Excess fluoride (F-) in drinking water poses a health threat to millions of people around the world. In the present work, activated alumina (AA) has been used as an adsorbent. Data obtained from batch experiments were fitted to the (i) pseudo-first order, (ii) pseudo-second order, and (iii) Langmuir kinetic model. Model (ii) performed better than model (i), and fitted the data well. However, the rate constant for adsorption ka had to be varied as a function of the initial concentration of F- in the liquid phase c0. A more satisfactory approach is provided by Langmuir model, which fitted the data reasonably even though ka was independent of c0. Shreyas (2008) developed a model for the batch adsorption of F- onto porous pellets of AA. Some errors were detected in his computer program were corrected. The parameters of the model were estimated by fitting predictions to data. The parameter values suggest that the adsorption process is likely to be diffusion limited. Column experiments were conducted as follows. The pellets were soaked in deionized water for a time ts before they were loaded into columns. A feed solution having a fluoride concentration cf = 3 mg/L was fed to column and the concentration of F- in the exit stream ce was measured at regular intervals. Breakthrough was deemed to have occurred when ce exceeded the permissible limit (= 1 mg/L). Constant values of the bed height H, and the empty bed contact time tc were used in the experiments. The volume of treated water V, scaled by the volume of the bed Vb, varied strongly with the soaking time ts, with a maximum at ts = 24 h. To understand the possible reasons for this behaviour, XRD, FESEM, and FTIR were used to characterize the surface of AA. Though the concentrations of the surface hydroxyl groups may influence the adsorption of F-, FTIR studies show there is no direct correlation between V/Vb and the concentrations of these groups. The FESEM and XRD studies indicate that fresh AA consists mainly of boehmite, which gradually converted to gibbsite during soaking. For fixed values of H and tc, the dimensionless volume of treated water V/Vb was a maximum at D = 45 mm. This behaviour may be caused by wall effects for small values of D and by occurrence of quasi-static regions near the wall for large values of D. The cost of treated of water was Rs. 0.42/L. It decreased slightly to Rs. 0.37/L after one regeneration cycle, but increased to Rs. 0.41/L after two cycles. The volume of treated water after two regeneration cycles was 595 L/kg. The concentration of Al3+ ions ca in the treated water increased and exceeded the permissible limit of 0.2 mg/L as the number of regeneration cycles increased. The concentration of F- in regeneration effluent cre was in the range 32-70 mg/L. The effluent was subjected to solar distillation, leading to a distillate whose fluoride concentration F- was in the range 9-12 mg/L. The distillate can be discharged into the public sewers, as the permissible limit is 15 mg/L.

No description available.

Excess Fluoride in drinking water is a cause for concern in several countries in the world. Various techniques have been developed to mitigate the harmful effects of fluoride. In the present work, a combined alum and activated alumina (AA) process has been investigated. Tap water with sodium fluoride dissolved in it to produce a solution having a fluoride concentration of 5 mg/L was used as the feed. It was found that pretreatment with alum extends the time required for the regeneration of the AA column. The volume of water treated increased by 89% compared to AA process alone. Though the regeneration of the AA column has been well documented, subtle issues have ot been reported. The disposal of regeneration effluent is a concern in adsorption-based processes. This study aims to examine some of the issues involved in the regeneration of the AA column such as disposal of effluent, and the quantity of acid and alkali required. The regeneration effluent from the combined process, which had a fluoride concentration of 10-16 mg/L was treated in a solar still. The distillate from the still had a fluoride concentration of 2-3 mg/L, which is much lower than the concentration of the regeneration effluent. The cost of treatment decreased with each regeneration cycle and after four regenerations the cost was Rs 0.5/L of treated water. The volume of water treated after four regenerations was 307 L/Kg of AA. Studies were also done using field water from Banavara, Hassan district, Karnataka, which had a fluoride concentration of 3,0-3.5 mg/L. The combined process successfully produced treated water having an acceptable fluoride concentration. After one regeneration cycle, the operating cost was Rs. 1/L of treated water. Studies have also been conducted on a point-of-use water filter containing a bed of AA pellets. The filter was provided by an organization called TIDE. The present results appear to suggest that a column with a smaller diameter than the TIDE filter has a better removal capacity. Ceramic candles are widely used for water filtration as they are readily available and inexpensive. Hence they are suitable for household water treatment purposes. In the present work, ceramic candles have been impregnated with nano-size alumina and nano-size magnesium oxide and tested for their defluoridation capacity. The nanoparticles were generated in situ in the pores of the candle by solution combustion synthesis. It has been found the candle impregnated with nano-size magnesium oxide has a higher defluoridation capacity than nano-size alumina. Estimation of the particle size in the samples of treated water did not give conclusive evidence for the presence or absence of nanoparticles. The volume of water treated was low and the cost of treatment was high (Rs. 12/L for the candle impregnated with MgO). Hence such candles are unsuitable for defluoridation. Batch adsorption has been employed to measure the adsorption capacity of adsorbents. A model to capture the overall picture of the batch adsorption process, obtaining the kinetic and transport parameters involved has been developed. The mathematical model takes into account external mass transfer resistance, intraparticle diffusion, adsorption, and desorption. The equilibrium adsorption data was fitted using the Langmuir isotherm. The governing equations were solved using a finite difference technique known as the Laasonen method. The parameters were estimated by fitting two sets of data using a MATLAB function. The values estimated suggest that the adsorption process may not be diffusion-limited, in contrast to the assumption commonly used in the literature. The estimated parameter values were used to predict the concentration profiles for the other data sets. It was found that predicted and measured profiles agreed reasonably well.

FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / Neste trabalho foram realizados estudos de adsorÃÃo em batelada e de oxidaÃÃo avanÃada para a remoÃÃo de fenol (F), 2-nitrofenol (2NF) e 4-nitrofenol (4NF) em soluÃÃo aquosa. Nos estudos de adsorÃÃo foram empregados como adsorventes o pà de bagaÃo da casca de coco in natura (BIN), pà de bagaÃo in natura tratado com HCl 1,0 M (BT) e carvÃo ativado (CA) proveniente da carbonizaÃÃo a 250ÂC do pà de bagaÃo tratado com Ãcido. Experimentos de equilÃbrio e cinÃtica de adsorÃÃo foram realizados nas temperaturas de 28, 40 e 50ÂC. Isotermas de Langmuir e Freundlich correlacionaram bem os dados de equilÃbrio, indicando capacidades de adsorÃÃo (qmÃx) que aumentaram na ordem: CA >>> BT > BIN. Este comportamento denota uma adsorÃÃo caracterizada pelas interaÃÃes entre os elÃtrons  dos anÃis aromÃticos e os elÃtrons  das camadas grafÃticas do carvÃo, a qual à mais intensa que a verificada nos materiais celulÃsicos onde predomina a formaÃÃo de complexos doador-receptor entre os sÃtios oxigenados localizados na superfÃcie do adsorvente e o anel aromÃtico dos compostos fenÃlicos. Os melhores resultados de qmÃx em carvÃo ativado e pà de bagaÃo tratado com Ãcido foram obtidos para a adsorÃÃo de 2-nitrofenol à temperatura ambiente (28ÂC), correspondentes aos valores de 17,1 e 1,39 mg/g, respectivamente. Do ponto de vista cinÃtico o modelo de pseudo-segunda ordem apresentou melhor ajuste dos dados experimentais. Por outro lado, processos oxidativos avanÃados (POAs) das molÃculas fenÃlicas foram conduzidos para os tratamentos fotolÃtico (UV), fotoquÃmico (UV/H2O2), Fenton (Fe2+/H2O2) e eletroquÃmico com anodos dimensionalmente estÃveis (ADEs) de Ru0,3Ti0,7O2, Ru0,3Ti0,4Sn0,3O2 e Ru0,3Sn0,7O2. Os processos Fenton e fotoassistidos apresentaram condiÃÃes Ãtimas nas concentraÃÃes de 1,0 mM em Ãons Fe2+e 3,0 mM em H2O2 e taxa de radiaÃÃo (I0) de 64 mW/cm2. Os Ãxidos eletrocatalÃticos foram preparados por termodecomposiÃÃo de cloretos precursores a 500oC atà a formaÃÃo de filmes com 2,0 Âm de espessura sobre um suporte de titÃnio. A caracterizaÃÃo pelas tÃcnicas de EDX, MEV e Voltametria CÃclica mostrou composiÃÃes praticamente estequiomÃtricas, morfologia estrutural tipo cracked mud e elevado sobrepotencial para a reaÃÃo de desprendimento de oxigÃnio (RDO). Estudos de oxidaÃÃo para as molÃculas fenÃlicas mostraram o 2-nitrofenol como a espÃcie mais oxidÃvel e o fenol comum como a espÃcie menos reativa. As eficiÃncias de degradaÃÃo dos processos fotoassistidos foram particularmente elevadas (superiores a 80%) enquanto o sistema Fenton apresentou taxas de remoÃÃo entre 60 e 78%. A modelagem cinÃtica segundo o modelo de pseudo-primeira ordem adotado permitiu um bom ajuste dos dados experimentais. Os valores da constante cinÃtica 1/ (min-1) a 28ÂC mostraram a seguinte ordem: Fenton (8,16 min-1) > fotoquÃmico (6,95 min-1) >> fotolÃtico (1,98 min-1). Em adiÃÃo, estudos usando anodos eletrocatalÃticos (ADEs) a potencial constante de eletrÃlise de 2,0 V mostraram degradaÃÃes superiores a 93% para os nitrofenÃis e entre 65 e 86% para o fenol. Em termos, considerado o tipo de ADE empregado, a eficiÃncia de eletrooxidaÃÃo à temperatura ambiente obedece a seguinte ordem de eficiÃncia: Ru0,3Ti0,7O2 > Ru0,3Ti0,4Sn0,3O2 > Ru0,3Sn0,7O2. A anÃlise espectroscÃpica para identificaÃÃo de co-produtos indicou completa mineralizaÃÃo dos compostos fenÃlicos nos processos fotoquÃmico e eletroquÃmico, enquanto que nos processos Fenton e fotolÃtico foram detectados traÃos de produtos hidroxilados. Em geral, os resultados obtidos confirmam os processos adsortivos e oxidativos como tratamentos promissores para a despoluiÃÃo de sistemas aquosos contendo fenÃis e nitrofenÃis / In the present work the batch adsorption and advanced oxidation of phenol (F), 2-nitrophenol (2NF) and 4-nitrophenol (4NF) in aqueous phase has been studied. The adsorption experiments were conducted onto coconut shell powder (BIN), coconut shell powder treated with HCl 1.0M (BT) and coconut shell-based activated carbon (CA) obtained from carbonization at low temperature (250ÂC). Equilibrium and kinetic studies were carried out at temperatures of 28, 40 and 50ÂC. Langmuir and Freundlich isotherms correlated well the equilibrium data, indicating the adsorption capacity (qmax) increased in the order: AC>>> BT> BIN. This behavior denotes an adsorption characterized by dispersive interactions between the -electrons of the graphitic carbon basal planes and those of the aromatic rings of the adsorbate, which is more intense when compared to the cellulose materials where are dominant the donor-acceptor complex formation between the oxygenated sites onto adsorbent and aromatic rings of phenol compounds. The best results of qmax in activated carbon and coconut shell powder treated with acid were obtained for the adsorption of 2-nitrophenol at room temperature (28ÂC), corresponding to values of 17.1 and 1.39 mg/g, respectively. In all cases, the adsorption kinetics could be satisfactorily fitted by a pseudo-second order model. Advanced oxidation processes (AOP) were carried out for treatments such photolytic (UV), photochemical (UV/H2O2), Fenton (Fe2+/H2O2) and electrochemical oxidation with dimensionally stable anodes (DSA) type Ti/Ru0.3Ti0.7O2, Ti/Ru0.3Ti0.4Sn0.3O2 and Ti/Ru0,3Sn0,7O2. The Fenton and photoassisted tests were performed to optimized conditions of 1.0 mM of Fe2+ ions, 3.0 mM of H2O2 and radiation intensity (I0) of 64 mW/cm2. Particularly, electrocatalytic oxides were prepared by thermal decomposition of chloride precursors to 500oC until the formation of films with thickness constant of 2μm on titanium support. The characterization by EDX, SEM and Cyclic Voltammetry techniques showed a nearly stoichiometric composition, morphology type âcracked mudâ and elevated overpotencial from oxygen evolution reaction (OER). Degradation efficiencies in photoassisted processes were particularly high (> 80%) while in the Fenton system this values ranged between 60 and 78%. The kinetic modelling using the equation of pseudo-first order adopted allowed a good fit of experimental data. The values of kinetic constant 1/ (min-1) at room temperature showed the following order: Fenton (8.16 min-1) > Photochemical (6.95 min-1) >> photolytic (1.98 min-1). In addition, studies using the electrocatalytic anodes at constant potential electrolysis of 2.0 V showed almost total degradation for the nitrophenols (> 93%) and moderate removal efficiencies for phenol (between 65 and 86%). In terms, considered the type of anode employed the electrooxidation efficiency at room temperature increase in the following order of reactivity: Ru0.3Ti0.7O2 > Ru0.3Ti0.4Sn0.3O2 > Ru0.3Sn0.7O2. Thus, the results confirm the applicability of adsorption and advanced oxidation processes as promising treatments in the remediation of aqueous systems containing phenol and nitrophenols

Onsite wastewater treatment systems in Sweden are getting old and many of them lack sufficient phosphorus, nitrogen and organic carbon reduction. Biochar is a material that has been suggested as an alternative to the common sand or soil used in onsite wastewater treatment systems. The objective of this study was to compare the phosphorus removal capacity between three different modified biochars and one untreated biochar in a batch adsorption and column filter experiment. The modifications included impregnation of ferric chloride (FeCl3), calcium oxide (CaO) and untreated biochar mixed with the commercial phosphorus removal product Polonite. To further study nitrogen removal a filter with one vertical unsaturated section followed by one saturated horizontal flow section was installed. The batch adsorption experiment showed that CaO impregnated biochar had the highest phosphorus adsorption, i.e. of 0.30 ± 0.03 mg/g in a 3.3 mg/L phosphorus solution. However, the maximum adsorption capacity was calculated to be higher for the FeCl3 impregnated biochar (3.21 ± 0.01 mg/g) than the other biochar types. The pseudo 2nd order kinetic model proved better fit than the pseudo 1st order model for all biochars which suggest that chemical adsorption was important. Phosphorus adsorption to the untreated and FeCl3 impregnated biochar fitted the Langmuir adsorption isotherm model best. This indicates that the adsorption can be modeled as a homogenous monolayer process. The CaO impregnated and Polonite mixed biochars fitted the Freundlich adsorption model best which is an indicative of heterogenic adsorption. CaO and FeCl3 impregnated biochars had the highest total phosphorus (Tot-P) reduction of 90 ± 8 % and 92 ± 4 % respectively. The Polonite mixed biochar had a Tot-P reduction of 65 ± 14 % and the untreated biochar had a reduction of 43 ± 24 %. However, the effluent of the CaO impregnated biochar filter acquired a red-brown tint and a precipitation that might be an indication of incomplete impregnation of the biochar. The FeCl3 effluent had a very low pH. This can be a problem if the material is to be used in full-scale treatment system together with biological treatment for nitrogen that require a higher pH. The nitrogen removal filter showed a total nitrogen removal of 62 ± 16 % which is high compared to conventional onsite wastewater treatment systems. Batch adsorption and filter experiment confirms impregnated biochar as a promising replacement or addition to onsite wastewater treatment systems for phosphorus removal. However the removal of organic carbon (as chemical oxygen demand COD) in the filters was lower than expected and further investigation of organic carbon removal needs to be studied to see if these four biochars are suitable in real onsite wastewater treatment systems. / Många av Sveriges små avloppssystem är gamla och saknar tillräcklig rening av fosfor, kväve och organiskt material. Följden är förorenat grundvatten samt övergödning i hav, sjöar och vattendrag. Lösningar för att förbättra fosfor- och kvävereningen finns på marknaden men många har visat brister i rening och robusthet. Biokol är ett material som har föreslagits som ersättare till jord eller sand i mark och infiltrationsbäddar. Denna studie syftade till att i skak- och kolonnfilterexperiment jämföra fosforreduktion mellan tre modifierade biokol och ett obehandlat biokol. Modifieringen av biokolet innebar impregnering med järnklorid (FeCl3), kalciumoxid (CaO) samt blandning med Polonite som är en kommersiell produkt för fosforrening. För att undersöka förbättring av kväverening installerades även ett filter med obehandlat biokol där en vertikal aerob modul kombinerades med en efterföljande horisontell anaerob modul. Skakstudien där biokolen skakades i 3.3 mg/L fosforlösning visade att adsorptionen var högst i det CaO-impregnerade biokolet, 0.3 ± 0.03 mg/g. Den maximala potentiella fosforadsorptionen beräknades dock vara högst för biokolet som impregnerats med FeCl3, 3.21 ± 0.01 mg/g. Skakförsöket visade också att fosforadsorptionen var främst kemisk då adsorptionen passade bättre med pseudo andra ordningens modell än pseudo första. Adsorption av fosfor på obehandlat biokol och FeCl3 impregnerat biokol modellerades bäst med Langmuir modellen, vilket tyder på en homogen adsorption. Det Polonite-blandade biokolet och CaO-impregnerade biokolet modellerades bäst med Freundlich modellen vilket är en indikation på en heterogen adsorptionsprocess. Biokol impregnerat med CaO och FeCl3 gav de högsta totalfosforreduktionerna på 90 ± 8 % respektive 92 ± 4 %. Biokolet som var blandat med Polonite hade en reduktion på 65 ± 14 % och det obehandlade biokolet 43 ± 24 %. Ett problem med filtratet från CaO-filtret var att det fick en rödbrun färg samt en fällning vilket kan ha berott på ofullständig pyrolysering och impregnering. Filtratet från det FeCl3 impregnerade biokolet hade mycket lågt pH vilket kan vara problematiskt om mikrobiologisk tillväxt i filtret för rening av kväve och organiskt material vill uppnås. Filtret för kväverening gav en total kvävereduktion på 62 ± 16 % vilket är högre än kommersiella system. Resultaten från skak och filterstudien visade på att impregnerade biokol kan ge en förbättrad fosforrening om de skulle användas i små avloppssystem. Rening av organiskt material, kemisk syreförbrukning (COD), var dock låg i alla filter och behöver studeras ytterligare för att avgöra om dessa biokol är lämpliga för småskalig avloppsvattenrening.

Finding economical and environmentally friendly processes to recover heavy metals (HMs) from spent batteries is a research priority to move toward sustainability. Adsorption seems an acceptable procedure to replace the current separation/purification stage of hydrometallurgical techniques. Chitosan is an efficient adsorbent for HM uptake from aqueous solutions. Nevertheless, in practice, chitosan modification is unavoidable to improve its physicochemical properties. Sodium tripolyphosphate is an environmentally benign crosslinker that can be used for chitosan modification. In addition, ion-imprinting technique could potentially enhance the adsorption efficiency and selectivity of crosslinked chitosan. Considering the above, the primary purposes of this research were: investigating the adsorption efficiency of chitosan for heavy metals uptake from synthetic solutions; modifying chitosan by crosslinking alone and combined with ion-imprinting techniques to improve the physicochemical properties as well as adsorption capacity and selectivity of chitosan; evaluating and comparing the adsorption efficiency of modified chitosan beads for the adsorption of Cd(II), Ni(II) and Co(II) in single and multicomponent batch adsorption systems. Chitosan and sodium tripolyphosphate crosslinked chitosan beads were prepared to remove Cd(II) from aqueous solution in the first phase. FTIR and XRD of the synthesized beads showed partial consumption of chitosan amine groups and a decrease in crystallinity of chitosan structure over crosslinking reaction. The isotherm and thermodynamic studies showed that Langmuir isotherm was the best fit to the experimental data of Cd(II) adsorption on crosslinked chitosan and all the adsorption reactions were endothermic and spontaneous. A reduced quadratic model, constructed by the Response Surface Methodology (RSM), indicated that the Cd(II) adsorption uptake of 99.87 (mg/g) was achieved at 55 °C and 2.92 % (w/v) crosslinking degree. Then, chitosan and crosslinked chitosan beads by sodium tripolyphosphate were used for Ni(II) adsorption from aqueous media in the second phase. The BET characterization showed that increasing the crosslinking degree reduced the chitosan beads' surface area and their total pore volume. The Langmuir model described the experimental results best and showed that the maximum adsorption capacity of chitosan (80.00 mg/g) decreased after crosslinking (52.36 mg/g). In addition, a reduced quadratic model with a correlation coefficient of 0.96 was established to correlate the adsorption uptake of Ni(II) with pH and crosslinking degree. In the third phase, the adsorption of Ni(II) and Cd(II) ions from single and binary metal ions solutions onto chitosan and crosslinked chitosan beads was studied. The extended Freundlich model fitted the adsorption equilibrium data in the binary system, implying the existence of preference in the order of Ni(II) > Cd(II). Desorption studies with a mixture of NaCl and H2SO4 were also conducted during this phase, demonstrating a desorption efficiency of greater than 85 %. In the fourth phase, the removal of cadmium from aqueous solution was examined using a novel Cd(II)-imprinted crosslinked chitosan. SEM, FTIR, TGA, and BET characterizations revealed that the ion-imprinted chitosan beads had better physicochemical properties than chitosan beads and superior potential adsorption properties than non-imprinted crosslinked chitosan beads. The isotherm and thermodynamic studies revealed that the Langmuir isotherm fitted the Cd(II) experimental data the best, and the adsorption reactions were spontaneous and endothermic. The kinetics data were also best fitted by the pseudo-second-order equation. Finally, the ion-imprinted crosslinked chitosan beads were employed for the selective adsorption of Cd(II) in a competitive adsorption system of Cd(II)-Ni(II)-Co(II) in phase five. The characterization of the prepared adsorbents was performed using XRD and BET, showing a higher surface area of ion-imprinted crosslinked chitosan than non-imprinted crosslinked chitosan beads. The Extended Langmuir model fitted the experimental results obtained from the multi-component system, indicating that ion-imprinted crosslinked chitosan had a higher total metal uptake with better selectivity toward Cd(II) uptake compared to non-imprinted crosslinked chitosan. Studying the adsorption mechanism in a ternary system showed that the adsorption was governed by chemical binding and ion exchange mechanisms in the ternary system. In conclusion, crosslinking by sodium tripolyphosphate improved chitosan physiochemical properties; however, it resulted in a decrease in HM adsorption uptake. The RSM was used to assess the effect of pH, temperature, and crosslinking degree and optimize the adsorption uptake of chitosan. Also, ion-imprinting was effective in enhancing the adsorption capacity and selectivity of crosslinked chitosan for the ion used as a template (Cd(II)) in preparing ion-imprinted crosslinked chitosan.