The role of limestone and dolomite tailings’ particle size in retention of heavy metals from liquid waste

Purpose. The study aims at investigating the role of particle size of mineral tailings derived from limestone, limestone marble, dolomite and dolomitic marble in heavy metal adsorption, in both batch and fixed bed conditions, so as to estimate whether grinding and/or sieving is necessary for their utilization. Methods. Fractions of different particle size have been studied. Adsorption has been examined in batch conditions from solutions of 5 mg/l Cd, 5 mg/l Pb, 100 mg/l Cu, 100 mg/l Zn, and their mixed solution simulating electroplating wastewater, and also in fixed bed conditions. Findings. Total Cd and Cu adsorption is achieved on all the mineral fractions, whereas Pb and Zn show a difference up to 20% depending on particle size. Referring to the mixed solution, Cd and Zn adsorption is lower, whereas no significant differences in Cu and Pb adsorption are observed. Adsorption capacity rises up to 0.03 mg/g Cd, 0.60 mg/g Cu, 0.03 mg/g Pb, 0.60 mg/g Zn. In fixed bed conditions, metal adsorption greater than 93% is achieved. Furthermore, leaching not exceeding 4% indicates a good metal retention. Finally, Taguchi method has proven that the particle size effect is not so strong compared to other parameters, including solution concentration and time. Originality. The particle size of mineral tailings has not yet been investigated as a parameter affecting heavy metal adsorption. Furthermore, heavy metal adsorption has been examined from separate metal solutions and not from a mixed one. The present study aims at contributing to these two research fields. Practical implications. Τhe differences in adsorption between mineral tailings’ fractions with different particle size are not as high as to make grinding of minerals necessary.Мета. Дослідження впливу розмірів частинок у хвостах збагачення вапняку, вапняного мармуру, доломіту та доломітового мармуру на процес адсорбції важких металів у нерухомому шарі для оцінки доцільності технології подрібнення й/або просіювання в подальшому використанні металів. Методика. Для виконання досліджень зразки вапняку та доломіту доставлені компанією, що займається виробництвом і продажем готових бетонів, а також кар’єрами у Греції. Хімічний і мінералогічний склад зразків був визначений рентгенівської флуоресценцією (XRF, ARL ADVANT XP), рентгенівської дифракцією (XRD, Siemens D-500) та атомно-абсорбційною спектрометрією (AAS, VARIAN AA240FS). Для дослідження механізму адсорбції були виміряні наступні параметри: рН відповідно до ISO 6588, пористість і питома площа поверхні за допомогою N2-адсорбції (NOVA-2200, версія 6.11) та катіонообмінна ємність (CEC) відповідно до EPA 9081 на основі змішування зразка з надлишком розчину ацетату натрію, в результаті якого потім визначались додані катіони натрію для матричних катіонів. Для сорбційних експериментів були використані окремі розчини, які містять 5 мг/л Cd, 5 мг/л Pb, 100 мг/л Cu, 100 мг/л Zn, отримані з аналітичних стандартних розчинів Fluka. Після сорбційних досліджень зібрані сорбенти були піддані дослідженням вилуговування. Результати. У процесі досліджень була досягнута повна адсорбція Cd і Cu з усіх мінеральних фракцій, проте до 20% адсорбції Pb і Zn визначалася розмірами частинок. Встановлено, що величина адсорбції Cd і Zn нижче у змішаному розчині, але при цьому даний показник для Cu і Pb залишається без змін. Поглинаюча здатність зростає до 0.03 мг/г Cd, 0.60 мг/г Cu, 0.03 мг/г Pb, 0.60 мг/г Zn. В умовах нерухомого шару досягається до 93% адсорбції металів. Більше того, витік, що не перевищує 4%, свідчить про ефективність вилучення металів. Доведено за методом Тагучі, що вплив розмірів частинок не є настільки значним, щоб не враховувати роль інших параметрів, таких як концентрація розчину і час. Вилуговування іонів металів (Cd, Cu, Pb, Zn), що зберігаються на всіх мінералах після адсорбції в періодичних умовах, не перевищує 4% та вказує на те, що вони досить зберігаються на поверхні мінералів. Це є важливим результатом для подальшого використання мінералів у якості субстратів на полігонах. Наукова новизна. Вперше розміри частинок у хвостах збагачення мінералів розглянуті як параметр, який впливає на процес адсорбції важких металів, при цьому даний процес вивчений також щодо окремих розчинів металів, а не тільки їх суміші. Практична значимість. Виявленні відмінності у показниках адсорбції для фракцій частинок різного розміру не такі значущі, щоб обумовлювати необхідність їх подрібнення в технологічному процесі.Цель. Исследование влияния размеров частиц в хвостах обогащения известняка, известкового мрамора, доломита и доломитового мрамора на процесс адсорбции тяжелых металлов в неподвижном слое для оценки целесообразности технологии измельчения и/или просеивания в дальнейшем использования металлов. Методика. Для выполнения исследований образцы известняка и доломита доставлены компанией, занимающейся производством и продажей готовых бетонов, а также карьерами в Греции. Химический и минералогический состав образцов был определен рентгеновской флуоресценцией (XRF, ARL ADVANT XP), рентгеновской дифракцией (XRD, Siemens D-500) и атомно-абсорбционной спектрометрией (AAS, VARIAN AA240FS). Для исследования механизма адсорбции были измерены следующие параметры: рН в соответствии с ISO 6588, пористость и удельная площадь поверхности с помощью N2-адсорбции (NOVA-2200, версия 6.11) и катионообменная емкость (CEC) в соответствии с EPA 9081 на основе смешивания образца с избытком раствора ацетата натрия, в результате которого затем определялись добавленные катионы натрия для матричных катионов. Для сорбционных экспериментов были использованы отдельные растворы, содержащие 5 мг/л Cd, 5 мг/л Pb, 100 мг/л Cu, 100 мг/л Zn, полученные из аналитических стандартных растворов Fluka. После сорбционных исследований собранные сорбенты были подвергнуты исследованиям выщелачивания. Результаты. В процессе исследований была достигнута полная адсорбция Cd и Cu из всех минеральных фракций, однако до 20% адсорбции Pb и Zn определялась размерами частиц. Установлено, что величина адсорбции Cd и Zn ниже в смешанном растворе, но при этом данный показатель для Cu и Pb остается без изменений. Поглощающая способность возрастает до 0.03 мг/г Cd, 0.60 мг/г Cu, 0.03 мг/г Pb, 0.60 мг/г Zn. В усло-виях неподвижного слоя достигается до 93% адсорбции металлов. Более того, утечка, не превышающая 4%, свидетельствует об эффективности извлечения металлов. Доказано по методу Тагучи, что влияние размеров частиц не является настолько значительным, чтобы не учитывать роль других параметров, таких как концентрация раствора и время. Выщелачивание ионов металлов (Cd, Cu, Pb, Zn), сохраняющихся на всех минералах после адсорбции в периодических условиях, не превышает 4% и указывает на то, что они достаточно сохраняются на поверхности минералов. Это является важным результатом для дальнейшего использования минералов в качестве субстратов на полигонах. Научная новизна. Впервые размеры частиц в хвостах обогащения минералов рассмотрены как параметр, оказывающий влияние на процесс адсорбции тяжелых металлов, при этом данный процесс изучен также в отношении отдельных растворов металлов, а не только их смеси. Практическая значимость. Выявленные различия в показателях адсорбции для фракций частиц различного размера не столь значимы, чтобы обусловливать необходимость их измельчения в технологическом процессе.The present study did not originate under any of project and no funding was raised for research. However, we would like to thank especially Professor Angeliki Moutsatsou and the personal of the Laboratory of Inorganic and Analytical Chemistry of the Chemical Engineering School in the National Technical University of Athens for their various support during the experimental work required for the successful realization of the present study

Production and evaluation of electrospun polyaniline/biopolymer composite nanofibres for medical applications

The aim of this study is the production of a nanofibrous electroactive mat and the investigation of its potential use in tissue engineering, and more specifically for wound dressing purposes. The limitations regarding electrospinnability of the conducting polymer will be identified and addressed and the factors related to its biological properties will be evaluated. To this end, conducting polymer, polyaniline (PANI) was chosen as the electroactive component and blend electrospinning was identified as the most suitable method to produce continuous nanofibres containing PANI. Various biocompatible polymers and solvent systems were investigated for their suitability to assist in electrospinning and PEO (polyethylene oxide) and CH (chitosan) were chosen as carrier polymers for blend electrospinning of PANI. Consequently, CSA (Camphor-10-sulfonic acid (β)) doped PANI/PEO and CSA doped PANI/CH conducting nanofibrous mats were produced by electrospinning. The electrospinning windows for both blends were determined by using full factorial experimental designs. The combined effects of the humidity, voltage and flow rate on the fibre morphology and diameter were examined for both blends, demonstrating that the ambient humidity is the critical factor affecting the electrospinning process and determining the electrospinning window for a conducting polymer. Low humidity favors the formation of defect free fibres while high humidity either hinders fibre formation or causes the formation of defects on the fibres. In the case of PANI/PEO blends, different levels of PANI doping were investigated, and high level of doping with CSA was found to lead to the formation of crystalline structures. Data fitting was used to explore the behavior of conducting polymers using the case of PANI/PEO electrospinning and very good agreement between experimental and theoretical predictions was obtained for only a limited range of experimental conditions, whereas deviation was observed for all other sets of conditions. In the case of PANI/CH, the effect of different ratios of conducting polymer in the blend (0:1, 1:3, 3:5 and 1:1) was examined, as for the electrospinnability, resulting 3 nanofibrous morphology, mat contact angle, electrical conductivity, antibacterial activity and cellular biocompatibility. The incorporation of PANI in the electrospinning blend, affected the electrospinnability of the solution, making it more susceptible to RH deviations, and contributed to the decrease of nanofibre diameter. Higher PANI content was found to result in more hydrophobic and more conducting mats. The method that was used to stabilize the PANI/CH mats was also found to affect antibacterial activity and conductivity. The produced blend mats, exhibited antibacterial activity which was higher against Gram positive B. subtilis and lower against gram negative E. coli. The cellular biocompatibility was assessed with human osteoblasts and fibroblasts, in terms of cell proliferation rate as well as cell attachment and morphology. Cells of both cell lines adhered well and showed good growth rates on nanofibrous substrates of all blend ratios when compared to standard tissue culture plastic. Finally, amongst the PANI containing mats, the one of 1:3 PANI:CH ratio, was identified as the best to support osteoblast and fibroblast cell proliferation when compared to the pure chitosan

Estrogen Receptor Signaling and Its Relationship to Cytokines in Systemic Lupus Erythematosus

Dysregulation of cytokines is among the main abnormalities in Systemic Lupus Erythematosus (SLE). However, although, estrogens, which are known to be involved in lupus disease, influence cytokine production, the underlying molecular mechanisms remain poorly defined. Recent evidence demonstrates the presence of estrogen receptor in various cell types of the immune system, while divergent effects of estrogens on the cytokine regulation are thought to be implicated. In this paper, we provide an overview of the current knowledge as to how estrogen-induced modulation of cytokine production in SLE is mediated by the estrogen receptor while simultaneously clarifying various aspects of estrogen receptor signaling in this disease. The estrogen receptor subtypes, their structure, and the mode of action of estrogens by gene activation and via extranuclear effects are briefly presented. Results regarding the possible correlation between estrogen receptor gene polymorphisms and quantitative changes in the receptor protein to SLE pathology and cytokine production are reviewed

Investigating of the conservation problems of oil paintings on paper supports

The initial results of a research project on the investigation of problems presented by a collection of oil paintings on paper supports are presented. The project focuses on the effect of the oil medium on the deterioration of cellulose, on the materials and techniques used by the artists and on comprehension of the resulting problems. Non destructive methodology was used to record the behaviour of the materials when examined in several regions of the electromagnetic spectrum which gives an indication of areas of damage. . Various analytical techniques were applied to investigate the painting materials and supports in original works of art. The increase in rate of the oxidation of cellulose in paper, when the paper is coated in oil, is investigated by analyzing volatile organic compounds emitted during ageing tests. The assessment of the results obtained will act as a pilot for a more extensive program of research, the ultimate aim of which is the formulation of a recommended methodology as a tool for the evaluation of the condition of these types of works, as well as the determination of conservation and care parameters

Transformation of Industrial By-Products into Composite Photocatalytic Materials

The transformation of both calcareous and siliceous Greek power station by-products (lignite ashes) into novel composite materials with photocatalytic properties for environmental application was investigated. Particularly, a comparison between the development of coated ceramic substrates and the modification of ash surfaces is attempted. Specifically, a) the sintering process (1000 °C, 2 h) of both fly and bottom ash (either calcareous or siliceous) for their conversion into compacted ceramic substrates coated with TiO2 slurry and then further thermally treated (500 °C, 1 h) to acquire TiO2 film consistency onto the ceramic substrate and b) the process of TiO2 precipitation on lignite ash surfaces in acidic solution after neutralization, and estimation of the TiO2 percentage, are compared. The microstructures obtained were examined by XRD and SEM-EDX analysis. Vickers microhardness was also determined for the ceramic microstructures, with satisfactory results (up to 356HV). The energy gap measurements of the coatings were found to be between 3.02eV and 3.17eV, which is located between the energy gap of anatase (3.23eV) and rutile (3.02eV). The coating mass was about 0.059 g/cm2. The photocatalytic activity under visible and UV irradiation was investigated in aqueous solutions of methylene blue and methyl orange organic dyes, with encouraging results. A main advantage of the processes proposed is the immobilization of TiO2 onto largely available secondary resources, which can lead to production of value-added ‘green’ photocatalysts for the treatment of industrial effluents in the framework of circular economy

Automation in cell and gene therapy manufacturing:from past to future

As more and more cell and gene therapies are being developed and with the increasing number of regulatory approvals being obtained, there is an emerging and pressing need for industrial translation. Process efficiency, associated cost drivers and regulatory requirements are issues that need to be addressed before industrialisation of cell and gene therapies can be established. Automation has the potential to address these issues and pave the way towards commercialisation and mass production as it has been the case for ‘classical’ production industries. This review provides an insight into how automation can help address the manufacturing issues arising from the development of large-scale manufacturing processes for modern cell and gene therapy. The existing automated technologies with applicability in cell and gene therapy manufacturing are summarized and evaluated here

Conductive PANI fibres and determining factors for the electrospinning window

Polyaniline doped with CSA / PEO conductive nanofibres were produced by electrospinning. The electrospinning window was determined by using a three level, full factorial experimental design. The combined effects of the humidity, voltage and flow rate on the fibre morphology and diameter were examined demonstrating that the ambient humidity is the critical factor affecting the electrospinning process and determining the electrospinning window for a conductive polymer. Low humidity favors the formation of defect free fibres while high humidity either hinders fibre formation or causes the formation of defects on the fibres either due to jet discharge or due to water absorption and phase separation. High level of doping with CSA led to the formation of crystalline structures. Data fitting was used to explore the behavior of conductive polymers in electrospinning and very good agreement between experimental and theoretical predictions was obtained for only a limited range of experimental conditions, whereas deviation was observed for all other sets of conditions

Utilisation of lignite fly ash in oil sorption and energy saving during clinker production

Abstract The present study aims at developing an environmental application of lignite fly ash, which constitutes the main by-product of power production by lignite combustion and whose greater amount remains unutilised. In particular, its application in oil spill cleanup and the further utilisation of the resultant oilfly ash mixtures in energy saving during clinker production has been investigated. For the amelioration of the floating ability and the oil sorption capacity of lignite fly ash, the mixing with a cheap, light and porous agricultural by-product, such as sawdust, has been applied. The addition of 30-50% w/w sawdust results not only in amelioration of the behaviour of lignite fly ash when added to oil spill in marine environment, by contributing to better floating and total oil removal, but also in increase in its oil sorption capacity by up to 50-80%. The higher calorific value of the resultant oil-lignite fly ashsawdust mixtures rising up to that of oil and bituminous coal encourages their utilisation as alternative fuels in cement industry. The remaining after their combustion ash varies from 18 to 58% w/w and its chemical and mineralogical composition differentiates slightly from the initial one. Analyses showed that it is enriched in Al 2 O 3 , SiO 2 , reactive SiO 2 , Fe 2 O 3 , CaO, CaO f and SO 3 . An increase in phases, such as anhydrite, gehlenite, gismondine, portlandite, and a decrease in lime and calcite are observed. However, the change observed in its composition is not expected to change the composition of clinker produced