Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.     

Adsorption characteristics of Cu(II) from aqueous solution onto biochar derived from swine manure

The purpose of this study was to investigate adsorption characteristic of swine manure biochars pyrolyzed at 400 °C and 700 °C for the removal of Cu(II) ions from aqueous solutions. The biochars were characterized using BET surface area, Fourier transform infrared spectroscopy (FTIR), zeta potential, scanning electron microscopy/energy dispersive spectrometer (SEM–EDS), and X-ray diffraction (XRD). The adsorption of Cu(II) ions by batch method was carried out and the optimum conditions were investigated. The adsorption processes of these biochars are well described by a pseudo-second-order kinetic model, and the adsorption isotherm closely fitted the Sips model. Thermodynamic analysis suggested that the adsorption was endothermic. The maximum Cu(II) adsorption capacities of biochars derived from fresh and composted swine manure at 400 °C were 17.71 and 21.94 mg g^?1, respectively, which were higher than those at 700 °C. XRD patterns indicated that the silicate and phosphate particles within the biochars served as adsorption sites for Cu(II). The removal of Cu(II) ions from industrial effluent indicated that the fresh swine manure biochar pyrolyzed at 400 °C can be considered as an effective adsorbent.     

Seizure modeling of Pb(II) and Cd(II) from aqueous solution by chemically modified sugarcane bagasse fly ash: isotherms, kinetics, and column study

Heavy metal pollution is a common environmental problem all over the world. The purpose of the research is to examine the applicability of bagasse fly ash (BFA)—an agricultural waste of sugar industry used for the synthesis of zeolitic material. The zeolitic material are used for the uptake of Pb(II) and Cd(II) heavy metal. Bagasse fly ash is used as a native material for the synthesis of zeolitic materials by conventional hydrothermal treatment without (conventional zeolitic bagasse fly ash (CZBFA)) and with electrolyte (conventional zeolitic bagasse fly ash in electrolyte media (ECZBFA)) media. Heavy metal ions Pb(II) and Cd(II) were successfully seized from aqueous media using these synthesized zeolitic materials. In this study, the zeolitic materials were well characterized by different instrumental methods such as Brunauer–Emmett–Teller, XRF, Fourier transform infrared spectroscopy, powder X-ray diffraction, and scanning electron microscopic microphotographs. The presence of analcime, phillipsite, and zeolite P in adsorbents confirms successful conversion of native BFA into zeolitic materials. Seizure modeling of Pb(II) and Cd(II) was achieved by batch sorption experiments, isotherms, and kinetic studies. These data were used to compare and evaluate the zeolitic materials as potential sorbents for the uptake of heavy metal ions from an aqueous media. The Langmuir isotherm correlation coefficient parameters best fit the equilibrium data which indicate the physical sorption. Pseudo-second-order and intra-particle diffusion model matches best which indicates that the rate of sorption was controlled by film diffusion. The column studies were performed for the practical function of sorbents, and breakthrough curves were obtained, which revealed higher sorption capacity as compared to batch method. Synthesized zeolitic material (CZBFA and ECZBFA), a low-cost sorbent, was proven as potential sorbent for the uptake of Pb(II) and Cd(II) heavy metal ions.     

Biosorption of cadmium(II) and copper(II) ions from aqueous solution by core of Artocarpus odoratissimus

Purpose

This research is on the evaluation of biosorption capability of the core of Artocarpus odoratissimus (Tarap), grown in Brunei Darussalam, towards Cd(II) and Cu(II) ions present in synthetic solutions, and to characterize the surface of Tarap particles.

Methods

Thermogravimetric analysis and surface titrations were conducted to characterize the surface of dried Tarap core particles. Atomic absorption spectroscopic measurements were conducted to determine the extent of removal of Cd(II) and Cu(II) under different experimental conditions.

Results

Mass reductions associated with many exothermic reaction peaks were observed beyond 200°C up to 650°C indicating the combustion of organic matter in Tarap. Dried particles of core of Tarap bear a negative surface charge promoting strong interaction towards positively charged ions, such as Cu(II) and Cd(II). Biosorption of the two metal ions on Tarap, which is relatively high beyond pH?=?4, occurs within a short period of exposure time. The extent of biosorption is enhanced by acid treatment of the biosorbent, and further it does not significantly depend on the presence of nonreacting ions up to an ionic strength of 2.0?M.

Conclusion

Strong attraction between each metal ion and the biosorbent is attributed to the negative surface charge on the biosorbent within a broad pH range. Acid treatment of the biosorbent improves sorption characteristics, suggesting that ion exchange plays an important role in the metal ion??biosorbent interaction process.     

Cu(II) removal using green adsorbents: kinetic modeling and plant scale-up design

Cu(II) adsorption in continuous column using green adsorbents like peanut and almond shell was investigated. Fourier transform infrared (FTIR) spectroscopy, Brunaer-Emmett-Teller (BET) analysis, scanning electron microscopy (SEM), and Point of Zero charge (pH_pzc) determination have been used for characterization of the adsorbents. Experiments were conducted at various operating conditions to calculate the adsorption capacity of the adsorbents. Adsorption studies signify that both the adsorbents have good adsorptive capacity for Cu(II) ion. Equilibrium of adsorption was described using Langmuir isotherm and the highest q_max value for both the adsorbent were obtained at an operating condition of 20 ml/min flow rate, 15 mg/L influent Cu(II) concentration, and 7 cm bed depth. Regeneration of both the adsorbents suggests that these adsorbents can be used several times for Cu(II) removal. Seven different kinetic models were tested among which the modified dose response model was fitted well for peanut shell and the Thomas model was fitted well for almond shell. These fitted models were further used for scale-up design. Regeneration studies show that peanut shell and almond shell are useful up to the fifth adsorption cycle. Application of these adsorbents with industrial effluent was also reported. This study reveals that peanut and almond shells can be used for Cu(II) removal for industrial wastewater.

     

Evaluation of Acinetobacter sp. B9 for Cr (VI) resistance and detoxification with potential application in bioremediation of heavy-metals-rich industrial wastewater

Present work demonstrates Cr (VI) detoxification and resistance mechanism of a newly isolated strain (B9) of Acinetobacter sp. Bioremediation potential of the strain B9 is shown by simultaneous removal of major heavy metals including chromium from heavy-metals-rich metal finishing industrial wastewater. Strain B9 tolerate up to 350 mg L^?1 of Cr (VI) and also shows level of tolerance to Ni (II), Zn (II), Pb (II), and Cd (II). The strain was capable of reducing 67 % of initial 7.0 mg L^?1 of Cr (VI) within 24 h of incubation, while in presence of Cu ions 100 % removal of initial 7.0 and 10 mg L^?1 of Cr (VI) was observed with in 24 h. pH in the range of 6.0–8.0 and inoculum size of 2 % (v/v) were determined to be optimum for dichromate reduction. Fourier transform infrared spectroscopy and transmission electron microscopy studies suggested absorption or intracellular accumulation and that might be one of the major mechanisms behind the chromium resistance by strain B9. Scanning electron microscopy showed morphological changes in the strain due to chromium stress. Relevance of the strain for treatment of heavy-metals-rich industrial wastewater resulted in 93.7, 55.4, and 68.94 % removal of initial 30 mg L^?1 Cr (VI), 246 mg L^?1 total Cr, and 51 mg L^?1 Ni, respectively, after 144 h of treatment in a batch mode.     

Effect of biochars on adsorption of Cu(II), Pb(II) and Cd(II) by three variable charge soils from southern China

The purpose of this study is to compare the relative contribution of different mechanisms to the enhanced adsorption of Cu(II), Pb(II) and Cd(II) by variable charge soils due to incorporation of biochars derived from crop straws. The biochars were prepared from the straws of canola and peanut using an oxygen-limited pyrolysis method at 350 °C. The effect of biochars on adsorption and desorption of Cu(II), Pb(II) and Cd(II) by and from three variable charge soils from southern China was investigated with batch experiments. Based on the desorption of pre-adsorbed heavy metals, the electrostatic and non-electrostatic adsorptions were separated. EDTA was used to replace the heavy metals complexed with biochars and to evaluate the complexing ability of the biochars with the metals. The incorporation of biochars increased the adsorption of Cu(II), Pb(II) and Cd(II) by the soil; peanut straw char induced a greater increase in the adsorption of the three metals. The increased percentage of Cd(II) adsorption induced by biochars was much greater than that for the adsorption of Cu(II) and Pb(II). Cu(II) adsorption on three variable charge soils was enhanced by the two biochars mainly through a non-electrostatic mechanism, while both electrostatic and non-electrostatic mechanisms contributed to the enhanced adsorption of Pb(II) and Cd(II) due to the biochars. Peanut straw char had a greater specific adsorption capacity than canola straw char and thus induced more non-electrostatic adsorption of Cu(II), Pb(II) and Cd(II) by the soils than did the canola straw char. The complexing ability of the biochars with Cu(II) and Pb(II) was much stronger than that with Cd(II) and thus induced more specific adsorption of Cu(II) and Pb(II) by the soils than that of Cd(II). Biochars increased heavy metal adsorption by the variable charge soils through electrostatic and non-electrostatic mechanisms, and the relative contribution of the two mechanisms varied with metals and biochars.     

Removal of Ni(II) and Cu(II) ions using native and acid treated Ni-hyperaccumulator plant Alyssum discolor from Turkish serpentine soil

Alyssum discolor biomass was collected from serpentine soil and was used for removal of metal ions. The plant species grown on serpentine soils are known to be rich with metals ions and thus have more capability for accumulating heavy metals. Native and acid-treated biomass of A. discolor (A. discolor) were utilized for the removal of Ni(II) and Cu(II) ions from aqueous solutions. The effects of contact time, initial concentration, and pH on the biosorption of Ni(II) and Cu(II) ions were investigated. Biosorption equilibrium was established in about 60 min. The surface properties of the biomass preparations were varied with pH, and the maximum amounts of Ni(II) and Cu(II) ions on both A. discolor biomass preparations were adsorbed at pH 5.0. The maximum biosorption capacities of the native, and acid-treated biomass preparations for Ni(II) were 13.1 and 34.7 mg g⁻¹ and for Cu(II) 6.15 and 17.8 mg g⁻¹ dry biomass, respectively. The biosorption of Ni(II) and Cu(II) ions from single and binary component systems can be successfully described by Langmuir and Freundlich isotherms. When the heavy metal ions were in competition, the amounts of biosorbed metal ions on the acid treated plant biomass were found to be 0.542 mmol g⁻¹ for Ni(II) and 0.162 mmol g⁻¹ for Cu(II), the A. discolor biomass was significantly selective for Ni(II) ions. The information gained from these studies was expected to indicate whether the native, and acid-treated forms can have the potential to be used for the removal and recovery of Ni(II) ions from wastewaters.     

Equilibrium, kinetic, and thermodynamic biosorption of Pb(II), Cr(III), and Cd(II) ions by dead anaerobic biomass from synthetic wastewater

Purpose

Heavy metals are toxic pollutants released into the environment as a result of different industrial activities. Biosorption of heavy metals from aqueous solutions is a new technology for the treatment of industrial wastewater. The aim of the present research is to highlight the basic biosorption theory to heavy metal removal.

Materials and methods

Heterogeneous cultures mostly dried anaerobic bacteria, yeast (fungi), and protozoa were used as low-cost material to remove metallic cations Pb(II), Cr(III), and Cd(II) from synthetic wastewater. Competitive biosorption of these metals was studied.

Results

The main biosorption mechanisms were complexation and physical adsorption onto natural active functional groups. It is observed that biosorption of these metals was a surface process. The main functional groups involved in these processes were hydroxyl (–OH) and carboxylic groups (C=O) with 37, 52, and 31 and 21, 14, and 34 % removal of Pb(II), Cr(III), and Cd(II), respectively. Langmuir was the best model for a single system. While extended Langmuir was the best model for binary and ternary metal systems. The maximum uptake capacities were 54.92, 34.78, and 29.99 mg/g and pore diffusion coefficients were 7.23, 3.15, and 2.76?×?10^?11 m²/s for Pb(II), Cr(III), and Cd(II), respectively. Optimum pH was found to be 4. Pseudo-second-order was the best model to predict the kinetic process. Biosorption process was exothermic and physical in nature.

Conclusions

Pb(II) offers the strongest component that is able to displace Cr(III) and Cd(II) from their sites, while Cd(II) ions are the weakest adsorbed component.     

Fixed-bed study for lanthanide (La, Eu, Yb) ions removal from aqueous solutions by immobilized Pseudomonas aeruginosa: experimental data and modelization

A fixed-bed study was carried out by using cells of Pseudomonas aeruginosa immobilized in polyacrylamide gel as a biosorbent for the removal of lanthanide (La, Eu, Yb) ions from aqueous solutions. The effects of superficial liquid velocity based on empty column, particle size, influent concentration and bed depth on the lanthanum breakthrough curves were investigated. Immobilized biomass effectively removed lanthanum from a 6 mM solution with a maximum adsorption capacity of 342 micromolg(-1) (+/-10%) corresponding closely to that observed in earlier batch studies with free bacterial cells. The Bohart and Adams sorption model was employed to determine characteristic parameters useful for process design. Results indicated that the immobilized cells of P. aeruginosa enable removal of lanthanum, europium and ytterbium ions from aqueous effluents with significant and similar maximum adsorption capacities. Experiments with a mixed cation solution showed that the sequence of preferential biosorption was Eu3+ > or = Yb3+ > La3+. Around 96+/-4% of the bound lanthanum was desorbed from the column and concentrated by eluting with a 0.1 M EDTA solution. The feasibility of regenerating and reusing the biomass through three adsorption/desorption cycles was suggested. Neural networks were used to model breakthrough curves performed in the dynamic process. The ability of this statistical tool to predict the breakthrough times was discussed.     

Simultaneous oxidation of EDTA and reduction of metal ions in mixed Cu(II)/Fe(III)-EDTA system by TiO2 photocatalysis

Both the photooxidation of EDTA and the photoreduction of metal ions in metal-EDTA systems were investigated. EDTA oxidation by TiO(2) photocatalysis occurred sequentially as Cu(II)-EDTA>Cu(II)/Fe(III)-EDTA>Fe(III)-EDTA. For Cu(II)-EDTA, EDTA was completely decomposed after only 60min of irradiation. The rate of EDTA decomposition was directly correlated with the initial Cu(II) concentration in the case of a mixed Cu(II)/Fe(III)-EDTA system. The metal ions in a single metal-EDTA complex were removed following significant decomposition of EDTA. For a mixed Cu(II)/Fe(III)-EDTA system, however, no copper was removed whereas almost all of the iron was removed. The iron and copper species deposited on the TiO(2) surface were identified via EPR and XPS as mixed FeO/Fe(3)O(4) and Cu(0)/Cu(2)O, respectively.     

Response surface optimization of a dynamic dye adsorption process: a case study of crystal violet adsorption onto NaOH-modified rice husk

The adsorption of crystal violet from aqueous solution by NaOH-modified rice husk was investigated in a laboratory-scale fixed-bed column. A two-level three factor (2³) full factorial central composite design with the help of Design Expert Version 7.1.6 (Stat Ease, USA) was used for optimisation of the dynamic dye adsorption process and evaluation of interaction effects of different operating parameters: initial dye concentration (100–200 mg L^?1), flow rate (10–30 mL min^?1) and bed height (5–25 cm). A correlation coefficient (R ²) value of 0.999, model F value of 1,936.59 and its low p value (<0.0001) along with lower value of coefficient of variation (1.38 %) indicated the fitness of the response surface quadratic model developed during the present study. Numerical optimisation applying desirability function was used to identify the optimum conditions for a targeted breakthrough time of 12 h. The optimum conditions were found to be initial solution pH?=?8.00, initial dye concentration?=?100 mg L^?1, flow rate?=?22.88 mL min^?1 and bed height?=?18.75 cm. A confirmatory experiment was performed to evaluate the accuracy of the optimised procedure. Under the optimised conditions, breakthrough appeared after 12.2 h and the column efficiency was determined as 99 %. The Thomas model showed excellent fit to the dynamic dye adsorption data obtained from the confirmatory experiment. Thereby, it was concluded that the current investigation gives valuable insights for designing and establishing a continuous wastewater treatment plant.     

Biosorption of Cr(VI) and Zn(II) ions from aqueous solution onto the solid biodiesel waste residue: mechanistic, kinetic and thermodynamic studies

In this present study, the biosorption of Cr(VI) and Zn(II) ions from synthetic aqueous solution on defatted J atropha oil cake (DJOC) was investigated. The effect of various process parameters such as the initial pH, adsorbent dosage, initial metal ion concentration and contact time has been studied in batch-stirred experiments. Maximum removal of Cr(VI) and Zn(II) ions in aqueous solution was observed at pH 2.0 and pH. 5.0, respectively. The removal efficiency of Cr(VI) and Zn(II) ions from the aqueous solution was found to be 72.56 and 79.81 %, respectively, for initial metal ion concentration of 500 mg/L at 6 g/L dosage concentration. The biosorbent was characterized by Fourier transform infrared, scanning electron microscopy and zero point charge. Equilibrium data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models and the best fit is found to be with the Freundlich isotherm for both Cr(VI) and Zn(II) metal ions. The kinetic data obtained at different metal ion concentration have been analysed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion models and were found to follow the pseudo-second-order kinetic model. The values of mass transfer diffusion coefficients (D _e) were determined by Boyd model and compared with literature values. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were analysed using the equilibrium constant values (K _e) obtained from experimental data at different temperatures. The results showed that biosorption of Cr(VI) and Zn(II) ions onto the DJOC system is more spontaneous and exothermic in nature. The results indicate that DJOC was shown to be a promising adsorbent for the removal of Cr(VI) and Zn(II) ions from aqueous solution.     

Removal of Pb(II) and Cd(II) ions from water by Fe and Ag nanoparticles prepared using electro-exploding wire technique

Purpose

This work aimed at investigating the adsorption of lead and cadmium onto Fe and Ag nanoparticles for use as a water contaminant removal agent as a function of particle type, sorbent concentration, and contact time.

Methods

Fe and Ag spherical nanoparticles were prepared in water by the lab-made electro-exploding wire (EEW) system and were investigated for their structure properties. Adsorption experiments were carried out at room temperature and pH 8.3 water solutions.

Results

The removal/adsorption of both Pb(II) and Cd(II) ions was found to be dependent on adsorbent dosage and contact time. Pb(II) adsorption onto Fe and Ag nanoparticles showed more or less similar efficiency and behavior. The kinetic data for the adsorption process obeyed pseudo second-order rate equations. The calculated equilibrium adsorption capacities (q _e) were 813 and 800 mg/g for Pb sorption onto Fe and Ag nanoparticles, respectively. Cd(II) ion adsorption onto Fe nanoparticles obeyed pseudo second-order rate equations with q _e equal to 242 mg/g, while their adsorption onto Ag nanoparticles obeyed pseudo first-order rate equations with q _e of 794 mg/g. The calculated q _es are in quite agreement with the experimental values. The removal/uptake mechanisms of metal ions involved interaction between the metal ion and the oxide/hydroxyl layer around the spherical metallic core of the nanoparticle in water medium.

Conclusion

Fe and Ag nanoparticles prepared using the EEW technique exhibited high potentials for the removal of metal ions from water with very high adsorption capacities, suggesting that the EEW technique can be enlarged to generate nanoparticles with large quantities for field or site water purification.     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

Removal of Cu, Zn, and Cd from aqueous solutions by the dairy manure-derived biochar

Purpose

Biochar derived from waste biomass is now gaining much attention for its function as a biosorbent for environmental remediation. The objective of this study was to determine the effectiveness of biochar as a sorbent in removing Cd, Cu, and Zn from aqueous solutions.

Methods

Biochar was produced from dairy manure (DM) at two temperatures: 200°C and 350°C, referred to as DM200 and DM350, respectively. The obtained biochars were then equilibrated with 0–5 mM Cu, Zn or Cd in 0.01 M NaNO₃ solution for 10 h. The changes in solution metal concentrations after sorption were evaluated for sorption capacity using isotherm modeling and chemical speciation Visual MINTEQ modeling, while the solid was collected for species characterization using infrared spectroscopy and X-ray elemental dot mapping techniques.

Results

The isotherms of Cu, Zn, and Cd sorption by DM200 were better fitted to Langmuir model, whereas Freundlich model well described the sorption of the three metals by DM350. The DM350 were more effective in sorbing all three metals than DM200 with both biochars had the highest affinity for Cu, followed by Zn and Cd. The maximum sorption capacities of Cu, Zn, and Cd by DM200 were 48.4, 31.6, and 31.9 mg g^?1, respectively, and those of Cu, Zn, and Cd by DM350 were 54.4, 32.8, and 51.4 mg g^?1, respectively. Sorption of the metals by the biochar was mainly attributed to their precipitation with PO ₄ ^3? or CO ₃ ^2? originating in biochar, with less to the surface complexation through –OH groups or delocalized π electrons. At the initial metal concentration of 5 mM, 80–100 % of Cu, Zn, and Cd retention by DM200 resulted from the precipitation, with less than 20 % from surface adsorption through phenonic –OH complexation. Among the precipitation, 20–30 % of the precipitation occurred as metal phosphate and 70–80 % as metal carbonate. For DM350, 75–100 % of Cu, Zn, and Cd retention were due to the precipitation, with less than 25 % to surface adsorption through complexation of heavy metal by phenonic –OH site or delocalized π electrons. Among the precipitation, only less than 10 % of the precipitation was present as metal phosphate and more than 90 % as metal carbonate.

Conclusions

Results indicated that dairy manure waste can be converted into value-added biochar as a sorbent for sorption of heavy metals, and the mineral components originated in the biochar play an important role in the biochar's high sorption capacity.     

Distribution of selected essential (Co, Cu, Fe, Mn, Mo, Se, and Zn) and nonessential (Cd, Pb) trace elements among protein fractions from hepatic cytosol of European chub (Squalius cephalus L.)

Association of selected essential (Co, Cu, Fe, Mn, Mo, Se, and Zn) and nonessential (Cd, Pb) trace elements with cytosolic proteins of different molecular masses was described for the liver of European chub (Squalius cephalus) from weakly contaminated Sutla River in Croatia. The principal aim was to establish basic trace element distributions among protein fractions characteristic for the fish living in the conditions of low metal exposure in the water. The fractionation of chub hepatic cytosols was carried out by size exclusion high performance liquid chromatography (SE-HPLC; Superdex? 200 10/300 GL column), and measurements were performed by high resolution inductively coupled plasma mass spectrometry (HR ICP-MS). Elution profiles of essential elements were mostly characterized by broad peaks covering wide range of molecular masses, as a sign of incorporation of essential elements in various proteins within hepatic cytosol. Exceptions were Cu and Fe, with elution profiles characterized by sharp, narrow peaks indicating their probable association with specific proteins, metallothionein (MT), and ferritin, respectively. The main feature of the elution profile of nonessential metal Cd was also single sharp, narrow peak, coinciding with MT elution time, and indicating almost complete Cd detoxification by MT under the conditions of weak metal exposure in the water (dissolved Cd concentration ≤0.3 μg L^?1). Contrary, nonessential metal Pb was observed to bind to wide spectrum of proteins, mostly of medium molecular masses (30–100 kDa), after exposure to dissolved Pb concentration of ~1 μg L^?1. The obtained information within this study presents the starting point for identification and characterization of specific metal/metalloid-binding proteins in chub hepatic cytosol, which could be further used as markers of metal/metalloid exposure or effect on fish.     

Nanocellulosic fiber-modified carbon paste electrode for ultra trace determination of Cd (II) and Pb (II) in aqueous solution

In recent years, increasing awareness of the environmental impact of heavy metals has prompted a demand for monitoring and decontaminating industrial wastes prior to discharging into natural water bodies. This paper describes the preparation and electrochemical application of carbon paste electrode modified with nanocellulosic fibers for the determination of cadmium and lead in water samples using anodic stripping voltammetry. First, cadmium and lead were adsorbed on the carbon paste electrode surface at open circuit potential, followed by anodic stripping voltammetric scan from -1 to 0 V. Different factors affecting sensitivity and precision of the electrode, including accumulating solvent, pH of the accumulating solvent, accumulation time, supporting electrolyte, and scan rate were investigated. The proposed method was also applied to the determination of Cd (II) and Pb (II) in the presence of other interfering metal ions and cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, and Triton X-100 as a representative of cationic, anionic, and neutral surfactants. Linear calibration curves were obtained in the concentration ranges of 150–650 μg?L^?1 and 80–300 μg?L^?1, respectively, for cadmium and lead at an accumulated time of 10 min with limits of detection 88 and 33 μg?L^?1. Optimized working conditions are defined as acetate buffer of pH?5 as accumulating solvent, hydrochloric acid as supporting electrolyte, and scan rate 50 mV/s. This technique does not use mercury and therefore has a positive environmental benefit. The method is reasonably sensitive and selective and has been successfully applied to the determination of trace amounts of Cd (II) and Pb (II) in water samples.     

Electrochemical Monitoring of Methylparathion Degradation in an Acid Aqueous Medium in Presence of Cu(II)

Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10^?3 s^?1 at pH 2, 5.5 × 10^?3 s^?1 at pH 4 and 9.0 × 10^?3 s^?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Distribution of potentially toxic elements (PTEs) in tailings,soils, and plants around Gol-E-Gohar iron mine,a case study in Iran

This study investigated the concentration of potentially toxic elements (PTEs) including Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, V, and Zn in 102 soils (in the Near and Far areas of the mine), 7 tailings, and 60 plant samples (shoots and roots of Artemisia sieberi and Zygophylum species) collected at the Gol-E-Gohar iron ore mine in Iran. The elemental concentrations in tailings and soil samples (in Near and Far areas) varied between 7.4 and 35.8 mg kg^?1 for As (with a mean of 25.39 mg kg^?1 for tailings), 7.9 and 261.5 mg kg^?1 (mean 189.83 mg kg^?1 for tailings) for Co, 17.7 and 885.03 mg kg^?1 (mean 472.77 mg kg^?1 for tailings) for Cu, 12,500 and 400,000 mg kg^?1 (mean 120,642.86 mg kg^?1 for tailings) for Fe, and 28.1 and 278.1 mg kg^?1 (mean 150.29 mg kg^?1 for tailings) for Ni. A number of physicochemical parameters and pollution index for soils were determined around the mine. Sequential extractions of tailings and soil samples indicated that Fe, Cr, and Co were the least mobile and that Mn, Zn, Cu, and As were potentially available for plants uptake. Similar to soil, the concentration of Al, As, Co, Cr, Cu, Fe, Mn, Mo, Ni, and Zn in plant samples decreased with the distance from the mining/processing areas. Data on plants showed that metal concentrations in shoots usually exceeded those in roots and varied significantly between the two investigated species (Artemisia sieberi > Zygophylum). All the reported results suggest that the soil and plants near the iron ore mine are contaminated with PTEs and that they can be potentially dispersed in the environment via aerosol transport and deposition.