Kinetic studies on the adsorption of Cd2+, Cu2+ and Zn2+ ions from aqueous solutions by cassava (Manihot sculenta Cranz) tuber bark waste

The kinetics of Cd2+, Cu2+ and Zn2+ adsorption onto pure and thioglycolic acid treated cassava tuber bark wastes (CTBW) were investigated using a batch sorption technique at 30 degrees C. Kinetic data suggested that the adsorption process was exothermic, the rate limiting sorption step was physisorption and adsorption rates could be best described by a pseudo-second order model. Rate coefficients were determined to range between 1.39x10(-2)min(-1) and 5.94x10(-2)min(-1), 1.46x10(-3)min(-1) and 5.76x10(-3)min(-1) and 0.69x10(-3)min(-1) and 5.8x10(-3)min(-1) for Cd2+, Cu2+ and Zn2+, respectively. The results from these studies indicated that the sorption process is fast and stable. The adsorption equilibria were evaluated using the Langmuir equation and the monolayer sorption capacity was found to range between 5.88-26.3mg/g, 33.3-90.9 mg/g and 22.2-83.3mg/g for Cd2+, Cu2+ and Zn2+, respectively. Negative values of DeltaG(ads)(0) indicated that the adsorption process was spontaneous and exothermic in nature.     

Evaluation of the marine algae Ulva fasciata and Sargassum sp. for the biosorption of Cu(II) from aqueous solutions

In this study, the adsorption properties of two different marine algae (Ulva fasciata (green algae) and Sargassum sp. (brown algae)) were investigated. Equilibrium isotherms and kinetics were studied to evaluate the relative ability of the two algae to sequester Cu(II) from aqueous solutions. The maximum biosorption capacity obtained was 73.5 mg g(-1) for U. fasciata and 72.5 mg g(-1) for Sargassum sp. at a solution pH of 5.5 +/- 0.5. A significant fraction of the total copper(II) uptake was achieved within 30 min. The copper(II) uptake by the biosorbents was best described by pseudo-second-order rate model.     

Application of Freundlich and Langmuir models to multistage purification process to remove heavy metal ions by using Schizomeris leibleinii

The adsorption of iron(III), lead(II) and cadmium(II) ions onto Schizomeris leibleinii, a green alga, was studied with respect to initial pH, temperature, initial metal ion and biomass concentration to determine the optimum adsorption conditions. Optimum initial pH for iron(III), lead(II) and cadmium(II) ions were 2.5, 4.5 and 5.0 at optimum temperature 30°C, respectively. The initial adsorption rates increased with increasing initial iron(III), lead(II) and cadmium(II) ion concentrations up to 100, 100 and 150 mg l⁻¹, respectively. The Freundlich and Langmuir adsorption isotherms were developed at various initial pH and temperature values. The adsorption of these metal ions to S. leibleinii was investigated in a two-stage mixed batch reactor. The residual metal ion concentrations (C_eq) at equilibrium at each stage for a given ‘quantity of dried algae (X₀)/volume of solution containing heavy metal ion (V₀)’ ratio were calculated using Freundlich and Langmuir isotherm constants. The experimental biosorption equilibrium data for iron(III), lead(II) and cadmium(II) ions were in good agreement with those calculated by both Freundlich and Langmuir models. The adsorbed iron(III), lead(II) and cadmium(II) ion concentrations increased with increasing X₀/V₀ ratios while the adsorbed metal quantities per unit mass of dried algae decreased.     

Screening of marine microalgae for bioremediation of cadmium-polluted seawater

Twenty four strains out of 191 marine microalgal strains exhibited cadmium (Cd) resistance. They were tested for their Cd removal ability in growth media containing 50 μM Cd. Six strains out of 19 green algae and one out of five cyanobacteria removed more than 10% of total Cd from the medium. The marine green alga Chlorella sp. NKG16014 showed the highest removal of Cd 48.7% of total. Cd removal by NKG16014 was further quantitatively evaluated by measuring the amount of cell adsorption and intracellular accumulation. After 12 days incubation, 67% of the removed Cd was accumulated intracellularly and 25% of the Cd removed was adsorbed on the algal cell surface. The maximum Cd adsorption (q_max) was estimated to be 37.0 mg Cd (g dry cells)⁻¹ using the Langmuir sorption model. The Cd removal by freeze-dried NKG16014 cells was also determined. Cd was more quickly adsorbed by dried cells than that by living cells, with a q_max of 91.0 mg Cd (g dry cells)⁻¹.     

The efficiency of the red alga Mastocarpus stellatus for remediation of cadmium pollution

This work reports the results of the study for cadmium binding by the dead red macroalga Mastocarpus stellatus. Kinetics sorption experiments demonstrated the high rate of metal biosorption: the system attained over 50% of the total biomass cadmium uptake within 2 min of contact and over 90% in the first 9 min. The kinetic data were successfully described by a pseudo-second order model with rate constants ranging from 1.06 to 10 gmmol(-1)min(-1), as a function of initial metal concentration and temperature. The equilibrium binding was accurately represented in terms of Langmuir and Langmuir-Freundlich models. The sorption isotherms at constant pH showed uptake values as 0.49 mmol g(-1) (at pH 2.4), 0.56 mmol g(-1) (at pH 4) and 0.59 mmol g(-1) (at pH 6), while the affinity constant values were between 0.6 and 5 mmol(-1) L (Langmuir fit). The acid-base properties of the alga were also studied, obtaining the total number of acid groups, 2.5 mmol g(-1), and their apparent pK value, 1.56, using the Katchalsky model. Desorption studies were conducted employing different HNO(3) concentrations and desorption times.     

Removal characteristics of metal ions using degreased coffee beans: adsorption equilibrium of cadmium(II)

The feasibility of using coffee beans after being dripped and degreased (DCB) as an adsorbent for base metals such as copper(II), zinc(II), lead(II), iron(III) and cadmium(II) were examined. The compositions of the DCB were characterized by Fourier transform infrared spectroscopy, scanning electronic micrograph and fluorescent X-ray. It was found that DCB contain sulfur and calcium from the analysis using fluorescent X-ray. The plant cell wall in DCB has the porous structure from the scanning electron microscopy (SEM) analysis, and the specific surface area was determined to be 1.2 m2/g using the specific surface area analyzer. Batch adsorption experiments on DCB were carried out at various pHs in order to elucidate the selectivity of metal ions. All metals were adsorbed at low pH region (3.0-5.0). Of particular interest was the adsorption characteristics of cadmium(II) on DCB. The adsorption isotherm for cadmium(II) at pH 8 fitted with a Langmuir equation to yield an adsorption equilibrium constant of 55.2 mmol dm(-3) and an adsorption capacity of 5.98 x 10(-2) mmol g(-1). The desorption of cadmium(II) was easily achieved over 90% by a single batchwise treatment with an aqueous solution of hydrochloric acid or nitric acid at more than 0.01 mol dm(-3). These results suggested that DCB behaves as a cation exchanger.     

Biosorption of cadmium by biomass of marine algae

Biomass of nonliving, dried brown marine algae Sargassum natans, Fucus vesiculosus, and Ascophyllum nodosum demonstrated high equilibrium uptake of cadmium from aqueous solutions. The metal uptake of cadmium from aqueous solutions. The metal uptake by these materials was quantitatively evaluated using sorption isotherms. Biomass of A. nodosum accumulated the highest amount of cadmium exceeding 100 mg Cd(2+)/g (at the residual concentration of 100 mg Cd/L and pH 3.5), outperforming a commercial ion exchange resin DUOLITE GT-73. A new biosorbent material based on A. nodosum biomass was obtained by reinforcing the algal biomass by formaldehyde cross-linking. The prepared sorbent possessed good mechanical properties, chemical stability of the cell wall polysaccharides and low swelling volume. Desorption of deposited cadmium with 0.1-0.5M HCI resulted in no changes of the biosorbent metal uptake capacity through five subsequent adsorption/desorption cycles. There was no damage to the biosorbent which retained its macroscopic appearance and performance in repeated metal uptake/elution cycles. (c) 1993 Wiley & Sons, Inc.     

Cadmium removal by living cells of the marine microalga Tetraselmis suecica

Cadmium removal by living cells of the marine microalga Tetraselmis suecica was tested in cultures exposed to different cadmium concentrations (0.6, 3, 6, 15, 30 and 45 mg/l). The EC50 for growth was 7.9 mg Cd/l after six days of exposure. The cadmium removed was proportional to the concentration of this metal in the medium and it was dependent on the time of exposure; cultures with higher cadmium concentration removed a higher amount of this metal. In cultures exposed to 0.6 mg/l, T suecica cells removed 98.1% of added cadmium with 0.392 x 10(-6) microg Cd/cell, whereas in cultures with 45 mg/l only 7.7% was removed with 16.052 x 10(-6) microg Cd/cell. The highest amount of cadmium removed per liter of culture was observed in cultures exposed to 6 mg/l, with 3.577 mg/l of cadmium. After six days of incubation, the higher proportion of cadmium was bioaccumulated intracellularly in all cultures except in 45 mg/l cultures, the percentage of intracellular cadmium being always more than 50%. The highest percentage of bioadsorbed cadmium (60.1%) was found in cells of cultures with the highest cadmium concentration (45 mg/l). Furthermore, a relation between intracellular cadmium and the concentration of sulfhydryl groups was observed.     

Entrapment of white-rot fungus Trametes versicolor in Ca-alginate beads: preparation and biosorption kinetic analysis for cadmium removal from an aqueous solution

The biosorption of cadmium ions onto entrapped Trametes versicolor mycelia has been studied in a batch system. The maximum experimental biosorption capacities for entrapped live and dead fungal mycelia of T. versicolor were found as 102.3 +/- 3.2 mg Cd(II) g(-1) and 120.6 +/- 3.8 mg Cd(II) g(-1), respectively. Biosorption equilibrium was established in about 1 h and biosorption was well described by the Langmuir and Freundlich biosorption isotherms. The change in the biosorption capacity with time was found to fit the pseudo-second-order equation. Since the biosorption capacities were relatively high for both entrapped live and dead forms, those fungal forms could be considered as suitable biosorbents for the removal of cadmium in wastewater-treatment systems. The biosorbents were reused in three consecutive adsorption/desorption cycles without a significant loss in the biosorption capacity.     

Accumulation of cadmium by Dunaliella tertiolecta Batcher

Cultures of Dunaliella tertiolecta were exposed to five concentrationsof cadmium in solution (0.1, 0.5, 1, 5 and 10ppm(mg 1^-1)). Theaccumulation of cadmium by the algae was found to have two phases,an initial rapid uptake followed by a stabilisation of the cellularcadmium levels. D. tertiolecta concentrated cadmium from solution(cone, factor approx. 1350) at exposures up to 1 ppm Cd butexposure to the higher concentrations caused no further increasein the accumulated cadmium concentration of the algae whichreached a nmriimim at about 1.5 µg Cd mg¹ Dunaliella.     

氮磷营养因子对赤潮异弯藻生长的影响

研究了N、P营养浓度对赤潮异弯藻(Heterosigma akashiwo)生长的影响.结果表明,该藻的生长速率与N、P营养因子浓度的关系符合Monod公式.在NO₃^--N浓度达到7.5 mg·L^-1时,赤潮异弯藻开始生长;浓度为3.75～75 mg·L^-1时,赤潮异弯藻的比生长速率与NO₃^--N浓度成正比关系.N营养充足时,赤潮异弯藻的最大生长速率μ_m-n=0.3475·d^-1,K_s-n=18.91 mg·L^-1.PO₄^--P浓度为0～1.0 mg·L^-1时,赤潮异弯藻的比生长速率与P浓度成正比关系;P营养充足时,赤潮异弯藻的最大生长速率μ_m-p=0.3024·d^-1,K_s-p=0.4086 mg·L^-1.N/P达到25后藻细胞浓度达到最大,表明N/P为25时最适合赤潮异弯藻生长.赤潮异弯藻最适合在N 37.5～225.0 mg·L^-1、P 5.0～50.0 mg·L^-1、N/P=25条件下生长.     

Biosurfactant Mediated Remediation Process Evaluation on a Mixture of Heavy Metal Spiked Topsoil Using Soil Column and Batch Washing Methods

This study investigated the effects of biosurfactant produced by a mangrove isolate on a heavy metal spiked soil remediation using two different methods of biosurfactant addition (pretreatment and direct application) at different concentrations (0.5%–5%) for 10 days employing column and batch method of washings. The FT-IR spectral and biochemical analysis confirmed the chemical nature of biosurfactant as a glycolipid. Pre-addition of biosurfactant at 0.5% concentrations and further incubation for a month resulted in better chromium removal than the direct biosurfactant washing method. A maximum recovery of lead (99.77%), nickel (98.23%), copper (99.62%), and cadmium (99.71%) were achieved with column washing method at 1% biosurfactant concentration. Release of 26% soluble fractions of nickel (pre-addition with biosurfactant) and 40% copper (direct application) were achieved by column washing method at 1.0% concentration of biosurfactant. A total of 0.034 mg/10 g of lead, 0.157 mg/10 g of nickel, 0.022 mg/10 g of copper, 0.025 mg/10 g of cadmium, and 0.538 mg/10 g of chromium were found to remain in the spiked soil after column washing with 1.0% biosurfactant solution. However, pre-addition of 0.5% biosurfactant treatment helps in maximum removal of chromium metal leaving a residual concentration of 0.426 mg/10 g of soil, suggesting effective removal at very low concentration. The average extraction concentration of metals in batch washings was between 93–100%, irrespective of the concentration of biosurfactant studied. In this study, the percentage removal of copper, cadmium, chromium, nickel, and lead from spiked soils by column washing was comparatively lower than batch washing.     

Kinetic modeling and equilibrium studies during cadmium biosorption by dead Sargassum sp. biomass

A basic investigation on the removal of cadmium(II) ions from aqueous solutions by dead Sargassum sp. was conducted in batch conditions. The influence of different experimental parameters; initial pH, shaking rate, sorption time, temperature and initial concentrations of cadmium ions on cadmium uptake was evaluated. Results indicated that cadmium uptake could be described by the Langmuir adsorption model, being the monolayer capacity negatively affected with an increase in temperature. Analogously, the adsorption equilibrium constant decreased with increasing temperature. The kinetics of the adsorption process followed a second-order adsorption, with characteristic constants increasing with increasing temperature. Activation energy of biosorption could be calculated as equal to 10 kcal/mol. The biomass used proved to be suitable for removal of cadmium from dilute solutions. Its maximum uptake capacity was 120 mg/g. It can be considered an optimal result when compared to conventional adsorbing materials. Thus Sargassum sp. has great potential for removing cadmium ions especially when concentration of this metal is low in samples such as wastewater streams.     

Hydrocarbon biodegradation in oxygen-limited sequential batch reactors by consortium from weathered, oil-contaminated soil

We studied the use of sequential batch reactors under oxygen limitation to improve and maintain consortium ability to biodegrade hydrocarbons. Air-agitated tubular reactors (2.5 L) were operated for 20 sequential 21-day cycles. Maya crude oil-paraffin mixture (13,000 mg/L) was used as the sole carbon source. The reactors were inoculated with a consortium from the rhizosphere of Cyperus laxus, a native plant that grows naturally in weathered, contaminated soil. Oxygen limitation was induced in the tubular reactor by maintaining low oxygen transfer coefficients (k(L)a < 20.6 h(-1)). The extent and biodegradation rates increased significantly up to the fourth cycle, maintaining values of about 66.33% and 460 mg x L(-1) x d(-1), respectively. Thereafter, sequential batch reactor operation exhibited a pattern with a constant general trend of biodegradation. The effect of oxygen limitation on consortium activity led to a low biomass yield and non-soluble metabolite (0.45 g SS/g hydrocarbons consumed). The average number of hydrocarbon-degrading microorganisms increased from 6.5 x 10(7) (cycles 1-3) to 2.2 x 10(8) (cycles 4-20). Five bacterial strains were identified: Achromobacter (Alcaligenes) xylosoxidans, Bacillus cereus, Bacillus subtilis, Brevibacterium luteum, and Pseudomonas pseudoalcaligenes. Asphaltene-free total petroleum hydrocarbons, extracted from a weathered, contaminated soil, were also biodegraded (97.1 mg x L(-1) x d(-1)) and mineralized (210.48 mg CO2 x L(-1) x d(-1)) by the enriched consortium without inhibition. Our results indicate that sequential batch reactors under oxygen limitation can be used to produce consortia with high and constant biodegradation ability for industrial applications of bioremediation.     

Mechanism of cadmium uptake by activated sludge

Summary The significance of metabolic activity in cadmium uptake by unacclimated activated sludge was studied. Below 30 mg/l cadmium in solution, biosorption was found to follow the Freundlich isotherm, which is the most common pattern for physico-chemical adsorption. More than 95% of total cadmium uptake was achieved within 5 min metal-sludge contact time. Biosorption increased strongly when the initial cadmium concentration in solution was raised from 10 to 100 mg/l, whereas in the same concentration range the metabolic activity of the sludge, as measured by respiratory activity and extracellular protein production, was very significantly inhibited. The addition of nutrients at low but significant levels failed to increase cadmium uptake in 2 h contact time, while in 24 h the addition of nutrients caused the biosorption to increase by only 5–10% without any significant growth of the biomass. Biosorption was found to increase with temperature between 5° C and 40° C, in correlation with an increase in the metabolic activity of the sludge. Pretreatment of the sludge with metabolic inhibitors (NaN₃ and UV rays) appeared to cause only a very slight decrease (5–10%) of biosorption. These results suggest that metabolic uptake of cadmium was low and that adsorption to the surface of the cells was the major mechanism of uptake.Offprint requests to: S. S. Sofer     

Biosorption of cadmium and chromium in duckweed Wolffia globosa

The biosorption of cadmium (Cd) and chromium (Cr) by using dried Wolffia globosa biomass were investigated using batch technique. The effects of concentration and pH solution on the adsorption isotherm were measured by determining the adsorption isotherm at initial metal concentrations from 10 to 400 mg/L and pH 4 to 7 for Cd, and pH 1.5 to 6 for Cr. The adsorption equilibria were found to follow Langmuir models. The maximum adsorption capacity (Xm) at pH 7 in W. globosa-Cd system was estimated to be 80.7 mg/g, while the maximum removal achieved at pH 4, pH 5, and pH 6 were 35.1, 48.8, and 65.4 mg/g, respectively. The Xm at pH 1.5 in W. globosa--Cr system was estimated to be 73.5 mg/g, while the maximum removal achieved at pH 3, pH 5, and pH 6 were 47.4, 33.1, and 12.9 mg/g, respectively. The effects of contact times on Cd and Cr sorption indicated that they were absorbed rapidly and more efficiently at lower concentrations.     

Toxic effects of mercury(II), cadmium(II) and lead(II) porphyrins on Trypanosoma brucei brucei growth

The effects of free mercury(II), cadmium(II) and lead(II) ions and their metalloporphyrin-derivatives on Trypanosoma brucei brucei growth in culture were studied. All experiments were conducted in the dark. IC(50) values on growth obtained in 24-h time-course experiments were 1.5 x 10(-7), 2.4 x 10(-6), 4.4 x 10(-6) and 2.6 x 10(-5) M for mercury(II) porphyrin, cadmium(II) porphyrin, lead(II) porphyrin and free base porphyrin, respectively. While the IC50 values for Hg2+, Cd2+ and Pb2+ were 3.6 x 10(-6), 1.5 x 10(-5) and 1.6 x 10(-5) M, respectively. These results clearly indicate that the toxicity of the metalloporphyrin complexes of mercury(II), cadmium(II) and lead(II) to T. b. brucei parasites was much higher compared to their free metal ions and free base porphyrin at low concentrations. It was also observed after 8 h incubation that the metalloporphyrins were effective in inhibiting the division of the parasites at concentrations >1.25 x 10(-7) M for mercury(II) porphyrin, concentrations >1.2 x 10(-6) M for cadmium(II) and lead(II) porphyrins and at concentrations >3.6 x 10(-6) M for Hg2+ ion. These observations were not detected in samples treated with the free metal ions and the free base porphyrin at the same concentrations. Interestingly, trypanosomes treated with metalloporphyrin complexes displayed different morphological features from those cells treated with free base porphyrin or metal ions. The chemotherapeutic potential of the metalloporphyrins of H2TMPyP for treatment of African trypanosomiasis is discussed.     

五倍子对池水细菌和藻类的影响

在试验水族箱内,研究不同浓度的五倍子药液对池水中细菌和藻类的影响.结果表明:用药72h时,细菌总数的减少与药液浓度呈显著相关(r=-0.84349,P<0.05);浓度高于3mg.L-1处理时,细菌总数平均下降了96.2%,其中革兰氏阴性细菌的菌群比例下降达最大值;超过72h,细菌总数呈上升趋势.一定浓度的五倍子药液对池水藻类具有短时间的抑制作用.用五倍子药液对养鱼池塘消毒防病,浓度以3mg.L-1,消毒时间以72h为宜.     

Removal of Cu2+ from aqueous solution by adsorption onto a novel activated nylon-based membrane

A novel activated nylon-based membrane was prepared and applied as an adsorbent for the removal of Cu2+ from aqueous solutions. It involved three stages: (i) deposition of a chitosan layer that functionalized the nylon membrane, (ii) cross-linking with epichlorohydrin to stabilize the polymer layer and enabling grafting, and (iii) iminodiacetic acid grafting. SEM and EDX techniques were used to characterize the composition of the membranes. Dynamic adsorption experiments on membranes were carried out at various pH values, contact times, adsorption dosages and initial metal concentrations to determine optimum membrane adsorption properties. The adsorption isotherm relating to Cu2+ fitted the Langmuir equation and an adsorption equilibrium constant and adsorption capacity of 2.345x10(-3)mg/ml and 10.794mg/g were determined, respectively. The experimental data was analyzed using two adsorption kinetic models, pseudo-first-order and pseudo-second-order with the latter system providing the best fit. Finally complete regeneration of the activated nylon membrane was possible using 100mmol/l Na2EDTA.