Removal of uranium(VI) from aqueous solutions and nuclear industry effluents using humic acid-immobilized zirconium-pillared clay

Removal of uranium [U(VI)] from aqueous solutions with humic acid-immobilized zirconium-pillared clay (HA-Zr-PILC) was investigated using a batch adsorption technique. The adsorbent was characterized using XRD, FTIR, SEM, TG/DTG, surface area analyzer and potentiometric titration. The effects of pH, contact time, initial concentration, adsorbent dose, and adsorption isotherm on the removal process were evaluated. A maximum removal of 97.6 ± 2.1 and 94.7 ± 3.3% was observed for an initial concentration of 50 and 100 mg L⁻¹, respectively at pH 6.0 and an adsorbent dose of 2.0 g L⁻¹. Equilibrium was achieved in approximately 180 min. The mechanism for the removal of U(VI) ions by HA-Zr-PILC was based on an ion exchange reaction. The experimental kinetic and isotherm data were analyzed using a second-order kinetic equation and Langmuir isotherm model, respectively. The monolayer adsorption capacity for U(VI) removal was found to be 132.68 ± 5.04 mg g⁻¹. An increase of temperature of the medium caused an increase in metal adsorption. Complete removal (≅100%) of U(VI) from 1.0 L of a simulated nuclear industry effluent sample containing 10.0 mg U(VI) ions was possible with 1.5 g of HA-Zr-PILC. The adsorbent was suitable for repeated use (over 4 cycles) without any noticeable loss of capacity.     

Removal of uranium (VI) from aqueous solution by adsorption of hematite

Hematite, a type of inorganic-sorptive medium, was used for the removal of U (VI) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature, calcium and magnesium ions were studied. The results indicated that the adsorption capacities are strongly affected by the solution pH, contact time and initial concentration. A higher pH favors higher U (VI) removal. The adsorption was also affected by temperature and calcium and magnesium ions, but the effect is very weak. The maximum adsorption capacity (q_m) only increased from 3.36 mg g⁻¹ to 3.54 mg g⁻¹ when the temperature was increased from 293 K to 318 K. A two-stage kinetic behavior was observed in the adsorption of uranium (VI): very rapid initial adsorption in a few minutes, followed by a long period of slower uptake. It was found that an increase in temperature resulted in a higher uranium (VI) loading per unit weight of the sorbent. The adsorption of uranium by hematite had good efficiency, and the equilibrium time of adsorbing uranium (VI) was about 6 h. The isothermal data were fitted with both Langmuir and Freundlich equations, but the data fitted the former better than the latter. The pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data, but the pseudo-second-order kinetic model was the best. The thermodynamic parameter ΔG⁰ were calculated, the negative ΔG⁰ values of uranium (VI) at different temperatures confirmed the adsorption processes were spontaneous.     

Removal of uranium(VI) from aqueous solutions by manganese oxide coated zeolite: discussion of adsorption isotherms and pH effect

This paper discusses the adsorption properties for uranium(VI) by manganese oxide coated zeolite (MOCZ). The removal of uranium(VI) from aqueous solution by adsorption onto MOCZ in a single-component system with various contact times, pH, competitive ions, temperatures and initial concentrations of uranium(VI) was investigated. The experimental results were fitted to the Langmuir, Freundlich and the three-parameter Redlich-Peterson model isotherms to obtain the characteristic parameters of each model. Both the Langmuir and Redlich-Peterson isotherms were found to best represent the measured adsorption data. According to the evaluation using the Langmuir equation, the maximum adsorption capacity of uranium(VI) ions onto MOCZ was 15.1 mg g(-1) at 293K and pH 4.0. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as DeltaG(0), DeltaH(0) and DeltaS(0), have been calculated. The thermodynamics of uranium(VI) ion/MOCZ system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent.     

Biosorption of uranium (VI) by immobilized Aspergillus fumigatus beads

Biosorption of uranium (VI) ions by immobilized Aspergillus fumigatus beads was investigated in a batch system. The influences of solution pH, biosorbent dose, U (VI) concentration, and contact time on U (VI) biosorption were studied. The results indicated that the adsorption capacity was strongly affected by the solution pH, the biosorbent dose and initial U (VI) concentration. Optimum biosorption was observed at pH 5.0, biosrobent dose (w/v) 2.5%, initial U (VI) concentration 60 mg L⁻¹. Biosorption equilibrium was established in 120 min. The adsorption process conformed to the Freunlich and Temkin isothermal adsorption models. The dynamic adsorption model conformed to pseudo-second order model.     

Redox chemistry of sulphate and uranium in a phosphogypsum tailings dump

The present study aims to assess the effect of redox conditions existing within the tailings dump on the stability of phosphogypsum (e.g. sulphate reduction) and uranium(VI). Phosphogypsum sampling and in-situ measurements were carried out at a coastal tailings dump in Vasiliko Cyprus, pH, E_H and solubility experiments were performed in simulated laboratory systems and thermodynamic calculations using MINTEQA2. Generally, in the open tailings dump oxidizing conditions predominate stabilizing sulphur and uranium in their hexavalent oxidation states. On the other hand, after the application of a soil/vegetative cover and in the presence of natural organic matter, anoxic conditions prevail (E_H < −70 mV) resulting in S(VI) and U(VI) reduction to S(−II) and U(IV), respectively. Although, the sulphide anion can form very insoluble compounds with heavy metal ions (e.g. Cd(II), Pb(II) etc.) and U(IV) oxide has very low solubility, partial reduction of sulphate to sulphide within gypsum may affect the stability of phosphogypsum resulting in enhanced erosion of the material by rain- and seawater and washing out of contaminants in particulate/colloidal form.     

Influence of Operating Conditions on the Removal Cd Ions from Aqueous Media by Adsorption Using Chlamydomonas Reinhardtii

Chlamydomonas reinhardtii(C.reinhardtii)was used to study adsorption of cadmium(Cd)from aqueous media within various experimental conditions.Results showed that the adsorption process was very fast,with most of the adsorption occurring within30 min of contact time and the equilibrium state was reached in about 60 min.The adsorption ability of the algae increases with the increasing adsorptions sites on cells.Maximum adsorption was observed at the initial Cd concentration of 100 mg/L and pH 6.0.The adsorption was markedly inhibited in the presence of calcium and magnesium ions at 10 mM and the Cd removal efficiency was reduced by 16.54% and 14.99% respectively.This study would be a finding of note with regard to practical wastewater treatment.     

Impact of water quality parameters on the sorption of U(VI) onto hematite

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH < 6.0, and outer-sphere surface complexation may be the main sorption mechanism. The sorption was independent of ionic strength at pH > 6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management.     

Equilibrium,kinetics and thermodynamics studies on adsorptive removal of cobalt ions from wastewater using MIL-100(Fe)

This study describes experiments in which MIL-100(Fe) was used to remove Co²⁺ ions from the waste water. The synthesised adsorbent was characterised by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction, Brunauer–Emmett–Teller (BET) and scanning electron microscope. Statistical analysis was used to investigate the effects of different parameters. From the obtained results, the removal efficiency was enhanced with increasing contact time and pH but decreased with increasing cobalt initial concentration. The maximum removal efficiency of Co⁺² was 93.4% under optimum conditions. The equilibrium adsorption data were best fitted to linearly transformed Freundlich isotherm. Adsorption kinetic data followed the pseudo second-order kinetic model. The maximum adsorption capacity of Co⁺² on to the MIL-100(Fe) was found to be 119 mg g^?1. The results showed that ?G of adsorption was negative, while ?H was positive which showed that the adsorption process was spontaneous and endothermic. The positive value of ?S showed that disordering and randomness increased at the solid–solution interface of cobalt ions with MIL-100(Fe) particles.     

Behavior and analysis of Cesium adsorption on montmorillonite mineral

The adsorption of Cs by montmorillonite and the effects of experimental conditions on adsorption were investigated by using ¹³⁴Cs as a radioactive tracer. Additionally, the Cs-adsorbed and the modified montmorillonite were analyzed by X-ray Diffractometer System (XRD) and Scanning Electron Microscopy (SEM). The results showed that the adsorption of Cs by montmorillonite was efficient in the initial concentration (C₀) of 30 μg/L Cs nitrate solution with 20 g/L montmorillonite at room temperature. In this condition, more than 98% Cs⁺ ions could be adsorbed at pH 8. The adsorption equilibrium was achieved within 5 min and the relationship between the concentration of Cs⁺ in aqueous solutions and adsorption capacities of Cs⁺ can be described by the Langmuir adsorption isotherm. The adsorption rate would decrease when temperature increase from 0 °C to 50 °C or in presence of coexistent K⁺, Na⁺ and Ca²⁺, while modification by (NH₄)₂SO₄, [Ag(NH₃)₂]⁺, [Cu(NH₃)₄]²⁺ or 450 °C could improve the adsorption abilities of montmorillonite for Cs⁺. However, more than 89% of adsorbed Cs⁺ on montmorillonite could be desorbed by 2 mol/L HNO₃ solutions. The XRD and SEM analysis further showed that the structure of the Cs-adsorbed or modified montmorillonite were different from that of the original one.     

Assessment of hydrothermally modified fly ash for the treatment of methylene blue dye in the textile industry wastewater

Dyes and pigments are one of the major water pollutants and if not discharged properly cause ecological disturbance. Considering this, the current study investigates the application of thermal power plant by-product, i.e., fly ash for the elimination of a hazardous methylene blue dye from its synthetic aqueous solution. Experiments were conducted in batch mode to study the effect of pH, temperature, adsorbent dose and contact time. Highest dye removal (94.3%) was achieved at pH 10 using adsorbent dose of 10 g/L in 90 min of contact time at 40 °C. However, for cost-effective operation at neutral pH and room temperature (30 °C), it yields 89.3% dye removal having similar dose and contact time. Equilibrium isotherms for adsorption were analyzed by Langmuir and Freundlich, Temkin and Dubinin–Radushkevich isotherm equations. The results revealed that the best fit model of adsorption closely followed Langmuir adsorption. Based on adsorption isotherm models, thermodynamics parameters ΔG, ΔH and ΔS were calculated. The negative value of ΔG and ΔH revealed that adsorption process was exothermic, spontaneous and physical. The present work suggests that through simple process hydrothermally modified fly ash has the potential to be used as cost-effective and efficient adsorbent for the treatment of wastewater from textile industries.     

Uranium isotopes in Tunisian bottled mineral waters

²³⁴U and ²³⁸U activity concentrations and their relative effective doses have been determined in 10 bottled mineral waters in Tunisia. Alpha spectrometry was used as technique to measure uranium isotopes. The obtained isotopic ratio ²³⁴U/²³⁸U varies between 1.1 and 3 which means that the two isotopes are not in radioactive equilibrium. Measured activity concentration varies between 3.2 and 40 mBq/l for ²³⁴U and between 1.5 and 26.3 mBq/l for ²³⁸U. Effective doses (assuming 2 litres per day of water consumption) coming from this two isotopes are found to vary between 0.16 and 2.02 μSv/a which is lower than the maximum recommended dose level by the WHO.     

Inhibition of microbial activity of activated sludge by ammonia in leachate

Leachate samples were collected from the West New Territory Landfill (WENT), Hong Kong, and characterized in the laboratory. The analytical results confirmed that it has a typical nature of aged leachate with a low BOD₅/COD ratio of 0.22 and a high strength of ammonia-nitrogen around 5 g/L. A lab-scale study was conducted to investigate the inhibition of microbial activity of the activated sludge. In the first test, glucose-based synthetic wastewater was used in two parallel reactors. The experimental results demonstrated that COD removal declined from 95.1 to 79.1% and the dehydrogenase activity of the sludge decreased from 11.04 to 4.22 μg TF/mg mixed liquor suspended solids (MLSS), when the ammonia-nitrogen concentration increased from 50 mg/L to 800 mg/L progressively. The remaining NH₃⁺-N residue in the treated wastewater increased from 0.58 mg/L to 649 mg/L extensively. In the second test, mixed wastewater samples containing glucose and raw leachate were fed into six parallel biological reactors and operated on batch mode. The experimental results showed COD removal decreased from 97.7 to 78.1% and the dehydrogenase activity decreased from 9.29 to 4.93 μg triphenyl formazon (TF)/mg MLSS, respectively, when the ammonia-nitrogen concentration increased within the same range. Microbial inhibition could also be substantiated by a decrease of specific oxygen uptake rate (SOUR) from 68 to 45 mg O₂/g MLSS. These results suggested leachate containing high-strength ammonia-nitrogen should be pretreated to an acceptable NH₄⁺-N level before it is fed into biological reactors.     

The removal of uranium from mining waste water using algal/microbial biomass

We describe a three step process for the removal of uranium (U) from dilute waste waters. Step one involves the sequestration of U on, in, and around aquatic plants such as algae. Cell wall ligands efficiently remove U(VI) from waste water. Growing algae continuously renew the cellular surface area. Step 2 is the removal of U-algal particulates from the water column to the sediments. Step 3 involves reducing U(VI) to U(IV) and transforming the ions into stable precipitates in the sediments. The algal cells provide organic carbon and other nutrients to heterotrophic microbial consortia to maintain the low E(H), within which the U is transformed. Among the microorganisms, algae are of predominant interest for the ecological engineer because of their ability to sequester U and because some algae can live under many extreme environments, often in abundance. Algae grow in a wide spectrum of water qualities, from alkaline environments (Chara, Nitella) to acidic mine drainage waste waters (Mougeotia, Ulothrix). If they could be induced to grow in waste waters, they would provide a simple, long-term means to remove U and other radionuclides from U mining effluents. This paper reviews the literature on algal and microbial adsorption, reduction, and transformation of U in waste streams, wetlands, lakes and oceans.     

Environmental tritium (³H) and hydrochemical investigations to evaluate groundwater in Varahi and Markandeya river basins, Karnataka, India

The present study aimed at assessing the activity of natural radionuclides (³H) and hydrochemical parameters (viz., pH, EC, F⁻, NO₃⁻, Cl⁻, Ca²⁺, Mg²⁺) in the groundwater used for domestic and irrigation purposes in the Varahi and Markandeya river basins to understand the levels of hydrochemical parameters in terms of the relative age(s) of the groundwater contained within the study area. The recorded environmental ³H content in Varahi and Markandeya river basins varied from 1.95 ± 0.25 T.U. to 11.35 ± 0.44 T.U. and 1.49 ± 0.75 T.U. to 9.17 ± 1.13 T.U. respectively. Majority of the samples in Varahi (93.34%) and Markandeya (93.75%) river basins being pre-modern water with modern recharge, significantly influenced by precipitation and river inflowing/sea water intrusion. The EC-Tritium and Tritium-Fluoride plots confirmed the existence of higher total dissolved solids (SEC > 500 μS/cm) and high fluoride (MAC > 1.5 mg/L) in groundwater of Markandeya river basin, attributed to relatively longer residence time of groundwater interacting with rock formations and vice versa in case of Varahi river basin. The tritium-EC and tritium-chloride plots indicated shallow and deep circulating groundwater types in Markandeya river basin and only shallow circulating groundwater type in Varahi river basin. Increasing Mg relative to Ca with decreasing tritium indicated the influence of incongruent dissolution of a dolomite phase. The samples with high nitrate (MAC > 45 mg/L) are waters that are actually mixtures of fresh water (containing very high nitrate, possibly from agricultural fertilizers) and older ‘unpolluted’ waters (containing low nitrate levels), strongly influenced by surface source.     

Uranium uptake by hydroponically cultivated crop plants

Hydroponicaly cultivated plants were grown on medium containing uranium. The appropriate concentrations of uranium for the experiments were selected on the basis of a standard ecotoxicity test. The most sensitive plant species was determined to be Lactuca sativa with an EC₅₀ value about 0.1 mM. Cucumis sativa represented the most resistant plant to uranium (EC₅₀ = 0.71 mM). Therefore, we used the uranium in a concentration range from 0.1 to 1 mM.Twenty different plant species were tested in hydroponic solution supplemented by 0.1 mM or 0.5 mM uranium concentration. The uranium accumulation of these plants varied from 0.16 mg/g DW to 0.011 mg/g DW. The highest uranium uptake was determined for Zea mays and the lowest for Arabidopsis thaliana. The amount of accumulated uranium was strongly influenced by uranium concentration in the cultivation medium. Autoradiography showed that uranium is mainly localized in the root system of the plants tested. Additional experiments demonstrated the possibility of influencing the uranium uptake from the cultivation medium by amendments. Tartaric acid was able to increase uranium uptake by Brassica oleracea and Sinapis alba up to 2.8 times or 1.9 times, respectively. Phosphate deficiency increased uranium uptake up to 4.5 times or 3.9 times, respectively, by Brassica oleracea and S. alba. In the case of deficiency of iron or presence of cadmium ions we did not find any increase in uranium accumulation.     

Combating dye pollution using cocoa pod husks: a sustainable approach

The adsorptive potential of activated carbon prepared by chemical activation of Cocoa pod husk (CPHAA) to remove Congo red (CR) dye from its aqueous solution was investigated in this study. CPHAA was characterised using Energy Dispersive X-Ray, Scanning Electron Micrograph and Fourier Transform Infrared Spectroscopy techniques. The effects of contact time, initial dye concentration, pH and solution temperature were studied. Equilibrium data were fitted to Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The equilibrium data were best represented by Langmuir isotherm model, with maximum monolayer adsorption capacity of 43.67 mg/g. The kinetic data were fitted to Pseudo-first-order, Pseudo-second-order, Elovich and Intraparticle diffusion models; the pseudo-second-order kinetic model provided the best correlation. Thermodynamic parameters such as standard enthalpy (ΔH^o), standard entropy (ΔS^o) and standard free energy (ΔG^o) were evaluated. The thermodynamic study showed that the process is endothermic, spontaneous and feasible. The mean free energy of adsorption shows that the mechanism is by physisorption. CPHAA was found to be an effective adsorbent for the removal of CR dye from aqueous solution.     

Highly elevated levels of perfluorooctane sulfonate and other perfluorinated acids found in biota and surface water downstream of an international airport, Hamilton, Ontario, Canada

Per- and poly-fluorinated compounds (PFCs), which include perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs) and various precursors, are used in a wide variety of industrial, commercial and domestic products. This includes aqueous film forming foam (AFFF), which is used by military and commercial airports as fire suppressants. In a preliminary assessment prior to this study, very high concentrations (> 1 ppm wet weight) of the PFSA, perfluorooctane sulfonate (PFOS), were discovered in the plasma of snapping turtles (Chelydra serpentina) collected in 2008 from Lake Niapenco in southern Ontario, Canada. We presently report on a suite of C₆ to C₁₅ PFCAs, C₄, C₆, C₈ and C₁₀ PFSAs, several PFC precursors (e.g. perfluorooctane sulfonamide, PFOSA), and a cyclic perfluorinated acid used in aircraft hydraulic fluid, perfluoroethylcyclohexane sulfonate (PFECHS) in surface water from the Welland River and Lake Niapenco, downstream of the John C. Munro International Airport, Hamilton, Ontario, Canada. Amphipods, shrimp, and water were sampled from the Welland River and Lake Niapenco, as well as local references. The same suite of PFCs in turtle plasma from Lake Niapenco was compared to those from other southern Ontario sites. PFOS dominated the sum PFCs in all substrates (e.g., > 99% in plasma of turtles downstream the Hamilton Airport, and 72.1 to 94.1% at all other sites). PFOS averaged 2223 (± 247.1 SE) ng/g in turtle plasma from Lake Niapenco, and ranged from 9.0 to 171.4 elsewhere. Mean PFOS in amphipods and in water were 518.1 (± 83.8) ng/g and 130.3 (± 43.6) ng/L downstream of the airport, and 19.1 (± 2.7) ng/g and 6.8 (± 0.5) ng/L at reference sites, respectively. Concentrations of selected PFCs declined with distance downstream from the airport. Although there was no known spill event or publicly reported use of AFFF associated with a fire event at the Hamilton airport, the airport is a likely major source of PFC contamination in the Welland River.     

Triclosan in wastewaters and biosolids from Australian wastewater treatment plants

Triclosan (TCS) is an antimicrobial agent widely used in many personal care products. This study investigated the occurrence of TCS in effluents, biosolids and surface waters, and its fate in wastewater treatment plants (WWTPs). The aqueous concentrations of TCS in nineteen effluents from Australian WWTPs ranged from 23 ng/L to 434 ng/L with a median concentration of 108 ng/L, while its concentrations in nineteen biosolids ranged from 0.09 mg/kg to 16.79 mg/kg on dry weight basis with a median concentration of 2.32 mg/kg. The removal rates for TCS in five selected WWTPs were found to range between 72% and 93%. Biological degradation was believed to be the predominant removal mechanism for TCS in the WWTPs. However, adsorption onto sludge also played a significant role in the removal of TCS in the WWTPs. TCS at concentrations up to 75 ng/L was detected in surface waters (outfall, upstream, and downstream) from five rivers receiving effluent discharge from WWTPs. Preliminary risk assessment based on the worst-case scenario showed that the TCS concentrations in surface waters might lead to risks to aquatic organisms such as algae. Based on the TCS levels in the biosolids, application of biosolids on agricultural land may also cause adverse effects in the soil environment.     

A rapid isotope ratio analysis protocol for nuclear solid materials using nano-second laser-ablation time-of-flight ICP-MS

The analysis of the isotopic composition of nuclear or non-nuclear solid materials is performed in a variety of fields, e.g., for quality assurance in the production of nuclear fuels, as signatures in forensics, nuclear safeguards, and non-proliferation control, in material characterization, geology, and archeology. We have investigated the capability of laser ablation (New Wave Research, 213 nm) coupled to time-of-flight (TOF) ICP-MS (GBC OptiMass 8000) as a rapid analytical protocol for multi-isotope screening of nuclear and non-nuclear solid samples. This includes natural and non-natural isotopic compositions for elements including Cu, Zr, Mo, Cd, In, Ba, Ta, W, Re, Pt, Pb, and U, in pure metals, alloys, and glasses. Without correcting for mass bias (mass fractionation), an overall precision and accuracy of about 4% (1σ) can be achieved by minimizing the deposited laser power and thus fractionation (mass removal based on thermal properties). The precision and accuracy in combination with literally no or minimized sample preparation enables a rapid isotope screening of solid samples that is of particular interest to support nuclear forensic and safeguard analysis.     

Study on biosorption kinetics and thermodynamics of uranium by Citrobacter freudii

Biosorption has been developed as an effective and economic method to treat wastewater containing low concentrations of metal pollutants. In this study, a bacterium, Citrobacter freudii, was used as a biosorbent to adsorb uranium ions. The thermodynamics and kinetics of this adsorption, as well as its mechanism, were investigated. The results indicated that the biosorption rate could be better described by a pseudo 2nd-order model than a pseudo 1st-order model. The adsorption of U (VI) proceeded very rapidly in the first 30min and subsequently slowed down continuously for a long period. The biosorption isotherm of uranium by C. freudii could be described well by the Langmuir or Freundlich isotherm, and the latter was better. The thermodynamics parameters, DeltaH degrees , DeltaG degrees , and DeltaS degrees were calculated according to the results of the experiment, which showed this biosorption as being endothermic and spontaneous. The authors investigated the active sites of bacteria for biosorption and the results proved that carboxyl in the cell wall played an important role in biosorption.