scholarly journals Trace metals in the open oceans: speciation modelling based on humic-type ligands

2011 ◽  
Vol 8 (3) ◽  
pp. 304 ◽  
Author(s):  
Anthony Stockdale ◽  
Edward Tipping ◽  
John Hamilton-Taylor ◽  
Stephen Lofts

Environmental contextSpeciation of trace metals in the oceans is typically explained by invoking the concept of metal binding to specific organic ligands. Here, using a speciation model widely used for freshwaters, we assess the extent to which non-specific humic-type ligands found in the ocean may explain chemical speciation of cationic metals. We found that the model can give good fits in some cases, and that experimental results do not give consistent variation from the model. This has implications for the way that the availability of trace elements is considered in ocean environments. AbstractThe speciation of trace metals in the oceans is typically explained by invoking the concept of metal binding to specific organic ligands, but a lack of detailed knowledge about the ligands has impeded the formulation of comprehensive models to predict speciation chemistry. The aim of our study was to shed further light on the possible role of humic-type ligands in trace metal complexation in the oceans by comparing published seawater (open ocean) speciation measurements with predictions obtained using a speciation model typically used for freshwater and soil systems (Windermere Humic Aqueous Model; WHAM). We show that in some cases, speciation of trace metals in seawater environments may be reasonably predicted using this model with its default parameter set, without any model fitting. The results support the idea that humic-type ligands may account for much of the observed organic binding at least in the cases of Fe, Cu and Pb. Although the model does not consistently provide agreement with the measured values, it provides a useful benchmark to compare different datasets and to examine variation in speciation as a result of varying levels of competing metal ion concentration and fulvic acid activity.

2021 ◽  
Vol 25 (1) ◽  
pp. 853-864
Author(s):  
Gideon Masedi Nii Ayi Lomoko ◽  
Dainius Paliulis ◽  
Karlis Valters

Abstract The discharge of wastewater containing heavy metals into waterbodies is a major environmental issue that can influence the quality of the water supply; therefore, it is important to remove the pollutants dangerous to living organisms. The adsorption of copper (II) ions on modified wheat bran was investigated with respect to initial solution pH (2.0-7.0), contact time (5–120 min), adsorbent mass (0.5 g and 1.0 g), and initial metal ion concentration (2.0–20 mg/L). The optimum adsorption conditions were found to be at pH 5.0 and a contact time of 60 min with an adsorbent mass of 1.0 g where the maximum efficiency was recorded as 84.5 %. The adsorption uptake (in mg/g) of copper (II) ions slowly reached equilibrium in around 30 min and this amount was 0.30 mg/g using an adsorbent mass of 0.5 g. The adsorption uptake of copper (II) ions decreased with increasing mass of adsorbent and the adsorption efficiency (in %) increased with increasing mass of adsorbent. The experimental results were described using the Langmuir and Freundlich models, with the Langmuir model fitting better than the Freundlich model. The maximum modelled adsorption capacity was 4.24 mg/g and the modelled specific surface area of modified wheat bran was 6.36 m2. It was observed that the adsorption of copper (II) ions on modified wheat bran is efficient and suitable, therefore modified wheat bran is a relatively good adsorbent for the removal of copper (II) ions from polluted water compared to other agricultural adsorbents.


2009 ◽  
Vol 2009 ◽  
pp. 1-7 ◽  
Author(s):  
Shiguo Chen ◽  
Changhu Xue ◽  
Jingfeng Wang ◽  
Hui Feng ◽  
Yuming Wang ◽  
...  

The adsorption of Cd(II) and Pb(II) by squid melanin was investigated. At a metal ion concentration of 2 mM/L, the biosorption efficiency of melanin reached 95% for Cd(II) and Pb(II). The maximum content of bound Cd(II) and Pb(II) was 0.93 mM/g and 0.65 mM/g, respectively. Temperature had no obvious effect on the adsorption of the metals, and in a pH range of 4.0–7.0, the adsorption yield was high and stable. Macrosalts such as NaCl,MgCl2, andCaCl2had no obvious effect on the binding of Pb(II) but greatly diminished the adsorption of Cd(II), which indicated that different functional groups in squid melanin are responsible for their adsorption. IR analysis of metal ion-enriched squid melanin demonstrated that the possible functional groups responsible for metal binding were phenolic hydroxyl (OH), carboxyl (COOH), and amine groups (NH). This study reports a new material for the removal of heavy metals from low-strength wastewater.


Materials ◽  
2020 ◽  
Vol 13 (14) ◽  
pp. 3208 ◽  
Author(s):  
Marjana Simonič ◽  
Lidija Fras Zemljič

In this paper, the aim of the research was to obtain a highly efficient wool-based sorbent for the removal of zinc Zn(II) from wastewater. To increase the functional groups for metal binding, the wool was functionalized with chitosan. Chitosan has amino groups through which metals can be complexed easily to chelates. The physical and chemical modification of chitosan on wool was performed to analyze the influence of the coating bond on the final ability of the wool to remove metals. The presence of functional chitosan groups onto wool after adsorption was verified by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FT-IR) spectra. The effective binding of chitosan to wool was also determined by potentiometric and polyelectrolyte titration methods. The latter titration was used to analyze the chitosan desorption. The main part of the study was the sorption of Zn(II) on natural and functionalized wool. The influence was investigated as a function of contact time, pH, metal ion concentration and temperature on the sorption process. The absorbent with the highest concentration of protonated amino groups (607.7 mmol/kg) and responding sorption capacity of 1.52 mg/g was obtained with wool physically modified by a macromolecular chitosan solution (1%) at pH = 7. Adsorption of Zn(II) onto pristine and modified wool corresponded to pseudo-second order kinetics (R2 > 0.9884). The Langmuir model was found to be more suitable (R2 > 0.9866) in comparison to the Freundlich model. The Zn(II) sorption process was spontaneous (∆G < 0) and exothermic (∆H < 0). The results found in this study are significant for escalating the possible use of wool modified with polysaccharide coatings as a sustainable source to improve or increase the metal sorption activity of wool.


2016 ◽  
Vol 7 (4) ◽  
pp. 429-441 ◽  
Author(s):  
K. Ramyakrishna ◽  
M. Sudhamani

Excess iron in water resources can lead to health hazards and problems. The ability of lactic acid bacteria to bind iron has not yet been widely studied. In the present study, sorption of iron ions from aqueous solutions onto lactic acid bacterium was determined. Elemental analyses were carried out by inductively coupled plasma optical emission spectrometry. The kinetics of Fe(III) biosorption was investigated at different initial concentrations of metal ion. The highest uptake capacity was found to be 16 mg of Fe(III) per gram of adsorbent with a contact time of 24 hr and at initial metal ion concentration of 34 mg/L. The uptake capacity of Fe(III) ion varied from 83.2 to 46.7% across the range of initial metal ion concentrations. The equilibrium data were evaluated by Langmuir and Freundlich isotherms, and were found to fit better with the latter (R2 = 0.9999). The surface morphology of the biomass and percentage of metal was characterized by using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy. The functional groups on the cell wall surface of biomass involved in biosorption of heavy metals were studied by Fourier transform infrared spectroscopy spectrum.


2019 ◽  
Vol 476 (21) ◽  
pp. 3333-3353 ◽  
Author(s):  
Malti Yadav ◽  
Kamalendu Pal ◽  
Udayaditya Sen

Cyclic dinucleotides (CDNs) have emerged as the central molecules that aid bacteria to adapt and thrive in changing environmental conditions. Therefore, tight regulation of intracellular CDN concentration by counteracting the action of dinucleotide cyclases and phosphodiesterases (PDEs) is critical. Here, we demonstrate that a putative stand-alone EAL domain PDE from Vibrio cholerae (VcEAL) is capable to degrade both the second messenger c-di-GMP and hybrid 3′3′-cyclic GMP–AMP (cGAMP). To unveil their degradation mechanism, we have determined high-resolution crystal structures of VcEAL with Ca2+, c-di-GMP-Ca2+, 5′-pGpG-Ca2+ and cGAMP-Ca2+, the latter provides the first structural basis of cGAMP hydrolysis. Structural studies reveal a typical triosephosphate isomerase barrel-fold with substrate c-di-GMP/cGAMP bound in an extended conformation. Highly conserved residues specifically bind the guanine base of c-di-GMP/cGAMP in the G2 site while the semi-conserved nature of residues at the G1 site could act as a specificity determinant. Two metal ions, co-ordinated with six stubbornly conserved residues and two non-bridging scissile phosphate oxygens of c-di-GMP/cGAMP, activate a water molecule for an in-line attack on the phosphodiester bond, supporting two-metal ion-based catalytic mechanism. PDE activity and biofilm assays of several prudently designed mutants collectively demonstrate that VcEAL active site is charge and size optimized. Intriguingly, in VcEAL-5′-pGpG-Ca2+ structure, β5–α5 loop adopts a novel conformation that along with conserved E131 creates a new metal-binding site. This novel conformation along with several subtle changes in the active site designate VcEAL-5′-pGpG-Ca2+ structure quite different from other 5′-pGpG bound structures reported earlier.


2019 ◽  
Author(s):  
Chem Int

A study of removal of heavy metal ions from heavy metal contaminated water using agro-waste was carried out with Musa paradisiaca peels as test adsorbent. The study was carried by adding known quantities of lead (II) ions and cadmium (II) ions each and respectively into specific volume of water and adding specific dose of the test adsorbent into the heavy metal ion solution, and the mixture was agitated for a specific period of time and then the concentration of the metal ion remaining in the solution was determined with Perkin Elmer Atomic absorption spectrophotometer model 2380. The effect of contact time, initial adsorbate concentration, adsorbent dose, pH and temperature were considered. From the effect of contact time results equilibrium concentration was established at 60minutes. The percentage removal of these metal ions studied, were all above 90%. Adsorption and percentage removal of Pb2+ and Cd2+ from their aqueous solutions were affected by change in initial metal ion concentration, adsorbent dose pH and temperature. Adsorption isotherm studies confirmed the adsorption of the metal ions on the test adsorbent with good mathematical fits into Langmuir and Freundlich adsorption isotherms. Regression correlation (R2) values of the isotherm plots are all positive (&gt;0.9), which suggests too, that the adsorption fitted into the isotherms considered.


2021 ◽  
Vol 22 (9) ◽  
pp. 4551
Author(s):  
Julie-Anne Fenger ◽  
Gregory T. Sigurdson ◽  
Rebecca J. Robbins ◽  
Thomas M. Collins ◽  
M. Mónica Giusti ◽  
...  

Red cabbage (RC) and purple sweet potato (PSP) are naturally rich in acylated cyanidin glycosides that can bind metal ions and develop intramolecular π-stacking interactions between the cyanidin chromophore and the phenolic acyl residues. In this work, a large set of RC and PSP anthocyanins was investigated for its coloring properties in the presence of iron and aluminum ions. Although relatively modest, the structural differences between RC and PSP anthocyanins, i.e., the acylation site at the external glucose of the sophorosyl moiety (C2-OH for RC vs. C6-OH for PSP) and the presence of coordinating acyl groups (caffeoyl) in PSP anthocyanins only, made a large difference in the color expressed by their metal complexes. For instance, the Al3+-induced bathochromic shifts for RC anthocyanins reached ca. 50 nm at pH 6 and pH 7, vs. at best ca. 20 nm for PSP anthocyanins. With Fe2+ (quickly oxidized to Fe3+ in the complexes), the bathochromic shifts for RC anthocyanins were higher, i.e., up to ca. 90 nm at pH 7 and 110 nm at pH 5.7. A kinetic analysis at different metal/ligand molar ratios combined with an investigation by high-resolution mass spectrometry suggested the formation of metal–anthocyanin complexes of 1:1, 1:2, and 1:3 stoichiometries. Contrary to predictions based on steric hindrance, acylation by noncoordinating acyl residues favored metal binding and resulted in complexes having much higher molar absorption coefficients. Moreover, the competition between metal binding and water addition to the free ligands (leading to colorless forms) was less severe, although very dependent on the acylation site(s). Overall, anthocyanins from purple sweet potato, and even more from red cabbage, have a strong potential for development as food colorants expressing red to blue hues depending on pH and metal ion.


Coatings ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 820
Author(s):  
Beibei Han ◽  
Mengyuan Yan ◽  
Dongying Ju ◽  
Maorong Chai ◽  
Susumu Sato

The amorphous hydrogenated (a-C:H) film-coated titanium, using different CH4/H2 and deposition times, was prepared by the ion beam deposition (IBD) method, which has the advantage of high adhesion because of the graded interface mixes at the atomic level. The chemical characterizations and corrosion behaviors of a-C:H film were investigated and evaluated by SEM, AFM, Raman spectroscopy, EPMA, TEM and XPS. An a-C:H film-coated titanium was corroded at 0.8 V, 90 °C in a 0.5 mol/L H2SO4 solution for 168 h. The metal ion concentration in the H2SO4 corrosion solution and the potentiodynamic polarization behavior were evaluated. Results indicate that a higher CH4/H2 of 1:0 and a deposition time of 12 h can result in a minimum ID/IG ratio of 0.827, Ra of 5.76 nm, metal ion concentration of 0.34 ppm in the corrosion solution and a corrosion current of 0.23 µA/cm2. The current density in this work meets the DOE’s 2020 target of 1 µA/cm2. Electrical conductivity is inversely proportional to the corrosion resistance. The significant improvement in the corrosion resistance of the a-C:H film was mainly attributed to the increased sp3 element and nanocrystalline TiC phase in the penetration layer. As a result, the a-C:H film-coated titanium at CH4/H2 = 1:0 with improved anti-corrosion behavior creates a great potential for PEMFC bipolar plates.


2012 ◽  
Vol 441 (3) ◽  
pp. 1017-1035 ◽  
Author(s):  
Katarzyna Banaszak ◽  
Vlad Martin-Diaconescu ◽  
Matteo Bellucci ◽  
Barbara Zambelli ◽  
Wojciech Rypniewski ◽  
...  

The survival and growth of the pathogen Helicobacter pylori in the gastric acidic environment is ensured by the activity of urease, an enzyme containing two essential Ni2+ ions in the active site. The metallo-chaperone UreE facilitates in vivo Ni2+ insertion into the apoenzyme. Crystals of apo-HpUreE (H. pylori UreE) and its Ni2+- and Zn2+-bound forms were obtained from protein solutions in the absence and presence of the metal ions. The crystal structures of the homodimeric protein, determined at 2.00 Å (apo), 1.59 Å (Ni2+) and 2.52 Å (Zn2+) resolution, show the conserved proximal and solvent-exposed His102 residues from two adjacent monomers invariably involved in metal binding. The C-terminal regions of the apoprotein are disordered in the crystal, but acquire significant ordering in the presence of the metal ions due to the binding of His152. The analysis of X-ray absorption spectral data obtained using solutions of Ni2+- and Zn2+-bound HpUreE provided accurate information of the metal-ion environment in the absence of solid-state effects. These results reveal the role of the histidine residues at the protein C-terminus in metal-ion binding, and the mutual influence of protein framework and metal-ion stereo-electronic properties in establishing co-ordination number and geometry leading to metal selectivity.


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