Search results for: exhaust pollution

Authors: Elisa Coraggio, Dawei Han, Weiru Liu, Theo Tryfonas

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Water is one of the most important resources for human society. The world is currently undergoing a wave of urban growth, and pollution problems are of a great impact. Monitoring water quality is a key task for the future of the environment and human species. In recent times, researchers, using Smart Cities technologies are trying to mitigate the problems generated by the population growth in urban areas. The availability of huge amounts of data collected by a pervasive urban IoT can increase the transparency of decision making. Several services have already been implemented in Smart Cities, but more and more services will be involved in the future. Water quality monitoring can successfully be implemented in the urban IoT. The combination of water quality sensors, cloud computing, smart city infrastructure, and IoT technology can lead to a bright future for environmental monitoring. In the past decades, lots of effort has been put on monitoring and predicting water quality using traditional approaches based on manual collection and laboratory-based analysis, which are slow and laborious. The present study proposes a methodology for implementing a water quality prediction model using artificial intelligence techniques and comparing the results obtained with different algorithms. Furthermore, a 3D numerical model will be created using the software D-Water Quality, and simulation results will be used as a training dataset for the artificial intelligence algorithm. This study derives the methodology and demonstrates its implementation based on information and data collected at the floating harbour in the city of Bristol (UK). The city of Bristol is blessed with the Bristol-Is-Open infrastructure that includes Wi-Fi network and virtual machines. It was also named the UK ’s smartest city in 2017.In recent times, researchers, using Smart Cities technologies are trying to mitigate the problems generated by the population growth in urban areas. The availability of huge amounts of data collected by a pervasive urban IoT can increase the transparency of decision making. Several services have already been implemented in Smart Cities, but more and more services will be involved in the future. Water quality monitoring can successfully be implemented in the urban IoT. The combination of water quality sensors, cloud computing, smart city infrastructure, and IoT technology can lead to a bright future for the environment monitoring. In the past decades, lots of effort has been put on monitoring and predicting water quality using traditional approaches based on manual collection and laboratory-based analysis, which are slow and laborious. The present study proposes a new methodology for implementing a water quality prediction model using artificial intelligence techniques and comparing the results obtained with different algorithms. Furthermore, a 3D numerical model will be created using the software D-Water Quality, and simulation results will be used as a training dataset for the Artificial Intelligence algorithm. This study derives the methodology and demonstrate its implementation based on information and data collected at the floating harbour in the city of Bristol (UK). The city of Bristol is blessed with the Bristol-Is-Open infrastructure that includes Wi-Fi network and virtual machines. It was also named the UK ’s smartest city in 2017.

Keywords: artificial intelligence, hydroinformatics, numerical modelling, smart cities, water quality

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Authors: Ariesny Vera, Rodrigo Montecinos

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The rare-earth elements (REEs) or rare-earth metals (REMs), correspond to seventeen chemical elements composed by the fifteen lanthanoids, as well as scandium and yttrium. Lanthanoids corresponds to lanthanum and the f-block elements, from cerium to lutetium. Scandium and yttrium are considered rare-earth elements because they have ionic radii similar to the lighter f-block elements. These elements were called rare earths because they are simply more difficult to extract and separate individually than the most metals and, generally, they do not accumulate in minerals, they are rarely found in easily mined ores and are often unfavorably distributed in common ores/minerals. REEs show unique chemical and physical properties, in comparison to the other metals in the periodic table. Nowadays, these physicochemical properties are utilized in a wide range of synthetic, catalytic, electronic, medicinal, and military applications. Because of their applications, the global demand for rare earth metals is becoming progressively more important in the transition to a self-sustaining society and greener economy. However, due to the difficult separation between lanthanoid ions, the high cost and pollution of these processes, the scientists search the development of a method that combines selectivity and quantitative separation of lanthanoids from the leaching liquor, while being more economical and environmentally friendly processes. This motivation has favored the design and development of more efficient and environmentally friendly cation extractors with the incorporation of compounds as ionic liquids, membrane inclusion polymers (PIM) and supramolecular systems. Supramolecular chemistry focuses on the development of host-guest systems, in which a host molecule can recognize and bind a certain guest molecule or ion. Normally, the formation of a host-guest complex involves non-covalent interactions Additionally, host-guest interactions can be influenced among others effects by the structural nature of host and guests. The different macrocyclic hosts for lanthanoid species that have been studied are crown ethers, cyclodextrins, cucurbituryls, calixarenes and pillararenes.Among all the factors that can influence and affect lanthanoid (III) coordination, perhaps the most basic of them is the systematic control using macrocyclic substituents that promote a selective coordination. In this sense, macrocycles pillar[n]arenes (P[n]As) present a relatively easy functionalization and they have more π-rich cavity than other host molecules. This gives to P[n]As a negative electrostatic potential in the cavity which would be responsible for the selectivity of these compounds towards cations. Furthermore, the cavity size, the linker, and the functional groups of the polar headgroups could be modified in order to control the association of lanthanoid cations. In this sense, different P[n]As systems, specifically derivatives of the pentamer P[5]A functionalized with amide, amine, phosphate and sulfate derivatives, have been designed in terms of experimental synthesis and molecular dynamics, and the interaction between these P[5]As and some lanthanoid ions such as La³+, Eu³+ and Lu³+ has been studied by physicochemical characterization by 1H-NMR, ITC and fluorescence in the case of Eu³+ systems. The molecular dynamics study of these systems was developed in hexane as solvent, also taking into account the lanthanoid ions mentioned above, and the respective comparison studies between the different ions.

Keywords: lanthanoids, macrocycles, pillar[n]arenes, rare-earth metal extraction, supramolecular chemistry, supramolecular complexes.

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Authors: Lya Porto, Giulia Giacchè, Mario Aquino Alves

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The paper aims to describe the linkage between government and civil society proposing a study on agro-ecological agriculture policy and urban action in São Paulo city underling the main achievements obtained. The negotiation processes between social movements and the government (inputs) and its results on political regulation and public action for Urban Agriculture (UA) in São Paulo city (outputs) have been investigated. The method adopted is qualitative, with techniques of semi-structured interviews, participant observation, and documental analysis. The authors conducted 30 semi-structured interviews with organic farmers, activists, governmental and non-governmental managers. Participant observation was conducted in public gardens, urban farms, public audiences, democratic councils, and social movements meetings. Finally, public plans and laws were also analyzed. São Paulo city with around 12 million inhabitants spread out in a 1522 km2 is the economic capital of Brazil, marked by spatial and socioeconomic segregation, currently aggravated by environmental crisis, characterized by water scarcity, pollution, and climate changes. In recent years, Urban Agriculture (UA) social movements gained strength and struggle for a different city with more green areas, organic food production, and public occupation. As the dynamics of UA occurs by the action of multiple actresses and institutions that struggle to build multiple senses on UA, the analysis will be based on literature about solidarity economy, governance, public action and networks. Those theories will mark out the analysis that will emphasize the approach of inter-subjectivity built between subjects, as well as the hybrid dynamics of multiple actors and spaces in the construction of policies for UA. Concerning UA we identified four main typologies based on land ownership, main function (economic or activist), form of organization of the space, and type of production (organic or not). The City Hall registers 500 productive unities of agriculture, with around 1500 producers, but researcher estimated a larger number of unities. Concerning the social movements we identified three categories that differ in goals and types of organization, but all of them work by networks of activists and/or organizations. The first category does not consider themselves as a movement, but a network. They occupy public spaces to grow organic food and to propose another type of social relations in the city. This action is similar to what became known as the green guerrillas. The second is configured as a movement that is structured to raise awareness about agro-ecological activities. The third one is a network of social movements, farmers, organizations and politicians that work focused on pressure and negotiation with executive and legislative government to approve regulations and policies on organic and agro-ecological Urban Agriculture. We conclude by highlighting how the interaction among institutions and civil society produced important achievements for recognition and implementation of UA within the city. Some results of this process are awareness for local production, legal and institutional recognition of the rural zone around the city into the planning tool, the investment on organic school public procurements, the establishment of participatory management of public squares, the inclusion of UA on Municipal Strategic Plan and Master Plan.

Keywords: public action, policies, agroecology, urban and peri-urban agriculture, Sao Paulo

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Authors: Carly Cummings, Maria Soledad Peresin

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Alabama has a long history of racial injustice and unsatisfactory educational performance. In the 1870s Jim Crow laws segregated public schools and disproportionally allocated funding and resources to white institutions across the South. Despite the Supreme Court ruling to integrate schools following Brown vs. the Board of Education in 1954, Alabama’s school system continued to exhibit signs of segregation, compounded by “white flight” and the establishment of exclusive private schools, which still exist today. This discriminatory history has had a lasting impact of the state’s education system, reflected in modern school demographics and achievement data. It is well known that Alabama struggles with education performance, especially in science education. On average, minority groups scored the lowest in science proficiency. In Alabama, minority populations are concentrated in a region known as the Black Belt, which was once home to countless slave plantations and was the epicenter of the Civil Rights Movement. Today the Black Belt is characterized by a high density of woodlands and plays a significant role in Alabama’s leading economic industry-forest products. Given the economic importance of forestry and agriculture to the state, environmental science proficiency is essential to its stability; however, it is neglected in areas where it is needed most. To better understand the inequity of science education within Alabama, our study first investigates how geographic location, demographics and school funding relate to science achievement scores using ArcGIS and Pearson’s correlation coefficient. Additionally, our study explores the implementation of a relevant, problem-based, active learning lesson in schools. Relevant learning engages students by connecting material to their personal experiences. Problem-based active learning involves real-world problem-solving through hands-on experiences. Given Alabama’s significant woodland coverage, educational materials on forest products were developed with consideration of its relevance to students, especially those located in the Black Belt. Furthermore, to incorporate problem solving and active learning, the lesson centered around students using forest products to solve environmental challenges, such as water pollution- an increasing challenge within the state due to climate change. Pre and post assessment surveys were provided to teachers to measure the effectiveness of the lesson. In addition to pedagogical practices, community and mentorship programs are known to positively impact educational achievements. To this end, our work examines the results of surveys measuring educational professionals’ attitudes toward a local mentorship group within the Black Belt and its potential to address environmental and science literacy. Additionally, our study presents survey results from participants who attended an educational community event, gauging its effectiveness in increasing environmental and science proficiency. Our results demonstrate positive improvements in environmental awareness and science literacy with relevant pedagogy, mentorship, and community involvement. Implementing these practices can help provide equitable and inclusive learning environments and can better equip students with the skills and knowledge needed to bridge this historic educational gap within Alabama.

Keywords: equitable education, environmental science, environmental education, science education, racial injustice, sustainability, rural education

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Authors: Julien Caudeville, Muriel Ismert

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Analyzing the relationship between environment and health has become a major preoccupation for public health as evidenced by the emergence of the French national plans for health and environment. These plans have identified the following two priorities: (1) to identify and manage geographic areas, where hotspot exposures are suspected to generate a potential hazard to human health; (2) to reduce exposure inequalities. At a regional scale and fine resolution of exposure outcome prerequisite, environmental monitoring networks are not sufficient to characterize the multidimensionality of the exposure concept. In an attempt to increase representativeness of spatial exposure assessment approaches, risk composite indicators could be built using additional available databases and theoretical framework approaches to combine factor risks. To achieve those objectives, combining data process and transfer modeling with a spatial approach is a fundamental prerequisite that implies the need to first overcome different scientific limitations: to define interest variables and indicators that could be built to associate and describe the global source-effect chain; to link and process data from different sources and different spatial supports; to develop adapted methods in order to improve spatial data representativeness and resolution. A GIS-based modeling platform for quantifying human exposure to chemical substances (PLAINE: environmental inequalities analysis platform) was used to build health risk indicators within the Lorraine region (France). Those indicators combined chemical substances (in soil, air and water) and noise risk factors. Tools have been developed using modeling, spatial analysis and geostatistic methods to build and discretize interest variables from different supports and resolutions on a 1 km2 regular grid within the Lorraine region. By example, surface soil concentrations have been estimated by developing a Kriging method able to integrate surface and point spatial supports. Then, an exposure model developed by INERIS was used to assess the transfer from soil to individual exposure through ingestion pathways. We used distance from polluted soil site to build a proxy for contaminated site. Air indicator combined modeled concentrations and estimated emissions to take in account 30 polluants in the analysis. For water, drinking water concentrations were compared to drinking water standards to build a score spatialized using a distribution unit serve map. The Lden (day-evening-night) indicator was used to map noise around road infrastructures. Aggregation of the different factor risks was made using different methodologies to discuss weighting and aggregation procedures impact on the effectiveness of risk maps to take decisions for safeguarding citizen health. Results permit to identify pollutant sources, determinants of exposure, and potential hotspots areas. A diagnostic tool was developed for stakeholders to visualize and analyze the composite indicators in an operational and accurate manner. The designed support system will be used in many applications and contexts: (1) mapping environmental disparities throughout the Lorraine region; (2) identifying vulnerable population and determinants of exposure to set priorities and target for pollution prevention, regulation and remediation; (3) providing exposure database to quantify relationships between environmental indicators and cancer mortality data provided by French Regional Health Observatories.

Keywords: health risk, environment, composite indicator, hotspot areas

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Authors: K. Raghu, M. N. Vathhsala, Naveen Aradya, Sharth

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River sand is the most preferred fine aggregate for mortar and concrete. River sand is a product of natural weathering of rocks over a period of millions of years and is mined from river beds. Sand mining has disastrous environmental consequences. The excessive mining of river bed is creating an ecological imbalance. This has lead to have restrictions imposed by ministry of environment on sand mining. Driven by the acute need for sand, stone dust or manufactured sand prepared from the crushing and screening of coarse aggregate is being used as sand in the recent past. However manufactured sand is also a natural material and has quarrying and quality issues. To reduce the burden on the environment, alternative materials to be used as fine aggregates are being extensively investigated all over the world. Looking to the quantum of requirements, quality and properties there has been a global consensus on a material – Granulated slags. Granulated slag has been proven as a suitable material for replacing natural sand / crushed fine aggregates. In developed countries, the use of granulated slag as fine aggregate to replace natural sand is well established and is in regular practice. In the present paper Granulated slag has been experimented for usage in mortar. Slags are the main by-products generated during iron and steel production in the steel industry. Over the past decades, the steel production has increased and, consequently, the higher volumes of by-products and residues generated which have driven to the reuse of these materials in an increasingly efficient way. In recent years new technologies have been developed to improve the recovery rates of slags. Increase of slags recovery and use in different fields of applications like cement making, construction and fertilizers help in preserving natural resources. In addition to the environment protection, these practices produced economic benefits, by providing sustainable solutions that can allow the steel industry to achieve its ambitious targets of “zero waste” in coming years. Slags are generated at two different stages of steel production, iron making and steel making known as BF(Blast Furnace) slag and steel slag respectively. The slagging agent or fluxes, such as lime stone, dolomite and quartzite added into BF or steel making furnaces in order to remove impurities from ore, scrap and other ferrous charges during smelting. The slag formation is the result of a complex series of physical and chemical reactions between the non-metallic charge(lime stone, dolomite, fluxes), the energy sources(coal, coke, oxygen, etc.) and refractory materials. Because of the high temperatures (about 15000 C) during their generation, slags do not contain any organic substances. Due to the fact that slags are lighter than the liquid metal, they float and get easily removed. The slags protect the metal bath from atmosphere and maintain temperature through a kind of liquid formation. These slags are in liquid state and solidified in air after dumping in the pit or granulated by impinging water systems. Generally, BF slags are granulated and used in cement making due to its high cementious properties, and steel slags are mostly dumped due to unfavourable physio-chemical conditions. The increasing dump of steel slag not only occupies a plenty of land but also wastes resources and can potentially have an impact on the environment due to water pollution. Since BF slag contains little Fe and can be used directly. BF slag has found a wide application, such as cement production, road construction, Civil Engineering work, fertilizer production, landfill daily cover, soil reclamation, prior to its application outside the iron and steel making process.

Keywords: steel slag, river sand, granulated slag, environmental

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Authors: Lina Wu

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The excessive discharge of nitrogen in sewage greatly intensifies the eutrophication of water bodies and threatens water quality. Nitrogen pollution control has become a global concern. The concentration of nitrogen in water is reduced by converting ammonia nitrogen, nitrate nitrogen and nitrite nitrogen into nitrogen-containing gas through biological treatment, physicochemical treatment and oxidation technology. However, some wastewater containing high ammonia nitrogen including landfill leachate, is difficult to be treated by traditional nitrification and denitrification because of its high COD content. The core process of denitrification is that denitrifying bacteria convert nitrous acid produced by nitrification into nitrite under anaerobic conditions. Still, its low-carbon nitrogen does not meet the conditions for denitrification. Many studies have shown that the natural autotrophic anammox bacteria can combine nitrous and ammonia nitrogen without a carbon source through functional genes to achieve total nitrogen removal, which is very suitable for removing nitrogen from leachate. In addition, the process also saves a lot of aeration energy consumption than the traditional nitrogen removal process. Therefore, anammox plays an important role in nitrogen conversion and energy saving. The short-range nitrification and denitrification coupled with anaerobic ammoX ensures total nitrogen removal. It improves the removal efficiency, meeting the needs of society for an ecologically friendly and cost-effective nutrient removal treatment technology. In recent years, research has found that the symbiotic system has more water treatment advantages because this process not only helps to improve the efficiency of wastewater treatment but also allows carbon dioxide reduction and resource recovery. Microalgae use carbon dioxide dissolved in water or released through bacterial respiration to produce oxygen for bacteria through photosynthesis under light, and bacteria, in turn, provide metabolites and inorganic carbon sources for the growth of microalgae, which may lead the algal bacteria symbiotic system save most or all of the aeration energy consumption. It has become a trend to make microalgae and light-avoiding anammox bacteria play synergistic roles by adjusting the light-to-dark ratio. Microalgae in the outer layer of light particles block most of the light and provide cofactors and amino acids to promote nitrogen removal. In particular, myxoccota MYX1 can degrade extracellular proteins produced by microalgae, providing amino acids for the entire bacterial community, which helps anammox bacteria save metabolic energy and adapt to light. As a result, initiating and maintaining the process of combining dominant algae and anaerobic denitrifying bacterial communities has great potential in treating landfill leachate. Chlorella has a brilliant removal effect and can withstand extreme environments in terms of high ammonia nitrogen, high salt and low temperature. It is urgent to study whether the algal mud mixture rich in denitrifying bacteria and chlorella can greatly improve the efficiency of landfill leachate treatment under an anaerobic environment where photosynthesis is stopped. The optimal dilution concentration of simulated landfill leachate can be found by determining the treatment effect of the same batch of bacteria and algae mixtures under different initial ammonia nitrogen concentrations and making a comparison. High-throughput sequencing technology was used to analyze the changes in microbial diversity, related functional genera and functional genes under optimal conditions, providing a theoretical and practical basis for the engineering application of novel bacteria-algae symbiosis system in biogas slurry treatment and resource utilization.

Keywords: nutrient removal and recovery, leachate, anammox, Partial nitrification, Algae-bacteria interaction

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Authors: Pejman Salimi, Sebastiano Tieuli, Somayeh Taghavi, Michela Signoretto, Remo Proietti Zaccaria

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Increasing the growth of industrial waste due to the large quantities of production leads to numerous environmental and economic challenges, such as climate change, soil and water contamination, human disease, etc. Energy recovery of waste can be applied to produce heat or electricity. This strategy allows for the reduction of energy produced using coal or other fuels and directly reduces greenhouse gas emissions. Among different factories, leather manufacturing plays a very important role in the whole world from the socio-economic point of view. The leather industry plays a very important role in our society from a socio-economic point of view. Even though the leather industry uses a by-product from the meat industry as raw material, it is considered as an activity demanding integrated prevention and control of pollution. Along the entire process from raw skins/hides to finished leather, a huge amount of solid and water waste is generated. Solid wastes include fleshings, raw trimmings, shavings, buffing dust, etc. One of the most abundant solid wastes generated throughout leather tanning is shaving waste. Leather shaving is a mechanical process that aims at reducing the tanned skin to a specific thickness before tanning and finishing. This product consists mainly of collagen and tanning agent. At present, most of the world's leather processing is chrome-tanned based. Consequently, large amounts of chromium-containing shaving wastes need to be treated. The major concern about the management of this kind of solid waste is ascribed to chrome content, which makes the conventional disposal methods, such as landfilling and incineration, not practicable. Therefore, many efforts have been developed in recent decades to promote eco-friendly/alternative leather production and more effective waste management. Herein, shaving waste resulting from metal-free tanning technology is proposed as low-cost precursors for the preparation of carbon material as anodes for lithium-ion batteries (LIBs). In line with the philosophy of a reduced environmental impact, for preparing fully sustainable and environmentally friendly LIBs anodes, deionized water and carboxymethyl cellulose (CMC) have been used as alternatives to toxic/teratogen N-methyl-2- pyrrolidone (NMP) and to biologically hazardous Polyvinylidene fluoride (PVdF), respectively. Furthermore, going towards the reduced cost, we employed water solvent and fluoride-free bio-derived CMC binder (as an alternative to NMP and PVdF, respectively) together with LiFePO₄ (LFP) when a full cell was considered. These actions make closer to the 2030 goal of having green LIBs at 100 $ kW h⁻¹. Besides, the preparation of the water-based electrodes does not need a controlled environment and due to the higher vapour pressure of water in comparison with NMP, the water-based electrode drying is much faster. This aspect determines an important consequence, namely a reduced energy consumption for the electrode preparation. The electrode derived from leather waste demonstrated a discharge capacity of 735 mAh g⁻¹ after 1000 charge and discharge cycles at 0.5 A g⁻¹. This promising performance is ascribed to the synergistic effect of defects, interlayer spacing, heteroatoms-doped (N, O, and S), high specific surface area, and hierarchical micro/mesopore structure of the biochar. Interestingly, these features of activated biochars derived from the leather industry open the way for possible applications in other EESDs as well.

Keywords: biowaste, lithium-ion batteries, physical activation, waste management, leather industry

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Authors: H. M. El-Askary, S. A. Abd El-Mawla, M. Allali, M. M. El-Hattab, M. El-Raey, A. M. Farahat, M. Kafatos, S. Nickovic, S. K. Park, A. K. Prasad, C. Rakovski, W. Sprigg, D. Struppa, A. Vukovic

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A clear distinction between weather and climate is a necessity because while they are closely related, there are still important differences. Climate change is identified when we compute the statistics of the observed changes in weather over space and time. In this work we will show how the changing climate contribute to the frequency, magnitude and extent of different extreme events using a multi sensor approach with some synergistic modeling activities. We are exploring satellite observations of dust over North Africa, Gulf Region and the Indo Gangetic basin as well as dust versus anthropogenic pollution events over the Delta region in Egypt and Seoul through remote sensing and utilize the behavior of the dust and haze on the aerosol optical properties. Dust impact on the retreat of the glaciers in the Himalayas is also presented. In this study we also focus on the identification and monitoring of a massive dust plume that blew off the western coast of Africa towards the Atlantic on October 8th, 2012 right before the development of Hurricane Sandy. There is evidence that dust aerosols played a non-trivial role in the cyclogenesis process of Sandy. Moreover, a special dust event "An American Haboob" in Arizona is discussed as it was predicted hours in advance because of the great improvement we have in numerical, land–atmosphere modeling, computing power and remote sensing of dust events. Therefore we performed a full numerical simulation to that event using the coupled atmospheric-dust model NMME–DREAM after generating a mask of the potentially dust productive regions using land cover and vegetation data obtained from satellites. Climate change also contributes to the deterioration of different marine habitats. In that regard we are also presenting some work dealing with change detection analysis of Marine Habitats over the city of Hurghada, Red Sea, Egypt. The motivation for this work came from the fact that coral reefs at Hurghada have undergone significant decline. They are damaged, displaced, polluted, stepped on, and blasted off, in addition to the effects of climate change on the reefs. One of the most pressing issues affecting reef health is mass coral bleaching that result from an interaction between human activities and climatic changes. Over another location, namely California, we have observed that it exhibits highly-variable amounts of precipitation across many timescales, from the hourly to the climate timescale. Frequently, heavy precipitation occurs, causing damage to property and life (floods, landslides, etc.). These extreme events, variability, and the lack of good, medium to long-range predictability of precipitation are already a challenge to those who manage wetlands, coastal infrastructure, agriculture and fresh water supply. Adding on to the current challenges for long-range planning is climate change issue. It is known that La Niña and El Niño affect precipitation patterns, which in turn are entwined with global climate patterns. We have studied ENSO impact on precipitation variability over different climate divisions in California. On the other hand the Nile Delta has experienced lately an increase in the underground water table as well as water logging, bogging and soil salinization. Those impacts would pose a major threat to the Delta region inheritance and existing communities. There has been an undergoing effort to address those vulnerabilities by looking into many adaptation strategies.

Keywords: remote sensing, modeling, long range transport, dust storms, North Africa, Gulf Region, India, California, climate extremes, sea level rise, coral reefs

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Authors: Katerina Zaharieva, Katya Milenova, Zara Cherkezova-Zheleva, Alexander Eliyas, Boris Kunev, Ivan Mitov

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The synthesized nanosized manganese ferrite-type of samples have been tested as photocatalysts in the reaction of oxidative degradation of model contaminant Reactive Black 5 (RB5) dye in aqueous solutions under UV irradiation. As it is known this azo dye is applied in the textile-coloring industry and it is discharged into the waterways causing pollution. The co-precipitation procedure has been used for the synthesis of manganese ferrite-type of materials: Sample 1 - Mn0.25Fe2.75O4, Sample 2 - Mn0.5Fe2.5O4 and Sample 3 - MnFe2O4 from 0.03M aqueous solutions of MnCl2•4H2O, FeCl2•4H2O and/or FeCl3•6H2O and 0.3M NaOH in appropriate amounts. The mechanochemical activation of co-precipitated ferrite-type of samples has been performed in argon (Samples 1 and 2) or in air atmosphere (Sample 3) for 2 hours at a milling speed of 500 rpm. The mechano-chemical treatment has been carried out in a high energy planetary ball mill type PM 100, Retsch, Germany. The mass ratio between balls and powder was 30:1. As a result mechanochemically activated Sample 4 - Mn0.25Fe2.75O4, Sample 5 - Mn0.5Fe2.5O4 and Sample 6 - MnFe2O4 have been obtained. The synthesized manganese ferrite-type photocatalysts have been characterized by X-ray diffraction method and Moessbauer spectroscopy. The registered X-ray diffraction patterns and Moessbauer spectra of co-precipitated ferrite-type of materials show the presence of manganese ferrite and additional akaganeite phase. The presence of manganese ferrite and small amounts of iron phases is established in the mechanochemically treated samples. The calculated average crystallite size of manganese ferrites varies within the range 7 – 13 nm. This result is confirmed by Moessbauer study. The registered spectra show superparamagnetic behavior of the prepared materials at room temperature. The photocatalytic investigations have been made using polychromatic UV-A light lamp (Sylvania BLB, 18 W) illumination with wavelength maximum at 365 nm. The intensity of light irradiation upon the manganese ferrite-type photocatalysts was 0.66 mW.cm-2. The photocatalytic reaction of oxidative degradation of RB5 dye was carried out in a semi-batch slurry photocatalytic reactor with 0.15 g of ferrite-type powder, 150 ml of 20 ppm dye aqueous solution under magnetic stirring at rate 400 rpm and continuously feeding air flow. The samples achieved adsorption-desorption equilibrium in the dark period for 30 min and then the UV-light was turned on. After regular time intervals aliquot parts from the suspension were taken out and centrifuged to separate the powder from solution. The residual concentrations of dye were established by a UV-Vis absorbance single beam spectrophotometer CamSpec M501 (UK) measuring in the wavelength region from 190 to 800 nm. The photocatalytic measurements determined that the apparent pseudo-first-order rate constants calculated by linear slopes approximating to first order kinetic equation, increase in following order: Sample 3 (1.1х10-3 min-1) < Sample 1 (2.2х10-3 min-1) < Sample 2 (3.3 х10-3 min-1) < Sample 4 (3.8х10-3 min-1) < Sample 6 (11х10-3 min-1) < Sample 5 (15.2х10-3 min-1). The mechanochemically activated manganese ferrite-type of photocatalyst samples show significantly higher degree of oxidative degradation of RB5 dye after 120 minutes of UV light illumination in comparison with co-precipitated ferrite-type samples: Sample 5 (92%) > Sample 6 (91%) > Sample 4 (63%) > Sample 2 (53%) > Sample 1 (42%) > Sample 3 (15%). Summarizing the obtained results we conclude that the mechanochemical activation leads to a significant enhancement of the degree of oxidative degradation of the RB5 dye and photocatalytic activity of tested manganese ferrite-type of catalyst samples under our experimental conditions. The mechanochemically activated Mn0.5Fe2.5O4 ferrite-type of material displays the highest photocatalytic activity (15.2х10-3 min-1) and degree of oxidative degradation of the RB5 dye (92%) compared to the other synthesized samples. Especially a significant improvement in the degree of oxidative degradation of RB5 dye (91%) has been determined for mechanochemically treated MnFe2O4 ferrite-type of sample with the highest extent of substitution of iron ions by manganese ions than in the case of the co-precipitated MnFe2O4 sample (15%). The mechanochemically activated manganese ferrite-type of samples show good photocatalytic properties in the reaction of oxidative degradation of RB5 azo dye in aqueous solutions and it could find potential application for dye removal from wastewaters originating from textile industry.

Keywords: nanostructured manganese ferrite-type materials, photocatalytic activity, Reactive Black 5, water treatment

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