Biosorption of cadmium(II), lead (II) and copper(II) with the filamentous fungus Phanerochaete chrysosporium

The biosorption from artificial wastewaters of heavy metals (Cd(II), Pb(II) and Cu(II)) onto the dry fungal biomass of Phanerochaete chryosporium was studied in the concentration range of 5-500 mg l(-1). The maximum absorption of different heavy metal ions on the fungal biomass was obtained at pH 6.0 and the biosorption equilibrium was established after about 6 h. The experimental biosorption data for Cd(II), Pb(II) and Cu(II) ions were in good agreement with those calculated by the Langmuir model.     

Ultrasensitive and dual functional colorimetric sensors for mercury (II) ions and hydrogen peroxide based on catalytic reduction property of silver nanoparticles

The method provides an innovative dual functional sensors for mercury (II) ions and hydrogen peroxide. The addition of H(2)O(2) to the mixture of silver nanoparticles (AgNPs) and Hg(2+) induced color changes of the solution within several seconds even at 2.0 nM Hg(2+). Other metallic ions could not induce color change even at 10 μM. Of importance, this probe was not only successfully applied to detect Hg(2+), but also it could be used to sense H(2)O(2) at a concentration as low as 50 nM (by naked-eye). The outstanding sensitivity and selectivity property for Hg(2+) and H(2)O(2) resulted from the AgNPs mediated reduction of Hg(2+) to elementary Hg in the presence of H(2)O(2), causing the aggregation and colorimetric response of AgNPs. This sensitive and selective colorimetric assay opens up a fresh insight of development facile and fast detection methods for metal ions and biomolecules using the special catalytic reactivity of AgNPs.     

Activation of pine cone using Fenton oxidation for Cd(II) and Pb(II) removal

This paper describes activation of pine cone with Fenton reagent and determines the removal of Cd(II) and Pb(II) ions from aqueous solution. Changes of the surface properties of adsorbent materials were determined by the FT-IR and SEM analysis after activation of pine cone. The effect of Fe(2+)/H(2)O(2) ratio, ORP, pH and contact time were determined. Different adsorption isotherms were also obtained using concentrations of heavy metal ions ranging from 0.1 to 150mgL(-1). The adsorption process follows pseudo-first-order reaction kinetics and follows the Langmuir adsorption isotherm. The study discusses thermodynamic parameters, including changes in Gibbs free energy, entropy, and enthalpy, for the adsorption of Cd(II) and Pb(II) on activated cone, and revealed that the adsorption process was spontaneous and exothermic under natural conditions. The maximum removal efficiencies were obtained as 91% and 89% at pH 7 with 90 and 105-min contact time for Cd(II) and Pb(II), respectively.     

Highly sensitive oligonucleotide-based fluorometric detection of mercury(II) in aqueous media

This paper describes a highly sensitive and selective Hg(2+) sensor using a label free Hg(2+) specific probe (5'-18T-3') and an intercalation dye SYBR Green I (SG). The Hg(2+) specific probe is composed of thymines (T) and readily forms T-Hg(2+)-T complexes in the presence of Hg(2+). This specific T-Hg(2+)-T formation affects the hybridization of the Hg(2+) specific probe and the intercalation of SG. Upon treatment of 1 nM 5'-18T-3' with different amount of Hg(2+) (0.1-10nM), which is followed by hybridization with 1 nM 5'-18T-3' and incubation with 1 microL of SG, the solution fluorescence gave a linear response (R=0.996) to the concentration of Hg(2+). The detection limit for Hg(2+) was 0.5 nM (0.1 ppb). The overall test only takes few minutes and very little interference is observed from non-specific metal ions. This approach may find potential applications in monitoring the Hg(2+) concentration in drinking water.     

Oligonucleotide probes applied for sensitive enzyme-amplified electrochemical assay of mercury(II) ions

We developed a novel electrochemical sensor for Hg(2+) detection using two mercury-specific oligonucleotide probes and streptavidin-horseradish peroxidase (HRP) enzymatic signal amplification. The two mercury-specific oligonucleotide probes comprised a thiolated capture probe and a biotinated signal probe. The thiolated capture probe was immobilized on a gold electrode. In the presence of Hg(2+), the thymine-Hg(2+)-thymine (T-Hg(2+)-T) interaction between the mismatched T-T base pairs directed the biotinated signal probe hybridizing to the capture probe and yielded a biotin-functioned electrode surface. HRP was then immobilized on the biotin-modified substrate via biotin-streptavidin interaction. The immobilized HRP catalyzed the oxidation of hydroquinone (H(2)Q) to benzoquinone (BQ) by hydrogen peroxide (H(2)O(2)) and the generated BQ was further electrochemically reduced at the modified gold electrode, producing a readout signal for quantitative detection of Hg(2+). The results showed that the enzyme-amplified electrochemical sensor system was highly sensitive to Hg(2+) in the concentration of 0.5 nM to 1 μM with a detection limit of 0.3 nM, and it also demonstrated excellent selectivity against other interferential metal ions.     

Peptidic models for the binding of Pb(II), Bi(III) and Cd(II) to mononuclear thiolate binding sites

Herein, we evaluate the binding of Pb(II) and Bi(III) to cysteine-substituted versions of the TRI peptides [AcG-(LKALEEK)₄G-NH₂] which have previously been shown to bind Hg(II) and Cd(II) in unusual geometries as compared with small-molecule thiol ligands in aqueous solutions. Studies of Pb(II) and Bi(III) with the peptides give rise to complexes consistent with the metal ions bound to three sulfur atoms with M–S distances of 2.63 and 2.54 Å, respectively. Competition experiments between the metal ions Pb(II), Cd(II), Hg(II) and Bi(III) for the peptides show that Hg(II) has the highest affinity, owing to the initial formation of the extremely strong HgS₂ bond. Cd(II) and Pb(II) have comparable binding affinities at pH > 8, while Bi(III) displays the weakest affinity, following the model, M(II) + (TRI LXC)₃ ^3? → M(II)(TRI LXC)₃ ^?. While the relevant equilibria for Hg(II) binding to the TRI peptides corresponds to a strong first step forming Hg(TRI LXC)₂(HTRI LXC), followed by a single deprotonation to give Hg(TRI LXC)₃ ^?, the binding of Cd(II) and Pb(II) is consistent with initial formation of M(II)(TRI LXC)(HTRI LXC)₂ ⁺ at pH < 5 followed by a two-proton dissociation step (pK _a2) yielding M(II)(TRI LXC)₃ ^?. Pb(II)(TRI LXC)(HTRI LXC)₂ ⁺ converts to Pb(II)(TRI LXC)₃ ^? at slightly lower pH values than the corresponding Cd(II)–peptide complexes. In addition, Pb(II) displays a lower pK _a of binding to the “d”-substituted peptide, (TRI L12C, pK _a2 = 12.0) compared with the “a”-substituted peptide, (TRI L16C, pK _a2 = 12.6), the reverse of the order seen for Hg(II) and Cd(II). Pb(II) also showed a stronger binding affinity for TRI L12C (K _bind = 3.2 × 10⁷ M^?1) compared with that with TRI L16C (K _bind = 1.2 × 10⁷ M^?1) at pH > 8.     

Sensitive label-free oligonucleotide-based microfluidic detection of mercury (II) ion by using exonuclease I

Mercury is a highly toxic metal that can cause significant harm to humans and aquatic ecosystems. This paper describes a novel approach for mercury (Hg(2+)) ion detection by using label-free oligonucleotide probes and Escherichia coli exonuclease I (Exo I) in a microfluidic electrophoretic separated platform. Two single-stranded DNAs (ssDNA) TT-21 and TT-44 with 7 Thymine-Thymine mispairs are employed to capture mercury ions. Due to the coordination structure of T-Hg(2+)-T, these ssDNAs are folded into hairpin-like double-stranded DNAs (dsDNA) which are more difficult to be digested by Exo I, as confirmed by polyacrylamide gel electrophoresis (PAGE) analysis. A series of microfluidic capillary electrophoretic separation studies are carried out to investigate the effect of Exo I and mercury ion concentrations on the detected fluorescence intensity. This method has demonstrated a high sensitivity of mercury ion detection with the limit of detection around 15 nM or 3 ppb. An excellent selectivity of the probe for mercury ions over five interference ions Fe(3+), Cd(2+), Pb(2+), Cu(2+) and Ca(2+) is also revealed. This method could potentially be used for mercury ion detection with high sensitivity and reliability.     

重金属离子对黑斑蛙胚胎及蝌蚪的毒性影响

本文研究了5种重金属对黑斑蛙胚胎期及蝌蚪期的毒性作用,结果表明,各重金属离子对胚胎期中的孵化期和开口期毒性较大,其余各期毒性较小。各重金属离子对胚胎的毒性顺序为Hg     

Adsorption of toxic mercury(II) by an extracellular biopolymer poly(gamma-glutamic acid)

Adsorption of mercury(II) by an extracellular biopolymer, poly(gamma-glutamic acid) (gamma-PGA), was studied as a function of pH, temperature, agitation time, ionic strength, light and heavy metal ions. An appreciable adsorption occurred at pH>3 and reached a maximum at pH 6. Isotherms were well predicted by Redlich-Peterson model with a dominating Freundlich behavior, implying the heterogeneous nature of mercury(II) adsorption. The adsorption followed an exothermic and spontaneous process with increased orderliness at solid/solution interface. The adsorption was rapid with 90% being attained within 5 min for a 80 mg/L mercury(II) solution, and the kinetic data were precisely described by pseudo second order model. Ionic strength due to added sodium salts reduced the mercury(II) binding with the coordinating ligands following the order: Cl(-) >SO(4)(2-) >NO(3)(-). Both light and heavy metal ions decreased mercury(II) binding by gamma-PGA, with calcium(II) ions showing a more pronounced effect than monovalent sodium and potassium ions, while the interfering heavy metal ions followed the order: Cu(2+) > Cd(2+) > Zn(2+). Distilled water adjusted to pH 2 using hydrochloric acid recovered 98.8% of mercury(II), and gamma-PGA reuse for five cycles of operation showed a loss of only 6.5%. IR spectra of gamma-PGA and Hg(II)-gamma-PGA revealed binding of mercury(II) with carboxylate and amide groups on gamma-PGA.     

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.     

Carbon nanoparticle for highly sensitive and selective fluorescent detection of mercury(II) ion in aqueous solution

In this article, carbon nanoparticles (CNPs) were used as a novel fluorescent sensing platform for highly sensitive and selective Hg(2+) detection. To the best of our knowledge, this is the first example of CNPs obtained from candle soot used in this type of sensor. The general concept used in this approach is based on that adsorption of the fluorescently labeled single-stranded DNA (ssDNA) probe by CNP via π-π stacking interactions between DNA bases and CNP leads to substantial dye fluorescence quenching; however, in the presence of Hg(2+), T-Hg(2+)-T induced hairpin structure does not adsorb on CNP and thus retains the dye fluorescence. A detection limit as low as 10nM was achieved. The present CNP-based biosensor for Hg(2+) detection exhibits remarkable specificity against other possible metal ions. Furthermore, superior selectivity performance was observed when Hg(2+) detection was carried out in the presence of a large amount of other interference ions. Finally, in order to evaluate its potential practical application, Hg(2+) detection was conducted with the use of lake water other than pure buffer and it is believed that it holds great promise for real sample analysis upon further development.     

A zinc(II)/lead(II)/cadmium(II)-inducible operon from the Cyanobacterium anabaena is regulated by AztR, an alpha3N ArsR/SmtB metalloregulator

A novel Zn(II)/Pb(II)/Cd(II)-responsive operon that consists of genes encoding a Zn(II)/Pb(II) CPx-ATPase efflux pump (aztA) and a Zn(II)/Cd(II)/Pb(II)-specific SmtB/ArsR family repressor (aztR) has been identified and characterized from the cyanobacterium Anabaena PCC 7120. In vivo real time quantitative RT-PCR assays reveal that both aztR and aztA expression are induced by divalent metal ions Zn(II), Cd(II), and Pb(II) but not by other divalent [Co(II), Ni(II)] or monovalent metal ions [Cu(I) and Ag(I)]. The introduction of a plasmid containing the azt operon into a Zn(II)/Cd(II)-hypersensitive Escherichia coli strain GG48 functionally restores Zn(II) and Pb(II) resistance with a limited effect on Cd(II) resistance. Gel mobility shift assays and aztR O/P-lacZ induction experiments confirm that AztR is the metal-regulated repressor of this operon. In vitro biochemical and mutagenesis studies indicate that AztR contains a sole metal-binding site, designated the alpha3N site, that binds Zn(II), Cd(II), and Pb(II) with a high affinity. Optical absorption spectra of Co(II)- and Cd(II)-substituted AztR and (113)Cd NMR spectroscopy of (113)Cd(II)-substituted AztR reveal that the sole alpha3N site in AztR is a CadC-like distorted tetrahedral S(3)(N,O) metal site. The first metal-coordination shell in the AztR alpha3N site differs from other alpha3N family members that sense Cd(II)/Pb(II) and those alpha5 repressors that sense Zn(II)/Co(II). Our results reveal that the alpha3N site in AztR mediates derepression of the azt operon in the presence of Zn(II), as well as Cd(II) and Pb(II); this might have provided Anabaena with an evolutionary advantage to adapt to heavy-metal-rich environments, while maintaining homeostasis of an essential metal ion, Zn(II).     

Target-induced structure-switching DNA hairpins for sensitive electrochemical monitoring of mercury (II)

A simple, sensitive and reusable electrochemical sensor was designed for determination of mercury (II) (Hg(2+)) by coupling target-induced conformational switch of DNA hairpins with thymine-Hg(2+)-thymine (T-Hg(2+)-T) coordination chemistry. The hairpin probe consisted of a stem of 6 base pairs enclosing a 14 nucleotide (nt) loop and an additional 12 nt sticky end at the 3' end. Each hairpin was labeled with ferrocene (Fc) redox tag in the middle of the loop, which was immobilized on the electrode via self-assembly of the terminal thiol moiety at the 5' end. In the presence of target analyte, Hg(2+)-mediated base pairs induced the conformational change from the sticky end to open the hairpins, resulting in the ferrocene tags close to the electrode for the increasing redox current. The strong coordination reaction of T-Hg(2+)-T resulted in a good repeatability and intermediate precision down to 10%. The dynamic concentration range spanned from 5.0nM to 1.0μM Hg(2+) with a detection limit of 2.5nM at the 3s(blank) level. The strategy afforded exquisite selectivity for Hg(2+) against other environmentally related metal ions. Inspiringly, the developed sensor could be reused by introduction of iodide (I(-)).     

Investigations of Hg(II) and Pb(II) tolerance,removal and bioaccumulation and their effects on antioxidant enzymes on thermophilic Exiguobacterium profundum

Abstract

Hg(II) and Pb(II) tolerance, removal, bioaccumulation and effects on antioxidant enzymes of thermophilic Exiguobacterium profundum were investigated. The results indicated that Hg(II) was more toxic than Pb(II) to E. profundum. E. profundum was also more tolerant in solid medium than in liquid medium for Pb(II) and Hg(II). The bacterial growth was not significantly influenced at 1.0 and 2.5?mg/L Pb(II) and Hg(II) for 24?h. The highest Hg(II) and Pb(II) bioaccumulation amounts were determined as 37.56 and 54.35?mg metal/dried bacteria, respectively. Bioaccumulation capacities of the cell membrane of E. profundum for Hg(II) and Pb(II) were determined. The different concentrations of Pb(II) and Hg(II) enhanced the SOD and CAT enzymes. In addition, variations of the surface macrostructure and the functionality of E. profundum after the interaction with Hg(II) and Pb(II) were investigated by the scanning electron microscope (SEM) and the Fourier transform infrared spectroscopy (FT-IR), respectively.

This investigation obviously showed that thermophilic E. profundum can also be applied for removal and recovery of toxic metals from industrial wastewater. Clearly, a further investigation should be utilized by thermophilic microorganisms. According to antioxidant enyzme activities, E. profundum can be also used as a bioindicator for the detection of toxic metal pollution in natural water samples.     

Sorption of Cu(II) and Cd(II) by extracellular polymeric substances (EPS) from Aspergillus fumigatus

Sorption of Cu(II) and Cd(II) onto the extracellular polymeric substances (EPS) produced by Aspergillus fumigatus was investigated for the initial pH of the solution, EPS concentrations, contact time, NaCl concentration, initial metal ion concentration and the presence of other ions in the solution. The results showed that the adsorption of metal ions was significantly affected by pH, EPS concentrations, initial metal concentration, NaCl concentration and co-ions. The sorption of Cu(II) and Cd(II) increased with increasing pH and initial metal ion concentration but decreased with an increase in the NaCl concentration. The maximum sorption capacities of A. fumigatus EPS calculated from the Langmuir model were 40 mg g⁻¹ EPS and 85.5 mg g⁻¹ EPS for Cu(II) and Cd(II), respectively. The binary metal sorption experiments showed a selective metal binding affinity in the order of Cu(II) > Pb(II) > Cd(II). Both the Freundlich and Langmuir adsorption models described the sorption of Cu(II) and Cd(II) by the EPS of A. fumigatus adequately. Fourier transform infrared spectroscopy (FTIR) analysis revealed that carboxyl, amide and hydroxyl functional groups were mainly correlated with the sorption of Cu(II) and Cd(II). Energy dispersive X-ray (EDX) system analysis revealed that the ion-exchange was an important mechanism involved in the Cu(II) and Cd(II) sorption process taking place on EPS.     

Synergistic Removal of Pb(II), Cd(II) and Humic Acid by Fe3O4@Mesoporous Silica-Graphene Oxide Composites

The synergistic adsorption of heavy metal ions and humic acid can be very challenging. This is largely because of their competitive adsorption onto most adsorbent materials. Hierarchically structured composites containing polyethylenimine-modified magnetic mesoporous silica and graphene oxide (MMSP-GO) were here prepared to address this. Magnetic mesoporous silica microspheres were synthesized and functionalized with PEI molecules, providing many amine groups for chemical conjugation with the carboxyl groups on GO sheets and enhanced the affinity between the pollutants and the mesoporous silica. The features of the composites were characterized using TEM, SEM, TGA, DLS, and VSM measurements. Series adsorption results proved that this system was suitable for simultaneous and efficient removal of heavy metal ions and humic acid using MMSP-GO composites as adsorbents. The maximum adsorption capacities of MMSP-GO for Pb(II) and Cd (II) were 333 and 167 mg g⁻¹ caculated by Langmuir model, respectively. HA enhances adsorption of heavy metals by MMSP-GO composites due to their interactions in aqueous solutions. The underlying mechanism of synergistic adsorption of heavy metal ions and humic acid were discussed. MMSP-GO composites have shown promise for use as adsorbents in the simultaneous removal of heavy metals and humic acid in wastewater treatment processes.     

Cd (II) stress response during the growth of Aspergillus niger B 77

Aims:  To investigate the relationship between growth, heavy metal ions uptake and participation of the antioxidant enzymes superoxide dismutase (SOD) and catalase (CAT) in the protection of Apergillus niger B 77 against cadmium stress.
Methods and Results:  The stress response of the model fungal strain, under conditions of a wide range of Cd (II) ion concentrations, was investigated by determining the biomass formation, protein biosynthesis, SOD and CAT activities and heavy metal uptake in growing cells. Exposure to heavy metal ions induced an increase in protein content, heavy metal uptake and SOD activity, and a heavy decrease in CAT activity.
Conclusion:  The results obtained indicated that the tolerance of A. niger to Cd (II) was correlated with the heavy metal uptake, reactive oxygen species generation in the cells and the efficiency of antioxidative defence system.
Significance and Impact of the Study:  Evidence is provided for the possibility that oxidative stress plays a major role in the effect of Cd (II) ions on A. niger . These data could offer useful information when creating new strategies and methodological improvements for bioremediation with the participation of fungi.     

Invertase inhibition based electrochemical sensor for the detection of heavy metal ions in aqueous system: Application of ultra-microelectrode to enhance sucrose biosensor's sensitivity

We are reporting fabrication and characterization of electrochemical sucrose biosensor using ultra-microelectrode (UME) for the detection of heavy metal ions (Hg(II), Ag(I), Pb(II) and Cd(II)). The working UME, with 25 microm diameter, was modified with invertase (INV, EC: 3.2.1.26) and glucose oxidase (GOD, EC: 1.1.3.4) entrapped in agarose-guar gum. The hydrophilic character of the agarose-guar gum composite matrix was checked by water contact angle measurement. The atomic force microscopy (AFM) images of the membranes showed proper confinement of both the enzymes during co-immobilization. The dynamic range for sucrose biosensor was achieved in the range of 1 x 10(-10) to 1 x 10(-7)M with lower detection limit 1 x 10(-10)M at pH 5.5 with 9 cycles of reuse. The spectrophotometric and electrochemical studies showed linear relationship between concentration of heavy metal ions and degree of inhibition of invertase. The toxicity sequence for invertase using both methods was observed as Hg(2+)>Pb(2+)>Ag(+)>Cd(2+). The dynamic linear range for mercury using electrochemical biosensor was observed in the range of 5 x 10(-10) to 12.5 x 10(-10)M for sucrose. The lower detection limit for the fabricated biosensor was found to be 5 x 10(-10)M. The reliability of the electrochemical biosensor was conformed by testing the spike samples and the results were comparable with the conventional photometric DNSA method.