacobs University, Germany

t.heine@jacobs-university.de

Tomas Hávlik Technical University of Kosice, Slovakia tomas.havlik@tuke.sk

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(1) AIIEGA. (2) Renato Ciminelli (CESUP). (3) Department of Chemistry - Institute of Exact Sciences – UFMG. (4) Department of General Biology - Institute of Biological Sciences – UFMG. (5) Maria de Lourdes de Almeida (CESUP). (6) School of Engineering - Department of Metallurgical and Materials Engineering and Department of Mining Engineering – UFMG. (7) Andréa Maria A. Nascimento, Francisco Antônio R. Barbosa and Paulina Maria Maia Barbosa (Department of General Biology - Institute of Biological Sciences – UFMG). (8) Guilherme Ferreira de Lima, Hélio Anderson Duarte and Heitor Avelino de Abreu (Department of Chemistry - Institute of Exact Sciences – UFMG). (9) José Galizia Tundisi and Takako Matsumura Tundisi (AIIEGA).

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(10) From left to right: Wander Luiz Vasconcelos, Evandro Moraes da Gama, Eduardo Henrique Martins Nunes, Maria Sylvia Silva Dantas, Emílio Osorio Neto, Itamar Daniel Delbem, Clauson de Souza, Claudia Lima Caldeira, Virginia S. T. Ciminelli, Daniel Majuste and Sonia Denise Ferreira Rocha (School of Engineering - Department of Metallurgical and Materials Engineering and Department of Mining Engineering – UFMG). (11) Jaime Wilson V. de Mello (UFV). (12) From left to right: Andréa Rodrigues Marques Guimarães, Angela de Mello Ferreira and Paulo Renato Perdigão Paiva (CEFET-MG). (13) From left to right: Paulo César Horta Rodrigues, Rubens Martins Moreira, Carlos Alberto de Carvalho Filho, Carlos Antônio de Morais, Ana Cláudia Queiroz Ladeira and Peter Marshall Fleming (CNEN/CDTN).

Headquarters

Universidade Federal de Minas Gerais – UFMG Escola de Engenharia – Bloco II Depto. de Engenharia Metalúrgica e de Materiais Av. Antonio Carlos, 6627 – 31270 - 901 Belo Horizonte – MG, Brazil

Telephone

+55 (31) 3409-1825 / 1810

E-mail

inct.acqua@demet.ufmg.br

Home Page

www.acqua-inct.org

INCT-ACQUA ACTIVITY REPORT - Expedient Editors

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