Integrated biosorption and photocatalytic oxidation treatment of di(2-ethylhexyl)phthalate

Di(2-ethylhexyl)phthalate (DEHP), a toxic phthalate ester, is a ubiquitous contaminant due to its extensive use and persistence. No available treatment method can cost-effectively remove it from industrial wastewater. In a previous study, DEHP was effectively removed from aqueous solution by adsorption onto the biomass of selected seaweed, i.e., beached seaweed and Sargassum siliquastrum. Since biosorption cannot detoxify DEHP, the degradation (and detoxification) of desorbed DEHP from seaweed biomass by photocatalytic oxidation (PCO) was attempted. The first part of this study was to optimize the conditions for the degradation of desorbed DEHP in aqueous solution by PCO. Under optimized conditions, a total degradation of 20 mg/L of DEHP was achieved within 45 min. The degradation intermediates/products such as phthalic anhydride and 2-ethyhexanol were identified by GC-MS analysis. Total organic carbon analysis was also used to ensure the complete mineralization of DEHP. The Microtox^® test was used to assess the toxicities of the parent and degraded compounds. In the second part of this study, DEHP was first removed and concentrated by adsorption onto seaweed biomass under the conditions optimized in the previous study. It was then desorbed from seaweed biomass and degraded by PCO. Results indicate that the treatment for DEHP by integrating biosorption and PCO is feasible.     

Repeated removal of cadmium and zinc from an industrial effluent by waste biomass Sargassum sp.

Waste biomass Sargassum sp. biosorbed 100% of Cd²⁺ and 99.4% of Zn²⁺ from a 3 and 98 mg l^–1 solution (pH 4.5), respectively, at the end of four serial experiments. Of the five desorbents studied in consecutive adsorption/desorption cycles, CaCl₂ 0.05 M eluted nearly 40% of both metals and decreased the biosorption in only 8% and 17% of Cd²⁺ and Zn²⁺, respectively. Although NaOH desorbent improved the heavy metal uptake from the second cycle onwards, it did not elute metals from the pre-loaded biomass.     

Biosorption of reactive dyes by the mycelium pellets of a new isolate of Penicillium oxalicum

Three reactive dyes were rapidly adsorbed by the mycelium pellets of Penicillium oxalicum. Dye removal of Reactive Blue 19 was up to 60% in 10 min and 91% in 80 min. Dye adsorption isotherms fitted Langmuir model well and the maximum adsorption capacities at 20 °C were calculated to be 160 mg g^–1 for Reactive Blue 19, 122 mg g^–1 for Reactive Red 241 and 137 mg g^–1 for Reactive Yellow 145, respectively. The pellets exhibited a high dye adsorption capacity (80–180 mg g^–1) for all of the 3 dyes over a wide pH range (pH 2–10), and the maximum adsorption was obtained at pH 2. The adsorption capacity was mildly increased by increasing salinity.     

Biosorption of an Azo Dye by <Emphasis Type="Italic">Aspergillus niger</Emphasis> and <Emphasis Type="Italic">Trichoderma</Emphasis> sp. Fungal Biomasses

Biosorption is an eco-friendly and cost-effective method for treating the dye house effluents. Aspergillus niger and Trichoderma sp. were cultivated in bulk and biomasses used as biosorbents for the biosorption of an azo dye Orange G. Batch biosorption studies were performed for the removal of Orange G from aqueous solutions by varying the parameters like initial aqueous phase pH, biomass dosage, and initial dye concentration. It was found that the maximum biosorption was occurred at pH 2. Experimental data were analyzed by model equations such as Langmuir and Freundlich isotherms, and it was found that both the isotherm models best fitted the adsorption data. The monolayer saturation capacity was 0.48 mg/g for Aspergillus niger and 0.45 mg/g for Trichoderma sp. biomasses. The biosorption kinetic data were tested with pseudo first-order and pseudo second-order rate equations, and it was found that the pseudo second-order model fitted the data well for both the biomasses. The rate constant for the pseudo second-order model was found to be 10–0.8 (g/mg min⁻¹) for Aspergillus niger and 8–0.4 (g/mg min⁻¹) for Trichoderma sp. by varying the initial dye concentrations from 5 to 25 mg/l. It was found that the biomass obtained from Aspergillus niger was a better biosorbent for the biosorption of Orange G dye when compared to Trichoderma sp.     

Interactive biosorption by microalgal biomass as a tool for fluoride removal

Maximum biosorption of Ca²⁺ was at 50 mg Ca²⁺ l^–1 with both Anabaena fertilissima (2.8 mg Ca²⁺ g^–1 dry wt) and Chlorococcum humicola (4.4 mg g^–1). Such Ca²⁺-treated biomasses, accumulated, respectively, 7 mg F g^–1 DW from an aqueous solution of 10 mg F l^–1 and 4.5 mg F g^–1 DW from 15 mg F l^–1. Data for both Ca²⁺ and F^– biosorption fitted the Langmuir adsorption isotherm indicating monolayer adsorption at a constant energy.     

Biosorption of acid violet dye from aqueous solutions using native biomass of a new isolate of Penicillium sp.

Laboratory investigation of the potential use of Penicillium sp. as biosorbent for the removal of acid violet dye from aqueous solution was studied with respect to pH, temperature, biosorbent, initial dye concentrations. Penicillium sp. decolourizes acid violet (30 mg l⁻¹) within 12 h agitation of 150 rpm at pH 5.7 and temperature of 35 °C. The pellets exhibited a high dye adsorption capacity (5.88 mg g⁻¹) for acid violet dye over a pH range (4–9); the maximum adsorption was obtained at pH 5.7. The increase of temperature favored biosorption for acid violet, but the optimum temperature was 35 °C. Adsorption kinetic data were tested using pseudo-first-order, pseudo-second-order and kinetic studies showed that the biosorption process follows pseudo-first-order rate kinetics with an average rate constant of 0.312 min⁻¹. Isotherm experiments were conducted to determine the sorbent–desorption behavior of examined dye from aqueous solutions using Langmuir and Freundlich equations. Langmuir parameter indicated a maximum adsorption capacity of 4.32 mg g⁻¹ for acid violet and R_L value of 0.377. Linear plot of log q_e vs log C_e shows that applicability of Freundlich adsorption isotherm model. These results suggest that this fungus can be used in biotreatment process as biosorbent for acid dyes.     

Biosorption of uranium(VI) by Aspergillus fumigatus

Aspergillus fumigatus removed uranium(VI) very rapidly and reached equilibrium within 1 h of contact of biomass with the aqueous metal solution. Biosorption data fitted to Langmuir model of isotherm and a maximum loading capacity of 423 mg U g^–1 dry wt was obtained. Distribution coefficient as high as 10,000 (mg U g^–1)/(mg U ml^–1) at a residual metal ion concentration of 19 mg l^–1 indicates its usefulness in removal of uranium(VI) from dilute waste streams. Optimum biosorption was seen at pH 5.0 and was independent of temperature (5–50°C ). Initial metal ion concentration significantly influenced uptake capacity which brought down % (w/w) uranium(VI) removal from 90 at 200 mg U l^–1 to 35 at 1000 mg U l^–1. Presence of 0.84 mmol Fe²⁺, Fe³⁺, Ca²⁺ and Zn²⁺ had no effect on uranium(VI) biosorption unlike Al³⁺ (0.84 mM) which was inhibitory.     

Chromium and aluminum biosorption on<Emphasis Type="Italic"> Chryseomonas luteola</Emphasis> TEM05

Cr(VI) and Al(III) are environmental pollutants that are frequently encountered together in industrial wastewaters, e.g., from mining iron-steel, metal cleaning, plating, metal processing, automobile parts, and the manufacturing and dye industries. In this work, several variables that affect the capacity for chromium and aluminum biosorption by Chryseomonas luteola TEM05 were studied, particularly the effects of pH, metal concentration and contact time. Optimum adsorption pH values of Cr(VI) and Al(III) were determined as 4.0 and 5.0, respectively. The biosorption equilibrium was described by Freundlich and Langmuir adsorption isotherms. The value of Q ^o appears to be significantly higher for the Al(III) C. luteola TEM05 system. Langmuir parameters of C. luteola TEM05 also indicated a maximum adsorption capacity of 55.2 mg g^–1 for Al(III) and 3.0 mg g^–1 for Cr(VI).     

Biosorption of Copper by Paenibacillus polymyxa Cells and their Exopolysaccharide

Summary Biosorption of heavy metals by gram-positive, non-pathogenic and non-toxicogenic Paenibacillus polymyxa P13 was evaluated. Copper was chosen as a model element because it is a pollutant originated from several industries. An EPS (exopolysaccharide)-producing phenotype exhibited significant Cu(II) biosorption capacity. Under optimal assay conditions (pH 6 and 25 °C), the adsorption isotherm for Cu(II) in aqueous solutions obeyed the Langmuir model. A high q value (biosorption capacity) was observed with whole cells (q_max=112 mgCu g⁻¹). EPS production was associated with hyperosmotic stress by high salt (1 M NaCl), which led to a significant increase in the biosorption capacity of whole cells (q_max=150 mgCu g⁻¹). Biosorption capacity for Cu(II) of the purified EPS was investigated. The maximum biosorption value (q) of 1602 mg g⁻¹ observed with purified EPS at 0.1 mg ml⁻¹ was particularly promising for use in field applications.     

Immobilization of blue green microalgae on loofa sponge to biosorb cadmium in repeated shake flask batch and continuous flow fixed bed column reactor system

Summary An indigenous strain of blue green microalga, Synechococcus sp., isolated from wastewater, was immobilized onto loofa sponge discs and investigated as a potential biosorbent for the removal of cadmium from aqueous solutions. Immobilization has enhanced the sorption of cadmium and an increase of biosorption (21%) at equilibrium was noted as compared to free biomass. The kinetics of cadmium biosorption was extremely rapid, with (96%) of adsorption within the first 5 min and equilibrium reached at 15 min. Increasing initial pH or initial cadmium concentration resulted in an increase in cadmium uptake. The maximum biosorption capacity of free and loofa immobilized biomass of Synechococcus sp. was found to be 47.73 and 57.76 mg g⁻¹ biomass respectively. The biosorption equilibrium was well described by Langmuir adsorption isotherm model. The biosorbed cadmium was desorbed by washing the immobilized biomass with dilute HCl (0.1 M) and desorbed biomass was reused in five biosorption–desorption cycles without an apparent decrease in its metal biosorption capacity. The metal removing capacity of loofa immobilized biomass was also tested in a continuous flow fixed-bed column bioreactor and was found to be highly effective in removing cadmium from aqueous solution. The results suggested that the loofa sponge-immobilized biomass of Synechococcus sp. could be used as a biosorbent for an efficient removal of heavy metal ions from aqueous solution.     

Reuse of waste beer yeast sludge for biosorptive decolorization of reactive blue 49 from aqueous solution

Reactive blue 49 was removed from aqueous solution by biosorption using powder waste sludge composed of Saccharomyces cerevisiae from the beer-brewing industry. The effect of initial pH, temperature and the biosorption thermodynamics, equilibrium, kinetics was investigated in this study. It was found that the biosorption capacity was at maximum at initial pH 3, that the effect of temperature on biosorption of reactive blue 49 was only slight in relation to the large biosorption capacity (25°C, 361 mg g⁻¹) according as the biosorption capacity decreased only 43 mg g⁻¹ at the temperature increased from 25 to 50°C. The biosorption was spontaneous, exothermic in nature and the dye molecules movements decreased slightly in random at the solid/liquid interface during the biosorption of dye on biosorbents. The biosorption equilibrium data could be described by Freundich isotherm model. The biosorption rates were found to be consistent with a pseudo-second-order kinetics model. The functional group interaction analysis between waste beer yeast sludge and reactive blue 49 by the aid of Fourier transform infrared (abbr. FTIR) spectroscopy indicated that amino components involved in protein participated in the biosorption process, which may be achieved by the mutual electrostatic adsorption process between the positively charged amino groups in waste beer yeast sludge with negatively charged sulfonic groups in reactive blue 49.     

Biosorption of Methylene Blue by De-Oiled Algal Biomass: Equilibrium,Kinetics and Artificial Neural Network Modelling

The main objective of the present study is to effectively utilize the de-oiled algal biomass (DAB) to minimize the waste streams from algal biofuel by using it as an adsorbent. Methylene blue (MB) was used as a sorbate for evaluating the potential of DAB as a biosorbent. The DAB was characterized by SEM, FTIR, pH_PZC, particle size, pore volume and pore diameter to understand the biosorption mechanism. The equilibrium studies were carried out by variation in different parameters, i.e., pH (2–9), temperature (293.16–323.16 K), biosorbent dosage (1–10 g L⁻¹), contact time (0–1,440 min), agitation speed (0–150 rpm) and dye concentration (25–2,500 mg L⁻¹). MB removal was greater than 90% in both acidic and basic pH. The optimum result of MB removal was found at 5–7 g L⁻¹ DAB concentration. DAB removes 86% dye in 5 minutes under static conditions and nearly 100% in 24 hours when agitated at 150 rpm. The highest adsorption capacity was found 139.11 mg g⁻¹ at 2,000 mg L⁻¹ initial MB concentration. The process attained equilibrium in 24 hours. It is an endothermic process whose spontaneity increases with temperature. MB biosorption by DAB follows pseudo-second order kinetics. Artificial neural network (ANN) model also validates the experimental dye removal efficiency (R² = 0.97) corresponding with theoretically predicted values. Sensitivity analysis suggests that temperature and agitation speed affect the process most with 23.62% and 21.08% influence on MB biosorption, respectively. Dye adsorption capacity of DAB in fixed bed column was 107.57 mg g⁻¹ in preliminary study while it went up to 139.11 mg g⁻¹ in batch studies. The probable mechanism for biosorption in this study is chemisorptions via surface active charges in the initial phase followed by physical sorption by occupying pores of DAB.     

Sites of cadmiun uptake in bacteria used for biosorption

Summary Electron microscopy and x-ray spectroscopy were used to determine location and type of cadmium biosorption on and in bacteria, some of which produced extracellular polymers. Examined Arthrobacter and Pseudomonas species appear to have detoxification systems that precipitate cadmium internally irrespective of whether of not they excrete polymers. Capsular Klebsiella aerogenes strains showed minimal intracellular uptake but over a 5–100 mg dm^–3 Cd range produced the highest net metal removal levels due to significant extracellular adsorption. Offprint requests to: J. A. Scott     

Interaction of Mercuric Ions with Different Marine Algal Species

The use of different seaweeds such as Sargassum sp., Turbinaria conoides, and Ulva sp. in removing mercury(II) from aqueous solutions were investigated. The initial experimental runs, conducted at different equilibrium pH conditions, demonstrated that brown seaweeds outperformed green seaweed in Hg(II) biosorption at all pH conditions. In particular, at pH 5, maximum biosorption capacities of 170.3 and 145.8 mg/g were recorded for the brown seaweeds T. conoides and Sargassum sp., respectively, compared with 138.4 mg/g for the green seaweed Ulva sp. Isotherm data were modeled and interpreted using the Langmuir, Freundlich, Redlich-Peterson, and Toth models, with the latter described the Hg(II) isotherms with high correlation coefficients and low % error values. The kinetic data indicate the rapidity of the biosorption process, with the equilibrium achieved within 90 min. Several models, including the Elovich, pseudo-first-order, and pseudo-second-order models, were examined for their suitability with the present data; the correlation coefficient and % error values, along with better prediction of equilibrium uptake values, favored the pseudo-first-order model. The desorption experiments were highly successful for T. conoides biomass with 0.05 M HCl, whereas for the other two seaweeds, 0.05 M HCl resulted in high biomass weight loss. Reusing T. conoides biomass in three successive sorption-desorption cycles resulted in only 8.8% reduction in Hg(II) biosorption capacity compared with its original uptake.     

Copper removal by immobilized Microcystis aeruginosa in continuous flow columns at different bed heights: study of the adsorption/desorption cycle

Microcystis aeruginosa immobilized in a natural polymer was tested for its potential to remove Cu²⁺ ions from aqueous solution in a continuous, downflow packed columnar reactor. Various parameters like flow rate, bed height and contact time required for maximum removal of test metals by the immobilized Microcystis aeruginosa were optimized. An increase in bed height from 2 to 10 cm resulted in an apparent decrease in biosorption capacity from 8.94 to 5.34 mg g^–1, but more Cu²⁺ solution was purified at the higher bed height. Efficiency of metal recovery from Cu²⁺-loaded biomass and its subsequent regeneration was also determined. Immobilized M. aeruginosa was found to be effective in Cu²⁺ removal from solution for up to 10 cycles of adsorption–desorption and 1 M HCl is very efficient desorbent for regeneration of Microcystis biomass for reuse.     

Biosorption of Cd(II) and Pb(II) onto brown seaweed, Lobophora variegata (Lamouroux): kinetic and equilibrium studies

The present work deals with the biosorption performance of raw and chemically modified biomass of the brown seaweed Lobophora variegata for removal of Cd(II) and Pb(II) from aqueous solution. The biosorption capacity was significantly altered by pH of the solution delineating that the higher the pH, the higher the Cd(II) and Pb(II) removal. Kinetic and isotherm experiments were carried out at the optimal pH 5.0. The metal removal rates were conspicuously rapid wherein 90% of the total sorption occurred within 90 min. Biomass treated with CaCl₂ demonstrated the highest potential for the sorption of the metal ions with the maximum uptake capacities i.e. 1.71 and 1.79 mmol g⁻¹ for Cd(II) and Pb(II), respectively. Kinetic data were satisfactorily manifested by a pseudo-second order chemical sorption process. The process mechanism consisting of both surface adsorption and pore diffusion was found to be complex. The sorption data have been analyzed and fitted to sorption isotherm of the Freundlich, Langmuir, and Redlich–Peterson models. The regression coefficient for both Langmuir and Redlich–Peterson isotherms were higher than those secured for Freundlich isotherm implying that the biosorption system is possibly monolayer coverage of the L. variegata surface by the cadmium and lead ions. FT-IR studies revealed that Cd(II) and Pb(II) binding to L. variegata occurred primarily through biomass carboxyl groups accompanied by momentous interactions of the biomass amino and amide groups. In this study, we have observed that L. variegata had maximum biosorption capacity for Cd(II) and Pb(II) reported so far for any marine algae. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Biosorption of chromium(VI) in aqueous solutions by chemically modified Strychnine tree fruit shell

Chromium(VI) was removed from aqueous solution using sulfuric- and phosphoric-acid-activated Strychnine tree fruit shells (SSTFS and PSTFS) as biosorbents. Effects of various parameters such as adsorbent dose (0.02–0.1 g/L), temperature (303–333 K), agitation speed, solution pH (2–9), contact time, and initial Cr(VI) concentration (50–250 mg/L) were studied for a batch adsorption system. The optimum pH range for Cr(VI) adsorption was determined as 2. Equilibrium adsorption data were analyzed with isotherm models and the Langmuir and Freundlich models got best fitted values for SSTFS (R² value – 0.994) and PSTFS (R² value – 0.996), respectively. The maximum adsorption capacities of SSTFS and PSTFS were 100 and 142.85 mg/g, respectively. The biosorption process was well explained by pseudo-second-order kinetic model with higher R² value (SSTFS – 0.996, PSTFS – 0.990) for both biosorbents. Characterization of biosorbents was done using Fourier transform infrared spectroscopy, scanning electron microscopy, elemental analysis, energy-dispersive X-ray analysis, and thermogravimetric analysis. Thermodynamic studies revealed the spontaneous, endothermic, and randomness in nature of the Cr(VI) adsorption process. Different concentrations of NaOH solutions were used to perform the desorption studies. The results demonstrated that both SSTFS and PSTFS can be used as an effective and low-cost biosorbent for removal of Cr(VI) from aqueous solutions.     

Development and operation of a trickling biofilter system for continuous treatment of gas-phase trichloroethylene

A parallel trickling biofilter (TBF) system that consists of two TBFs units in parallel, one for biodegradation of trichloroethylene (TCE) and the other for reactivation of an inactivated biofilm, was developed and operated for continuous treatment of gas-phase TCE by Burkholderia cepacia G4. For inlet loadings below 8.6 mg TCE l^–1 d^–1, complete removal of TCE was achieved. The maximal TCE elimination capacity was 17 mg l^–1 d^–1.     

Competitive biosorption of Acid Blue 25 and Acid Red 337 onto unmodified and CDAB-modified biomass of Aspergillus oryzae

The performance of unmodified and cetyldimethylethyl ammonium bromide (CDAB) modified nonviable Aspergillus oryzae for removal of Acid Blue 25 (AB 25) and Acid Red 337 (AR 337) was investigated in single and binary systems. In single system, the biosorption capacities of CDAB-modified biosorbent reached 160.36 and 280.39 mg g⁻¹ for AB 25 and AR 337, respectively, which were 1.52 and 1.66 times higher than that of unmodified biosorbent. In binary system, the biosorption capacities of unmodified and CDAB-modified biosorbents for both dyes decreased significantly compared to that in single system. Relative competitiveness analysis demonstrated that there existed critical initial concentration ratio which determined the predominance of dyes during biosorption process. The biosorption of AB 25 was found to be in dominant position at initial concentration ratio of [AB 25]/[AR 337] above 0.63. Kinetic analysis indicated that intraparticle diffusion was the limiting step for biosorption of two dyes onto biosorbents.     

Biosorption of nonylphenol on dead biomass of Rhizopus arrhizus encapsulated in chitosan beads

The nonylphenol (NP) biosorption and desorption potential for fungal biomass used under batch conditions was investigated using kinetics and isotherm models. Fungal biomass of Rhizopus arrhizus TISTR 3610 exhibited preferential uptake of NP, an endocrine disrupting chemicals. Sporangiospores, asexual spores, were immobilised in chitosan beads. The biosorption data of NP on the moist heat inactivated R. arrhizus–chitosan beads were analyzed using four popular adsorption isotherms and, by using non-linear least-regression with the solver add-in in Microsoft Excel, correlated in order with the Fritz–Schluender > Redlich–Peterson > Freundlich > Langmuir isotherms. The pseudo first-order kinetics was found to have the best fit with the experimental data. The diffusivity of NP in the R. arrhizus–chitosan beads was calculated using the shrinking core model, and the diffusivity values were in the ranges of 2.3736 × 10⁻⁴–1.8950 × 10⁻⁴ cm² s⁻¹. Desorption to recover the adsorbed NP from the beads was performed in methanol and was best described using a pseudo second-order kinetic model.