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.     

Surface Water Contamination by Uranium Mining/Milling Activities in Northern Guangdong Province,China

The northern region of Guangdong Province, China, has suffered from the extensive mining/milling of uranium for several decades. In this study, surface waters in the region were analyzed by inductively coupled plasma optical emission spectrometry (ICP‐OES) for the concentrations of uranium (U), thorium (Th), and non‐radioactive metals (Fe, Mn, Mg, Li, Co, Cu, Ni, and Zn). Results showed highly elevated concentrations of the studied radionuclides and metals in the discharged effluents and the tailing seepage of the U mining/milling sites. Radionuclide and heavy metal concentrations were also observed to be overall enhanced in the recipient stream that collected the discharged effluents from the industrial site, compared to the control streams, and rivers with no impacts from the U mining/milling sites. They displayed significant spatial variations and a general decrease downstream away from upper point‐source discharges of the industrial site. In addition, obvious positive correlations were found between U and Th, Fe, Zn, Li, and Co (R² > 0.93, n = 28) in the studied water samples, which suggest for an identical source and transport pathway of these elements. In combination with present surface water chemistry and chemical compositions of uraniferous minerals, the elevation of the analyzed elements in the recipient stream most likely arose from the liquid effluents, processing water, and acid drainage from the U mining/milling facilities. The dispersion of radionuclides and hazardous metals is actually limited to a small area at present, but some potential risk should not be negligible for local ecosystem. The results indicate that environmental remediation work is required to implement and future cleaner production technology should be oriented to avoid wide dispersion of radioactivity and non‐radioactive hazards in U mining/milling sites.     

Bioreduction of Hexavalent Chromium by Live and Active Phanerochaete chrysosporium: Kinetics and Modeling

In this work the potential of live and active Phanerochaete chryosporium, a white rot fungi, to remove lower Cr(VI) concentration from aqueous solutions was reported for the first time. A medium pH had significant effect on the growth of the fungus and bioremoval of Cr(VI). Substrate inhibition on the growth of Phanerochaete chrysosporium was evident beyond 20 g L^?1 of dextrose concentration. A maximum biomass concentration of 15.64 g L^?1 was obtained for an initial dextrose concentration of 20 g L^?1 in metal free medium at pH 6.0. An increase in Cr(VI) concentration beyond 10 mg L^?1 inhibited the growth of the fungi, thereby, reducing the chromium bioremoval efficiency. A maximum reduction efficiency of 98.92% was reported for an initial metal concentration of 10 mg L^?1. A mathematical expression for the bioreduction of Cr(VI) considering the organic compounds in the cells was proposed.     

Dynamic,Mechanistic, and Thermodynamic Modeling of Zn(II) Ion Biosorption onto Zinc Sequestering Bacterium VMSDCM

The surface of the bacterial cells before the biosorption of Zn(II) ion has been found rough, heterogeneous, and non‐crystalline together with tremendous protrusions and negatively charged functional groups. The bacterium was characterized as rod shaped with Gram‐negative type of cell wall structure. In reaction dynamics, pseudo‐second‐order kinetics with higher linear correlation coefficient (R²) ranging between 0.97 and 0.99, lower sum of square errors (SSE) (0.035–0.081) and chi (χ²) (0.0013–0.009) provided a better explanation of sorption of Zn(II) ion on bacterium surface as compared to pseudo‐first‐order model. The removal of Zn(II) was governed by both film and intra‐particle diffusion at onset and later stage of sorption of metal ion on the surface of bacterial cells. The R² (0.92–0.94) for intra‐particle diffusion model was quite higher with lower values of SSE (9.56–16.33) and chi (χ²) (11.26–19.65) against the Bangham's model. The positive value of ΔH (16.628 × 10^?6 kJ/mol) and ΔS (5320.90 kJ/mol/K) showed that the biosorption of Zn(II) ion across liquid phase on bacterial surface was endothermic with increased randomness at solid–liquid interface. The negative values of ΔG demarcated the whole process as spontaneous in nature. In the present work, the distribution coefficient was found to be > 0.5 at various temperature ranges. At the attainment of equilibrium, the residual concentration of Zn(II) ion in liquid phase was around 0.6 mg/L, which was much below the limit described by United States Environmental Protection Agency (USEPA), i.e. 5 mg/L.     

Recent Progress on Biosorption of Heavy Metals from Liquids Using Low Cost Biosorbents: Characterization,Biosorption Parameters and Mechanism Studies

A significant number of biosorption studies on the removal of heavy metal from aqueous solutions have been conducted worldwide. Nearly all of them have been directed towards optimizing biosorption parameters to obtain the highest removal efficiency while the rest of them are concerned with the biosorption mechanism. Combinations of FTIR, SEM‐EDX, TEM as well as classical methods such as titrations are extremely useful in determining the main processes on the surfaces of biosorbents. Diverse functional groups represented by carboxyl, hydroxyl, sulfate and amino groups play significant roles in the biosorption process. Solution pH normally has a large impact on biosorption performance. In brief, ion exchange and complexation can be pointed out as the most prevalent mechanisms for the biosorption of most heavy metals.     

Biosorption of Cd(II) and Zn(II) by Nostoc commune: Isotherm and Kinetics Studies

In this study, Nostoc commune (cyanobacterium) was used as an inexpensive and efficient biosorbent for Cd(II) and Zn(II) removal from aqueous solutions. The effect of various physicochemical factors on Cd(II) and Zn(II) biosorption such as pH 2.0–7.0, initial metal concentration 0.0–300 mg/L and contact time 0–120 min were studied. Optimum pH for removal of Cd(II) and Zn(II) was 6.0, while the contact time was 30 min at room temperature. The nature of biosorbent and metal ion interaction was evaluated by infrared (IR) technique. IR analysis of bacterial biomass revealed the presence of amino, carboxyl, hydroxyl, and carbonyl groups, which are responsible for biosorption of Cd(II) and Zn (II). The maximum biosorption capacities for Cd(II) and Zn(II) biosorption by N. commune calculated from Langmuir biosorption isotherm were 126.32 and 115.41 mg/g, respectively. The biosorption isotherm for two biosorbents fitted well with Freundlich isotherm than Langmuir model with correlation coefficient (r² < 0.99). The biosorption kinetic data were fitted well with the pseudo‐second‐order kinetic model. Thus, this study indicated that the N. commune is an efficient biosorbent for the removal of Cd(II) and Zn(II) from aqueous solutions.     

Response Surface Modeling of Cu(II) Removal from Electroplating Waste by Adsorption: Application of Box–Behnken Experimental Design

The use of kaolinite‐based clay minerals as a low‐cost natural adsorbent for the removal of Cu(II) from electroplating waste leachate was studied. Batch experiments were conducted to determine the effects of varying adsorbent loading, initial pH, adsorbent dosage, and contact time. Box–Behnken design with three variables like initial pH, adsorbent dosage, and contact time at three different levels was studied to identify a significant correlation between the effects of these variables to the amount of Cu(II) adsorbed. The methodology identifies the principal experimental variables, which have the greatest effect on the adsorption process. After optimizing the input variables by using Simplex algorithm, the adsorption of Cu(II) was maximal (99.9% with a maximum (positive) standard deviation of 9.4) at pH 6.24, adsorbent dosage of 0.83 g L^?1, and contact time of 97 min, respectively. Furthermore, the experimental values are in good agreement with predicted values, the correlation coefficient and adjusted correlation coefficients were found to be 0.96 and 0.87, respectively.     

Effect of Sample Digestion,Air Filter Contamination,and Post‐adsorption on the Analysis of Trace Elements in Air Particulate Matter

Inductively coupled plasma atomic emission spectrometry and inductively coupled plasma MS are the major analytical tools for trace elements in environmental matrices, however, the underestimate of certain trace elements in analysis of air particulate matter by these two techniques has long been observed. This has been attributed to incomplete sample digestion. Here, we demonstrate that the combined effects of sample digestion, air filter impurities, and post‐adsorption of the analytes contribute to the interference of the analysis. Particular attention should be paid to post‐adsorption of analytes onto air filters after acid digestion.     

Biosorption of Cd(II), Ni(II) and Pb(II) from Aqueous Solution by Dried Biomass of Aspergillus niger: Application of Response Surface Methodology to the Optimization of Process Parameters

In this study, the biosorption of Cd(II), Ni(II) and Pb(II) on Aspergillus niger in a batch system was investigated, and optimal condition determined by means of central composite design (CCD) under response surface methodology (RSM). Biomass inactivated by heat and pretreated by alkali solution was used in the determination of optimal conditions. The effect of initial solution pH, biomass dose and initial ion concentration on the removal efficiency of metal ions by A. niger was optimized using a design of experiment (DOE) method. Experimental results indicated that the optimal conditions for biosorption were 5.22 g/L, 89.93 mg/L and 6.01 for biomass dose, initial ion concentration and solution pH, respectively. Enhancement of metal biosorption capacity of the dried biomass by pretreatment with sodium hydroxide was observed. Maximal removal efficiencies for Cd(II), Ni(III) and Pb(II) ions of 98, 80 and 99% were achieved, respectively. The biosorption capacity of A. niger biomass obtained for Cd(II), Ni(II) and Pb(II) ions was 2.2, 1.6 and 4.7 mg/g, respectively. According to these observations the fungal biomass of A. niger is a suitable biosorbent for the removal of heavy metals from aqueous solutions. Multiple response optimization was applied to the experimental data to discover the optimal conditions for a set of responses, simultaneously, by using a desirability function.     

Soil Microbial and Enzyme Activities Response to Pollution Near an Aluminium Smelter

The aim of this research was to assess the impact caused by a long‐term pollution by fluoride and heavy metals in two soils (PS1 and PS2) near an aluminium smelter in Slovakia, on soil microbial biomass C (MBC), basal respiration, metabolic quotient (qCO₂) water‐soluble organic C (WSOC) and enzymes activities involved in the C, N and P biogeochemical cycles. An unpolluted soil was used as control (C0). Results obtained for soil fluoride content reflected a gradient of fluoride exposure in topsoils of contaminated sites. Decreases in microbial and enzymatic activities and in MBC to organic C ratio were found in PS2 site, which is closer to the smelter and exhibited the highest fluoride content. PS1‐soil showed an extreme alkaline pH caused by leaching of waste effluents from the smelter dumping site, higher contents of Zn, Cu, Pb and Cd, significantly larger MBC, qCO₂ and catalase and urease activities, and much larger basal respiration and dehydrogenase activity than PS2 and C0‐soil. Phosphatase, β‐glucosidase and BAA‐protease were negatively correlated with WSOC, basal respiration and dehydrogenase activity, and showed some degree of inhibition in polluted sites. These results may indicate different responses of microbial communities to ecosystem disturbances, caused by the drastic changes in soil's physicochemical properties as result of the long‐term emissions of fly ash with high levels of contaminants that are still affecting soil microbial and enzymatic activities.     

Bioremediation and fodder potentials of two Sargassum spp. in coastal waters of Shenzhen,South China

In this study, the bioremediation potentials of two seaweeds (Sargassum hemiphyllum and S. henslowianum) against pollution in a coastal mariculture area of Shenzhen, South China, were investigated by comparing the growth, nutrient bioaccumulation capacity of plants from the seaweed bed (control site) with plants from the fish farm. Results indicated that both species are potential candidates for bioremediation in the fish farm areas in terms of their high growth rates and high bioaccumulation capacities on inorganic nutrients. Both Sargassum spp. contain high levels of crude protein (11.7–14.0%) and crude fat (2.2–2.7%), suggesting high nutritional values. The S. hemiphyllum may serve as a good aquaculture fodder with high nutritional compositions and low heavy metal contents. However, heavy metals (Cr, Pb and Cd) of S. henslowianum exceed the maximum allowable concentrations as aquatic feed, which restricts its fodder application. In general, the results of this study may contribute to the marine pollution bioremediation in the coastal areas of South China, especially in mariculture zones.     

Ionic Liquid Modified Resin for the Adsorptive Removal of Dibutyl Phthalate: Equilibrium,Kinetic, and Thermodynamic Studies

This study evaluated the adsorptive properties of dibutyl phthalate (DBP) on room temperature ionic liquid (RTIL) modified XAD‐4 resin. The modified RTIL‐XAD 4 sorbent was characterized by FTIR. Effect of varying experimental conditions such as pH, contact time, temperature, shaking speed, concentrations, and interfering species were investigated by batch adsorption experiments. Adsorption was found to be most favorable at pH 6 within 30 min. Experimental data were evaluated in terms of kinetic, equilibrium, and thermodynamic modeling. Kinetics of the sorption was found to follow pseudo second order rate equation whereas Freundlich and D–R isotherms were the most suitable models to explain sorption phenomenon. Thermodynamically sorption was endothermic, irreversible, and spontaneous in nature.     

Equilibrium,Thermodynamic, and Kinetic Studies on Lead (II) Biosorption from Aqueous Solution by Saccharomyces cerevisiae Biomass

This paper presents a biosorption procedure for the preconcentration of Pb²⁺ ions using Saccharomyces cerevisiae biomass. The influence of several factors including pH, biomass dosage, contact time, and temperature on biosorption efficiency were optimized. At optimum value of all the equilibrium, thermodynamic, and kinetic parameters of Pb²⁺ ion biosorption was investigated by testing the Langmuir and Freundlich models and first and second order kinetic models were applied. The biosorption capacity of S. cerevisiae biomass was determined 89.6 mg/g, while the retained Pb²⁺ ions by S. cerevisiae were reversibly eluted using 5 mol/L HNO₃. Due to the high stability of S. cerevisiae the applied biomass can be used successively ten times with a slightly decrease (about 20%) in the recovery of Pb²⁺ ions. The calculated thermodynamic parameters, ΔG°, ΔH°, and ΔS° showed that the biosorption of Pb²⁺ ion onto S. cerevisiae biomass was feasible, spontaneous, and endothermic under examined conditions. The results of kinetic analysis showed that the biosorption processes of Pb²⁺ ions onto S. cerevisiae biomass followed pseudo second order kinetics.