Base Treated Cogon Grass (Imperata cylindrica) as an Adsorbent for the Removal of Ni(II): Kinetic,Isothermal and Fixed‐bed Column Studies

The adsorption of Ni(II) from aqueous solutions using base treated cogon grass or Imperata cylindrica (NHIC) was performed under batch and column modes. Batch experiments were conducted to determine the factors affecting adsorption such as pH, adsorbent dosage, initial nickel concentration, contact time and temperature. The fixed‐bed column experiment was performed to determine the practical applicability of NHIC and to obtain the breakthrough curve. Adsorption was fast as equilibrium was achieved within 60 min, and was best described by the pseudo second order model. According to the Langmuir model, a maximum adsorption capacity of 6.96 mg/g was observed at pH 5 and at a temperature of 313 K. Thermodynamic parameters such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated, and indicated that adsorption was a spontaneous and endothermic process. The mechanistic pathway of Ni(II) uptake was examined by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) spectroscopy. The Thomas and Yoon‐Nelson models were used to analyze the fixed‐bed column data.     

Removal of Copper,Nickel, and Zinc Ions from Electroplating Rinse Water

Removal of copper, nickel, and zinc ions from synthetic electroplating rinse water was investigated using cationic exchange resin (Ceralite IR 120). Batch ion exchange studies were carried out to optimize the various experimental parameters (such as contact time, pH, and dosage). Influence of co‐existing cations, chelating agent EDTA on the removal of metal ion of interest was also studied. Sorption isotherm data obtained at different experimental conditions were fitted with Langmuir, Freundlich, Redlich–Peterson, and Toth models. A maximum adsorption capacity of 164 mg g^?1 for Cu(II), 109 mg g^?1 for Ni(II), and 105 mg g^?1 for Zn(II) was observed at optimum experimental conditions according to Langmuir model. The kinetic data for metal ions adsorption process follows pseudo second‐order. Presence of EDTA and co‐ions markedly alters the metal ion removal. Continuous column ion exchange experiments were also conducted. The breakeven point of the column was obtained after recovering effectively several liters of rinse water. The treated rinse water could be recycled in rinsing operations. The Thomas and Adams–Bohart models were applied to column studies and the constants were evaluated. Desorption of the adsorbed metal ions from the resin column was studied by conducting a model experiments with Cu(II) ions loaded ion exchange resin column using sulfuric acid as eluant. A novel lead oxide coated Ti substrate dimensionally stable (DSA) anode was prepared for recovery of copper ions as metal foil from regenerated liquor by electro winning at different current densities (50–300 A cm^?2).     

Biosorption of Cadmium(II) Ions by Citrus Peels in a Packed Bed Column: Effect of Process Parameters and Comparison of Different Breakthrough Curve Models

The efficiency of low cost citrus peels as biosorbents for removal of cadmium ions from aqueous solution was investigated in a fixed bed column, a process that could be applied to treat industrial wastewaters similar to commonly used ion exchange columns. Effluent concentration versus time profiles (i.e., breakthrough curves) were experimentally determined in a laboratory‐scale packed bed column for varying operational parameters such as flow rate (2, 9, and 15.5 mL/min), influent cadmium concentration (5, 10, and 15 mg/L), and bed height (24, 48, and 72 cm) at pH 5.5. Column operation was most efficient for empty bed contact times of at least 10 min, which were apparently necessary for mass transfer. While the sorption capacity was largely unaffected by operational variables, the Thomas (Th) rate constant increased with the flow rate, and slightly decreased with increasing column length. Three widely used semi‐mechanistic models (Th, Bohart–Adams, and Yoon–Nelson) were shown to be equivalent and the generalized model was compared with a two‐parameter empirical model (dose‐response). The latter was found to be able to better simulate the breakthrough curve in the region of breakthrough and saturation.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

Biosorption of Nickel from Synthetic and Electroplating Industrial Solutions using a Green Marine Algae Ulva reticulata

The present work investigated the biosorption of nickel from synthetic and electroplating industrial effluents using a green marine algae Ulva reticulata. Preliminary batch results imply that pH 4.5 was optimum for nickel uptake and the isotherm experiments conducted at this pH condition indicated that U. reticulata can biosorb 62.3 mg g^–1 nickel ions from synthetic solutions, according to the Langmuir model. Desorption was effective and practical using 0.1 M CaCl₂ (pH 2.5, HCl) and the biomass was regenerated and reused for three cycles. Continuous biosorption experiments were performed in an upflow packed column (2 cm I.D and 35 cm height). Among the two electroplating effluents used, effluent‐1 is characterized by excess co‐ions and high nickel ion content. This influenced the column nickel uptake with U. reticulata exhibiting 52.1 mg g^–1 in the case of effluent‐1 compared to 56.5 mg g^–1 in the case of synthetic solution. On the other hand U. reticulata performed well in effluent‐2 with uptakes of 53.3 and 54.3 mg g^–1 for effluent‐2 and synthetic solution, respectively. Mathematical modeling of column experimental data was performed using nonlinear forms of the Thomas‐ and modified dose‐response models, with the latter able to simulate breakthrough curves with high correlation coefficients.     

Kinetics,Mechanistic and Thermodynamics of Zn(II) Ion Sorption: A Modeling Approach

Biosorption potential of Cedrus deodara sawdust (CDS) in terms of sorption of Zn(II) ion across liquid phase has been evaluated in the present investigation. The surface of the CDS biomass before the sorption of Zn(II) ions seemed to be more porous, non‐crystalline and heterogeneous. The maximum uptake capacity of CDS was 97.39 mg g^?1. Sorption of Zn(II) ion on the surface of CDS sawdust was maximum at pH 5, temperature 45°C, initial concentration of Zn(II) ion 100 mg L^?1, biomass dose 1 g L^?1, contact time 150 min, and agitation rate 160 rpm. Pseudo second‐order kinetics with the highest linear regression coefficient (R² = 0.99), and lowest values of error functions, i.e., chi (χ²) and sum of square errors (SSE) against pseudo first‐order rate kinetics showed that the sorption of Zn(II) ion on the surface of CDS was mediated by chemosoprtive forces of attraction rather than physical adsorption. Mechanistically, relatively higher proportion of sorption of Zn(II) ion in early phase of contact time was profoundly explained by Bangham's equation and film diffusivity (D^f). Intraparticle or pore diffusion (D_p) of Zn(II) ion inside the pores of CDS was rate limiting step at the later stage of contact time. Furthermore, the thermodynamic study on sorption of metal ion delineated the fact that the Zn(II) sorption on the surface of CDS was spontaneous, endothermic together with increased entropy at solid liquid interface.     

Packed‐Column of Granular Activated Carbons for Removal of Chemical Oxygen Demand from Industrial Wastewater

In the present study, chemical oxygen demand (COD) removal by packed‐columns of activated carbon (AC) derived from two different materials (coal activated carbon, CAC and wood activated carbon, WAC) is reported as part of an on‐site wastewater treatment system for handling small volumes of wastewater generated at wood‐floor industries for which there are no proper on‐site treatment options available in the market. The performance of the sorbents, the effect of bed depth (0.19 and 0.57 m) and volumetric load (0.10 and 0.24 m h^?1) on the breakthrough curve of sorption systems were studied. The results indicated the feasibility of using both ACs to treat these wastewaters. At the bed depth (0.57 m), volumetric load (0.24 m h^?1), and 30% breakthrough, CAC and WAC showed treatment capacity of 40.5 L kg^?1 in 250 h and 23.8 L kg^?1 in 63 h, respectively. This indicated that CAC requires longer retention times to reach a performance similar to WAC. The experimental data was fit into the bed depth‐service time model showing that under the same conditions, CAC had higher maximum sorption capacity (N₀) than WAC. Moreover, thermal regeneration at 500°C temperature could be a cost‐effective procedure since the reuse of spent AC through such regeneration process for further treatment could still achieve 90% of the initial sorption capacity, reducing then costs for the use of new sorbents and also the need for waste disposal.     

Study of the Interaction Mechanism in the Biosorption of Copper(II) Ions onto Posidonia oceanica and Peat

A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption–desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4–6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q_max) at pH 6 of 85.78 and 49.69 mg g^?1, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO₃)₂, and EDTA was applied to copper‐saturated biosorbents. Around 65–70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH₂, and CH₃ in aliphatic structures, COO^? and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si? O groups on the surface of peat. The results of SEM‐EDX and FTIR analysis of copper‐saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption–desorption processes affected the thermal stability of the biosorbents.     

Groundwater Defluoridation with Raw Bauxite,Gypsum, Magnesite,and Their Composites

Breakthrough characteristics, kinetics, and dose‐effect in defluoridation with bauxite, gypsum, magnesite, and their composites were determined. The aim was to identify optimum filter and configuration viable for groundwater defluoridation. Bed depth service time (BDST) design model and empty bed residence time (EBRT) optimization model were employed to characterize breakthrough. Higher doses obtained lower loading capacities but higher sorption percentages and breakthrough times. Breakthrough times obtained were 50 400, 32 400, 25 200, and 19 800 s for 150, 120, 75, and 45 g, respectively. The equation ? = 1.0 × 10^?4 δ² ?0.022 δ + 1.5053 defined the operating line with ?, adsorbent exhaustion rate, in g L^?1 and δ, EBRT, in seconds. A critical bed depth (Z_o) of 6.56 cm was obtained. Second order kinetic rate constants were 0.73, 1.17, and 1.81 g mg^?1 s^?1 for magnesite, gypsum, and bauxite, respectively. The composite, gypsum and bauxite decreased water pH but magnesite increased pH in water defluoridation. Experimental data did not fit the two‐parameter logistics model; model values were significantly different from experimental values. Optimum defluoridation characteristics were obtained in fixed bed. Despite high residual sulphates and apparent color, fixed‐bed defluoridation with raw composites of these materials, treated in this manner, is viable.     

Zur Konzentrationsabhängigkeit der Sorption von Co(II) an Titanschwamm

The sorption of Co(II) from aqueous solutions on granulated titanium dioxide was investigated in dependence on pH-value (pH = 6 … 10) and solution concentration (c_L = 10^?7 … 10^?2 mol/kg) at 83 °C. The precipitation in the solution occurred at high pH-values and solution concentrations was determined by control experiments without the adsorber. The adsorption isotherms are S-shaped. This can be interpreted as transition from chemisorption at the basic material to surface precipitation.     

Removal of Heavy Metals from Synthetic Mixture as well as Pharmaceutical Sample Via Cation Exchange Resin Modified with Rhodamine B: Its Thermodynamic and Kinetic Studies

A new sorbent was prepared by loading rhodamine B on Amberlite IR‐120. Various physico‐chemical parameters such as effects of adsorbate concentration, contact time, pH, and temperature on the sorption of the dye have been studied. Thermodynamic parameters (ΔH° and ΔS°) were also evaluated for the sorption of dye. Kinetic studies revealed that the sorption of the dye was best fit for pseudo‐second‐order kinetic. The metal ion uptake in different solvent systems has been explored through column studies. On the basis of distribution coefficient (K_d), some heavy metal ions of analytical interest from binary mixtures have been separated. The limit of detection (LOD) for the Ni²⁺ and Fe³⁺ metal ions was 0.81 and 0.60 µg L^?1, and the limit of quantification (LOQ) was found to be 2.72 and 2.0 µg L^?1. This sorbent has also been successfully applied in the analysis of multivitamin formulation. The applicability of the modified resin in the separation of heavy metals constituting real and synthetic samples has been explored.     

Competitive Sorption of Antimony with Zinc,Nickel, and Aluminum in a Seaweed Based Fixed‐bed Sorption Column

The removal of heavy metals such as Ni(II), Zn(II), Al(III), and Sb(III) from aqueous metal solutions was investigated using novel, cost effective, seaweed derived sorbents. Studies with a laboratory scale fixed‐bed sorption column, using a seaweed waste material (referred to as waste Ascophyllum product (WAP)) from the processing of Ascophyllum nodosum as biosorbent, demonstrated high removal efficiencies (RE) for a variety of heavy metals including Ni(II), Zn(II) and Al(III), with 90, 90 and 74% RE achieved from initial 10 mg/L metal solutions, respectively. The presence of Sb(III) in multi component metal solutions suppressed the removal of Ni(II), Zn(II) and Al(III), reducing the RE to 28, 17 and 24%, respectively. The use of Polysiphonia lanosa as a biosorbent showed a 67% RE for Sb(III), both alone and in combination with other metals. Potentiometric and conductometric titrations, X‐ray photoelectron and mid‐infrared spectroscopic analysis demonstrated that carboxyl, alcohol, sulfonate and ether groups were heavily involved in Sb(III) binding by P. lanosa. Only carboxyl and sulfonate groups were involved in Sb(III) binding by WAP. Furthermore, a greater amount of weak acidic groups (mainly carboxylic functions) were involved in Sb(III) binding by P. lanosa, compared to WAP which involved a greater concentration of strong acidic groups (mainly sulfonates).     

Adsorption of Cadmium from Aqueous Solution by Ficus religiosa Leaf Powder and Characterization of Loaded Biosorbent

The present investigation evaluates the adsorption effectiveness of Cd(II) ions on Ficus religiosa leaf powder (FRL). The experimental parameters chosen included time, pH, particle size, temperature, adsorbate, anion, and Pb(II) concentrations. The time data followed pseudo‐second‐order kinetics. Cd(II) adsorption increased from 1.38 to 75.17% with the increase in pH from 2 to 4 and further increase in pH to 5.5 resulted in its marginal increase to 77.52%. Based on regression coefficient values, the isothermic data fitted the various models in the order Langmuir > Redlich–Peterson > Temkin > Freundlich model. The maximum loading capacity of FRL was estimated to be 27.14 mg g^?1. The presence of Cl^?, , or Pb²⁺ exhibited adverse effect on Cd(II) uptake. The thermodynamic parameters of enthalpy (ΔH⁰) and entropy (ΔS⁰) were estimated to be 8.31 kJ mol^?1 and 38.22 J mol^?1 K^?1, respectively. SEM‐EPMA of the loaded FRL showed Cd(II) distribution at specific sites. The XRD patterns of Cd(II) loaded FRL sample showed disappearance of some peaks corresponding to β‐Ca(PO₃)₂; shifting of peaks and decrease in %RI corresponding to γ‐CaSO₄ phase. Positive shift of IR bands for the Cd(II) loaded sample was observed.     

Preconcentration by Coprecipitation of Copper and Nickel with Mo(VI)/Triazole Derivative System and Their Determinations by Flame Atomic Absorption Spectrometry in Food and Water Samples

A new separation and preconcentration technique based on coprecipitation of Cu(II) and Ni(II) ions by the aid of Mo(VI)/di‐tert‐butyl{methylenebis[5‐(chlorobenzyl)‐4H‐1,2,4‐triazol‐3,4‐diyl]}biscarbamate (BUMECTAC) precipitate has been established. The Mo(VI)/BUMECTAC precipitate was dissolved by concentrated HNO₃ and the solution was completed to 5.0 mL with distilled/deionized water. The levels of the analyte ions were determined by flame atomic absorption spectrometer. The effects of experimental conditions like HNO₃ concentration, amount of BUMECTAC and Mo(VI), sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of analyte ions. The preconcentration factors were found to be 40 for Cu(II) and 100 for Ni(II) ions. The detection limits for Cu(II) and Ni(II) ions based on 3σ (N:10) were 0.43 and 0.70 µg L^?1, respectively. The relative standard deviations were found to be lower than 4.0% for both analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of two certified reference materials (Environment Canada TM‐25.3 and CRM‐SA‐C Sandy Soil C). The procedure was successfully applied to sea water and stream water as liquid samples and baby food as solid sample in order to determine the levels of Cu(II) and Ni(II) ions.     

Adsorption of Thallium(I) Ions Using Eucalyptus Leaves Powder

Using batch method, the adsorption of thallium(I) ions from aqueous solutions on eucalyptus leaves powder, as a low cost adsorbent, was studied. The effect of various modification of considered adsorbent on the adsorption percentage of Tl(I) is an important feature of this study. The results showed that the unmodified and acidic modified adsorbent are the poor adsorbents for the Tl(I) ions while basic modified adsorbent is a suitable adsorbent. Also, the effect of some experimental conditions such as solution initial pH, agitation speed, contact time, sorbent dosage, temperature, particle size, and thallium initial concentration was studied. The results showed that the adsorption percentage depends on the conditions and the process is strongly pH‐dependent. The satisfactory adsorption percentage of Tl(I) ions, 81.5%, obtained at 25 ± 1°C. The equilibrium data agreed fairly better with Langmuir isotherm than Freundlich and Temkin models. The value of q_m that was obtained by extrapolation method is 80.65 mg g^?1. Separation factor values, R_L, showed that eucalyptus leaves powder is favorable for the sorption of Tl(I). The negative values of ΔH⁰ and ΔS⁰ showed that the Tl(I) sorption is an exothermic process and along with decrease of randomness at the solid–solution interface during sorption, respectively.     

Sorption of ortho‐Phenylphenol to Soils

Conflicting sorption coefficients for ortho‐phenylphenol (OPP) have been reported in the literatures, which resulted in the conflicting assessments on OPP mobility in soil. To ascertain the sorption coefficient of OPP, batch experiments were performed based on OECD guideline 106, using three types of soils. Headspace solid‐phase microextraction (HS‐SPME) and GC‐MS were applied to the determination of OPP concentration in the liquid phase. The sorption isotherms obtained for all three soils under equilibrium conditions were described well, assuming linear sorption. The organic carbon normalized distribution coefficients (K_oc) ranged from 894 to 1703 L kg^?1, which suggested that OPP is moderately mobile in soil. The results also showed that the K_oc value of OPP can be predicted precisely from K_ow, whereas it was underestimated by one order of magnitude when water solubility is used.     

Hyperspectral feature analysis of chlorophyll a and suspended solids using field measurements from Taihu Lake,eastern China

Abstract

We report results of three field campaigns conducted at 39 stations. At each station, we measured reflectance spectra in situ and collected water samples for measuring chlorophyll a (CHL) and suspended solids (SS) concentrations in the laboratory. To identify the indicative bands and develop suitable estimation models for CHL (C _CHL) and SS (C _SS) concentrations in Taihu Lake, a spectral-feature method and a derivative method were applied. The following conclusions were drawn: (a) the critical C _CHL and C _SS probably causing their spectral variation are, respectively: 0, 10, 50 and 75 μg L^?1, and 0, 10, 50 and 100 mg L^?1; (b) the derivative method is better than the spectral-feature method for estimating C _CHL and C _SS; (c) the optimal variable for CHL is a reflectance second-order derivative at 501 nm or a reflectance first-order derivative at 698 nm; the optimal variable for SS can change when its concentration is low and the range is narrow; otherwise, the optimal variable is a reflectance first-order derivative at 878 nm; and (d) the CHL and SS have an effect on one another's retrieval. The C _CHL estimation accuracy would benefit from narrowing the C _SS range. With C _CHL increasing and its range broadening, the corresponding C _SS estimation accuracy decreases gradually.     

Regeneration and Reuse of a Seaweed‐Based Biosorbent in Single and Multi‐Metal Systems

A seaweed‐waste material resulting from the processing of Ascophyllum nodosum was previously shown to be very efficient at removing Zn(II), Ni(II) and Al(III) both in single and multi‐metal waste streams. In this study, the regeneration of the biosorbent using an acid wash resulted in the release of high metal concentrations during multiple desorption cycles. Maximum desorption efficiencies (DE) of 183, 122 and 91% were achieved for Zn(II), Ni(II) and Al(III), respectively, for subsequent metal loading cycles, significantly exceeding the desorption rates observed for conventional sorbents. The regeneration of the sorbent was accomplished with very little loss in metal removal efficiency (RE) for both single and multi‐metal systems. Values of 92, 96 and 94% RE were achieved for Zn(II), Ni(II) and Al(III), respectively, for the 5^th sorption cycle in single metal aqueous solutions. A slight decrease was observed for the same metals in multi‐metal systems with maximum REs of 85, 82 and 82% for Zn(II), Ni(II) and Al(III), respectively. This study showed that the novel sorbent derived from a seaweed industrial waste would be suitable for multiple metal sorption cycles without any significant loss in RE.     

Displacement and transport of marked pebbles,cobbles and boulders during floods in a steep mountain stream

In a small experimental catchment of the Dolomites (Rio Cordon, 5 km²) field observations have been carried out on the movement of various sized bed material particles. Displacement length of 860 marked pebbles, cobbles and boulders (0·032 < D < 0·512 m) has been measured along the river bed during individual snowmelt and flood events in the periods 1993–1994 and 1996–1998. Floods were grouped into two categories. The first includes ‘ordinary’ events, which are characterized by peak discharges with a return period of 1–5 years and by an hourly bedload rate not exceeding 20 m³ h^?1. The second refers to ‘exceptional’ events with a return period of 50–60 years. A flood of this latter type occurred on 14 September 1994, with a peak discharge of 10·4 m³ s^?1 and average hourly bedload rate of 324 m³ h^?1. The variation according to grain size of total displacement length L_i depends on the degree of mobilization of the individual fractions of the bed surface: L_i is independent of D_i for smaller, fully mobile grain sizes and decreases rapidly with D_i for larger fractions in a state of partial transport. Sustained selective transport without a supply of sediment from upstream leads to the development of a stable coarse armoured surface through progressive winnowing of finer material from the bed surface. With supply unlimited conditions for transport, both the occurrence of extreme events and the duration of a sequences of ‘ordinary’ floods play an important role in the degree of mobilization of the individual fractions of the bed. Copyright © 2004 John Wiley & Sons, Ltd.