Factors affecting the partitioning of Cu, Zn and Pb in boulder coatings and stream sediments in the vicinity of a polymetallic sulfide deposit

USGS Publications Warehouse

Filipek, L.H.; Chao, T.T.; Carpenter, R.H.

1981-01-01

A sequential extraction scheme is utilized to determine the geochemical partitioning of Cu, Zn and Pb among hydrous Mn- and Fe-oxides, organics and residual crystalline silicates and oxides in the minus-80-mesh ( Fe-oxides > Mn-oxides; Zn, Mn-oxides {reversed tilde equals} organics > Fe-oxides; Pb, Fe-oxides > organics > Mn-oxides. In the sediments, organics are the most efficient scavengers of all three ore metals. These results emphasize the importance of organics as sinks for the ore metals, even in environments with high concentrations of Mn- and Fe-oxides. Of the ore metals, Zn appears to be the most mobile, and is partitioned most strongly into the coatings. However, anomaly contrast for hydromorphic Zn, normalized to the MnFe-oxide or organic content, is similar in sediments and coatings. Cu shows the highest anomaly on the boulder coatings, probably due to precipitation of a secondary Cu mineral. In contrast, detrital Pb in the pan concentrates shows a better anomaly than any hydromorphic Pb component. ?? 1981.

Whole-Genome Sequence of Cupriavidus sp. Strain BIS7, a Heavy-Metal-Resistant Bacterium

PubMed Central

Hong, Kar Wai; Thinagaran, Dinaiz a/l; Gan, Han Ming; Yin, Wai-Fong

2012-01-01

Cupriavidus sp. strain BIS7 is a Malaysian tropical soil bacterium that exhibits broad heavy-metal resistance [Co(II), Zn(II), Ni(II), Se(IV), Cu(II), chromate, Co(III), Fe(II), and Fe(III)]. It is particularly resistant to Fe(II), Fe(III), and Zn(II). Here we present the assembly and annotation of its genome. PMID:23115161

Triple-mixture of Zn, Mn, and Fe increases bioaccumulation and causes oxidative stress in freshwater neotropical fish.

PubMed

de Oliveira, Luciana Fernandes; Santos, Caroline; Risso, Wagner Ezequiel; Dos Reis Martinez, Claudia Bueno

2018-06-01

Metal bioaccumulation and oxidative stress biomarkers were determined in Prochilodus lineatus to understand the effects of short-term exposure to a triple-mixture of Zn, Mn, and Fe. Three independent tests were carried out, in which fish were exposed to 3 concentrations of Zn (0.18, 1.0, and 5.0 mg L -1 ), Mn (0.1, 0.5, and 5.0 mg L -1 ), and in the mix test to Fe (5.0 mg L -1 ) and a mixture of Zn (1.0 mg L -1 ) + Mn (0.5 mg L -1 ), with and without Fe. After exposure for 96 h, tissues were removed for metal bioaccumulation analysis and oxidative stress biomarkers were determined in liver, along with DNA damage in blood cells. Our results revealed that Zn and Mn were bioaccumulated in fish tissues after exposure to 5.0 mg L -1 , whereas Fe only bioaccumulated in muscle and gills after mixture exposure. Results indicated that 1 metal interfered with the other's bioaccumulation. In P. lineatus, 5 mg L -1 of both Mn and Fe were toxic, because damage was observed (lipid peroxidation [LPO] in liver and DNA damage in blood cells), whereas Zn induced liver responses (metallothionein [MT] and reduced glutathione [GSH] increases) to prevent damage. In terms of bioaccumulation and alterations of oxidative stress biomarkers, we showed that Zn, Mn, and Fe triple-mixture enhances individual metal toxicity in Neotropical fish P. lineatus. Environ Toxicol Chem 2018;37:1749-1756. © 2018 SETAC. © 2018 SETAC.

Total and water-soluble trace metal content of urban background PM 10, PM 2.5 and black smoke in Edinburgh, UK

NASA Astrophysics Data System (ADS)

Heal, Mathew R.; Hibbs, Leon R.; Agius, Raymond M.; Beverland, Iain J.

Toxicological studies have implicated trace metals in airborne particles as possible contributors to respiratory and/or cardiovascular inflammation. As part of an epidemiological study, co-located 24 h samples of PM 10, PM 2.5 and black smoke (BS) were collected for 1 year at an urban background site in Edinburgh, and each sample sequentially extracted with ultra-pure water, then concentrated HNO 3/HCl, and analysed for Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd and Pb. This yields a comprehensive data set for UK urban airborne trace metal. The median ( n>349) daily water-soluble metal concentration in PM 2.5 ranged from 0.05 ng m -3 for Ti to 5.1 ng m -3 for Pb; and in PM 10 from 0.18 ng m -3 for Ti to 11.7 ng m -3 for Fe. Median daily total (i.e. water+acid-extractable) metal concentration in PM 2.5 ranged from 0.3 ng m -3 for As to 27.6 ng m -3 for Fe; and in PM 10 from 0.37 ng m -3 for As to 183 ng m -3 for Fe. The PM 2.5:PM 10 ratio varied considerably with metal, from <17%, on average, for Ti and Fe, to >70% for V, As, Cd and Pb. The 11 trace metals constituted proportionally more of the PM 10-2.5 fraction than of the PM 2.5 fraction (0.9%). The proportion of water-soluble metal in each size-fraction varied considerably, from <10% water-soluble Fe and Ti in PM 10-2.5, to >50% water-soluble V, Zn, As and Cd in PM 2.5. Although Fe generally dominated the trace metal, water-soluble metal also contained significant Zn, Pb and Cu, and for all size and solubility fractions >90% of trace metal was comprised of Fe, Zn, Pb and Cu. Statistical analyses suggested three main sources: traffic; static combustion; and crustal. The association of metals with traffic (Cu, Fe, Mn, Pb, Zn) was consistent with traffic-induced non-exhaust "resuspension" rather than direct exhaust emission. Meteorology contributed to the wide variation in daily trace metal concentration. The proportion of trace metal in particles varied significantly with the air mass source and was highest on days for trajectories traversing over land. For Mn, Fe, Cu, Zn, As and Pb there was greater correlation of metal concentration with BS mass than with either PM 10 or PM 2.5 mass, suggesting that BS reflectance monitoring could be a cost-effective surrogate measure of particle metal concentration in urban background air.

Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines.

PubMed

Modin, Hanna; Persson, Kenneth M; Andersson, Anna; van Praagh, Martijn

2011-05-30

Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation. Copyright © 2011 Elsevier B.V. All rights reserved.

NASA Astrophysics Data System (ADS)

Yao, Jinhuan; Li, Yanwei; Li, Xuanhai; Le, Shiru

2014-07-01

The geometric structure, electronic structure, and stability of In-substituted ZnFe2O4 (Zn7InFe16O32 and Zn8Fe15InO32) are investigated by the density functional theory at generalized gradient approximation level. Compared with the perfect ZnFe2O4 (Zn8Fe16O32), the unit cell volume of In-substituted ZnFe2O4 increases and the structure deforms slightly. The formation energy of In substitution for Zn is smaller than that of In substitution for Fe, indicating that Zn7InFe16O32 is easier to be formed than Zn8Fe15InO32. In substitution changes the properties of ZnFe2O4 from semiconducting character to metallic character. For ZnFe2O4 and In-substituted ZnFe2O4, the strength of O-Zn bond is stronger than O-Fe bond and both of them have a covalent bond character. The strength of O-In bond is similar to that of O-Zn bond in Zn7InFe16O32, but weaker than O-Fe in Zn8Fe15InO32. In substitution for Zn causes the strength of O-Fe bonds around In atom to weaken. In substitution for Fe causes the strength of O-Zn bonds around In atom to weaken obviously, while the strength of O-Fe bonds strengthen slightly.

Synchrotron study of metal localization in Typha latifolia L. root sections

DOE PAGES

Qian, Yu; Jones, Keith W.; Feng, Huan; ...

2015-09-15

Understanding mechanisms that control plant root metal assimilation in soil is critical to the sustainable management of metal-contaminated land. With the assistance of the synchrotron X-ray fluorescence technique, this study investigated possible mechanisms that control the localization of Fe, Cu, Mn, Pb and Zn in the root tissues of Typha latifolia L. collected from a contaminated wetland. Metal localizations especially in the case of Fe and Pb in the dermal tissue and the vascular bundles were different. Cluster analysis was performed to divide the dermal tissue into iron-plaque-enriched dermal tissue and regular dermal tissue based on the spatial distribution ofmore » Pb and Fe. Factor analysis showed that Cu and Zn were closely correlated to each other in the dermal tissues. The association of Cu, Zn and Mn with Fe was strong in both regular dermal tissue and iron-plaque-enriched dermal tissue, while significant (p < 0.05) correlation of Fe with Pb was only observed in tissues enriched with iron plaque. In the vascular bundles, Zn, Mn and Cu showed strong association, suggesting that the localization of these three elements was controlled by a similar mechanism. Iron plaque in the peripheral dermal tissues acted as a barrier for Pb and a buffer for Zn, Cu and Mn. Furthermore, the Casparian strip regulated the transportation of metals from dermal tissues to the vascular bundles. The results suggested that the mechanisms controlling metal localization in root tissues varied with both tissue types and metals.« less

Insights into the effect of iron and cobalt doping on the structure of nanosized ZnO.

PubMed

Giuli, Gabriele; Trapananti, Angela; Mueller, Franziska; Bresser, Dominic; d'Acapito, Francesco; Passerini, Stefano

2015-10-05

Here we report an in-depth structural characterization of transition metal-doped zinc oxide nanoparticles that have recently been used as anode materials for Li-ion batteries. Structural refinement of powder X-ray diffraction (XRD) data allowed the determination of small though reproducible changes in the unit cell dimensions of four ZnO samples (wurtzite structure) prepared with different dopants or different synthesis conditions. Moreover, large variations of the full width at half-maximum of the XRD reflections indicate that the crystallinity of the samples decreases in the order ZnO, Zn0.9Co0.1O, Zn0.9Fe0.1O/C, and Zn0.9Fe0.1O (the crystallite sizes as determined by Williamson-Hall plots are 42, 29, 15, and 13 nm, respectively). X-ray absorption spectroscopy data indicate that Co is divalent, whereas Fe is purely trivalent in Zn0.9Fe0.1O and 95% trivalent (Fe(3+)/(Fe(3+) + Fe(2+)) ratio = 0.95) in Zn0.9Fe0.1O/C. The aliovalent substitution of Fe(3+) for Zn(2+) implies the formation of local defects around Fe(3+) such as cationic vacancies or interstitial oxygen for charge balance. The EXAFS (extended X-ray absorption fine structure) data, besides providing local Fe-O and Co-O bond distances, are consistent with a large amount of charge-compensating defects. The Co-doped sample displays similar EXAFS features to those of pure ZnO, suggesting the absence of a large concentration of defects as found in the Fe-doped samples. These results are of substantial importance for understanding and elucidating the modified electrochemical lithiation mechanism by introducing transition metal dopants into the ZnO structure for the application as lithium-ion anode material.

[Heavy metal concentration in Nanjing urban soils and their affecting factors].

PubMed

Lu, Ying; Gong, Zitong; Zhang, Ganlin; Zhang, Bo

2004-01-01

The concentration and source of heavy metals in Nanjing urban soils and their relationships with soil properties were studied. The results indicated that the soils in Nanjing urban were not obviously polluted by Fe, Ni, Co and V, but polluted by Mn, Cr, Cu, Zn, and Pb to a certain extent. The heavy metals were irregularly distributed in soil profiles. Fe, Ni, Co, and V were originated from soil materials, but Cu, Zn, Pb, and Cr were anthropogenic input. Probably, Mn had different origins in different soils. There were positive correlations among Fe, Cr, Ni, Co, and V concentration, and among Cu, Zn, Pb, and Cr concentration. The Fe, Co, V, and Ni concentration were positively correlated with soil clay content and CEC, and the Cu, Zn and Pb concentration were negatively correlated with clay content. There were positive correlations between Cu, Zn, Pb and Cr concentration and organic C content, and between Pb concentration and soil pH.

Toxicity of Metals to a Freshwater Ostracod: Stenocypris major

PubMed Central

Shuhaimi-Othman, Mohammad; Yakub, Nadzifah; Ramle, Nur-Amalina; Abas, Ahmad

2011-01-01

Adults of freshwater ostracod Stenocypris major (Crustacea, Candonidae) were exposed for a four-day period in laboratory conditions to a range of copper (Cu), cadmium (Cd), zinc (Zn), lead (Pb), nickel (Ni), iron (Fe), aluminium (Al), and manganese (Mn) concentrations. Mortality was assessed, and median lethal times (LT50) and concentrations (LC50) were calculated. LT50 and LC50 increased with the decrease in mean exposure concentrations and times, respectively, for all metals. LC50s for 96 hours for Cu, Cd, Zn, Pb, Ni, Fe, Al, and Mn were 25.2, 13.1, 1189.8, 526.2, 19743.7, 278.9, 3101.9, and 510.2 μg/L, respectively. Metals bioconcentration in S. major increases with exposure to increasing concentrations, and Cd was the most toxic to S. major, followed by Cu, Fe, Mn, Pb, Zn, Al, and Ni (Cd>Cu>Fe>Mn>Pb>Zn>Al>Ni). Comparison of LC50 values for metals for this species with those for other freshwater crustacean reveals that S. major is equally or more sensitive to metals than most other tested crustacean. PMID:21559091

Unveiling the True Metallicity and Stellar Populations of Planetary Nebula Progenitor Stars

NASA Astrophysics Data System (ADS)

Dinerstein, Harriet L.; Geballe, T. R.; Sterling, N. C.

2011-01-01

We have measured the recently identified 3.625 micron [Zn IV] fine-structure line (Dinerstein & Geballe 2001, ApJ, 562, 515) in a dozen Galactic planetary nebulae (Dinerstein et al. 2007, BAAS, 211, 100.14). Because Zn is the least refractory of the Fe peak elements, the gas phase [Zn/H] abundance can be used as a proxy for the elemental [Fe/H] in the progenitor star, in contrast to Fe itself, which is heavily depleted into dust. We find that the observed Milky Way nebulae fall into two categories: objects which have roughly solar values of [Zn/H] and [O/Zn]; and nebulae with low Zn (clustering around [Zn/H] = -0.6) and elevated [O/H]. Most of the latter group have high radial velocities, |vrad| > 60 km/s. Our interpretation is that the objects with solar abundances and low velocities originate from thin disk stars, while the nebulae with low Zn are descendants of thick disk stars. A further implication is that the common assumption that O and other alpha species are reliable indicators of metallicity in planetary nebulae is not necessarily valid, and can lead to erroneous conclusions about the parent stellar population. This effect is particularly acute for O since [O/Fe] can be large, especially in metal-poor populations. In a planetary nebula formed by a star with this abundance pattern, a high value of [(O, alpha)/Fe] can offset a low [Fe/H], producing near-solar abundances for O and other alpha species. This can make it appear that the star belongs to a more metal-rich (in [Fe/H]) population than is actually the case. Obtaining Zn abundances for larger samples of planetary nebulae will be crucial to disentangling these abundance ratios and breaking the potential degeneracy of the O and alpha abundances. (This research was supported by NSF grant 0708245.)

Zn(II) stimulation of Fe(II)-activated repression in the iron-dependent repressor from Mycobacterium tuberculosis.

PubMed

Stapleton, Brian; Walker, Lawrence R; Logan, Timothy M

2013-03-19

Thermodynamic measurements of Fe(II) binding and activation of repressor function in the iron-dependent repressor from Mycobacterium tuberculosis (IdeR) are reported. IdeR, a member of the diphtheria toxin repressor family of proteins, regulates iron homeostasis and contributes to the virulence response in M. tuberculosis. Although iron is the physiological ligand, this is the first detailed analysis of iron binding and activation in this protein. The results showed that IdeR binds 2 equiv of Fe(II) with dissociation constants that differ by a factor of 25. The high- and low-affinity iron binding sites were assigned to physical binding sites I and II, respectively, using metal binding site mutants. IdeR was also found to contain a high-affinity Zn(II) binding site that was assigned to physical metal binding site II through the use of binding site mutants and metal competition assays. Fe(II) binding was modestly weaker in the presence of Zn(II), but the coupled metal binding-DNA binding affinity was significantly stronger, requiring 30-fold less Fe(II) to activate DNA binding compared to Fe(II) alone. Together, these results suggest that IdeR is a mixed-metal repressor, where Zn(II) acts as a structural metal and Fe(II) acts to trigger the physiologically relevant promoter binding. This new model for IdeR activation provides a better understanding of IdeR and the biology of iron homeostasis in M. tuberculosis.

Adsorption of multi-heavy metals Zn and Cu onto surficial sediments: modeling and adsorption capacity analysis.

PubMed

Li, Shanshan; Zhang, Chen; Wang, Meng; Li, Yu

2014-01-01

Improved multiple regression adsorption models (IMRAMs) was developed to estimate the adsorption capacity of the components [Fe oxides (Fe), Mn oxides (Mn), organic materials (OMs), residuals] in surficial sediments for multi-heavy metal Zn and Cu. IMRAM is an improved version over MRAM, which introduces a computer program in the model developing process. As MRAM, Zn(Cu) IMRAM, and Cu(Zn) IMRAM again confirmed that there is significant interaction effects that control the adsorption of compounded Zn and Cu, which was neglected by additional adsorption model. The verification experiment shows that the relative deviation of the IMRAMs is less than 13%. It is revealed by the IMRAMs that Mn, which has the greatest adsorption capability for compounded Zn and Cu (54.889 and 161.180 mg/l, respectively), follows by interference adsorption capacity of Fe/Mn (-1.072 and -24.591 mg/l respectively). Zn and Cu influence each other through different mechanisms. When Zn is the adsorbate, compounded Cu mainly affects the adsorption capacities of Fe/Mn and Fe/Mn/OMs; while when Cu is the adsorbate, compounded Zn mainly exerts its effect on Mn, Fe/Mn, and Mn/OMs. It also shows that the compounded Zn or Cu weakened the interference adsorption of Fe/Mn, and meanwhile, strengthened the interference adsorption of Mn/OMs.

Electronic and magnetic properties of Zn1-xFexSe alloys

NASA Astrophysics Data System (ADS)

Khatta, Swati; Tripathi, S. K.; Prakash, Satya

2017-12-01

The spin polarized density functional theory along with self consistent plane wave pseudopotential method is used to investigate electronic and magnetic properties of ternary Zn1-xFexSe alloys with x = 0.125, 0.25, 0.5 and 0.75. The exchange-correlation potential treated within generalized gradient approximation is used. The calculated spin-polarized band structures, partial and total density of states reveal that Zn0.875Fe0.125Se and Zn0.75Fe0.25Se exhibit half metallic ferromagnetic characteristics and Zn0.50Fe0.50Se is nearly half metallic in nature. The half metallic band gaps for x = 0.125 and 0.25 are 0.69 and 0.39 eV respectively, while the corresponding band gaps are 0.86 and 0.81 eV. The p-d hybridization reduces the magnetic moment of Fe atoms from its free space charge value of 4 μB and induces the small magnetic moments on Zn and Se sites. The results are compared with available experimental data.

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

USGS Publications Warehouse

Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

Distribution of dissolved and labile particulate trace metals in the overlying bottom water in the Vistula River plume (southern Baltic Sea).

PubMed

Sokolowski, A; Wolowicz, M; Hummel, H

2001-10-01

Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.

DETECTION OF PHOSPHORUS, SULPHUR, AND ZINC IN THE CARBON-ENHANCED METAL-POOR STAR BD+44 493

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roederer, Ian U.; Placco, Vinicius M.; Beers, Timothy C., E-mail: iur@umich.edu

2016-06-20

The carbon-enhanced metal-poor star BD+44°493 ([Fe/H] = −3.9) has been proposed as a candidate second-generation star enriched by metals from a single Pop III star. We report the first detections of P and S and the second detection of Zn in any extremely metal-poor carbon-enhanced star, using new spectra of BD+44°493 collected by the Cosmic Origins Spectrograph on the Hubble Space Telescope . We derive [P/Fe] = −0.34 ± 0.21, [S/Fe] = +0.07 ± 0.41, and [Zn/Fe] = −0.10 ± 0.24. We increase by 10-fold the number of Si i lines detected in BD+44°493, yielding [Si/Fe] = +0.15 ± 0.22.more » The [S/Fe] and [Zn/Fe] ratios exclude the hypothesis that the abundance pattern in BD+44°493 results from depletion of refractory elements onto dust grains. Comparison with zero-metallicity supernova (SN) models suggests that the stellar progenitor that enriched BD+44°493 was massive and ejected much less than 0.07 M {sub ⊙} of {sup 56}Ni, characteristic of a faint SN.« less

Photoelectron spectroscopy of the bis(dithiolene) anions [M(mnt)2]n- (M = Fe - Zn; n = 1, 2): changes in electronic structure with variation of metal center and with oxidation.

PubMed

Waters, Tom; Wang, Xue-Bin; Woo, Hin-Koon; Wang, Lai-Sheng

2006-07-24

A detailed understanding of the electronic structures of transition metal bis(dithiolene) centers is important in the context of their interesting redox, magnetic, and optical properties. The electronic structures of the series [M(mnt)2]n- (M = Fe - Zn; mnt = 1,2-S2C2(CN)2; n = 1, 2) were examined by a combination of photodetachment photoelectron spectroscopy and density functional theory calculations, providing insights into changes in electronic structure with variation of the metal center and with oxidation. Significant changes were observed for the dianions [M(mnt)2]2- due to stabilization of the metal 3d levels from Fe to Zn and the transition from square-planar to tetrahedral coordination about the metal center (Fe-Ni, D(2h) --> Cu D2 --> Zn, D(2d). Changes with oxidation from [M(mnt)2]2- to [M(mnt)2]1- were largely dependent on the nature of the redox-active orbital in the couple [M(mnt)2](2-/1-). In particular, the first detachment feature for [Fe(mnt)2]2- originated from a metal-based orbital (Fe(II) --> Fe(III)) while that for [Fe(mnt)2]1- originated from a ligand-based orbital, a consequence of stabilization of Fe 3d levels in the latter. In contrast, the first detachment feature for both of [Ni(mnt)2]2- and [Ni(mnt)2]1- originated from the same ligand-based orbital in both cases, a result of occupied Ni 3d levels being stabilized relative those of Fe 3d and occurring below the highest energy occupied ligand-based orbital for both of [Ni(mnt)2]2- and [Ni(mnt)2]1- . The combined data illustrate the subtle interplay between metal- and ligand-based redox chemistry in these species and demonstrate changes in their electronic structures with variation of metal center, oxidation, and coordination geometry.

Pilot test of pollution control and metal resource recovery for acid mine drainage.

PubMed

Yan, Bo; Mai, Ge; Chen, Tao; Lei, Chang; Xiao, Xianming

2015-01-01

The study was undertaken in order to recover the metal resources from acid mine drainage (AMD). A 300 m(3)/d continuous system was designed and fractional precipitation technology employed for the main metals Fe, Cu, Zn, and Mn recovery. The system was operated for six months using actual AMD in situ. The chemicals' input and also the retention time was optimized. Furthermore, the material balance was investigated. With the system, the heavy metals of the effluent after the Mn neutralization precipitation were below the threshold value of the Chinese integrated wastewater discharge limit. The precipitates generated contained 42%, 12%, 31%, and 18% for Fe, Cu, Zn, and Mn, respectively, and the recovery rates of Fe, Cu, Zn, and Mn were 82%, 79%, 83%, and 83%, respectively. The yield range of the precipitate had significant correlation with the influent metal content. Using the X-ray diffraction analysis, the refinement for Fe, Cu, and Zn could be achieved through the processes of roasting and floatation. Cost-benefit was also discussed; the benefit from the recycled metal was able to pay for the cost of chemical reagents used. Most important of all, through the use of this technology, the frustrating sludge problems were solved.

Toxicity of Metals to a Freshwater Snail, Melanoides tuberculata

PubMed Central

Shuhaimi-Othman, M.; Nur-Amalina, R.; Nadzifah, Y.

2012-01-01

Adult freshwater snails Melanoides tuberculata (Gastropod, Thiaridae) were exposed for a four-day period in laboratory conditions to a range of copper (Cu), cadmium (Cd), zinc (Zn), lead (Pb), nickel (Ni), iron (Fe), aluminium (Al), and manganese (Mn) concentrations. Mortality was assessed and median lethal times (LT50) and concentrations (LC50) were calculated. LT50 and LC50 increased with the decrease in mean exposure concentrations and times, respectively, for all metals. The LC50 values for the 96-hour exposures to Cu, Cd, Zn, Pb, Ni, Fe, Al, and Mn were 0.14, 1.49, 3.90, 6.82, 8.46, 8.49, 68.23, and 45.59 mg L−1, respectively. Cu was the most toxic metal to M. tuberculata, followed by Cd, Zn, Pb, Ni, Fe, Mn, and Al (Cu > Cd > Zn > Pb > Ni > Fe > Mn > Al). Metals bioconcentration in M. tuberculata increases with exposure to increasing concentrations and Cu has the highest accumulation (concentration factor) in the soft tissues. A comparison of LC50 values for metals for this species with those for other freshwater gastropods reveals that M. tuberculata is equally sensitive to metals. PMID:22666089

Disturbances to metal partitioning during toxicity testing of iron(II)-rich estuarine pore waters and whole sediments.

PubMed

Simpson, Stuart L; Batley, Graeme E

2003-02-01

Metal partitioning is altered when suboxic estuarine sediments containing Fe(II)-rich pore waters are disturbed during collection, preparation, and toxicity testing. Experiments with model Fe(II)-rich pore waters demonstrated the rates at which adsorptive losses of Cd, Cu, Ni, Mn, Pb, and Zn occur upon exposure to air. Experiments with Zn-contaminated estuarine sediments demonstrated large and often unpredictable changes to metal partitioning during sediment storage, removal of organisms, and homogenization before testing. Small modifications to conditions, such as aeration of overlying waters, caused large changes to the metal partitioning. Disturbances caused by sediment collection required many weeks for reestablishment of equilibrium. Bioturbation by benthic organisms led to oxidation of pore-water Fe(II) and lower Zn fluxes because of the formation of Fe hydroxide precipitates that adsorb pore-water Zn. For five weeks after the addition of organisms to sediments, Zn fluxes increased slowly as the organisms established themselves in the sediments, indicating that the establishment of equilibrium was not rapid. The results are discussed in terms of the dynamic nature of suboxic, Fe(II)-rich estuarine sediments, how organisms perturb their environment, and the importance of understanding chemistry in toxicity testing with whole sediments or pore water. Recommendations are provided for the handling of sediments for toxicity testing.

Biomonitoring of heavy metals in feathers of eleven common bird species in urban and rural environments of Tiruchirappalli, India.

PubMed

Manjula, Menon; Mohanraj, R; Devi, M Prashanthi

2015-05-01

Heavy metals continue to remain as a major environmental concern in spite of emission control measures. In this study, we analyzed the concentrations of heavy metals (Fe, Cr, Mn, Ni, Cu, Zn, and Cd) in the feathers of 11 species of birds collected from urban and rural areas of Tiruchirappalli, Southern India. Metal concentrations followed the order: Fe > Cu > Zn > Cr > Mn > Ni > Cd. Irrespective of sample locations, heavy metals such as Fe, Cr, Ni, Zn, and Cu were detected in high concentrations, while Cd and Mn were observed in lower concentrations. In contrary to our assumption, there were no statistically significant intraspecific and urban-rural differences in the metal concentrations except for Zn. Pairwise comparisons among species irrespective of metal type showed significant interspecific differences between Acridotheres tristis and Centropus phasianinus, A. tristis and Milvus migrans, C. phasianinus and M. migrans, M. migrans and Eudynamys scolopaceus, and Psittacula krameri and E. scolopaceus. Principal component analysis carried out for urban data extracted Ni, Mn, Zn, Fe, and Cu accounting for 48% variance implying dietary intake and external contamination as important sources for metals. In the rural, association of Zn, Cd, Ni, and Cr suggests the impact of metal fabrication industries and leather tanning operations.

Zinc abundances in Galactic bulge field red giants: Implications for damped Lyman-α systems

NASA Astrophysics Data System (ADS)

Barbuy, B.; Friaça, A. C. S.; da Silveira, C. R.; Hill, V.; Zoccali, M.; Minniti, D.; Renzini, A.; Ortolani, S.; Gómez, A.

2015-08-01

Context. Zinc in stars is an important reference element because it is a proxy to Fe in studies of damped Lyman-α systems (DLAs), permitting a comparison of chemical evolution histories of bulge stellar populations and DLAs. In terms of nucleosynthesis, it behaves as an alpha element because it is enhanced in metal-poor stars. Abundance studies in different stellar populations can give hints to the Zn production in different sites. Aims: The aim of this work is to derive the iron-peak element Zn abundances in 56 bulge giants from high resolution spectra. These results are compared with data from other bulge samples, as well as from disk and halo stars, and damped Lyman-α systems, in order to better understand the chemical evolution in these environments. Methods: High-resolution spectra were obtained using FLAMES+UVES on the Very Large Telescope. We computed the Zn abundances using the Zn i lines at 4810.53 and 6362.34 Å. We considered the strong depression in the continuum of the Zn i 6362.34 Å line, which is caused by the wings of the Ca i 6361.79 Å line suffering from autoionization. CN lines blending the Zn i 6362.34 Å line are also included in the calculations. Results: We find [Zn/Fe] = +0.24 ± 0.02 in the range -1.3 < [Fe/H] < -0.5 and [Zn/Fe] = + 0.06 ± 0.02 in the range -0.5 < [Fe/H] < -0.1, whereas for [Fe/H] ≥ -0.1, it shows a spread of -0.60 < [Zn/Fe] < + 0.15, with most of these stars having low [Zn/Fe] < 0.0. These low zinc abundances at the high metallicity end of the bulge define a decreasing trend in [Zn/Fe] with increasing metallicities. A comparison with Zn abundances in DLA systems is presented, where a dust-depletion correction was applied for both Zn and Fe. When we take these corrections into account, the [Zn/Fe] vs. [Fe/H] of the DLAs fall in the same region as the thick disk and bulge stars. Finally, we present a chemical evolution model of Zn enrichment in massive spheroids, representing a typical classical bulge evolution. Observations collected both at the European Southern Observatory, Paranal, Chile (ESO programmes 71.B-0617A, 73.B0074A, and GTO 71.B-0196).Table 6 is available in electronic form at http://www.aanda.org

The Role of Magmatic Volatile Input, Near-surface Seawater Entrainment and Sulfide Deposition in Regulating Metal Concentrations Within Manus Basin Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Craddock, P. R.; Tivey, M. K.; Seewald, J. S.; Rouxel, O.; Bach, W.

2007-12-01

Analyses of Fe, Mn, Cu, Zn, Pb, Ag, Cd, Co and Sb in vent fluid samples from four hydrothermal systems in the Manus back-arc basin, Papua New Guinea, were carried out by ICP-MS. Vienna Woods is located on the well- defined, basalt-dominated Manus Spreading Center, while the other systems are hosted in felsic volcanics on the Pual Ridge (PACMANUS), within a caldera (DESMOS), and on volcanic cones (SuSu Knolls). Metal concentrations were coupled with other fluid data (pH, SO4, Ca, H2S) to discriminate effects of deep- seated water-rock reaction and magmatic volatile input from near surface seawater entrainment, mixing, and consequent mineral precipitation and metal remobilization. Both magmatic volatile input (e.g. SO2, HCl, HF) and sulfide precipitation can increase fluid acidity and thus affect the aqueous mobility of metals. At Vienna Woods, 280°C end-member (Mg = 0) fluids have high pH (>4.2) and low metal contents (Fe <160 uM, Cu <10 uM, Zn <40 uM) relative to most mid-ocean ridge (MOR) vent fluids. The high pH and lack of evidence for magmatic volatile input are consistent with fluid compositions regulated by subsurface seawater- basalt/andesite reactions. Despite low aqueous Zn concentrations, Zn-rich (wurtzite-lined) chimneys are common at Vienna Woods active vents, reflecting deposition from fluids characterized by low Fe and Cu and high pH. At PACMANUS, black smoker fluids (T >300°C, pH ~ 2.7) are enriched in sulfide-forming metals by an order of magnitude relative to Vienna Woods fluids. Enrichments at PACMANUS reflect efficient leaching of metals at low pH, with the lower pH likely a result of input of magmatic volatiles. In addition, some vents fluids show clear evidence for seawater entrainment, subsurface precipitation of Cu-Fe-sulfides and preferential remobilization of Zn-sulfides (lower T, non-zero Mg, lower Fe, Cu, H2S and pH (2.3-2.4), but higher Zn, Pb, Cd and Ag, compared to black smokers). The higher metal concentrations and lower pH of fluids from PACMANUS versus Vienna Woods are reflected in chimney deposit compositions with Zn-poor sulfide linings composed of Cu-Fe-sulfides and As-Sb-sulfosalts in high T and lower T vents, respectively. At DESMOS caldera, fluid data suggest extensive magmatic volatile input (e.g. pH <1.5, elevated F and SO4) but lesser reaction with the basement felsic rocks (low Li, Rb, Mn). Sampled "acid-sulfate" fluids are low temperature (T ~180°C) with Mg >46 mM, and very high concentrations of some metals for these Mg concentrations (Fe >5 mM, Zn >50 - 400 uM). At SuSu Knolls, vent fluid compositions similar to those at both PACMANUS and DESMOS are observed. Smoker fluids have high but variable metal concentrations of similar magnitude to PACMANUS. Acid-sulfate fluids from North Su have low pH (<2), non-zero Mg (>40 mM), and high Fe and Zn concentrations, similar to DESMOS fluids. At SuSu Knolls, fluid compositions reflect either high temperature water-rock reaction (smoker fluids) or magmatic volatile input (acid-sulfate fluids). As at PACMANUS, chimney deposits that correspond to venting fluids are Cu-Fe-As-Sb-rich and Zn-poor, likely reflecting deposition from low pH, high Cu and Fe fluids.

Mixed Metal Oxides of the Type CoxZn1-xFe2O4 as Photocatalysts for Malachite Green Degradation Under UV Light Irradiation.

PubMed

Tzvetkov, Martin; Milanova, Maria; Cherkezova-Zheleva, Zara; Spassova, Ivanka; Valcheva, Evgenia; Zaharieva, Joana; Ivan, Mitov

2017-06-01

A combination of thermal and mechanical (high energy ball milling) treatment was applied in an attempt to obtain polycrystalline mixed metal binary and ternary oxides of the type CoxZn1-xFe2O4 (x = 0; 0.25; 0.5; 0.75; 1). The synthetic procedure used successfully produced single-phased, homogeneous ZnFe2O4, CoFe2O4, and Co0.75Zn0.25Fe2O4, as well as mixed oxides, whose composition depended both on the duration of the high energy ball milling and the ratio Zn(II)/Co(II). The formation of spinel-like structures was proved by XRD, Mössbauer spectroscopy and Raman spectroscopy. For the characterization of the samples low-temperature N2 adsorption, UV/Vis spectroscopy and transmission electron microscopy were applied. The energy band gap of the samples was calculated, suggesting they are promising photocatalysts. The decomposition of the Malachite Green in model water solutions under UV-light irradiation was successfully achieved in the presence of the samples as photocatalysts. The highest rate constant was obtained for the sample synthesized at longer milling time in combination with higher Zn(II)/Co(II) ratio. The photocatalytic activity of the ternary mixed oxides was compared with the pure hematite, α-Fe2O3, and the binary ZnFe2O4 and CoFe2O4 ferrites with spinel structure that were treated in the same way. A synergetic effect of α-Fe2O3 and the spinel-like structure on the photocatalytic properties of ternary mixed metal oxides was detected.

Efficient metal adsorption and microbial reduction from Rawal Lake wastewater using metal nanoparticle coated cotton.

PubMed

Ali, Attarad; Gul, Ayesha; Mannan, Abdul; Zia, Muhammad

2018-05-17

This study was designed to investigate removal of toxic metals and reduction of bacterial count from Rawal Lake wastewater with novel nanocomposite sorbents. Iron, zinc and silver oxide nanoparticles (NPs) were attached on cotton. The nanocomposites (iron NPs on cotton (FeCt), zinc NPs on cotton (ZnCt) and silver NPs on cotton (AgCt)) were characterized by FTIR, XRD and SEM, which showed successful adsorption of 10-30 nm size nanoparticles. Batch experiments were performed to determine the adsorption capacity of nanocomposite for metal removal. All the three adsorbents demonstrated 100% adsorption efficiency for Ag + , Co 2+ , Fe 3+ , Zn 2+ and Cu 2+ whereas less adsorption for Cd 2+ and Cr 3+ . The maximum adsorbance (qe) was exhibited by Co 2+ on ZnCt, FeCt and AgCt as 125.0, 111.1 and 100.0 mg g -1 , respectively. The efficiency of adsorbents for metal ions sorption was found as AgCt > ZnCt > FeCt while the order of adsorption for metals was observed as Fe 3+  > Co 2+  > Zn 2+  > Cu 2+  > Ag +  > Cr 3+  > Cd 2 + . The adsorption mechanism mostly follow Langmuir isotherm and pseudo-second order kinetic model. The maximum microbial reduction was exhibited by AgCt followed by ZnCt and FeCt. The microbes were further processed for staining and biochemical characteristics to evaluate resistance and sensitive microbes. The study concludes that the NPs doped on cotton can be effectively used for adsorption of heavy metals and reduction of microbial count from natural wastewater making it valuable for human consumption. In addition, the nanoparticles impregnated cotton can be efficiently used in water filtration plants. Copyright © 2018. Published by Elsevier B.V.

Synchrotron study of metal localization in Typha latifolia  L. root sections

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qian, Yu; Feng, Huan; Gallagher, Frank J.

2015-10-13

Understanding mechanisms that control plant root metal assimilation in soil is critical to the sustainable management of metal-contaminated land. With the assistance of the synchrotron X-ray fluorescence technique, this study investigated possible mechanisms that control the localization of Fe, Cu, Mn, Pb and Zn in the root tissues ofTypha latifolia L. collected from a contaminated wetland. Metal localizations especially in the case of Fe and Pb in the dermal tissue and the vascular bundles were different. Cluster analysis was performed to divide the dermal tissue into iron-plaque-enriched dermal tissue and regular dermal tissue based on the spatial distribution of Pb andmore » Fe. Factor analysis showed that Cu and Zn were closely correlated to each other in the dermal tissues. The association of Cu, Zn and Mn with Fe was strong in both regular dermal tissue and iron-plaque-enriched dermal tissue, while significant (p< 0.05) correlation of Fe with Pb was only observed in tissues enriched with iron plaque. In the vascular bundles, Zn, Mn and Cu showed strong association, suggesting that the localization of these three elements was controlled by a similar mechanism. Iron plaque in the peripheral dermal tissues acted as a barrier for Pb and a buffer for Zn, Cu and Mn. The Casparian strip regulated the transportation of metals from dermal tissues to the vascular bundles. The results suggested that the mechanisms controlling metal localization in root tissues varied with both tissue types and metals.« less

Structural and Magnetic Properties of Transition-Metal-Doped Zn 1-x Fe x O.

PubMed

Abdel-Baset, T A; Fang, Yue-Wen; Anis, B; Duan, Chun-Gang; Abdel-Hafiez, Mahmoud

2016-12-01

The ability to produce high-quality single-phase diluted magnetic semiconductors (DMS) is the driving factor to study DMS for spintronics applications. Fe-doped ZnO was synthesized by using a low-temperature co-precipitation technique producing Zn 1-x Fe x O nanoparticles (x= 0, 0.02, 0.04, 0.06, 0.08, and 0.1). Structural, Raman, density functional calculations, and magnetic studies have been carried out in studying the electronic structure and magnetic properties of Fe-doped ZnO. The results show that Fe atoms are substituted by Zn ions successfully. Due to the small ionic radius of Fe ions compared to that of a Zn ions, the crystal size decreases with an increasing dopant concentration. First-principle calculations indicate that the charge state of iron is Fe (2+) and Fe (3+) with a zinc vacancy or an interstitial oxygen anion, respectively. The calculations predict that the exchange interaction between transition metal ions can switch from the antiferromagnetic coupling into its quasi-degenerate ferromagnetic coupling by external perturbations. This is further supported and explains the observed ferromagnetic bahaviour at magnetic measurements. Magnetic measurements reveal that decreasing particle size increases the ferromagnetism volume fraction. Furthermore, introducing Fe into ZnO induces a strong magnetic moment without any distortion in the geometrical symmetry; it also reveals the ferromagnetic coupling.

Assessment of heavy metal tolerance in native plant species from soils contaminated with electroplating effluent.

PubMed

Sainger, Poonam Ahlawat; Dhankhar, Rajesh; Sainger, Manish; Kaushik, Anubha; Singh, Rana Pratap

2011-11-01

Heavy metals concentrations of (Cr, Zn, Fe, Cu and Ni) were determined in plants and soils contaminated with electroplating industrial effluent. The ranges of total soil Cr, Zn, Fe, Cu and Ni concentrations were found to be 1443-3240, 1376-3112, 683-2228, 263-374 and 234-335 mg kg⁻¹, respectively. Metal accumulation, along with hyperaccumulative characteristics of the screened plants was investigated. Present study highlighted that metal accumulation in different plants varied with species, tissues and metals. Only one plant (Amaranthus viridis) accumulated Fe concentrations over 1000 mg kg⁻¹. On the basis of TF, eight plant species for Zn and Fe, three plant species for Cu and two plant species for Ni, could be used in phytoextraction technology. Although BAF of all plant species was lesser than one, these species exhibited high metal adaptability and could be considered as potential hyperaccumulators. Phytoremediation potential of these plants can be used to remediate metal contaminated soils, though further investigation is still needed. Copyright © 2011 Elsevier Inc. All rights reserved.

Metallic ions catalysis for improving bioleaching yield of Zn and Mn from spent Zn-Mn batteries at high pulp density of 10.

PubMed

Niu, Zhirui; Huang, Qifei; Wang, Jia; Yang, Yiran; Xin, Baoping; Chen, Shi

2015-11-15

Bioleaching of spent batteries was often conducted at pulp density of 1.0% or lower. In this work, metallic ions catalytic bioleaching was used for release Zn and Mn from spent ZMBs at 10% of pulp density. The results showed only Cu(2+) improved mobilization of Zn and Mn from the spent batteries among tested four metallic ions. When Cu(2+) content increased from 0 to 0.8 g/L, the maximum release efficiency elevated from 47.7% to 62.5% for Zn and from 30.9% to 62.4% for Mn, respectively. The Cu(2+) catalysis boosted bioleaching of resistant hetaerolite through forming a possible intermediate CuMn2O4 which was subject to be attacked by Fe(3+) based on a cycle of Fe(3+)/Fe(2+). However, poor growth of cells, formation of KFe3(SO4)2(OH)6 and its possible blockage between cells and energy matters destroyed the cycle of Fe(3+)/Fe(2+), stopping bioleaching of hetaerolite. The chemical reaction controlled model fitted best for describing Cu(2+) catalytic bioleaching of spent ZMBs. Copyright © 2015 Elsevier B.V. All rights reserved.

Transverse excitations in liquid Fe, Cu and Zn

NASA Astrophysics Data System (ADS)

Hosokawa, S.; Inui, M.; Kajihara, Y.; Tsutsui, S.; Baron, A. Q. R.

2015-05-01

Transverse acoustic (TA) excitation modes were observed in inelastic x-ray scattering spectra of liquid Fe, Cu and Zn. From the analysis of current correlation functions, we concluded that TA excitation modes can experimentally be detected through the quasi-TA branches in the longitudinal current correlation spectra in these liquid metals. The microscopic elastic constants are estimated and a characteristic difference from macroscopic polycrystalline value was found in Poisson's ratio of liquid Fe, which shows an extremely softer value of ∼0.38 compared with the macroscopic value of ∼0.275. The lifetime of the TA modes were determined to be ∼0.45 ps for liquid Fe and Cu and ∼0.55 ps for liquid Zn, reflecting different interatomic correlations between liquid transition metals and non-transition metals. The propagation length of the TA modes are ∼0.85 nm in all of liquid metals, corresponding to the size of icosahedral or similar size of cages formed instantaneously in these liquid metals.

Compositional dependence of elastic moduli for transition-metal oxide spinels

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Jacobsen, S. D.; Boffa Ballaran, T.

2012-12-01

Spinel phases (AB2O4) are common non-silicate oxides in the Earth's crust and upper mantle. A characteristic of this mineral group is the ability to host a wide range of transition metals. Here we summarize the influence of transition metals (Fe, Zn, and Mn) on the pressure dependence of elastic moduli of related spinels (magnetite, gahnite, and franklinite) using GHz-ultrasonic interferometry. Measurements were carried out up to 10 GPa in diamond-anvil cells using hydrostatic pressure media. Transition metals with unfilled 3d orbitals strongly influence the elastic properties of spinels. Franklinite (Zn,Mn)Fe2O4 and magnetite Fe3O4 with transition metals on both A and B cation sites exhibit pressure-induced mode softening of C44, whereas C44 of gahnite(ZnAl2O4) and spinel (MgAl2O4) exhibit positive pressure derivatives of the shear moduli. Spinels with two transition elements tend to undergo phase changes at a lower pressure than those with none or only one transition metal. Along the Mn-Zn solid solution, the variation of moduli with composition is non-linear, and a mid-range franklinite composition studied here shows a minimum in C44 compared with either end-member: MnFe2O 4 or ZnFe2O4. In general, the linear variation of sound velocity with density (Birch's Law) is followed by spinels, however spinels containing only one or no transition metals follow a distinct slope from those containing transition metals on both A and B sites. The Cauchy relation, 0.5(C12 - C44) = P is fulfilled by spinels with only one or no transition metals, suggesting that that Coulomb interactions dominate. Spinels with two transition metals fail to meet the Cauchy relation, indicating strong directional dependence and covalent character of bonding. The bonding character of transition metals is crucial to understanding the elastic behavior of natural and synthetic spinel solid solutions containing transition metals.

Electroplating sludge derived zinc-ferrite catalyst for the efficient photo-Fenton degradation of dye.

PubMed

Cao, Zhenbang; Zhang, Jia; Zhou, Jizhi; Ruan, Xiuxiu; Chen, Dan; Liu, Jianyong; Liu, Qiang; Qian, Guangren

2017-05-15

A zinc-dominant ferrite catalyst for efficient degradation of organic dye was prepared by the calcination of electroplating sludge (ES). Characterizations indicated that zinc ferrite (ZnFe 2 O 4 ) coexisted with Fe 2 O 3 structure was the predominant phase in the calcined electroplating sludge (CES). CES displayed a high decolorization ratio (88.3%) of methylene blue (MB) in the presence of H 2 O 2 combined with UV irradiation. The high efficiency could be ascribed to the photocatalytic process induced by ZnFe 2 O 4 and the photo-Fenton dye degradation by ferrous content, and a small amount of Al and Mg in the sludge might also contribute to the catalysis. Moreover, the degradation capability of dye by CES was supported by the synthetic ZnFe 2 O 4 with different Zn to Fe molar ratio (n(Zn): n(Fe)), as 84.81%-86.83% of dye was removed with n(Zn): n(Fe) ranged from 1:0.5 to 1:3. All synthetic ferrite samples in the simulation achieved adjacent equilibrium decolorization ratio, the flexible proportioning of divalent metal ions (M 2+ ) to trivalent metal ions (M 3+ ) applied in the synthesis indicated that the catalyst has a high availability. Therefore, an efficacious catalyst for the degradation of dye can potentially be derived from heavy metal-containing ES, it's a novel approach for the reutilization of ES. Copyright © 2016 Elsevier Ltd. All rights reserved.

Distribution of trace metals in surface seawater and zooplankton of the Bay of Bengal, off Rushikulya estuary, East Coast of India.

PubMed

Srichandan, Suchismita; Panigrahy, R C; Baliarsingh, S K; Rao B, Srinivasa; Pati, Premalata; Sahu, Biraja K; Sahu, K C

2016-10-15

Concentrations of trace metals such as iron (Fe), copper (Cu), zinc (Zn), cobalt (Co), nickel (Ni), manganese (Mn), lead (Pb), cadmium (Cd), chromium (Cr), arsenic (As), vanadium (V), and selenium (Se) were determined in seawater and zooplankton from the surface waters off Rushikulya estuary, north-western Bay of Bengal. During the study period, the concentration of trace metals in seawater and zooplankton showed significant spatio-temporal variation. Cu and Co levels in seawater mostly remained non-detectable. Other elements were found at higher concentrations and exhibited marked variations. The rank order distribution of trace metals in terms of their average concentration in seawater was observed as Fe>Ni>Mn>Pb>As>Zn>Cr>V>Se>Cd while in zooplankton it was Fe>Mn>Cd>As>Pb>Ni>Cr>Zn>V>Se. The bioaccumulation factor (BAF) of Fe was highest followed by Zn and the lowest value was observed with Ni. Results of correlation analysis discerned positive affinity and good relationship among the majority of the trace metals, both in seawater and zooplankton suggesting their strong affinity and coexistence. Copyright © 2016 Elsevier Ltd. All rights reserved.

Structural and functional responses of periphyton and macroinvertebrate communities to ferric Fe, Cu, and Zn in stream mesocosms.

PubMed

Cadmus, Pete; Guasch, Helena; Herdrich, Adam T; Bonet, Berta; Urrea, Gemma; Clements, William H

2018-05-01

Two mesocosm experiments were conducted to examine effects of ferric iron (Fe) and mixtures of ferric Fe with aqueous metals (Cu, Zn) on stream benthic communities. Naturally colonized benthic communities were exposed to a gradient of ferric Fe (0, 0.4, 1.0, 2.5, 6.2, and 15.6 mg/L) that bracketed the current US Environmental Protection Agency water quality criterion value (1.0 mg/L). After 10 d of exposure to ferric Fe, total macroinvertebrate abundance, number of taxa, and abundance of all major macroinvertebrate groups (Ephemeroptera, Plecoptera, Trichoptera, and Diptera) were significantly reduced. Heptageniid mayflies and chironomids were especially sensitive to Fe oxide deposition and were significantly reduced at 0.4 and 1.0 mg/L total Fe, respectively. In a second mesocosm experiment, periphyton and macroinvertebrate communities were exposed to ferric Fe (0.60 mg/L) with or without aqueous Cu and Zn at 2 treatment levels: low (0.01 mg/L Cu + 0.1 mg/L Zn) and high (0.05 mg/L Cu + 0.5 mg/L Zn). In contrast to previous research, we observed no evidence of a protective effect of Fe on toxicity of metals. Growth rates and protein content of periphyton were significantly reduced by both ferric Fe and aqueous metals, whereas abundance of heptageniid mayflies (Cinygmula) and whole community metabolism were significantly reduced by ferric Fe alone. We hypothesize that Fe oxides inhibited algal growth and enhanced metal accumulation, leading to a reduction in the quantity and quality of food resources for grazers. Mesocosm experiments conducted using natural benthic communities provide a unique opportunity to quantify the relative importance of indirect physical effects and to develop a better understanding of the relationship between basal food resources and consumers in natural stream ecosystems. Environ Toxicol Chem 2018;37:1320-1329. © 2017 SETAC. © 2017 SETAC.

Determination of some heavy metals (Fe, Cu, Zn and Pb) in blood by total reflection X-ray fluorescence

NASA Astrophysics Data System (ADS)

Bounakhla, M.; Doukkali, A.; Lalaoui, K.; Aguenaou, H.; Mokhtar, N.; Attrassi, B.

2003-05-01

The main purpose of this study is the interaction between nutrition (micronutrients heavy metals: Fe, Zn, Cu) and toxic heavy metals such as Pb in blood of children living in Gharb region of Morocco. This region receives all pollution carried by the Sebou river coming mainly from industrial activities. A rapid and simple analytical procedure was used for the determination of Fe, Cu and Zn trace amounts in blood by total-reflection X-ray fluorescence technique. This method is an energy dispersive XRF technique in a special geometry of primary beam, sample and detector. The sample is deposited on a plane polished surface of a suitable reflector material. It is presented as a few drops (25 μl) from a solution of blood digested in a mixture of HNO3 and H2O2 using a microwaves accelerated reaction system. The accuracy of measurements has been investigated by using certified materials. The concentration of Cu was found to be normal in all samples (\\cong1 ppm) which ruled out any interaction between this element and the others. On the other hand, amounts of Fe and Zn are very variables, suggesting an interaction between Fe and Zn. However, amounts of Pb in blood are inferior to 50 ppb, suggesting that no interaction exist with this metal and micronutrients.

Assessing bioavailability levels of metals in effluent-affected rivers: effect of Fe(III) and chelating agents on the distribution of metal speciation.

PubMed

Han, Shuping; Naito, Wataru; Masunaga, Shigeki

To assess the effects of Fe(III) and anthropogenic ligands on the bioavailability of Ni, Cu, Zn, and Pb, concentrations of bioavailable metals were measured by the DGT (diffusive gradients in thin films) method in some urban rivers, and were compared with concentrations calculated by a chemical equilibrium model (WHAM 7.0). Assuming that dissolved Fe(III) (<0.45 μm membrane filtered) was in equilibrium with colloidal iron oxide, the WHAM 7.0 model estimated that bioavailable concentrations of Ni, Cu, and Zn were slightly higher than the corresponding values estimated assuming that dissolved Fe(III) was absent. In contrast, lower levels of free Pb were predicted by the WHAM 7.0 model when dissolved Fe(III) was included. Estimates showed that most of the dissolved Pb was present as colloidal iron-Pb complex. Ethylene-diamine-tetra-acetic acid (EDTA) concentrations at sampling sites were predicted from the relationship between EDTA and the calculated bioavailable concentration of Zn. When both colloidal iron and predicted EDTA concentrations were included in the WHAM 7.0 calculations, dissolved metals showed a strong tendency to form EDTA complexes, in the order Ni > Cu > Zn > Pb. With the inclusion of EDTA, bioavailable concentrations of Ni, Cu, and Zn predicted by WHAM 7.0 were different from those predicted considering only humic substances and colloidal iron.

Inert anode containing oxides of nickel, iron and zinc useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Weirauch, Jr., Douglas A.; Liu, Xinghua

2002-01-01

An inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode includes a ceramic oxide material preferably made from NiO, Fe.sub.2 O.sub.3 and ZnO. The inert anode composition may comprise the following mole fractions of NiO, Fe.sub.2 O.sub.3 and ZnO: 0.2 to 0.99 NiO; 0.0001 to 0.8 Fe.sub.2 O.sub.3 ; and 0.0001 to 0.3 ZnO. The inert anode may optionally include other oxides and/or at least one metal phase, such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. The Ni--Fe--Co--O ceramic material exhibits very low solubility in Hall cell baths used to produce aluminum.

An investigation on the potential of metal recovery from the municipal waste incinerator in Taiwan.

PubMed

Kuo, Nae-Wen; Ma, Hwong-Wen; Yang, Ya-Mei; Hsiao, Teng-Yuan; Huang, Chin-Ming

2007-01-01

This study aimed to identify distribution of metals and to estimate the amount of these metals that can be potentially recovered from incineration residues. First, the partitioning behavior of Cr, Cu, Fe, Cd, Al, Zn, and Pb in bottom ash and fly ash was investigated in one large municipal waste incinerator in Taiwan. In addition, the material flow analysis (MFA) method was used to estimate the material flux of metals within incinerator plant, and to calculate the amount of metal recovery. According to the findings of this study, six metals (Fe, Al, Cu, Zn, Cr, and Pb) concentrated in bottom ash mostly, while Cd existed primarily in fly ash. The weight percentages of Fe (4.49%), Al (5.24%), Cu (1.29%), Zn (2.21%), and Pb (0.58%) in incinerator ash are high, and even higher than the compositions of natural minerals. Finally, the amount of Cr, Cu, Fe, Cd, Al, Zn and Pb that can be potentially recovered from incineration residues will reach 2.69 x 10(2), 1.46 x 10(4), 4.91 x 10(4), 6.92 x 10(1), 5.10 x 10(4), 1.85 x 10(4) and 4.66 x 10(3) ton/yr, respectively.

Effects of chemical composition of fly ash on efficiency of metal separation in ash-melting of municipal solid waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okada, Takashi, E-mail: t-okada@u-fukui.ac.jp; Tomikawa, Hiroki

2013-03-15

Highlights: ► Separation of Pb and Zn from Fe and Cu in ash-melting of municipal solid waste. ► Molar ratio of Cl to Na and K in fly ash affected the metal-separation efficiency. ► The low molar ratio and a non-oxidative atmosphere were better for the separation. - Abstract: In the process of metal separation by ash-melting, Fe and Cu in the incineration residue remain in the melting furnace as molten metal, whereas Pb and Zn in the residue are volatilized. This study investigated the effects of the chemical composition of incineration fly ash on the metal-separation efficiency of themore » ash-melting process. Incineration fly ash with different chemical compositions was melted with bottom ash in a lab-scale reactor, and the efficiency with which Pb and Zn were volatilized preventing the volatilization of Fe and Cu was evaluated. In addition, the behavior of these metals was simulated by thermodynamic equilibrium calculations. Depending on the exhaust gas treatment system used in the incinerator, the relationships among Na, K, and Cl concentrations in the incineration fly ash differed, which affected the efficiency of the metal separation. The amounts of Fe and Cu volatilized decreased by the decrease in the molar ratio of Cl to Na and K in the ash, promoting metal separation. The thermodynamic simulation predicted that the chlorination volatilization of Fe and Cu was prevented by the decrease in the molar ratio, as mentioned before. By melting incineration fly ash with the low molar ratio in a non-oxidative atmosphere, most of the Pb and Zn in the ash were volatilized leaving behind Fe and Cu.« less

Colloid formation and metal transport through two mixing zones affected by acid mine drainage near Silverton, Colorado

USGS Publications Warehouse

Schemel, L.E.; Kimball, B.A.; Bencala, K.E.

2000-01-01

Stream discharges and concentrations of dissolved and colloidal metals (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn), SO4, and dissolved silica were measured to identify chemical transformations and determine mass transports through two mixing zones in the Animas River that receive the inflows from Cement and Mineral Creeks. The creeks were the dominant sources of Al, Cu, Fe, and Pb, whereas the upstream Animas River supplied about half of the Zn. With the exception of Fe, which was present in dissolved and colloidal forms, the metals were dissolved in the acidic, high-SO4 waters of Cement Creek (pH 3.8). Mixing of Cement Creek with the Animas River increased pH to near-neutral values and transformed Al and some additional Fe into colloids which also contained Cu and Pb. Aluminium and Fe colloids had already formed in the mildly acidic conditions in Mineral Creek (pH 6.6) upstream of the confluence with the Animas River. Colloidal Fe continued to form downstream of both mixing zones. The Fe- and Al-rich colloids were important for transport of Cu, Pb, and Zn, which appeared to have sorbed to them. Partitioning of Zn between dissolved and colloidal phases was dependent on pH and colloid concentration. Mass balances showed conservative transports for Ca, Mg, Mn, SO4, and dissolved silica through the two mixing zones and small losses (< 10%) of colloidal Al, Fe and Zn from the water column.

Chemical fractionation of heavy metals in urban soils of Guangzhou, China.

PubMed

Lu, Ying; Zhu, Feng; Chen, Jie; Gan, Haihua; Guo, Yanbiao

2007-11-01

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominantly located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron-Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.

Assessment of trace metals contamination in the coastal sediments of the Egyptian Mediterranean coast

NASA Astrophysics Data System (ADS)

El Baz, Sherif M.; Khalil, Mohamed M.

2018-07-01

Trace metals contamination has been recently increased in the Egyptian Mediterranean coast owing to the nearby anthropological activities. This investigation aimed to detect the concentrations of six different trace metals (Fe, Mn, Cu, Cd, Pb and Zn) in surface sediments from the central part of the Egyptian Mediterranean coast, and to assess their state of contamination from different indices and risk factor calculations. Mean concentrations of Cu, Pb and Zn were lower and the mean concentration of Cd was higher compared to the background values. The assessment of pollution was mainly based on the contamination indices. Based on the contamination factor, Pb was the most enriched element followed by Cd, Mn, Zn and Cu. Most of the sites show low contamination with respect to Pb, Mn, Cd, Fe, Zn and Cu. The pollution load index also suggests that all the coastal sediments are unpolluted. According to the geoaccumulation index, the sediments were classified into unpolluted with Mn, Cd, Fe and Pb, and unpolluted to moderately polluted with Pb. Risk evaluation revealed that Cd had the greatest ecological risk, followed by Pb, Cu, Mn, while Zn had the lowest risk. With the aid of statistical methods, the origin of metals is classified into two clusters (A and B). Group A consists of Fe, Mn and Cu, whereas group B contains Zn, Pb and Cd. In the first cluster Fe and Mn are joined to each other at a positive and significant similarity (0.68). Fe is recognized as an indicator of lithogenous origin, therefore, its higher similarity with Mn may be indicative of the similar origin for Manganese. In the second cluster Pb and Zn are joined to each other at a positive and significant similarity (0.80). Pb is recognized as an indicator of anthropogenic origin, therefore, its higher similarity with Zn may be indicative of the similar origin for Zinc.

Assessment of heavy metals in sediments of the Don Hoi Lot area in the Mae Klong estuary, Thailand.

PubMed

Pengthamkeerati, Patthra; Kornkanitnan, Narumol; Sawangarreruks, Suchat; Wanichacheva, Nantanit; Wainiphithapong, Chantana; Sananwai, Nipawan

2013-01-01

The status and seasonal variation of heavy metals in surface sediment were investigated at Don Hoi Lot, located in the Mae Klong estuary, Thailand. Results revealed that all the measured heavy metals, except Zn, in the sediments had lower concentrations than in other nearby estuaries. Only Zn may be of concern for potential negative effects on estuarine biota in the study area. With the exception of Fe, all the studied heavy metals showed seasonal variation, but the patterns were diverse. Organic matter and the clay fraction in sediments were good sinks for heavy metals, excluding Zn, while Fe and Mn were good catchers. Principal component analysis suggested that Zn might have different origins and/or mechanisms of transport, accumulation and circulation, compared with the other heavy metals studied. A better understanding of sources and the behavior of Zn would enhance the efficiency of the estuary management plan in this study area.

Trace metal concentrations in tropical mangrove sediments, NE Brazil.

PubMed

Miola, Brígida; Morais, Jáder Onofre de; Pinheiro, Lidriana de Souza

2016-01-15

Sediment cores were taken from the mangroves of the Coreaú River estuary off the northeast coast of Brazil. They were analyzed for grain size, CaCO3, organic matter, and trace metal (Cd, Pb, Zn, Cu, Al, and Fe) contents. Mud texture was the predominant texture. Levels of trace metals in surface sediments indicated strong influence of anthropogenic processes, and diagenetic processes controlled the trace metal enrichment of core sediments of this estuary. The positive relationships between trace metals and Al and Fe indicate that Cu, Zn, Pb, and Cd concentrations are associated mainly with Al and Fe oxy-hydroxides and have natural sources. Copyright © 2015 Elsevier Ltd. All rights reserved.

Heavy metal displacement in chelate-irrigated soil during phytoremediation

NASA Astrophysics Data System (ADS)

Madrid, F.; Liphadzi, M. S.; Kirkham, M. B.

2003-03-01

Heavy metals in wastewater sewage sludge (biosolids), applied to land, contaminate soils. Phytoremediation, the use of plants to clean up toxic heavy metals, might remove them. Chelating agents are added to soil to solubilize the metals for enhanced phytoextraction. Yet no studies follow the displacement and leaching of heavy metals in soil with and without roots following solubilization with chelates. The objective of this work was to determine the mobility of heavy metals in biosolids applied to the surface of soil columns (76 cm long; 17 cm diam.) with or without plants (barley; Hordeum vulgare L.). Three weeks after barley was planted, all columns were irrigated with the disodium salt of the chelating agent, EDTA (ethylenediamine tetraacetic acid) (0.5 g/kg soil). Drainage water, soil, and plants were analyzed for heavy metals (Cd, Cu, Fe, Mn, Ni, Pb, Zn). Total concentrations of the heavy metals in all columns at the end of the experiment generally were lower in the top 30 cm of soil with EDTA than without EDTA. The chelate increased concentrations of heavy metals in shoots. With or without plants, the EDTA mobilized Cd, Fe, Mn, Ni, Pb, and Zn, which leached to drainage water. Drainage water from columns without EDTA had concentrations of these heavy metals below detection limits. Only Cu did not leach in the presence of EDTA. Even though roots retarded the movement of Cd, Fe, Mn, Ni, Pb, and Zn through the EDTA-treated soil from 1 d (Cd) to 5 d (Fe), the drainage water from columns with EDTA had concentrations of Cd, Fe, Mn, and Pb that exceeded drinking water standards by 1.3, 500, 620, and 8.6 times, respectively. Because the chelate rendered Cd, Fe, Mn, Ni, Pb, and Zn mobile, it is suggested that the theory for leaching of soluble salts, put forward by Nielsen and associates in 1965, could be applied to control movement of the heavy metals for maximum uptake during chelate-assisted phytoremediation.

Fixed distance photoinduced electron transfer between Fe and Zn porphyrins encapsulated within the Zn HKUST-1 metal organic framework.

PubMed

Larsen, Randy W; Wojtas, Lukasz

2015-02-21

An attractive strategy for the development of photocatalytic metal organic framework (MOF) materials is to co-encapsulate a photoactive electron donor with a catalytic electron acceptor within the MOF. Here we report the co-encapsulation of both Zn(ii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Zn4SP) and Fe(iii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Fe4SP) into an HKUST-1 (Zn) MOF and demonstrate photoinduced electron transfer (ET) between the co-encapsulated guest. Photo-excitation of the Zn4SP results in fixed-distance inter-molecular ET between the encapsulated (3)Zn4SP and the Fe(iii)4SP as evident by the reduction in the encapsulated (3)Zn4SP lifetime from 890 μs (kobs = 1.1 × 10(3) s(-1)) to 83 μs (kobs = 1.2 × 10(4) s(-1)) in the presence of Fe4SP giving a kET ∼ 1.1 × 10(4) s(-1). The data are consistent with ET taking place between encapsulated porphyrins that are two cages apart in distance with a reorganizational energy of ∼1.65 eV, β = 1.25 and ΔG° = -0.97 eV (within a semi-classical Marcus theory framework).

Heavy metal concentrations in redeveloping soil of mine spoil under plantations of certain native woody species in dry tropical environment, India.

PubMed

Singh, Anand N; Zeng, De-hui; Chen, Fu-sheng

2005-01-01

Total concentration of heavy metals (Cd, Cr, Cu, Fe, Pb, Ni, Mn and Zn) was estimated in the redeveloping soil of mine spoil under 5-yr old plantations of four woody species namely: Albizia lebbeck, Albizia procera, Tectona grandis and Dendrocalamus strictus. The data recorded in the present study were compared with other unplanted coal mine spoil colliery, which was around to the study site and adjoining area of dry tropical forest. Among all the heavy metals, the maximum concentration was found for Fe and minimum for Cd. However, among all four species, total concentrations of these heavy metals were recorded maximally in the plantation plots of T. grandis except for Fe, while minimally in A. lebbeck except for Zn, whereas, the maximum concentration of Fe and Zn was in the plantation plots of D. strictus and A. procera. Statistical analysis revealed significant differences due to species for all the heavy metals except Cu. Among four species, A. lebbeck, A. procera and D. strictus showed more efficient for reducing heavy metal concentrations whereas T. grandis was not more effective to reduce heavy metal concentrations in redeveloping soil of mine spoil.

Rates of zinc and trace metal release from dissolving sphalerite at pH 2.0-4.0

USGS Publications Warehouse

Stanton, M.R.; Gemery-Hill, P. A.; Shanks, Wayne C.; Taylor, C.D.

2008-01-01

High-Fe and low-Fe sphalerite samples were reacted under controlled pH conditions to determine nonoxidative rates of release of Zn and trace metals from the solid-phase. The release (solubilization) of trace metals from dissolving sphalerite to the aqueous phase can be characterized by a kinetic distribution coefficient, (Dtr), which is defined as [(Rtr/X(tr)Sph)/(RZn/X(Zn) Sph)], where R is the trace metal or Zn release rate, and X is the mole fraction of the trace metal or Zn in sphalerite. This coefficient describes the relationship of the sphalerite dissolution rate to the trace metal mole fraction in the solid and its aqueous concentration. The distribution was used to determine some controls on metal release during the dissolution of sphalerite. Departures from the ideal Dtr of 1.0 suggest that some trace metals may be released via different pathways or that other processes (e.g., adsorption, solubility of trace minerals such as galena) affect the observed concentration of metals. Nonoxidative sphalerite dissolution (mediated by H+) is characterized by a "fast" stage in the first 24-30 h, followed by a "slow" stage for the remainder of the reaction. Over the pH range 2.0-4.0, and for similar extent of reaction (reaction time), sphalerite composition, and surface area, the rates of release of Zn, Fe, Cd, Cu, Mn and Pb from sphalerite generally increase with lower pH. Zinc and Fe exhibit the fastest rates of release, Mn and Pb have intermediate rates of release, and Cd and Cu show the slowest rates of release. The largest variations in metal release rates occur at pH 2.0. At pH 3.0 and 4.0, release rates show less variation and appear less dependent on the metal abundance in the solid. For the same extent of reaction (100 h), rates of Zn release range from 1.53 ?? 10-11 to 5.72 ?? 10-10 mol/m2/s; for Fe, the range is from 4.59 ?? 10-13 to 1.99 ?? 10-10 mol/m2/s. Trace metal release rates are generally 1-5 orders of magnitude slower than the Zn or Fe rates. Results indicate that the distributions of Fe and Cd are directly related to the rate of sphalerite dissolution throughout the reaction at pH 3.0 and 4.0 because these two elements substitute readily into sphalerite. These two metals are likely to be more amenable to usage in predictive acid dissolution models because of this behavior. The Pb distribution shows no strong relation to sphalerite dissolution and appears to be controlled by pH-dependent solubility, most likely related to trace amounts of galena. The distribution of Cu is similar to that of Fe but is the most-dependent of all metals on its mole fraction ratio (Zn:Cu) in sphalerite. The Mn distributions suggest an increase in the rate of Mn release relative to sphalerite dissolution occurs in low Mn samples as pH increases. The Mn distribution in high Mn samples is nearly independent of pH and sphalerite dissolution at pH 2.0 but shows a dependence on these two parameters at higher pH (3.0-4.0).

Heavy Metals in Soils and Vegetables Irrigated with Urban Grey Waste Water in Fagge, Kano, Nigeria.

PubMed

Chiroma, T M; Ebewele, R O; Hymore, F K

2014-01-01

There is currently an increased consumption of vegetables within the local urban community. However, contamination of these vegetables with heavy metals poses a potential health hazard. Consequently, the potential contamination problem due to the effect of levels of some heavy metals (Fe, Mg, Zn, Mn, Cu and Cr) in soils and vegetables irrigated with drainage urban grey waste water were investigated. The maximum levels of Fe, Zn, Mn, Cu and Cr in the urban grey waste waters were respectively 2.8, 2.1, 19.5, 2.3 and 143.1 times, higher than the maximum recommended concentrations of these metals: 5.0 μg/mL, 2.0 μg/mL, 0.2 μg/mL, 0.2 μg/mL and 0.1 μg/mL, respectively, for irrigation waters. The soils were found to be contaminated with these metals to levels that range between 24 to 84 percent contaminations. Although the heavy metals concentration ranking in vegetable parts vary with plant specie, the concentrations of Fe, Zn, Mn, Cu and Cr in most parts of the vegetables were above their critical concentrations of 750 - 1000 μg/g, 100 - 400 μg/g, 300 - 500 μg/g, 20 - 100 μg/g and 5 - 30 μg/g, respectively, in plants. This suggests potential toxicity of these parts of vegetables. It was however found that over 40 percent of the concentrations of Fe, Mg, Zn and Cu in Onions, Fe in Okro, Cr in Bushgreen, Cu in Roselle and Zn, Cu in Carrot leaves can be easily removed by washing the leaves with water. However, only Cu concentration in Onions and Bushgreen leaves met the acceptable permissible level in plants after washing.

Geochemical fractionation and pollution assessment of Zn, Cu, and Fe in surface sediments from Shadegan Wildlife Refuge, southwest of Iran.

PubMed

Chaharlang, Behnam Heidari; Bakhtiari, Alireza Riyahi; Mohammadi, Jahangard; Farshchi, Parvin

2017-09-01

This research focuses on the fractionation and distribution patterns of heavy metals (Zn, Cu, and Fe) in surficial sediments collected from Shadegan Wildlife Refuge, the biggest wetland in southern part of Iran, to provide an overall classification for the sources of metals in the study area using a sequential extraction method. For this purpose, a four-step sequential extraction technique was applied to define the partitioning of the metals into different geochemical phases of the sediment. The results illustrated that the average total level of Zn, Cu, and Fe in surface sediments were 55.20 ± 16.04, 22.86 ± 5.68, and 25,979.01 ± 6917.91 μg/g dw, respectively. On the average, the chemical partitioning of all metals in most stations was in the order of residual >oxidizable-organic > acid-reducible > exchangeable. In the same way, the results of calculated geochemical indices revealed that Cu, Zn, and Fe concentrations are mainly influenced by lithogenic origins. Compared with consensus-based SQGs, Cu was likely to result in occasionally harmful biological effects on the biota.

Biosorption of heavy metals from industrial waste water by Geobacillus thermodenitrificans.

PubMed

Chatterjee, S K; Bhattacharjee, I; Chandra, G

2010-03-15

The metal binding capacity of the thermophilic bacteria Geobacillus thermodenitrificans isolated from Damodar river, India was assessed using synthetic metal solutions and industrial waste water. Biosorption preference of dead biomass of G. thermodenitrificans for the synthetic metal solutions was in the following order Fe(+3)>Cr(+3)>Co(+2)>Cu(+2)>Zn(+2)>Cd(+2)>Ag(+)>Pb(+2). It reduced the concentration of Fe(+3) (91.31%), Cr(+3) (80.80%), Co(+2) (79.71%), Cu(+2) (57.14%), Zn(+2) (55.14%), Cd(+2) (49.02%), Ag(+) (43.25%) and Pb(+2) (36.86%) at different optimum pH within 720 min. When this strain was applied in the industrial waste water biosorption preference was in the following order Fe(+3)>Cr(+3)>Cd(+2)>Pb(+2)>Cu(+2)>Co(+2)>Zn(+2)>Ag(+) and concentrations reduced up to 43.94% for Fe(+3), 39.2% for Cr(+3), 35.88% for Cd(+2), 18.22% for Pb(+2), 13.03% for Cu(+2), 11.43% for Co(+2), 9.02% for Zn(+2) and 7.65% for Ag(+) within 120 min. (c) 2009 Elsevier B.V. All rights reserved.

Sustainable synthesis of metals-doped ZnO nanoparticles from zinc-bearing dust for photodegradation of phenol.

PubMed

Wu, Zhao-Jin; Huang, Wei; Cui, Ke-Ke; Gao, Zhi-Fang; Wang, Ping

2014-08-15

A novel strategy of waste-cleaning-waste is proposed in the present work. A metals-doped ZnO (M-ZnO, M = Fe, Mg, Ca and Al) nanomaterial has been prepared from a metallurgical zinc-containing solid waste "fabric filter dust" by combining sulfolysis and co-precipitation processes, and is found to be a favorable photocatalyst for photodegradation of organic substances in wastewater under visible light irradiation. All the zinc and dopants (Fe, Mg, Ca and Al) for preparing M-ZnO are recovered from the fabric filter dust, without any addition of chemical as elemental source. The dust-derived M-ZnO samples deliver single phase indexed as the hexagonal ZnO crystal, with controllable dopants species. The photocatalytic activity of the dust-derived M-ZnO samples is characterized by photodegradation of phenol aqueous solution under visible light irradiation, giving more prominent photocatalytic behaviors than undoped ZnO. Such enhancements may be attributed to incorporation of the dust-derived metal elements (Fe, Mg, Ca and Al) into ZnO structure, which lead to the modification of band gap and refinement of grain size. The results show a feasibility to utilize the industrial waste as a resource of photodegradating organic substances in wastewater treatments. Copyright © 2014 Elsevier B.V. All rights reserved.

Ab initio understanding of magnetic properties in Zn2+ substitution of Fe3O4 ultra-thin film with dilute Zn substitution

NASA Astrophysics Data System (ADS)

Huang, Zhaocong; Chen, Qian; Jiang, Sheng; Dong, Shuai; Zhai, Ya

2018-05-01

The mechanism of the magnetic properties on the Zn2+ substituted Fe3O4 film have been investigated based on first principle calculations. It is found that the surface effect plays an important role in the occupation of Zn ion, and in turn changes the magnetic moment. It may also destroy the half metallic behavior of Fe3O4 film even if the Zn2+ concentration only is one Zn2+ per unit cell (4%), which is different from that in bulk material.

Surface chemistry, friction, and wear of Ni-Zn and Mn-Zn ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

X-ray photoelectron and Auger electron spectroscopy analysis were used in sliding friction experiments. These experiments were conducted with hot-pressed polycrystalline Ni-Zn and Mn-Zn ferrites, and single-crystal Mn-Zn ferrite in contact with various transition metals at room temperature in both vacuum and argon. The results indicate that Ni2O3 and Fe3O4 were present on the Ni-Zn ferrite surface in addition to the nominal bulk constituents, while MnO2 and Fe3O4 were present on the Mn-Zn ferrite surface in addition to the nominal bulk constituents. The coefficients of friction for the ferrites in contact with metals were related to the relative chemical activity of these metals. The more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites were correlated with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite does strengthen the metal-ferrite contact and increase the friction. The ferrites exhibit local cracking and fracture with sliding under adhesive conditions. All the metals transferred to the surfaces of the ferrites in sliding. Previously announced in STAR as N83-19901

Surface chemistry, friction and wear of Ni-Zn and Mn-Zn ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron and Auger electron spectroscopy analysis were used in sliding friction experiments. These experiments were conducted with hot-pressed polycrystalline Ni-Zn and Mn-Zn ferrites, and single-crystal Mn-Zn ferrite in contact with various transition metals at room temperature in both vacuum and argon. The results indicate that Ni2O3 and Fe3O4 were present on the Ni-Zn ferrite surface in addition to the nominal bulk constituents, while MnO2 and Fe3O4 were present on the Mn-Zn ferrite surface in addition to the nominal bulk constituents. The coefficients of friction for the ferrites in contact with metals were related to the relative chemical activity of these metals. The more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites were correlated with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite does strengthen the metal-ferrite contact and increase the friction. The ferrites exhibit local cracking and fracture with sliding under adhesive conditions. All the metals transferred to he surfaces of the ferrites in sliding.

Risk assessment of mineral and heavy metal content of selected tea products from the Ghanaian market.

PubMed

Nkansah, Marian Asantewah; Opoku, Francis; Ackumey, Abiathar Abraham

2016-06-01

Food consumption is the most likely route of human exposure to metals. Tea (Camellia sinensis L.) is among the most widely consumed non-alcoholic beverages. Concentrations of heavy metals and minerals in tea from 15 different brands in Kumasi, Ghana were measured to assess the health risk associated with their consumption. The mineral and metal contents (Fe, Cu, Zn, Pb, As, Cd) were analyzed using atomic absorption spectrophotometer (Z-8100 polarized Zeeman). The results revealed that the mean concentrations were in the order: Ca > Fe > As > Cd > Zn > Pb. The average contents of Ca, Fe, Zn, Pb, Cd, and As in the samples were 94.08, 6.15, 0.20, 0.16, 0.36, and 1.66 mg/kg, respectively. All the minerals and heavy metals were below the maximum permissible limits stipulated by the World Health Organization (WHO) and US Pharmacopeia (USP). Metal-to-metal correlation indicated strong correlations between As/Zn, Cd/Zn, Cd/As, and Pb/As pairs. Factor analysis demonstrated a clear separation between minerals, grouped on one side, and heavy metals, clustered on another side. Both the target hazard quotient (THQ) and hazard index (HI) levels in green tea were far below 1, suggesting that consumption of green tea should pose no potential risk to human health. However, carcinogenic risk levels for arsenic were high; R > 10(-6). The results showed that residents in Kumasi consume tea could be at risk from exposure to these heavy metals and minerals.

Stable room temperature magnetocurrent in electrodeposited permeable n-type metal base transistor

NASA Astrophysics Data System (ADS)

Silva, G. V. O.; Teixeira, H. A.; Mello, S. L. A.; de Araujo, C. I. L.

2018-02-01

We investigated a permeable metal base transistor consisting of a ZnO/NiFe/Si heterostructure. Both ZnO and NiFe layers were grown by electrodeposition techniques, using only adhesive tape masks to define deposition regions. The base permeability can thus be controlled by varying the NiFe deposition time. We report here our best results obtained for the permeable NiFe base close to the electrical percolation threshold, which gives reasonable sensitivity to the device. Magnetocurrent measurements carried out at room temperature show that this permeable metal base transistor is stable and sensitive under applied magnetic fields of low intensities, ˜100 Oe, required for electronics integration.

A time-course analysis of changes in cerebral metal levels following a controlled cortical impact.

PubMed

Portbury, Stuart D; Hare, Dominic J; Sgambelloni, Charlotte; Finkelstein, David I; Adlard, Paul A

2016-02-01

Traumatic brain injury (TBI) is complicated by a sudden and dramatic change in brain metal levels, including iron (Fe), copper (Cu) and zinc (Zn). Specific 'metallo-pathological' features of TBI include increased non-heme bound Fe and the liberation of free Zn ions, both of which may contribute to the pathogenesis of TBI. To further characterise the metal dyshomeostasis that occurs following brain trauma, we performed a quantitative time-course survey of spatial Fe, Cu and Zn distribution in mice receiving a controlled cortical impact TBI. Images of brain metal levels produced using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in the upper quadrant of the ipsilateral hemisphere were compared to the corresponding contralateral hemisphere, together with regional areas radiating toward the center of the brain from the site of lesion. Significant regional and time point specific elevations in Fe, Zn and Cu were detected immediately and up to 28 days after TBI. The magnitude and timeframe of many of these changes suggest that TBI results in a pronounced and sustained alteration in normal metal levels within the brain. Such alterations are likely to play a role in both the short- and long-term consequences of head trauma and suggest that pharmacological modulation to normalize these metal levels may be efficacious in improving functional outcome.

Inversion domain boundaries in ZnO with additions of Fe2O3 studied by high-resolution ADF imaging.

PubMed

Wolf, Frank; Freitag, Bert H; Mader, Werner

2007-01-01

Columns of metal atoms in the polytypoid compound Fe2O3(ZnO)15 could be resolved by high angle annular dark field imaging in a transmission electron microscopy (TEM)/STEM electron microscope--a result which could not be realized by high-resolution bright field imaging due to inherent strain from inversion domains and inversion domain boundaries (IDBs) in the crystals. The basal plane IDB was imaged in [11 00] yielding the spacing of the two adjacent ZnO domains, while imaging in [21 1 0] yields the position of single metal ions. The images allow the construction of the entire domain structure including the stacking sequence and positions of the oxygen ions. The IDB consists of a single layer of octahedrally co-ordinated Fe3+ ions, and the inverted ZnO domains are related by point symmetry at the iron position. The FeO6 octahedrons are compressed along the ZnO c-axis resulting in a FeO bond length of 0.208 nm which is in the range of FeO distances in iron containing oxides. The model of the basal plane boundary resembles that of the IDB in polytypoid ZnO-In2O3 compounds.

Effect of MgO on Liquidus Temperatures in the ZnO-"FeO"-Al2O3-CaO-SiO2-MgO System in Equilibrium with Metallic Iron

NASA Astrophysics Data System (ADS)

Zhao, Baojun; Hayes, Peter C.; Jak, Evgueni

2011-06-01

The phase equilibria in the ZnO-"FeO"-Al2O3-CaO-SiO2-MgO system have been determined experimentally in equilibrium with metallic iron. Synthetic slags were equilibrated at a high temperature, quenched, and then the compositions of the phases in equilibrium were measured using electron probe X-ray microanalysis. Pseudoternary sections of the form ZnO-"FeO"-(Al2O3 + CaO + SiO2) for CaO/SiO2 = 0.71, (CaO + SiO2)/Al2O3 = 5 and fixed MgO concentrations of 2, 4, and 6 wt pct have been constructed. Wustite (Fe2+,Mg,Zn)O and spinel (Fe2+,Mg,Zn)O·(Al,Fe3+)2O3 are the major primary phases in the temperature and composition ranges investigated. The liquidus temperatures are increased by 140 K in the wustite primary phase field and by 70 K in the spinel primary phase field with the addition of 6 wt pct MgO in the slag. The partitioning of MgO and ZnO between the solid and liquid phases has been discussed.

An alternative approach to recovering valuable metals from zinc phosphating sludge.

PubMed

Kuo, Yi-Ming

2012-01-30

This study used a vitrification process (with good potential for commercialization) to recover valuable metals from Zn phosphating sludge. The involved vitrification process achieves two major goals: it transformed hazardous Zn phosphating sludge into inert slag and it concentrated Fe (83.5%) and Zn (92.8%) into ingot and fine particulate-phase material, respectively. The Fe content in the ingot was 278,000 mg/kg, making the ingot a potential raw material for iron making. The fine particulate-phase material (collected from flue gas) contained abundant Zn (544,000 mg/kg) in the form of ZnO. The content (67.7%) of ZnO was high, so it can be directly sold to refineries. The recovered coarse particulate-phase material, with insufficient amount of ZnO, can be recycled as a feeding material for Zn re-concentration. Therefore, the vitrification process can not only treat hazardous materials but also effectively recover valuable metals. Copyright © 2011 Elsevier B.V. All rights reserved.

For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.

2002-01-01

A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase including an oxide of Ni, Fe and M, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mo, Hf and rare earths, preferably Zn and/or Co. Preferred ceramic compositions comprise Fe.sub.2 O.sub.3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

Application of sequential leaching, risk indices and multivariate statistics to evaluate heavy metal contamination of estuarine sediments: Dhamara Estuary, East Coast of India.

PubMed

Asa, Subas Chandra; Rath, Prasanta; Panda, Unmesh Chandra; Parhi, Pankaj Kumar; Bramha, Satyanarayan

2013-08-01

In the present study, concentration of some selected trace metals (Fe, Mn, Ni, Co, Pb, Zn, Cu, Cr and Cd) are measured in Brahmani, Baitarani river complex along with Dhamara estuary and its near shore. Chemical partitioning has been made to establish association of metals into different geochemical phases. The exchangeable fraction is having high environmental risk among non-lithogeneous phases due to greater potential for mobility into pore water. The metals with highest bio-availability being Cd, Zn and Cr. The metals like Mn, Zn, Cd and Cu represent an appreciable portion in carbonate phase. Fe-Mn oxides act as efficient scavenger for most of the metals playing a prime role in controlling their fate and transport. Among non-lithogeneous phases apart from reducible, Cr showed a significant enrichment in organic phase. Risk assessment code values indicate that all metals except Fe fall under medium-risk zone. In estuarine zone Cd, Zn, Pb and Cr are released to 32.43, 26.10, 21.81 and 20 %, respectively, indicating their significant bio-availability pose high ecological risk. A quantitative approach has been made through the use of different risk indices like enrichment factor, geo-accumulation index and pollution load index. Factor analysis indicates that in riverine zone, Fe-Mn oxides/hydroxides seem to play an important role in scavenging metals, in estuarine zone, organic precipitation and adsorption to the fine silt and clay particles while in coastal zone, co-precipitation with Fe could be the mechanism for the same. Canonical discriminant function indicates that it is highly successful in discriminating the groups as predicted.

Distribution and solid-phase speciation of toxic heavy metals of bed sediments of Bharali tributary of Brahmaputra River.

PubMed

Hoque, Raza Rafiqul; Goswami, K G; Kusre, B C; Sarma, K P

2011-06-01

Heavy metal (Fe, Mn, Zn, Cu, Ni, Pb, and Cd) concentrations and their chemical speciations were investigated for the first time in bed sediments of Bharali River, a major tributary of the Brahmaputra River of the Eastern Himalayas. Levels of Fe, Mn, Pb, and Cd in the bed sediments were much below the average Indian rivers; however, Cu and Zn exhibit levels on the higher side. Enrichment factors (EF) of all metals was greater than 1 and a higher trend of EF was seen in the abandoned channel for most metals. Pb showed maximum EF of 32 at site near an urban center. The geoaccumulation indices indicate that Bharali river is moderately polluted. The metals speciations, done by a sequential extraction regime, show that Cd, Cu, and Pb exhibit considerable presence in the exchangeable and carbonate fraction, thereby showing higher mobility and bioavailability. On the other hand, Ni, Mn, and Fe exhibit greater presence in the residual fraction and Zn was dominant in the Fe-Mn oxide phase. Inter-species correlations at three sites did not show similar trends for metal pairs indicating potential variations in the contributing sources.

Structures of E. coli peptide deformylase bound to formate: insight into the preference for Fe2+ over Zn2+ as the active site metal.

PubMed

Jain, Rinku; Hao, Bing; Liu, Ren-Peng; Chan, Michael K

2005-04-06

E. coli peptide deformylase (PDF) catalyzes the deformylation of nascent polypeptides generated during protein synthesis. While PDF was originally thought to be a zinc enzyme, subsequent studies revealed that the active site metal is iron. In an attempt to understand this unusual metal preference, high-resolution structures of Fe-, Co-, and Zn-PDF were determined in complex with its deformylation product, formate. In all three structures, the formate ion binds the metal and forms hydrogen-bonding interactions with the backbone nitrogen of Leu91, the amide side chain of Gln50, and the carboxylate side chain of Glu133. One key difference, however, is how the formate binds the metal. In Fe-PDF and Co-PDF, formate binds in a bidentate fashion, while in Zn-PDF, it binds in a monodentate fashion. Importantly, these structural results provide the first clues into the origins of PDF's metal-dependent activity differences. On the basis of these structures, we propose that the basis for the higher activity of Fe-PDF stems from the better ability of iron to bind and activate the tetrahedral transition state required for cleavage of the N-terminal formyl group.

The influence of manganese treatment on the distribution of metal elements in rats and the protection by sodium para-amino salicylic acid.

PubMed

Yuan, Zong-Xiang; Chen, Hai-Bin; Li, Shao-Jun; Huang, Xiao-Wei; Mo, Yu-Huan; Luo, Yi-Ni; He, Sheng-Nan; Deng, Xiang-Fa; Lu, Guo-Dong; Jiang, Yue-Ming

2016-07-01

Manganese (Mn) overexposure induced neurological damages, which could be potentially protected by sodium para-aminosalicylic acid (PAS-Na). In this study, we systematically detected the changes of divalent metal elements in most of the organs and analyzed the distribution of the metals in Mn-exposed rats and the protection by PAS-Na. Sprague Dawley (SD) rats received intraperitoneal injections of 15mg/kg MnCl2·4H2O (5d/week for 3 weeks), followed by subcutaneous (back) injections of PAS-Na (100 and 200mg/kg, everyday for 5 weeks). The concentrations of Mn and other metal elements [Iron (Fe), Copper (Cu), Zinc (Zn), Magnesium (Mg), Calcium (Ca)] in major organs (liver, spleen, kidney, thighbone and iliac bone, cerebral cortex, hippocampus and testes) and blood by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). The results showed that Mn overexposure significantly increased Mn in most organs, Fe and Zn in liver, Fe and Mg in blood; however decreased Fe, Cu, Zn, Mg and Ca in cortex, Cu and Zn in kidney, Cu and Mg in iliac bone, and Zn in blood. In contrast, PAS-Na treatment restored most changes particularly in cortex. In conclusion, excessive Mn exposure disturbed the balance of other metal elements but PAS-Na post-treatments could restore these alterations. Copyright © 2016 Elsevier GmbH. All rights reserved.

Color Tuning in Garnet Oxides: The Role of Tetrahedral Coordination Geometry for 3 d Metal Ions and Ligand-Metal Charge Transfer (Band-Gap Manipulation).

PubMed

Bhim, Anupam; Laha, Sourav; Gopalakrishnan, Jagannatha; Natarajan, Srinivasan

2017-10-18

We explored garnet-structured oxide materials containing 3d transition-metal ions (e.g., Co 2+ , Ni 2+ , Cu 2+ , and Fe 3+ ) for the development of new inorganic colored materials. For this purpose, we synthesized new garnets, Ca 3 Sb 2 Ga 2 ZnO 12 (I) and Ca 3 Sb 2 Fe 2 ZnO 12 (II), that were isostructural with Ca 3 Te 2 Zn 3 O 12 . Substitution of Co 2+ , Ni 2+ , and Cu 2+ at the tetrahedral Zn 2+ sites in I and II gave rise to brilliantly colored materials (different shades of blue, green, turquoise, and red). The materials were characterized by optical absorption spectroscopy and CIE chromaticity diagrams. The Fe 3+ -containing oxides showed band-gap narrowing (owing to strong sp-d exchange interactions between Zn 2+ and the transition-metal ion), and this tuned the color of these materials uniquely. We also characterized the color and optical absorption properties of Ca 3 Te 2 Zn 3-x Co x O 12 (0

Examining Two Sets of Introgression Lines in Rice (Oryza sativa L.) Reveals Favorable Alleles that Improve Grain Zn and Fe Concentrations

PubMed Central

Hu, Xia; Cheng, Li-Rui; Xu, Jian-Long; Shi, Yu-Min; Li, Zhi-Kang

2015-01-01

In the modern world, the grain mineral concentration (GMC) in rice (Oryza sativa L.) not only includes important micronutrient elements such as iron (Fe) and zinc (Zn), but it also includes toxic heavy metal elements, especially cadmium (Cd) and lead (Pb). To date, the genetic mechanisms underlying the regulation of GMC, especially the genetic background and G × E effects of GMC, remain largely unknown. In this study, we adopted two sets of backcross introgression lines (BILs) derived from IR75862 (a Zn-dense rice variety) as the donor parent and two elite indica varieties, Ce258 and Zhongguangxiang1, as recurrent parents to detect QTL affecting GMC traits including Fe, Zn, Cd and Pb concentrations in two environments. We detected a total of 22 loci responsible for GMC traits, which are distributed on all 12 rice chromosomes except 5, 9 and 10. Six genetic overlap (GO) regions affecting multiple elements were found, in which most donor alleles had synergistic effects on GMC. Some toxic heavy metal-independent loci (such as qFe1, qFe2 and qZn12) and some regions that have opposite genetic effects on micronutrient (Fe and Zn) and heavy metal element (Pb) concentrations (such as GO-IV) may be useful for marker-assisted biofortification breeding in rice. We discuss three important points affecting biofortification breeding efforts in rice, including correlations between different GMC traits, the genetic background effect and the G × E effect. PMID:26161553

Metals in some lagoons of Mexico.

PubMed

Vazquez, F G; Sharma, V K; Alexander, V H; Frausto, C A

1995-02-01

The concentrations of metals, Cd, Cu, Fe, Mn, Ni, Pb, and Zn were determined in some lagoons to establish the level of metal pollution. The lagoons studied were Alvarado lagoon, Veracruz; San Andres lagoon, Tamaulipas; and Terminos lagoon, Campeche. The concentrations were determined in water, oyster (Crassostrea virginica), and sediments. Metals were accumulated in either oysters or sediments. Cu and Zn were higher in oysters and Fe and Mn were higher in sediments. The results in water samples were compared with the limit established by the Secretaria de Ecologia and Desarrollo Urbano Report and briefly discussed.

A comparison of trace metal bioaccumulation and distribution in Typha latifolia and Phragmites australis: implication for phytoremediation.

PubMed

Klink, Agnieszka

2017-02-01

The aims of the present investigation were to reveal various trace metal accumulation abilities of two common helophytes Typha latifolia and Phragmites australis and to investigate their potential use in the phytoremediation of environmental metal pollution. The concentrations of Fe, Mn, Zn, Cu, Cd, Pb and Ni were determined in roots, rhizomes, stems and leaves of both species studied as well as in corresponding water and bottom sediments from 19 sites selected within seven lakes in western Poland (Leszczyńskie Lakeland). The principal component and classification analysis showed that P. australis leaves were correlated with the highest Mn, Fe and Cd concentrations, but T. latifolia leaves with the highest Pb, Zn and Cu concentrations. However, roots of the P. australis were correlated with the highest Mn, Fe and Cu concentrations, while T. latifolia roots had the highest Pb, Zn and Cd concentrations. Despite the differences in trace metal accumulation ability between the species studied, Fe, Cu, Zn, Pb and Ni concentrations in the P. australis and T. latifolia exhibited the following accumulation scheme: roots > rhizomes > leaves > stems, while Mn decreased in the following order: root > leaf > rhizome > stem. The high values of bioaccumulation factors and low values of translocation factors for Zn, Mn, Pb and Cu indicated the potential application of T. latifolia and P. australis in the phytostabilisation of contaminated aquatic ecosystems. Due to high biomass of aboveground organs of both species, the amount of trace metals stored in these organs during the vegetation period was considerably high, despite of the small trace metals transport.

The effect of abandoned mining ponds on trace elements dynamics in the soil-plant system

NASA Astrophysics Data System (ADS)

Gabarrón, María; Faz, Ángel; Zornoza, Raúl; Acosta, Jose A.

2017-04-01

In semiarid climate regions lack of vegetation and dryer climate contribute to erosion of abandoned mining surface areas making them up important potential sources of metal pollution into the environment. The objectives of this study were to determine the influence of mine ponds in agriculture and forest soils, and identify the dynamic of metals in the soil-plant system for native plant species (Ballota hirsuta) and crop species (Hordeum vulgare) in two ancient mining districts: La Unión and Mazarrón. To achieve these objectives, wastes samples from mine ponds and soil samples (rhizosphere and non-rhizosphere soils) from natural and agricultural lands were collected. In addition, six plants (Ballota hirsuta) from natural area and 3 plants (Hordeum vulgare) from crops were collected. Physicochemical properties and total, water soluble and bioavailable metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) and arsenic were measured in waste/soil samples. The chemical speciation of metals in soil was estimated by a sequential extraction procedure. For plants analyses, each plant were divided in roots, stem and leaves and metal content measured by ICP-MS. Results indicated that mine, natural and agricultural soils were contaminated by As, Cd, Cu, Pb, and Zn. Chemical partitioning revealed higher mobility of metals in mine ponds than natural and agriculture soils while only Fe and As are completely bound to the soil matrix due to the mineralogical compositions of soils. The accumulation of metals in Ballota hirsuta in La Union decrease as Fe>As>Cr>Ni>Cu>Zn>Cd>Mn>Co>Pb while in Mazarrón did as As>Fe>Cr>Pb>Cu>Ni>Co>Mn>Zn>Cd. Ballota hirsuta showed high ability to bio-accumulate Cu, Cr, Fe, Ni, and As, transferring a large amount to edible parts without exceeding the toxicity limits for animals. Results for barley plants (Hordeum vulgare) showed the ability to absorb and accumulate As, Fe, Mn, Pb and Zn, although the transfer ability of As, Cd and Pb was lower. Although the behavior of metals reflects a root barrier effect, the amount of Pb in grain overreached the permissible limit in aliments.

Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings.

PubMed

Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A H

2015-01-01

Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal.

Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings

PubMed Central

Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A. H.

2015-01-01

Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal. PMID:26295582

Photoinduced formation of reactive oxygen species and electrons from metal oxide-silica nanocomposite: An EPR spin-trapping study

NASA Astrophysics Data System (ADS)

Zhao, Hongxia; Chen, Xiuying; Li, Xintong; Shen, Chen; Qu, Baocheng; Gao, Jingsuo; Chen, Jingwen; Quan, Xie

2017-09-01

Metal oxide nanocomposites with photocatalytic activity have the potential for many applications in environmental remediation and biomedicine. In this study, we investigated the formation and stabilization of electrons/holes from three metal oxide-silica nanocomposites (CuO-SiO2, Fe2O3-SiO2 and ZnO-SiO2) under irradiation by electron paramagnetic resonance (EPR) technology. The characteristic EPR signals with g = 2.00070-2.00105, ΔHp-p = 2.17-2.37 G were determined, which corresponded to lattice-trapped electrons. Moreover, the generation of active species from CuO-SiO2, Fe2O3-SiO2 and ZnO-SiO2 in aqueous solution under irradiation was also systematically studied. The results showed that all the three nanocomposites could generate hydroxyl radical, singlet oxygen and electron. CuO-SiO2 was more effective than Fe2O3-SiO2 and ZnO-SiO2 in producing hydroxyl radical and electrons, while ZnO-SiO2 was the most efficient in generating singlet oxygen. In addition, CuO-SiO2 exhibited most obviously photocatalytic activity toward degradation of bisphenol A, followed by Fe2O3-SiO2 and ZnO-SiO2. These findings will provide vital insights into photocatalytic mechanisms and potentially photoinduced toxicity of metal oxide-silica nanocomposites.

Coexistence of Cu, Fe, Pb, and Zn oxides and chlorides as a determinant of chlorinated aromatics generation in municipal solid waste incinerator fly ash.

PubMed

Fujimori, Takashi; Tanino, Yuta; Takaoka, Masaki

2014-01-01

We investigated chemical determinants of the generation of chlorinated aromatic compounds (aromatic-Cls), such as polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs), in fly ash from municipal solid waste incineration. The influences of the following on aromatic-Cls formation in model fly ash (MFA) were systematically examined quantitatively and statistically: (i) inorganic chlorides (KCl, NaCl, CaCl2), (ii) base materials (SiO2, Al2O3, CaCO3), (iii) metal oxides (CuO, Fe2O3, PbO, ZnO), (iv) metal chlorides (CuCl2, FeCl3, PbCl2, ZnCl2), and (v) "coexisting multi-models." On the basis of aromatic-Cls concentrations, the ∑CBzs/∑PCBs ratio, and the similarity between distribution patterns, MFAs were categorized into six groups. The results and analysis indicated that the formation of aromatic-Cls depended strongly on the "coexistence condition", namely multimodels composed of not only metal chlorides, but also of metal oxides. The precise replication of metal chloride to oxide ratios, such as the precise ratios of Cu-, Fe-, Pb-, and Zn-chlorides and oxides, may be an essential factor in changing the thermochemical formation patterns of aromatic-Cls. Although CuCl2 acted as a promoter of aromatic-Cls generation, statistical analyses implied that FeCl3 also largely influenced the generation of aromatic-Cls under mixture conditions. Various additional components of fly ash were also comprehensively analyzed.

Biomonitoring Heavy Metal Pollution Using an Aquatic Apex Predator, the American Alligator, and Its Parasites

PubMed Central

Tellez, Marisa; Merchant, Mark

2015-01-01

Monitoring the bioaccumulation of chemical elements within various organismal tissues has become a useful tool to survey current or chronic levels of heavy metal exposure within an environment. In this study, we compared the bioaccumulations of As, Cd, Cu, Fe, Pb, Se, and Zn between the American alligator, Alligator mississippiensis, and its parasites in order to establish their use as bioindicators of heavy metal pollution. Concomitant with these results, we were interested to determine if parasites were more sensitive bioindicators of heavy metals relative to alligators. We found parasites collectively accumulated higher levels of As, Cu, Se, and Zn in comparison to their alligator hosts, whereas Fe, Cd, and Pb concentrations were higher in alligators. Interestingly, Fe levels were significantly greater in intestinal trematodes than their alligator hosts when analyzed independently from other parasitic taxa. Further analyses showed alligator intestinal trematodes concentrated As, Cu, Fe, Se, and Zn at significantly higher levels than intestinal nematodes and parasites from other organs. However, pentastomids also employed the role as a good biomagnifier of As. Interestingly, parasitic abundance decreased as levels of As increased. Stomach and intestinal nematodes were the poorest bioaccumulators of metals, yet stomach nematodes showed their ability to concentrate Pb at orders of magnitude higher in comparison to other parasites. Conclusively, we suggest that parasites, particularly intestinal trematodes, are superior biomagnifiers of As, Cu, Se, and Zn, whereas alligators are likely good biological indicators of Fe, Cd, and Pb levels within the environment. PMID:26555363

Source analysis of radiocesium in river waters using road dust tracers.

PubMed

Murakami, Michio; Saha, Mahua; Iwasaki, Yuichi; Yamashita, Rei; Koibuchi, Yukio; Tsukada, Hirofumi; Takada, Hideshige; Sueki, Keisuke; Yasutaka, Tetsuo

2017-11-01

Following the Fukushima Dai-ichi Nuclear Power Station accident, regional road dust, heavily contaminated with radiocesium, now represents a potential source of radiocesium pollution in river water. To promote effective countermeasures for reducing the risk from radiocesium pollution, it is important to understand its sources. This study evaluated the utility of metals, including Al, Fe, and Zn as road dust tracers, and applied them to analyze sources of 137 Cs in rivers around Fukushima during wet weather. Concentrations of Zn in road dust were higher than agricultural and forest soils, whereas concentrations of Fe and Al were the opposite. Concentrations of Zn were weakly but significantly correlated with benzothiazole, a molecular marker of tires, indicating Zn represents an effective tracer of road dust. Al, Fe, and Zn were frequently detected in suspended solids in river water during wet weather. Distribution coefficients of these metals and 137 Cs exceeded 10 4 , suggesting sorptive behavior in water. Although concentrations of Al, Fe, Zn, and 137 Cs were higher in fine fractions of road dust and soils than in coarse fractions, use of ratios of 137 Cs to Al, Fe, or Zn showed smaller differences among size fractions. The results demonstrate that combinations of these metals and 137 Cs are useful for analyzing sources of radiocesium in water. These ratios in river water during wet weather were found to be comparable with or lower than during dry weather and were closer to soils than road dust, suggesting a limited contribution from road dust to radiocesium pollution in river water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biomonitoring of Trace Metals in the Keban Dam Reservoir (Turkey) Using Mussels (Unio elongatulus eucirrus) and Crayfish (Astacus leptodactylus).

PubMed

Varol, Memet; Sünbül, Muhammet Raşit

2018-01-03

Freshwater mussels and crayfish are commonly used as biomonitors of trace metals. In the present study, the concentrations of ten metals were determined in mussels (Unio elongatulus eucirrus) and crayfish (Astacus leptodactylus) collected from the Keban Dam Reservoir in Turkey. The significant spatial differences in concentrations of studied metals except As in mussels were not found. However, Co, Cr, Cu, and Zn concentrations in mussels and As, Co, Cu, Fe, Pb, and Zn concentrations in crayfish showed significant seasonal differences. As, Cd, and Mn levels in mussels were about nine times higher than those in crayfish. The concentrations of Cd, Cr, Cu, Pb, Zn, and inorganic As in crayfish and mussels were lower than maximum permissible levels. When compared with other biomonitoring studies using mussels and crayfish, high concentrations of As, Cd, Co, Cr, and Ni in mussels and Cr and Ni in crayfish were observed due to lithogenic sources and anthropogenic activities in the basin. Bioconcentration factor values of Fe, Mn, Cd, and Zn in mussels and Zn, Cu, Fe, and Co in crayfish were > 1000, which indicates that both U. e. eucirrus and A. leptodactylus have potential to bioaccumulate these metals. Therefore, attention should be paid to mussels and crayfish from ecological and human health perspective, because they are potential vectors of metals to higher trophic levels.

Heavy metals and polycyclic aromatic hydrocarbons: pollution and ecological risk assessment in street dust of Tehran.

PubMed

Saeedi, Mohsen; Li, Loretta Y; Salmanzadeh, Mahdiyeh

2012-08-15

50 street dust samples from four major streets in eastern and southern Tehran, the capital of Iran, were analyzed for metal pollution (Cu, Cr, Pb, Ni, Cd, Zn, Fe, Mn and Li). Hakanson's method was used to determine the Risk Index (RI) and ecological risks. Amongst these samples, 21 were also analyzed for polycyclic aromatic hydrocarbons (PAHs). Correlation, cluster and principal component analyses identified probable natural and anthropogenic sources of contaminants. The dust had elevated concentrations of Pb, Cd, Cu, Cr, Ni, Zn, Fe and PAHs. Enrichment factors of Cu, Pb, Cd and Zn showed that the dust is extremely enriched in these metals. Multivariate statistical analyses revealed that Cu, Pb, Zn, Fe and PAHs and, to a lesser extent, Cr and Ni have common anthropogenic sources. While Mn and Li were identified to have natural sources, Cd may have different anthropogenic origins. All samples demonstrated high ecological risk. Traffic and related activities, petrogenic and pyrogenic sources are likely to be the main anthropogenic sources of heavy metals and PAHs in Tehran dust. Copyright © 2012 Elsevier B.V. All rights reserved.

Mobility and fractionation of Fe, Pb and Zn in river sediments from a silver and base-metals mining area: Taxco, México.

PubMed

Espinosa, E; Armienta, M A

2007-08-01

The impact of mining wastes on both the concentration and environmental mobility of Zn, Pb and Fe was studied in a shallow river. The studied tributary of the Taxco river is located south of the historical Ag, Zn, Cu and Pb mining area of Taxco, about 150 km south of México City. Methodology included total concentration determinations and sequential extraction analyses of the operational defined fractions of sediments. Results indicated that Fe, Pb and Zn concentrations are up to 5, 100 and 390 times respectively, greater than regional background concentrations. Higher contents of Pb and Zn were observed in the rainy season versus the dry season, whereas Fe was lower in the rainy season. Zinc and lead increased downflow in the dry season, and did not show any trend during the rainy season. Speciation showed that Zn was mainly linked to the carbonatic fraction (25-39%), to the hydrous Fe/Mn oxides fraction (15-25%) and to the organic matter and sulfide fraction (14-48%); lead was mainly associated to the hydrous Fe/Mn oxides (49-59%) and residual (22-39%) fractions; finally, iron was contained mainly in the residual (65-78%) and the hydrous Fe/Mn oxides fraction (15%). Mobility decreased according to the relation: Zn > Pb > Fe. Sediments were classified as strongly polluted in zinc, strongly to very strongly polluted in Pb, and moderately to strongly polluted in iron. However, a low proportion of metals in the exchangeable fractions, indicates low bioavailability. Limestone presence played a very important role on Zn and Pb fractionation and environmental mobility. Results show the importance of including geological background in river pollution studies.

Synchrotron micro-scale study of trace metal transport and distribution in Spartina alterniflora root system in Yangtze River intertidal zone

DOE PAGES

Feng, Huan; Tappero, Ryan; Zhang, Weiguo; ...

2015-07-26

This study is focused on micro-scale measurement of metal (Ca, Cl, Fe, K, Mn, Cu, Pb, and Zn) distributions in Spartina alterniflora root system. The root samples were collected in the Yangtze River intertidal zone in July 2013. Synchrotron X-ray fluorescence (XRF), computed microtomography (CMT), and X-ray absorption near-edge structure (XANES) techniques, which provide micro-meter scale analytical resolution, were applied to this study. Although it was found that the metals of interest were distributed in both epidermis and vascular tissue with the varying concentrations, the results showed that Fe plaque was mainly distributed in the root epidermis. Other metals (e.g.,more » Cu, Mn, Pb, and Zn) were correlated with Fe in the epidermis possibly due to scavenge by Fe plaque. Relatively high metal concentrations were observed in the root hair tip. As a result, this micro-scale investigation provides insights of understanding the metal uptake and spatial distribution as well as the function of Fe plaque governing metal transport in the root system.« less

[Pollution Characteristics and Potential Ecological Risk of Heavy Metals in Urban Surface Water Sediments from Yongkang].

PubMed

Qi, Peng; Yu, Shu-quan; Zhang, Chao; Liang, Li-cheng; Che, Ji-lu

2015-12-01

In order to understand the pollution characteristics of heavy metals in surface water sediments of Yongkang, we analyzed the concentrations of 10 heavy metals including Ti, Cr, Mn, Co, Ni, Cu, Zn, As, Pb and Fe in 122 sediment samples, explored the underlying source of heavy metals and then assessed the potential ecological risks of those metals by methods of the index of geo-accumulation and the potential ecological risk. The study results showed that: 10 heavy metal contents followed the order: Fe > Ti > Mn > Zn > Cr > Cu > Ph > Ni > As > Co, all heavy metals except for Ti were 1. 17 to 3.78 times higher than those of Zhejiang Jinhua- Quzhou basin natural soils background values; The concentrations of all heavy metals had a significantly correlation between each other, indicating that those heavy metals had similar sources of pollution, and it mainly came from industrial and vehicle pollutions; The pollution extent of heavy metals in sediments by geo-accumulation index (Igeo) followed the order: Cr > Zn > Ni > Cu > Fe > As > Pb >Mn > Ti, thereinto, Cr, Zn, Cu and Ni were moderately polluted or heavily polluted at some sampling sites; The potential ecological risk of 9 heavy metals in sediments were in the following order: Cu > As > Ni > Cr > Pb > Co > Zn > Mn > Ti, Cu and As contributed the most to the total potential ecological risk, accounting for 22.84% and 21. 62% , others had a total of 55.54% , through the ecological risk assessment, 89. 34% of the potential ecological risk indexes ( RI) were low and 10. 66% were higher. The contamination level of heavy metals in Yongkang was slight in total, but was heavy in local areas.

Study on the Electrochemical Reaction Mechanism of ZnFe2O4 by In Situ Transmission Electron Microscopy

PubMed Central

Su, Qingmei; Wang, Shixin; Yao, Libing; Li, Haojie; Du, Gaohui; Ye, Huiqun; Fang, Yunzhang

2016-01-01

A family of mixed transition–metal oxides (MTMOs) has great potential for applications as anodes for lithium ion batteries (LIBs). However, the reaction mechanism of MTMOs anodes during lithiation/delithiation is remain unclear. Here, the lithiation/delithiation processes of ZnFe2O4 nanoparticles are observed dynamically using in situ transmission electron microscopy (TEM). Our results suggest that during the first lithiation process the ZnFe2O4 nanoparticles undergo a conversion process and generate a composite structure of 1–3 nm Fe and Zn nanograins within Li2O matrix. During the delithiation process, volume contraction and the conversion of Zn and Fe take place with the disappearance of Li2O, followed by the complete conversion to Fe2O3 and ZnO not the original phase ZnFe2O4. The following cycles are dominated by the full reversible phase conversion between Zn, Fe and ZnO, Fe2O3. The Fe valence evolution during cycles evidenced by electron energy–loss spectroscopy (EELS) techniques also exhibit the reversible conversion between Fe and Fe2O3 after the first lithiation, agreeing well with the in situ TEM results. Such in situ TEM observations provide valuable phenomenological insights into electrochemical reaction of MTMOs, which may help to optimize the composition of anode materials for further improved electrochemical performance. PMID:27306189

Effect of flood events on transport of suspended sediments, organic matter and particulate metals in a forest watershed in the Basque Country (Northern Spain).

PubMed

Peraza-Castro, M; Sauvage, S; Sánchez-Pérez, J M; Ruiz-Romera, E

2016-11-01

An understanding of the processes controlling sediment, organic matter and metal export is critical to assessing and anticipating risk situations in water systems. Concentrations of suspended particulate matter (SPM), dissolved (DOC) and particulate (POC) organic carbon and metals (Cu, Ni, Pb, Cr, Zn, Mn, Fe) in dissolved and particulate phases were monitored in a forest watershed in the Basque Country (Northern Spain) (31.5km(2)) over three hydrological years (2009-2012), to evaluate the effect of flood events on the transport of these materials. Good regression was found between SPM and particulate metal concentration, making it possible to compute the load during the twenty five flood events that occurred during the study period at an annual scale. Particulate metals were exported in the following order: Fe>Mn>Zn>Cr>Pb>Cu>Ni. Annual mean loads of SPM, DOC and POC were estimated at 2267t, 104t and 57t, respectively, and the load (kg) of particulate metals at 76 (Ni), 83 (Cu), 135 (Pb), 256 (Cr), 532 (Zn), 1783 (Mn) and 95170 (Fe). Flood events constituted 91%-SPM, 65%-DOC, 71%-POC, 80%-Cu, 85%-Ni, 72%-Pb, 84%-Cr, 74%-Zn, 87%-Mn and 88%-Fe of total load exported during the three years studied. Flood events were classified into three categories according to their capacity for transporting organic carbon and particulate metals. High intensity flood events are those with high transport capacity of SPM, organic carbon and particulate metals. Most of the SPM, DOC, POC and particulate metal load was exported by this type of flood event, which contributed 59% of SPM, 45% of organic carbon and 54% of metals. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of Fe-based core@ZnO shell nanopowders by laser pyrolysis for biomedical applications

NASA Astrophysics Data System (ADS)

Gavrila-Florescu, Lavinia; Dumitrache, Florian; Balas, Mihaela; Fleaca, Claudiu Teodor; Scarisoreanu, Monica; Morjan, Iuliana P.; Dutu, Elena; Ilie, Alina; Banici, Ana-Maria; Locovei, Claudiu; Prodan, Gabriel

2017-12-01

Nano-sized Fe-based (metallic, carbidic and/or oxidic) core@ZnO shell particles have been successfully synthesized in one step by the laser-induced pyrolysis method in an oxygen-deficient environment. The specific precursors were separately introduced through a three concentric nozzles injector: Fe(CO)5 vapors carried by C2H4 sensitizer (central flow), Zn(C2H5)2 vapors carried and diluted with Ar (middle annular coflow) and Ar containing low amount of O2 (external flow). Keeping constant the ethylene-carried Fe(CO)5 and O2 flows, while diminishing the Zn(C2H5)2 flow, we observed an increase of the Fe/Zn ratio in the resulted nanopowders. Also, using the same metal precursor flows, a nonlinear correlation between O2 external flow and nanocomposite atomic oxygen content is evidenced, indicating a possible interference of supplementary oxidation after air exposure. However, the lowest oxygen content along with metallic zinc was found in the sample synthesized in the most oxygen-deficient environment. Transmission electron microscopy (TEM), high-resolution electron microscopy (HRTEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDS), X-ray photoelectron spectroscopy (XPS) and magnetic analyses were performed for a comprehensive characterization. The aqueous Fe-based@ZnO nanoparticles (NPs) suspensions were prepared using L-Dopa ( l-3,4-dihydroxy-phenylalanine) as stabilizing agent in physiologic media. Also, a biocompatibility in vitro study was performed for PBS (phosphate buffered saline)-dispersed L-Dopa-stabilized Fe-based@ZnO nanoparticles with the best core-shell structural features on both human normal lung fibroblasts and tumoral colorectal cells. Our results proved the ability of these newly synthesized nanostructures to target cancer cells in order to induce cytotoxicity and to exhibit biocompatibility on normal cells for maintaining the proper function of healthy tissue.

Gain-of-function mutations identify amino acids within transmembrane domains of the yeast vacuolar transporter Zrc1 that determine metal specificity

PubMed Central

Lin, Huilan; Burton, Damali; Li, Liangtao; Warner, David E.; Phillips, John D.; Ward, Diane McVEY; Kaplan, Jerry

2015-01-01

Cation diffusion facilitator transporters are found in all three Kingdoms of life and are involved in transporting transition metals out of the cytosol. The metals they transport include Zn2+, Co2+, Fe2+, Cd2+, Ni2+ and Mn2+; however, no single transporter transports all metals. Previously we showed that a single amino acid mutation in the yeast vacuolar zinc transporter Zrc1 changed its substrate specificity from Zn2+ to Fe2+ and Mn2+ [Lin, Kumanovics, Nelson, Warner, Ward and Kaplan (2008) J. Biol. Chem. 283, 33865–33873]. Mutant Zrc1 that gained iron transport activity could protect cells with a deletion in the vacuolar iron transporter (CCC1) from high iron toxicity. Utilizing suppression of high iron toxicity and PCR mutagenesis of ZRC1, we identified other amino acid substitutions within ZRC1 that changed its metal specificity. All Zrc1 mutants that transported Fe2+ could also transport Mn2+. Some Zrc1 mutants lost the ability to transport Zn2+, but others retained the ability to transport Zn2+. All of the amino acid substitutions that resulted in a gain in Fe2+ transport activity were found in transmembrane domains. In addition to alteration of residues adjacent to the putative metal-binding site in two transmembrane domains, alteration of residues distant from the binding site affected substrate specificity. These results suggest that substrate selection involves co-operativity between transmembrane domains. PMID:19538181

Trace metals in Bermuda rainwater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jickells, T.D.; Knap, A.H.; Church, T.M.

1984-02-20

The concentration of Cd, Cu, Fe, Mn, Ni, Pb, and Zn have been measured in Bermuda rainwater. Factor analysis indicates that Fe, Mn, and Pb have similar to acidic components derived from North America. The other metals all behave simiarly but differently to the acides. Sea salt, even after allowances for fractionation, apparently contributes minor amounts of Cu, Pb, and Zn and uncertain amounts of Fe, Mn, and Cd to Atlantic Ocean precipitation. Wash out ratios, calculated from this data along with earlier measurements of atmospheric trace metal concentration on Bermuda, are of the same order as those reported frommore » other remote ocean areas. The wet depositional fluxes of Cu, Ni, Pb, and Zn to the western Atlantic Ocean are significant compared to measured oceanic flux rates. However, the wet depositional fluxes of Fe and Mn to this area are relatively small, suggesting additional inputs, while an excess wet depositional flux of Cd suggests large-scale atmospheric recycling of this element.« less

Tracing Sources and Contamination Assessments of Heavy Metals in Road and Foliar Dusts in a Typical Mining City, China

PubMed Central

Yang, Jie; Teng, Yanguo; Song, Liuting; Zuo, Rui

2016-01-01

Road and foliar dust samples from four land-use districts of Panzhihua City, a famous V-Ti magnetite production area of China, were collected to investigate the sources and distribution characteristics of 9 heavy metals (V, Pb, Cd, Cu, Zn, Ni, Cr, Fe, and Mn). The results suggest that foliar samples had smaller particle size and higher heavy metal contents than road dusts. The contamination assessments of heavy metals were as follows: Pb and V (significant enrichment) > Zn, Ni, Cr, Fe, and Mn (moderate enrichment) > Cd and Ni (minimal enrichment). Statistical analyses showed Pb, as the primary pollution element, originated from waste incineration and lead-fuel combustion. The sources of Zn, Ni, Cr, Fe, V, and Mn were fugitive dust and traffic activities. Potential origins of Cu were corrosion of alloys used in vehicle components, vehicle covers, or other metallic surfaces and materials. The sources of Cd were different from any other heavy metals. Traffic and industrial activities were the main anthropogenic origins of heavy metals in dusts of Panzhihua, and more attention should be paid to heavy metal pollution in agricultural area. PMID:27992518

Tracing Sources and Contamination Assessments of Heavy Metals in Road and Foliar Dusts in a Typical Mining City, China.

PubMed

Yang, Jie; Teng, Yanguo; Song, Liuting; Zuo, Rui

2016-01-01

Road and foliar dust samples from four land-use districts of Panzhihua City, a famous V-Ti magnetite production area of China, were collected to investigate the sources and distribution characteristics of 9 heavy metals (V, Pb, Cd, Cu, Zn, Ni, Cr, Fe, and Mn). The results suggest that foliar samples had smaller particle size and higher heavy metal contents than road dusts. The contamination assessments of heavy metals were as follows: Pb and V (significant enrichment) > Zn, Ni, Cr, Fe, and Mn (moderate enrichment) > Cd and Ni (minimal enrichment). Statistical analyses showed Pb, as the primary pollution element, originated from waste incineration and lead-fuel combustion. The sources of Zn, Ni, Cr, Fe, V, and Mn were fugitive dust and traffic activities. Potential origins of Cu were corrosion of alloys used in vehicle components, vehicle covers, or other metallic surfaces and materials. The sources of Cd were different from any other heavy metals. Traffic and industrial activities were the main anthropogenic origins of heavy metals in dusts of Panzhihua, and more attention should be paid to heavy metal pollution in agricultural area.

Trace metal dynamics in zooplankton from the Bay of Bengal during summer monsoon.

PubMed

Rejomon, G; Kumar, P K Dinesh; Nair, M; Muraleedharan, K R

2010-12-01

Trace metal (Fe, Co, Ni, Cu, Zn, Cd, and Pb) concentrations in zooplankton from the mixed layer were investigated at 8 coastal and 20 offshore stations in the western Bay of Bengal during the summer monsoon of 2003. The ecotoxicological importance of trace metal uptake was apparent within the Bay of Bengal zooplankton. There was a distinct spatial heterogeneity of metals, with highest concentrations in the upwelling zones of the southeast coast, moderate concentrations in the cyclonic eddy of the northeast coast, and lowest concentrations in the open ocean warm gyre regions. The average trace metal concentrations (μg g⁻¹) in coastal zooplankton (Fe, 44894.1 ± 12198.2; Co, 46.2 ± 4.6; Ni, 62.8 ± 6.5; Cu, 84.9 ± 6.7; Zn, 7546.8 ± 1051.7; Cd, 46.2 ± 5.6; Pb, 19.2 ± 2.6) were higher than in offshore zooplankton (Fe, 3423.4 ± 681.6; Co, 19.5 ± 3.81; Ni, 25.3 ± 7.3; Cu, 29.4 ± 4.2; Zn, 502.3 ± 124.3; Cd, 14.3 ± 2.9; Pb, 3.2 ± 2.0). A comparison of average trace metal concentrations in zooplankton from the Bay of Bengal showed enrichment of Fe, Co, Ni, Cu, Zn, Cd, and Pb in coastal zooplankton may be related to metal absorption from primary producers, and differences in metal concentrations in phytoplankton from coastal waters (upwelling zone and cyclonic eddy) compared with offshore waters (warm gyre). Zooplankton showed a great capacity for accumulations of trace metals, with average concentration factors of 4 867 929 ± 569 971, 246 757 ± 51 321, 337 180 ± 125 725, 43 480 ± 11 212, 1 046 371 ± 110 286, 601 679 ± 213 949, and 15 420 ± 9201 for Fe, Co, Ni, Cu, Zn, Cd, and Pb with respect to dissolved concentrations in coastal and offshore waters of the Bay of Bengal. © 2009 Wiley Periodicals, Inc. Environ Toxicol, 2009. Copyright © 2009 Wiley Periodicals, Inc.

Evaluation of heavy metal leaching from coal ash-versus conventional concrete monoliths and debris.

PubMed

Gwenzi, Willis; Mupatsi, Nyarai M

2016-03-01

Application of coal ash in construction materials is constrained by the potential risk of heavy metal leaching. Limited information is available on the comparative heavy metal leaching from coal ash-versus conventional concrete. The current study compared total and leached heavy metal concentrations in unbound coal ash, cement and sand; and investigated the effect of initial leachant pH on heavy metal leaching from coal-ash versus conventional concrete monoliths and their debris. Total Pb, Mn and Zn in coal ash were lower than or similar to that of other materials, while Cu and Fe showed the opposite trend. Leached concentrations of Zn, Pb, Mn, Cu and Fe in unbound coal ash, its concrete and debris were comparable and in some cases even lower than that for conventional concrete. In all cases, leached concentrations accounted for just <1% of the total concentrations. Log-log plots of concentration and cumulative release of Fe versus time based on tank leaching data showed that leaching was dominated by diffusion. Overall, the risk of Zn, Pb, Mn, Cu and Fe leaching from coal ash and its concrete was minimal and comparable to that of conventional concrete, a finding in contrast to widely held public perceptions and earlier results reported in other regions such as India. In the current study the coal ash, and its concrete and debris had highly alkaline pH indicative of high acid neutralizing and pH buffering capacity, which account for the stabilization of Zn, Pb, Mn, Cu and Fe. Based on the low risk of Zn, Pb, Mn, Cu and Fe leaching from the coal ash imply that such coal ash can be incorporated in construction materials such as concrete without adverse impacts on public and environmental health from these constituents. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dye-Sensitized Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) Nanofibers for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Gonce, Mehmet Kerem; Aslan, Emre; Ozel, Faruk; Hatay Patir, Imren

2016-03-21

The photocatalytic hydrogen evolution activities of low-cost and noble-metal-free Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofiber catalysts have been investigated using triethanolamine as an electron donor and eosin Y as a photosensitizer under visible-light irradiation. The rates of hydrogen evolution by Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofibers have been compared with each other and with that of the noble metal Pt. The hydrogen evolution rates for the nanofibers change in the order Cu2 NiSnS4 >Cu2 FeSnS4 >Cu2 CoSnS4 >Cu2 ZnSnS4 >Cu2 MnSnS4 (2028, 1870, 1926, 1420, and 389 μmol g(-1) h(-1) , respectively). The differences between the hydrogen evolution rates of the nanofibers could be attributed to their energy levels. Moreover, Cu2 NiSnS4, Cu2 FeSnS4 , and Cu2 CoSnS4 nanofibers show higher and more stable photocatalytic hydrogen production rates than that of the noble metal Pt under long-term irradiation with visible light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal concentrations in demersal fish species from Santa Maria Bay, Baja California Sur, Mexico (Pacific coast).

PubMed

Jonathan, M P; Aurioles-Gamboa, David; Villegas, Lorena Elizabeth Campos; Bohórquez-Herrera, Jimena; Hernández-Camacho, Claudia J; Sujitha, S B

2015-10-15

Concentrations of 11 trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd, As, Hg) in 40 fish species from Santa Maria Bay, Baja California Sur, Mexico, the strategically important area for marine mammals and organisms were analyzed. Based on their concentrations the ranking of metals Fe>Zn>Ni>Cr>Mn>Pb>Cu>Co>As>Cd>Hg suggests that organism size, metabolism and feeding habits are correlated with metal concentrations. Local geological formations affect the concentrations of different metals in the aquatic environment and are subsequently transferred to fishes. The correlation analysis suggests that metabolism and nurturing habits impact the concentration of metals. Concentrations of Fe and Mn appear to be influenced by scavenging and absorption processes, which vary by species. The considerable variability in the metal concentrations obtained in different species underscores the importance of regular monitoring. Copyright © 2015 Elsevier Ltd. All rights reserved.

[Content of selected metals in forest fruits depending on the harvest site].

PubMed

Rusinek, Elzbieta; Sembratowicz, Iwona; Ognik, Katarzyna

2008-01-01

Contents of selected metals (Pb, Cd, Cu, Zn, Fe, Mn) were determined in samples of forest fruits: blueberry, raspberry and wild strawberry harvested in Lublin region from areas considered as potentially not exposed to pollution (Skierbieszów Landscape Park) and potentially polluted areas (Cement Factory Rejowiec S.A.). Analyzed fruits originating from stands more exposed to pollution were characterized by higher lead (except from raspberry) as well as other metals contents than those from Krasiczyn commune. Among studied fruits, blueberry was distinguished by the lowest contents of Pb, Zn, Fe, Mn, wild strawberry contained the highest levels of Pb, Zn and Mn. Cadmium content in analyzed plant materials was high.

Bioassessment of heavy metal toxicity and enhancement of heavy metal removal by sulfate-reducing bacteria in the presence of zero valent iron.

PubMed

Guo, Jing; Kang, Yong; Feng, Ying

2017-12-01

A simple and valid toxicity evaluation of Zn 2+ , Mn 2+ and Cr 6+ on sulfate-reducing bacteria (SRB) and heavy metal removal were investigated using the SRB system and SRB+Fe 0 system. The heavy metal toxicity coefficient (β) and the heavy metal concentration resulting in 50% inhibition of sulfate reduction (I) from a modeling process were proposed to evaluate the heavy metal toxicity and nonlinear regression was applied to search for evaluation indices β and I. The heavy metal toxicity order was Cr 6+  > Mn 2+  > Zn 2+ . Compared with the SRB system, the SRB+Fe 0 system exhibited a better capability for sulfate reduction and heavy metal removal. The heavy metal removal was above 99% in the SRB+Fe 0 system, except for Mn 2+ . The energy-dispersive spectroscopy (EDS) analysis showed that the precipitates were removed primarily as sulfide for Zn 2+ and hydroxide for Mn 2+ and Cr 6+ .The method of evaluating the heavy metal toxicity on SRB was of great significance to understand the fundamentals of the heavy metal toxicity and inhibition effects on the microorganism and regulate the process of microbial sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metals in some lagoons of Mexico.

PubMed Central

Vazquez, F G; Sharma, V K; Alexander, V H; Frausto, C A

1995-01-01

The concentrations of metals, Cd, Cu, Fe, Mn, Ni, Pb, and Zn were determined in some lagoons to establish the level of metal pollution. The lagoons studied were Alvarado lagoon, Veracruz; San Andres lagoon, Tamaulipas; and Terminos lagoon, Campeche. The concentrations were determined in water, oyster (Crassostrea virginica), and sediments. Metals were accumulated in either oysters or sediments. Cu and Zn were higher in oysters and Fe and Mn were higher in sediments. The results in water samples were compared with the limit established by the Secretaria de Ecologia and Desarrollo Urbano Report and briefly discussed. PMID:7621796

Metal selectivity of the E. coli nickel metallochaperone, SlyD

PubMed Central

Kaluarachchi, Harini; Siebel, Judith F.; Kaluarachchi-Duffy, Supipi; Krecisz, Sandra; Sutherland, Duncan E. K.; Stillman, Martin J.; Zamble, Deborah B.

2012-01-01

SlyD is a Ni(II)-binding protein that contributes to nickel homeostasis in Escherichia coli. The C-terminal domain of SlyD contains a rich variety of metal-binding amino acids, suggesting broader metal-binding capabilities, and previous work demonstrated that the protein can coordinate several types of first row transition metals. However, the binding of SlyD to metals other than Ni(II) has not been previously characterized. To further our understanding of the in vitro metal-binding activity of SlyD and how it correlates with the in vivo function of this protein, the interactions between SlyD and the series of biologically relevant transition metals Mn(II), Fe(II), Co(II), Cu(I) and Zn(II) were examined by using a combination of optical spectroscopy and mass spectrometry. SlyD binding to Mn(II) or to Fe(II) ions was not detected but the protein coordinates multiple ions of Co(II), Zn(II) and Cu(I) with appreciable affinities (KD ≤ nM), highlighting the promiscuous nature of this protein. The order of affinities of SlyD for the metals examined is Mn(II), Fe(II) < Co(II) < Ni(II) ~ Zn(II) ≪ Cu(I). Although the purified protein is unable to overcome the large thermodynamic preference for Cu(I) and exclude Zn(II) chelation in the presence of Ni(II), in vivo studies reveal a Ni(II)-specific function for the protein. Furthermore, these latter experiments support a specific role for SlyD as a [NiFe]-hydrogenase enzyme maturation factor. The implications of the divergence between the metal selectivity of SlyD in vitro and the specific activity in vivo are discussed. PMID:22047179

Marine molluscs as biomonitors for heavy metal levels in the Gulf of Suez, Red Sea

NASA Astrophysics Data System (ADS)

Hamed, Mohamed A.; Emara, Ahmed M.

2006-05-01

Levels of the heavy metals Copper (Cu), Zinc (Zn), Lead (Pb), Cadmium (Cd), Chromium (Cr), Nickel (Ni), Iron (Fe) and Manganese (Mn) were determined in coastal water, sediments and soft tissues of the gastropod limpet, Patella caerulea, and the bivalve, Barbatus barbatus, from seven different stations in the western coast of the Gulf of Suez. The concentrations of heavy metals in water ranged between 3.37-4.78, 18.83-21.46, 2.75-3.17, 0.22-0.27, 0.99-1.21, 2.69-3.65, 3.75-4.56 μg L - 1 and 23.82-32.78 mg g - 1 for Cu, Zn, Pb, Cd, Cr, Ni, Mn and Fe, respectively. The corresponding concentration values in the sediments were 8.65-12.16, 51.78-58.06, 36.52-42.15, 3.23-3.98, 9.03-12.75, 34.31-49.63, 3.28-4.56 and 64.20-70.22 μg g - 1 for Cu, Zn, Pb, Cd, Cr, Ni, Mn and Fe, respectively. The highest accumulated metals were Fe, Zn and Mn in both P. caerulea and B. barbatus, while the lowest one was Cd. The accumulation of metals was more pronounced in P. caerulea than B. barbatus. The highest concentrations of all metals in water, sediments and mollusca were recorded at Adabiya harbour north of the Gulf, while the lowest concentrations were recorded at Gabal El-Zeit and Hurghada. Land based activities and ships awaiting berth are the main source of metal pollution in the northern part of the Gulf.

Fractionation profile and mobility pattern of metals in sediments from the Mediterranean Coast, Libya.

PubMed

Nasr, Samir M; Okbah, Mohamed A; El Haddad, Huda S; Soliman, Naglaa F

2015-07-01

A five-step sequential extraction technique, following Tessier's protocol, has been applied to determine the chemical association of Cd, Cu, Fe, Pb, and Zn with major sedimentary phases (exchangeable, carbonate, manganese and iron oxides, organic and residual fraction) in surface sediments from 14 stations off the Libyan Mediterranean coast. This study is a first approach of chemical fractionation of these metals in one of the most economically important area of the Libyan coastline in Mediterranean Sea. The total metal content was also determined. The total concentration of metals ranged from 5-10.5 mg/kg for Cd, 9.1-22.7 mg/kg for Cu, 141.8-1056.8 mg/kg for Fe, 18.9-56.9 mg/kg for Pb, and 11.6-30.5 mg/kg for Zn. The results of the partitioning study showed that the residual form was the dominant fraction of the selected metals among most of the studied locations. The degree of surface sediment contamination was computed for risk assessment code (RAC), individual contamination factor (ICF), and Global contamination factor (GCF). Risk assessment code classification showed that the relative amounts of easily dissolved phase of trace metals in the sediments are in the order of Pb>Zn>Cd>Cu>Fe. The results of ICF and GCF showed that Sirt and Abu Kammashand had higher GCF than other sites indicating higher environmental risk. In terms of ICF value, a decrease order in environmental risk by trace metals was Pb>Zn>Cu>Cd>Fe. Therefore, Pb had highest risk to water body.

Spatial evolution of Zn-Fe-Pb isotopes of sphalerite within a single ore body: A case study from the Dongshengmiao ore deposit, Inner Mongolia, China

NASA Astrophysics Data System (ADS)

Gao, Zhaofu; Zhu, Xiangkun; Sun, Jian; Luo, Zhaohua; Bao, Chuang; Tang, Chao; Ma, Jianxiong

2018-01-01

Analyses of sphalerite minerals from the characteristic brecciated Zn-Pb ores of the main ore body in the giant Dongshengmiao deposit have revealed variations in δ66Zn from 0.17 to 0.40‰ and in δ56Fe from -1.78 to -0.35‰. Further, the investigated pyrrhotite samples have iron that is isotopically similar to that of associated sphalerite minerals. The most distinctive pattern revealed by the zinc and iron isotope data is the lateral trend of increasing δ66Zn and δ56Fe values from southwest to northeast within the main ore body. The lead isotopic homogeneity of ore sulfides from the main ore body suggests that there is only one significant source for metal, thus precluding the mixing of multiple metal sources as the key factor controlling spatial variations of zinc and iron isotopes. The most likely control on spatial variations is Rayleigh fractionation during hydrothermal fluid flow, with lighter Zn and Fe isotopes preferentially incorporated into the earliest sulfides to precipitate from fluids. Precipitations of sphalerite and pyrrhotite have played vital roles in the Zn and Fe isotopic variations, respectively, of the ore-forming system. Accordingly, the larger isotopic variability for Fe than Zn within the same hydrothermal system perhaps resulted from a larger proportion of precipitation for pyrrhotite than for sphalerite. The lateral trend pattern revealed by the zinc and iron isotope data is consistent with the occurrence of a cystic-shaped breccia zone, which is characterized by marked elevation in Cu. The results further confirm that Zn and Fe isotopes can be used as a vectoring tool for mineral prospecting.

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE PAGES

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2017-04-24

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

Bioavailable metals in tourist beaches of Richards Bay, Kwazulu-Natal, South Africa.

PubMed

Vetrimurugan, E; Jonathan, M P; Roy, Priyadarsi D; Shruti, V C; Ndwandwe, O M

2016-04-15

Acid Leachable Trace Metal (ALTMs) concentrations in tourist beaches of Richards Bay, Kwazulu-Natal, South Africa were assessed. 53 surface sediment samples were collected from five different beaches (Kwambonambi Long Beach; Nhlabane Beach; Five Mile Beach; Alkanstrand Beach and Port Durnford Beach). The results of ALTMs (Fe, Mn, Cr, Cu, Ni, Co, Pb, Cd, Zn, As, Hg) suggest that they are enriched naturally and with some local industrial sources for (avg. in μgg(-1)) Fe (3530-7219), Mn (46-107.11), Cd (0.43-1.00) and Zn (48-103.98). Statistical results indicate that metal concentrations were from natural origin attributed to leaching, weathering process and industrial sources. Comparative studies of metal concentrations with sediment quality guidelines and ecotoxicological values indicate that there is no adverse biological effect. Enrichment factor and geoaccumulation indices results indicate moderate enhancement of Fe (Igeo class 1 in FMB), Cd (EF>50; Igeo classes 2-4) and Zn (Igeo classes 1 & 2). Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal-Ion Effects on the Polarization of Metal-Bound Water and Infrared Vibrational Modes of the Coordinated Metal Center of Mycobacterium tuberculosis Pyrazinamidase via Quantum Mechanical Calculations

PubMed Central

2014-01-01

Mycobacterium tuberculosis pyrazinamidase (PZAse) is a key enzyme to activate the pro-drug pyrazinamide (PZA). PZAse is a metalloenzyme that coordinates in vitro different divalent metal cofactors in the metal coordination site (MCS). Several metals including Co2+, Mn2+, and Zn2+ are able to reactivate the metal-depleted PZAse in vitro. We use quantum mechanical calculations to investigate the Zn2+, Fe2+, and Mn2+ metal cofactor effects on the local MCS structure, metal–ligand or metal–residue binding energy, and charge distribution. Results suggest that the major metal-dependent changes occur in the metal–ligand binding energy and charge distribution. Zn2+ shows the highest binding energy to the ligands (residues). In addition, Zn2+ and Mn2+ within the PZAse MCS highly polarize the O–H bond of coordinated water molecules in comparison with Fe2+. This suggests that the coordination of Zn2+ or Mn2+ to the PZAse protein facilitates the deprotonation of coordinated water to generate a nucleophile for catalysis as in carboxypeptidase A. Because metal ion binding is relevant to enzymatic reaction, identification of the metal binding event is important. The infrared vibrational mode shift of the C=Nε (His) bond from the M. tuberculosis MCS is the best IR probe to metal complexation. PMID:25055049

Watershed-scale assessment of background concentrations and guidance values for heavy metals in soils from a semiarid and coastal zone of Brazil.

PubMed

da Silva, Yuri Jacques Agra Bezerra; do Nascimento, Clístenes Williams Araújo; Cantalice, José Ramon Barros; da Silva, Ygor Jacques Agra Bezerra; Cruz, Cinthia Maria Cordeiro Atanázio

2015-09-01

Determining heavy metal background concentrations in soils is fundamental in order to support the monitoring of potentially contaminated areas. This is particularly important to areas submitted to high environmental impact where an intensive and local monitoring is required. To this end, the aim of this study was to establish background concentrations and quality reference values (QRVs) for the heavy metals Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn, As, and Hg in an environmentally impacted watershed from Brazil. Geochemical associations among Fe, Mn, and trace elements were also assessed to provide an alternative tool for establishing background concentrations. A total of one hundred and four samples comprised twenty-six composite soil samples from areas of native forest or minimal anthropic influence. Samples were digested (USEPA method 3051A), and the metals were determined by ICP-OES, except for As and Hg measured by atomic absorption spectrophotometer. Background concentrations of heavy metals in soils had the following decreasing order: Fe > Mn > Zn > Cr > Pb > Ni > Cu > As > Cd > Hg. These values were usually lower than those observed in the international and national literature. The QRVs for Ipojuca watershed followed the order (mg kg(-1)) Fe (13,020.40) > Mn (91.80) > Zn (30.12) > Cr (15.00) > Pb (13.12) > Cu (3.53) > Ni (3.30) > As (0.51) > Cd (0.08) > Hg (0.04). Significant correlation among Fe, Mn, and heavy metals shows that solubilization by the method 3051A provides a reasonable estimate for predicting background concentrations for Cd, Cr, and Cu as well as Zn, Cr, Cu, and Ni.

Characterization of metal adsorption variability in a sand and gravel aquifer, Cape Cod, Massachusetts, U.S.A

USGS Publications Warehouse

Fuller, C.C.; Davis, J.A.; Coston, J.A.; Dixon, E.

1996-01-01

Several geochemical properties of an aquifer sediment that control metal-ion adsorption were investigated to determine their potential use as indicators of the spatial variability of metal adsorption. Over the length of a 4.5-m-long core from a sand and gravel aquifer, lead (Pb2+) and zinc (Zn2+) adsorption at constant chemical conditions (pH 5.3) varied by a factor of 2 and 4, respectively. Pb2+ and Zn2+ were adsorbed primarily by Fe- and Al-oxide coatings on quartz-grain surfaces. Per unit surface area, both Pb2+ and Zn2+ adsorption were significantly correlated with the amount of Fe and Al that dissolved from the aquifer material in a partial chemical extraction. The variability in conditional binding constants for Pb2+ and Zn2+ adsorption (log KADS) derived from a simple non-electrostatic surface complexation model were also predicted by extracted Fe and Al normalized to surface area. Because the abundance of Fe- and Al-oxide coatings that dominate adsorption does not vary inversely with grain size by a simple linear relationship, only a weak, negative correlation was found between the spatial variability of Pb2+ adsorption and grain size in this aquifer. The correlation between Zn2+ adsorption and grain size was not significant. Partial chemical extractions combined with surface-area measurements have potential use for estimating metal adsorption variability in other sand and gravel aquifers of negligible carbonate and organic carbon content.

Ultrasmall water-soluble metal-iron oxide nanoparticles as T1-weighted contrast agents for magnetic resonance imaging.

PubMed

Zeng, Leyong; Ren, Wenzhi; Zheng, Jianjun; Cui, Ping; Wu, Aiguo

2012-02-28

Using an improved hydrolysis method of inorganic salts assisted with water-bath incubation, ultrasmall water-soluble metal-iron oxide nanoparticles (including Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles) were synthesized in aqueous solutions, which were used as T(1)-weighted contrast agents for magnetic resonance imaging (MRI). The morphology, structure, MRI relaxation properties and cytotoxicity of the as-prepared metal-iron oxide nanoparticles were characterized, respectively. The results showed that the average sizes of nanoparticles were about 4 nm, 4 nm and 5 nm for Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles, respectively. Moreover, the nanoparticles have good water dispersibility and low cytotoxicity. The MRI test showed the strong T(1)-weighted, but the weak T(2)-weighted MRI performance of metal-iron oxide nanoparticles. The high T(1)-weighted MRI performance can be attributed to the ultrasmall size of metal-iron oxide nanoparticles. Therefore, the as-prepared metal-iron oxide nanoparticles with good water dispersibility and ultrasmall size can have potential applications as T(1)-weighted contrast agent materials for MRI.

Survey on composition and bioconcentration potential of 12 metallic elements in King Bolete (Boletus edulis) mushroom that emerged at 11 spatially distant sites.

PubMed

Falandysz, Jerzy; Frankowska, Aneta; Jarzynska, Grazyna; Dryzałowska, Anna; Kojta, Anna K; Zhang, Dan

2011-01-01

This paper provides data on baseline concentrations, interrelationships and bioconcentration potential of 12 metallic elements by King Bolete collected from 11 spatially distant sites across Poland. There are significant differences in concentrations of metals (Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr, Zn) and their bioconcentration potential in King Bolete Boletus edulis at 11 spatially distant sites surveyed across Poland. These have resulted from significant geographical differences in trace metal concentrations in a layer (0-10 cm) of organic and mineral soil underneath to fruiting bodies and possible local bioavailabilities of macro- (Ca, K, Mg, Na) and trace metals (Al, Ba, Cd, Cu, Fe, Mn, Sr, Zn) to King Bolete. The use of highly appreciated wild-grown edible King Bolete mushroom has established a baseline measure of regional minerals status, heavy metals pollution and assessment of intake rates for wild mushroom dish fanciers against which future changes can be compared. Data on Cd, Cu and Zn from this study and from literature search can be useful to set the maximum limit of these metals in King Bolete collected from uncontaminated (background) areas. In this report also reviewed are data on Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr and Zn accumulation in King Bolete.

Characterization of the products attained from a thermal treatment of a mix of zinc-carbon and alkaline batteries.

PubMed

Kuo, Yi-Ming; Lin, Chitsan; Wang, Jian-Wen; Huang, Kuo-Lin; Tsai, Cheng-Hsien; Wang, Chih-Ta

2016-01-01

This study applies a thermal separation process (TSP) to recover Fe, Mn, and Zn from hazardous spent zinc-carbon and alkaline batteries. In the TSP, the batteries were heated together with a reducing additive and the metals in batteries, according to their boiling points and densities, were found to move into three major output materials: slag, ingot (mainly Fe and Mn), and particulate (particularly Zn). The slag well encapsulated the heavy metals of interest and can be recycled for road pavement or building materials. The ingot had high levels of Fe (522,000 mg/kg) and Mn (253,000 mg/kg) and can serve as an additive for stainless steel-making processes. The particulate phase had a Zn level of 694,000 mg/kg which is high enough to be directly sold for refinement. Overall, the TSP effectively recovered valuable metals from the hazardous batteries.

Interactions of iron with manganese, zinc, chromium, and selenium as related to prophylaxis and treatment of iron deficiency.

PubMed

Bjørklund, Geir; Aaseth, Jan; Skalny, Anatoly V; Suliburska, Joanna; Skalnaya, Margarita G; Nikonorov, Alexandr A; Tinkov, Alexey A

2017-05-01

Iron (Fe) deficiency is considered as the most common nutritional deficiency. Iron deficiency is usually associated with low Fe intake, blood loss, diseases, poor absorption, gastrointestinal parasites, or increased physiological demands as in pregnancy. Nutritional Fe deficiency is usually treated with Fe tablets, sometimes with Fe-containing multimineral tablets. Trace element interactions may have a significant impact on Fe status. Existing data demonstrate a tight interaction between manganese (Mn) and Fe, especially in Fe-deficient state. The influence of Mn on Fe homeostasis may be mediated through its influence on Fe absorption, circulating transporters like transferrin, and regulatory proteins. The existing data demonstrate that the influence of zinc (Zn) on Fe status may be related to their competition for metal transporters. Moreover, Zn may be involved in regulation of hepcidin production. At the same time, human data on the interplay between Fe and Zn especially in terms of Fe-deficiency and supplementation are contradictory, demonstrating both positive and negative influence of Zn on Fe status. Numerous data also demonstrate the possibility of competition between Fe and chromium (Cr) for transferrin binding. At the same time, human data on the interaction between these metals are contradictory. Therefore, while managing hypoferremia and Fe-deficiency anemia, it is recommended to assess the level of other trace elements in parallel with indices of Fe homeostasis. It is supposed that simultaneous correction of trace element status in Fe deficiency may help to decrease possible antagonistic or increase synergistic interactions. Copyright © 2017 Elsevier GmbH. All rights reserved.

[Spatial variations of heavy metals in precipitation at Mount Taishan region].

PubMed

Wang, Yan; Liu, Xiao-Huan; Jin, Ling-Ren; Yue, Tai-Xing; Wang, De-Zhong; Wang, Wen-Xing

2007-11-01

Zn, Al, Mn, Fe, Pb, Cu, Ni, Cr, As, Cd in rain samples collected from two sites at Mount Taishan region were determined by ICP-MS, to evaluate the spatial variation characteristics of heavy metals in precipitation. Individual rain events were sampled for one whole year from Jan. to Dec. 2006. High concentrations of heavy metals were found at both sites, indicating serious heavy metal pollution. Zn was the most abundant element, accounting for 54% - 57% of the total metals concentrations. Its volume-weighted mean concentrations of precipitation at Mt-top and Mt-foot sites were 92.94 microg/L and 70.41 microg/L respectively. The following elements were Fe, Al and Mn and their concentrations were much higher than toxic heavy metals (As, Cd and Cd) except Pb (8.04 microg/L and 7.79 microg/L at two sites respectively). Comparison results between two sites suggested that heavy metal characteristics of precipitation at two sites were different, due to the influences of different ambient air conditions. Correlation analysis between two sites showed that Al, Mn, Fe, As, Cd, Pb influenced by air mass origin greatly, while Ni, Cu, Zn affected by other different factors.

Application of mucilage from Dicerocaryum eriocarpum plant as biosorption medium in the removal of selected heavy metal ions.

PubMed

Jones, Bassey O; John, Odiyo O; Luke, Chimuka; Ochieng, Aoyi; Bassey, Bridget J

2016-07-15

The ability of mucilage from Dicerocaryum eriocarpum (DE) plant to act as biosorption medium in the removal of metals ions from aqueous solution was investigated. Functional groups present in the mucilage were identified using Fourier transform infrared spectroscopy (FTIR). Mucilage was modified with sodium and potassium chlorides. This was aimed at assessing the biosorption efficiency of modified mucilage: potassium mucilage (PCE) and sodium mucilage (SCE) and comparing it with non-modified deionised water mucilage (DCE) in the uptake of metal ions. FTIR results showed that the functional groups providing the active sites in PCE and SCE and DCE include: carboxyl, hydroxyl and carbonyl groups. The chloride used in the modification of the mucilage did not introduce new functional groups but increased the intensity of the already existing functional groups in the mucilage. Results from biosorption experiment showed that DE mucilage displays good binding affinity with metals ions [Zn(II), Cd(II) Ni(II), Cr(III) and Fe(II)] in the aqueous solution. Increase in the aqueous solution pH, metal ions initial concentration and mucilage concentration increased the biosorption efficiency of DE mucilage. The maximum contact time varied with each species of metal ions. Optimum pH for [Zn(II), Cd(II) Ni(II) and Fe(II)] occurred at pH 4 and pH 6 for Cr(III). Kinetic models result fitted well to pseudo-second-order with a coefficient values of R(2) = 1 for Cd(II), Ni(II), Cr(III), Fe(II) and R(2) = 0.9974 for Zn(II). Biosorption isotherms conforms best with Freundlich model for all the metal ions with correlation factors of 0.9994, 0.9987, 0.9554, 0.9621 and 0.937 for Zn(II), Ni(II), Fe(II), Cr(III) and Cd(II), respectively. Biosorption capacity of DE mucilage was 0.010, 2.387, 4.902, 0688 and 0.125 for Zn(II), Cr(III), Fe(II), Cd(II) and Ni(II) respectively. The modified mucilage was found to be highly efficient in the removal of metal ions than the unmodified mucilage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Probing the Structure, Stability and Hydrogen Adsorption of Lithium Functionalized Isoreticular MOF-5 (Fe, Cu, Co, Ni and Zn) by Density Functional Theory

PubMed Central

Venkataramanan, Natarajan Sathiyamoorthy; Sahara, Ryoji; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

2009-01-01

Li adsorption on isoreticular MOFs with metal Fe, Cu, Co, Ni and Zn was studied using density function theory. Li functionalization shows a considerable structural change associated with a volume change in isoreticular MOF-5 except for the Zn metal center. Hydrogen binding energies on Li functionalized MOFs are seen to be in the range of 0.2 eV, which is the desired value for an ideal reversible storage system. This study has clearly shown that Li doping is possible only in Zn-based MOF-5, which would be better candidate to reversibly store hydrogen. PMID:19468328

Land Contamination and Soil-Plant Interactions in the Imperina Valley Mine (Belluno, Venetian Region, Italy)

NASA Astrophysics Data System (ADS)

Bini, Claudio; Wahsha, Mohammad; Fontana, Silvia; Zilioli, Diana

2010-05-01

In Italy, ore exploitation, particularly that of mixed sulphides, has been abandoned since the final thirty years of the last century, and a quantity of mine dumps has been discharged in wide areas of the land, provoking evident environmental damages to landscape, soil and vegetation, with potential risk for human health. The present study concerns the distribution and mobility of heavy metals (Ni, Cr, Cu, Pb, Zn, Fe and Mn) in the soils of a mine site and their transfer to wild flora. Soils and wild plants were sampled from mixed sulphides mine dumps in Imperina valley (Belluno, Italy), and the concentrations of heavy metals were determined. Chemical analyses carried out on 10 soil profiles (mostly entisols) of the mineralised area revealed metal concentrations generally above the international target levels (Cu up to 3160 mg kg-1 , Pb up to 23600 mg kg-1, Zn up to 1588 mg kg-1, Fe up to 52,30 %). The concentrations of Ni, Cr and Mn, instead, are below the reference limits. Moreover, a highly significant correlation was observed between the concentrations of metals in soils (Fe, Pb, Zn and Cu). Metal concentration in selected wild plants of the mineralized area is moderately high, in particolar Cu, Pb, Zn in the roots of Plantago major, Pb and Zn in the leaves of Taraxacum officinale, Zn and Pb in Salix spp. The translocation coefficient (BAC) from soil to plant (hypogean portion), and within the plant (epigean portion) vary from 0,37 in Plantago major to 2,97 in Silene dioica, two known accumulator plants. Salix spp present high translocation coefficients from soil to plant, and from roots to leaves. In particular, essential metals present a translocation coefficient ≥1 (with the order Mn>Zn>Cu>Fe), while toxic metals have coefficients <1 (Pb

The Role of Metal Oxides in Nanothermite Reactions: Evidence of Condensed Phase Initiation

DTIC Science & Technology

2010-01-01

ignition on the gaseous oxidizer release from the metal oxides CuO, Fe2O3, and ZnO .[14] However, there is uncertainty as to whether oxidizer release to the...and how it differs from some other systems. In our previous work, we studied the nanothermite reaction of Al/CuO, Al/Fe2O3, and Al/ ZnO .[9] For...Jomard, Oxygen Diffusion in Bi2O3-doped ZnO , Materials Research-Ibero-American Journal of Materials, 11 (2008) 221-225. [20] T. Ivetic, M.V. Nikolic

Trace metal characterization of aerosol particles and cloud water during HCCT 2010

NASA Astrophysics Data System (ADS)

Fomba, K. W.; van Pinxteren, D.; Müller, K.; Iinuma, Y.; Lee, T.; Collett, J. L., Jr.; Herrmann, H.

2015-08-01

Trace metal characterization of bulk and size-resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCEs) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2-111.6 and 1.1-32.1 ng m-3, respectively. Fe, Mn, and Ti were mainly found in coarse mode aerosols while Zn, Pb, and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe and Mn were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L-1, respectively. A non-uniform distribution of soluble Fe, Cu, and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm, while Mn was found mostly in larger drops greater than 22 μm. Fe(III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L-1. In contrast to other studies, Fe(II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol-cloud interaction did not lead to a marked increase in soluble trace metal concentrations; rather it led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces.

Trace metal characterization of aerosol particles and cloud water during HCCT 2010

NASA Astrophysics Data System (ADS)

Fomba, K. W.; van Pinxteren, D.; Müller, K.; Iinuma, Y.; Lee, T.; Collet, J., Jr.; Herrmann, H.

2015-04-01

Trace metal characterization of bulk and size resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCE) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2-111.6 and 1.1-32.1 ng m-3, respectively. Fe, Mn and Ti were mainly found in coarse mode aerosols while Zn, Pb and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe, Mn, were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L-1, respectively. A non-uniform distribution of soluble Fe, Cu and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm while Mn was found mostly in larger drops greater than 22 μm. Fe (III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L-1. In contrast to other studies, Fe (II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol cloud interaction did not lead to a mark increase in soluble trace metal concentrations, but led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces.

Impact of biogenic nanoscale metals Fe, Cu, Zn and Se on reproductive LV chickens

NASA Astrophysics Data System (ADS)

Khiem Nguyen, Quy; Dieu Nguyen, Duy; Kien Nguyen, Van; Thinh Nguyen, Khac; Chau Nguyen, Hoai; Tin Tran, Xuan; Nguyen, Huu Cuong; Tien Phung, Duc

2015-09-01

Using biogenic nanoscale metals (Fe, Cu, ZnO, Se) to supplement into diet premix of reproductive LV (a Vietnamese Luong Phuong chicken breed) chickens resulted in certain improvement of poultry farming. The experimental data obtained showed that the farming indices depend mainly on the quantity of nanocrystalline metals which replaced the inorganic mineral component in the feed premix. All four experimental groups with different quantities of the replacement nano component grew and developed normally with livability reaching 91 to 94%, hen’s bodyweight at 38 weeks of age and egg weight ranged from 2.53-2.60 kg/hen and 50.86-51.55 g/egg, respectively. All these farming indices together with laying rate, egg productivity and chick hatchability peaked at group 5 with 25% of nanoscale metals compared to the standard inorganic mineral supplement, while feed consumption was lowest. The results also confirmed that nanocrystalline metals Fe, Cu, ZnO and Se supplemented to chicken feed were able to decrease inorganic minerals in the diet premixes at least four times, allowing animals to more effectively absorb feed minerals, consequently decreasing environmental pollution risks.

[Distribution characteristics of heavy metals along an elevation gradient of montane forest].

PubMed

Wan, Jia-rong; Nie, Ming; Zou, Qin; Hu, Shao-chang; Chen, Jia-kuan

2011-12-01

In the present paper, the concentrations of fourteen heavy metals (Fe, Al, Ti, Cu, Cr, Mn, V, Zn, Ni, Co, Pb, Se, Cd and As) were determined by ICP-AES and atomic absorption spectroscopy along an elevation gradient of montane forest. The results show that the elevation gradient had significant effects on the concentrations of Fe, Al, Ti, V, Pb and As. And the concentrations of Cu, Cr, Mn, Zn, Ni, Co, Se and Cd were not significantly affected by the elevation gradient. Because the studying area is red soil, the elevation gradient had significant effects on the concentrations of Fe, Al and Ti which are characteristic heavy metals of red soil, suggesting that the red soil at different elevations has different intensities of weathering desilication and bioaccumulation. Other heavy metals have different relationships with the elevation gradient, such as the concentrations of Cr, Zn and Cd were high at relatively high elevation and Pb and As were high at relatively low elevation. These results suggest that the different elevations of montane forest soils were polluted by differently types of heavy metals.

Heavy metals translocation and accumulation from the rhizosphere soils to the edible parts of the medicinal plant Fengdan (Paeonia ostii) grown on a metal mining area, China.

PubMed

Shen, Zhang Jun; Xu, De Cong; Chen, Yan Song; Zhang, Zhen

2017-09-01

Fengdan (Paeonia ostii) is one of Chinese 34 famous medicinal materials. This study investigated the concentrations of Arsenic (As), Chromium (Cr), Cadmium (Cd), Copper (Cu), Lead (Pb), Iron (Fe), Manganese (Mn), and Zinc (Zn) in rhizosphere soils, cortex mouton and seeds of Fengdan planted in a metal mining area, China. The mean concentrations of As, Cd, Cu, and Zn in the rhizosphere soils were above the limits set by the Chinese Soil Environmental Quality Standard (GB 15618-1995). The contamination factor (CF) of Cd was >5, while it was >2for As, Cu, Pb, and Zn in all the soils. The integrated pollution index for all the soils was >3 and ˂ 5. Metal concentrations in the edible parts of Fengdan were in the following decreasing order: Mn>Fe>Zn>Cu>Pb>As>Cr≥Cd. The transfer factor mean values for As, Cu, Cd and Fe in the cortex moutan of old Fengdan (over 6 years) were significantly higher than in young Fengdan. Available metal concentrations, pH and soil organic matter content influenced the metal concentrations of the cortex moutan. The results indicated that mining and smelting operations have led to heavy metals contamination of soils and medicinal parts of Fengdan. The major metal pollutants were elemental Cd, Cu, Pb, and Zn. Heavy metals mainly accumulated in the cortex moutan of Fengdan. The mean concentrations of Cd, Cu, and Pb in the old cortex moutan (over 6 years) were above those of the Chinese Green Trade Standards for Medicinal Plants and Preparations in Foreign Trade (WM/T2-2004). Copyright © 2017. Published by Elsevier Inc.

The potential of selected macroalgal species for treatment of AMD at different pH ranges in temperate regions.

PubMed

Oberholster, Paul J; Cheng, Po-Hsun; Botha, Anna-Maria; Genthe, Bettina

2014-09-01

The metal bioaccumulation potential of selected macroalgae species at different pH ranges was study for usage as part of a possible secondary passive acid mine drainage (AMD) treatment technology in algae ponds. Two separate studies were conducted to determine the suitability of macroalgae for passive treatment when metabolic processes in macrophytes and microorganisms in constructed wetlands decrease during winter months. In the field study, the bioconcentration of metals (mg/kg dry weight) measured in the benthic macroalgae mats was in the following order: site 1. Oedogonium crassum Al > Fe > Mn > Zn; site 2. Klebsormidium klebsii, Al > Fe > Mn > Zn; site 3. Microspora tumidula, Fe > Al > Mn > Zn and site 4. M. tumidula, Fe > Mn > Al > Zn. In the laboratory study, cultured macroalgae K. klebsii, O. crassum and M. tumidula isolated from the field sampling sites were exposed to three different pH values (3, 5 and 7), while bioaccumulation of the metals, Al, Fe, Mn and Zn and glutathione S-transferase (GST) activity were measured in the different selected algae species at a constant water temperature of 14 °C. Bioaccumulation of Al was the highest for O. crassum followed by K. klebsii and M. tumidula (p < 0.0001). From the study it was evident that the highest metal bioaccumulation occurred in the macroalgae O. crassum at all three tested pH values under constant low water temperature. Copyright © 2014 Elsevier Ltd. All rights reserved.

Exposure of women to trace elements through the skin by direct contact with underwear clothing.

PubMed

Nguyen, Thao; Saleh, Mahmoud A

2017-01-02

Heavy metals pose a potential danger to human health when present in textile materials. In the present study, inductive coupled plasma mass spectrometry (ICPMS) was used to determine the concentrations and the identity of extractable inorganic elements from different brands of women undergarments. A total of 120 samples consisting of 63 cottons, 44 nylons and 13 polyesters manufactured in 14 different countries having different colors were analyzed for their extractable metals contents. Elements analyzed were Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Ti, V and Zn. Cotton undergarments were rich in Al, Fe and Zn, nylon undergarments had high levels of Cr, Cu and Al, while polyester fabrics contained higher levels of Ni and Fe compared to cotton or nylon. With respect to manufacturing countries, China, Egypt and India showed the highest concentrations of metals in all fabrics. With respect to the color, black garments were characteristic by high concentration of Fe, blue colors with Cu, brown garments with Fe and Cu, green garments with Cu and Fe, pink garments with Al, purple garments with Al and Cu and red garments with Cr, Zn and Al. The consumer should be made aware of the potential dangers of these metals in their clothing.

The impact of processing parameters on the properties of Zn-bonded Nd-Fe-B magnets

NASA Astrophysics Data System (ADS)

Kelhar, Luka; Zavašnik, Janez; McGuiness, Paul; Kobe, Spomenka

2016-12-01

We report on the effect of loading factor and pressure on the density and the magnetic properties of Zn-bonded Nd-Fe-B magnets produced by pulsed-electric-current sintering (PECS). The idea behind this study is to fabricate bonded magnets with a metallic binder in order for the bonded magnet to operate at temperatures higher than 180 °C: the current upper-limit for polymer-bonded magnets. These composites are made of hard-magnetic powder in the form of melt-spun ribbons bonded with the low-melting-point metal Zn. The binder additions were varied from 10 to 30 wt%, and pressures of 50 and 500 MPa were applied. The high-pressure mode with 20 wt% Zn resulted in a 24% increase of Jr, compared to the low-pressure mode. The magnetic measurements revealed a maximum remanence of 0.64 T for 10 wt% Zn, while the coercivity is largely unaffected by the processing conditions. The density of the composites was up to 7.0 g/cm3, corresponding to 94% of the theoretical density. Compared to commercial polymer-bonded magnets, the Zn-bonded counterparts exhibit a slightly lower Jr, but the coercivity is retained. We show that there is a minor diffusion of Zn into the Nd-Fe-B, forming a 1 μm thin transition layer, but it does not harm the magnetic properties. These metal-bonded Nd-Fe-B magnets are ideal for use in high-temperature automotive applications like under-the-hood sensors and other magnet-based devices that are close to the engine.

Petrographic and spectroscopic characterization of phosphate-stabilized mine tailings from Leadville, Colorado.

PubMed

Eusden, J D; Gallagher, L; Eighmy, T T; Crannell, B S; Krzanowski, J R; Butler, L G; Cartledge, F K; Emery, E F; Shaw, E L; Francis, C A

2002-01-01

The use of soluble PO4(3-) and lime as a heavy metal chemical stabilization agent was evaluated for mine tailings from Leadville, Colorado. The tailings are from piles associated with the Wolftone and Maid of Erin mines; ore material that was originally mined around 1900, reprocessed in the 1940s, and now requires stabilization. The dominant minerals in the tailings are galena (PbS), cerrusite (PbCO3), pyromorphite (Pb5(PO4)3Cl), plumbojarosite (Pb0.5Fe3(SO4)2(OH)6), and chalcophanites ((Pb,Fe,Zn,Mn)Mn2O5 x 2H2O). The tailings were treated with soluble PO4(3-) and lime to convert soluble heavy metals (principally Pb, Zn, Cu, Cd) into insoluble metal phosphate precipitates. The treatment process caused bulk mineralogical transformations as well as the formation of a reaction rind around the particles dominated by Ca and P. Within the mineral grains, Fe-Pb phosphosulfates, Fe-Pb sulfates (plumbojarosite), and galena convert to Fe-Ca-Pb hydroxides. The Mn-Pb hydroxides and Mn-(+/-Fe)-Pb hydroxides (chalcophanites) undergo chemical alteration throughout the grains during treatment. Bulk and surface spectroscopies showed that the insoluble reaction products in the rind are tertiary metal phosphate (e.g. (Cu,Ca2)(PO4)2) and apatite (e.g. Pb5(PO4)3Cl) family minerals. pH-dependent leaching (pH 4,6,8) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 150 for many metals; particularly Pb2+, Zn2+, Cd2+, and Cu2+. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca2+, PO4(3-) Pb2+, Zn2+, Cd2+, and Cu2+ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids.

Trace Metals in Urban Stormwater Runoff and their Management

NASA Astrophysics Data System (ADS)

Li, T.; Hall, K.; Li, L. Y.; Schreier, H.

2009-04-01

In past decades, due to the rapid urbanization, land development has replaced forests, fields and meadows with impervious surfaces such as roofs, parking lots and roads, significantly affecting watershed quality and having an impact on aquatic systems. In this study, non-point source pollution from a diesel bus loop was assessed for the extent of trace metal contamination of Cu, Mn, Fe, and Zn in the storm water runoff. The study was carried out at the University of British Columbia (UBC) in the Greater Vancouver Regional District (GVRD) of British Columbia, Canada. Fifteen storm events were monitored at 3 sites from the diesel bus loop to determine spatial and temporal variations of dissolved and total metal concentrations in the storm water runoff. The dissolved metal concentrations were compared with the provincial government discharge criteria and the bus loop storm water quality was also compared with previous studies conducted across the GVRD urban area. To prevent storm water with hazardous levels of contaminants from being discharged into the urban drainage system, a storm water catch basin filter was installed and evaluated for its efficiency of contaminants removal. The perlite filter media adsorption capacities for the trace metals, oil and grease were studied for better maintenance of the catch basin filter. Dissolved copper exceeded the discharge criteria limit in 2 out of 15 cases, whereas dissolved zinc exceeded the criteria in 4 out of 15 cases, and dissolved manganese was below the criteria in all of the events sampled. Dissolved Cu and Zn accounted for 36 and 45% of the total concentration, whereas Mn and Fe only accounted for 20 and 4% of their total concentration, respectively. Since they are more mobile and have higher bioaccumulation potentials, Zn and Cu are considered to be more hazardous to the aquatic environment than Fe and Mn. With high imperviousness (100%) and intensive traffic at the UBC diesel bus loop, trace metal concentrations were 3, 0.7, 9, and 3.2 times higher than the GVRD urban area limits for Cu, Mn, Fe, and Zn, respectively. The filter showed high and stable capture efficiencies in total metals (Cu 62%, Mn 75%, Fe 83%, Zn 62%), dissolved metals (Cu 39%, Mn 37%, Fe 47%, Zn 32%), turbidity (72%), and suspended solids (74%) removal during the first month of operation. After that, there was gradual degradation. The catch basin filter performance improved significantly for the suspended solids and total metal removal after cleaning. However, the perlite filter medium showed poor performance for dissolved metal removal in the second study period. Based on the findings, a catch basin filter is effective in storm water management to control suspended solids loading from storm water runoff.

Ferrate(VI) oxidation of zinc-cyanide complex.

PubMed

Yngard, Ria; Damrongsiri, Seelawut; Osathaphan, Khemarath; Sharma, Virender K

2007-10-01

Zinc-cyanide complexes are found in gold mining effluents and in metal finishing rinse water. The effect of Zn(II) on the oxidation of cyanide by ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was thus investigated by studying the kinetics of the reaction of Fe(VI) with cyanide present in a potassium salt of a zinc cyanide complex (K(2)Zn(CN)(4)) and in a mixture of Zn(II) and cyanide solutions as a function of pH (9.0-11.0). The rate-law for the oxidation of Zn(CN)(4)(2-) by Fe(VI) was found to be -d[Fe(VI)]/dt=k[Fe(VI)][Zn(CN)(4)(2-)](0.5). The rate constant, k, decreased with an increase in pH. The effect of temperature (15-45 degrees C) on the oxidation was studied at pH 9.0, which gave an activation energy of 45.7+/-1.5kJmol(-1). The cyanide oxidation rate decreased in the presence of the Zn(II) ions. However, Zn(II) ions had no effect on the cyanide removal efficiency by Fe(VI) and the stoichiometry of Fe(VI) to cyanide was approximately 1:1; similar to the stoichiometry in absence of Zn(II) ions. The destruction of cyanide by Fe(VI) resulted in cyanate. The experiments on removal of cyanide from rinse water using Fe(VI) demonstrated complete conversion of cyanide to cyanate.

New approach for the quantification of metallic species in healthcare products based on optical switching of a Schiff base possessing ONO donor set.

PubMed

Singh, Jaswant; Parkash, Jyoti; Kaur, Varinder; Singh, Raghubir

2017-10-05

A new method is reported for the quantification of some metallic components of healthcare products utilizing a Schiff base chelator derived from 2-hydroxyacetophenone and ethanolamine. The Schiff base chelator recognizes some metallic species such as iron, copper and zinc (important components of some healthcare products), and cadmium (common contaminant in healthcare products) giving colorimetric/fluorimetric response. It coordinates with Fe 2+ /Fe 3+ and Cu 2+ ions via ONO donor set and switches the colour to bright red, green and orange, respectively. Similarly, it switches 'ON' a fluorometric response when coordinates with Zn 2+ and Cd 2+ ions. In the present approach, detailed studies on the colorimetric and fluorimetric response of ONO Schiff base is investigated in detail. The Job plot for the complexation of ONO switch with various metal ions suggested formation of 1:1 (metal-chelator) complex with Fe 2+ , Fe 3+ , and Cu 2+ while 1:2 (metal-chelator) for Zn 2+ and Cd 2+ ions. The limit of detection, limit of quantification are 6.73, 18.0, 25.0, 0.65, 1.10μM and 27.0, 72.0, 100.0, 2.60 and 4.40μM for Fe 2+ , Fe 3+ , Cu 2+ , Zn 2+ and Cd 2+ ions, respectively. Under the optimized conditions, chelator was used for the quantification of important metals present in healthcare products via direct dissolution and furnace treatment during sample preparation. The results were found precise and accurate for both sample preparation techniques using the developed method. Copyright © 2017 Elsevier B.V. All rights reserved.

Controls on Fe(II)-Activated Trace Element Release from Goethite and Hematite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-03-26

Electron transfer and atom exchange (ETAE) between aqueous Fe(II) and Fe(III) oxides induces surface growth and dissolution that affects trace element fate and transport. We have recently demonstrated Ni(II) cycling through goethite and hematite (adsorbed Ni incorporates into the mineral structure and preincorporated Ni releases to solution) during Fe(II)-Fe(III) ETAE. However, the chemical parameters affecting net trace element release remain unknown. Here, we examine the chemical controls on Ni(II) and Zn(II) release from Ni- and Zn-substituted goethite and hematite during reaction with Fe(II). Release follows a rate law consistent with surface reaction limited mineral dissolution and suggests that release occursmore » near sites of Fe(III) reductive dissolution during Fe(II)-Fe(III) ETAE. Metal substituent type affects reactivity; Zn release is more pronounced from hematite than goethite, whereas the opposite trend occurs for Ni. Buildup of Ni or Zn in solution inhibits further release but this resumes upon fluid exchange, suggesting that sustained release is possible under flow conditions. Mineral and aqueous Fe(II) concentrations as well as pH strongly affect sorbed Fe(II) concentrations, which directly control the reaction rates and final metal concentrations. Our results demonstrate that structurally incorporated trace elements are mobilized from iron oxides into fluids without abiotic or microbial net iron reduction. Such release may affect micronutrient availability, contaminant transport, and the distribution of redox-inactive trace elements in natural and engineered systems.« less

Metal concentrations in the growth bands of Porites sp.: A baseline record on the history of marine pollution in the Gulf of Mannar, India.

PubMed

Krishnakumar, S; Ramasamy, S; Magesh, N S; Chandrasekar, N; Simon Peter, T

2015-12-15

The present study was carried out on the Porites coral growth bands (1979 to 2014) to measure the metal accumulation for assessing the environmental pollution status. The concentrations of studied metals are compared with similar global studies, which indicate that the metals are probably derived from natural sources. The identical peaks of Fe and Mn are perfectly matched with Cu, Cr and Ni concentrations. However, the metal profile trend is slightly depressed from a regular trend in Zn, Cd and Pb peaks. The metal accumulation affinity of the reef skeleton is ranked in the following order Cr>Cd>Pb>Fe>Mn>Cu>Ni>Zn. The distribution of metal constituents in coral growth bands is primarily controlled by Fe and Mn in the reef skeleton. Other reef associated metals such as Pb and Cd are derived from other sources like coastal developments and anthropogenic sources. Copyright © 2015 Elsevier Ltd. All rights reserved.

Heavy metal distribution in sediments from Calabar River, southeastern Nigeria

NASA Astrophysics Data System (ADS)

Ntekim, E. E. U.; Ekwere, S. J.; Ukpong, E. E.

1993-08-01

The concentration and areal distribution of selected metals (Pb, Zn, Cu, Cd, Ni, Fe, and Cr) in the sediments of the Calabar River were studied to determine the extent of anthropogenic input and to estimate the effects of dumping industrial waste materials into the river. The concentrations of Pb, Zn, and Cu indicate relatively moderate pollution mainly on the left-hand side of the river while Ni, Cr, Co, Cd, and Fe levels are below values found to have adverse effects on the lives of marine biota. High metal contents are found close to industrial establishments and so enhanced metal concentrations are related to industrial sewage and metal leaching from garbage and solid waste dumps.

In Situ, High-Resolution Profiles of Labile Metals in Sediments of Lake Taihu

PubMed Central

Wang, Dan; Gong, Mengdan; Li, Yangyang; Xu, Lv; Wang, Yan; Jing, Rui; Ding, Shiming; Zhang, Chaosheng

2016-01-01

Characterizing labile metal distribution and biogeochemical behavior in sediments is crucial for understanding their contamination characteristics in lakes, for which in situ, high-resolution data is scare. The diffusive gradient in thin films (DGT) technique was used in-situ at five sites across Lake Taihu in the Yangtze River delta in China to characterize the distribution and mobility of eight labile metals (Fe, Mn, Zn, Ni, Cu, Pb, Co and Cd) in sediments at a 3 mm spatial resolution. The results showed a great spatial heterogeneity in the distributions of redox-sensitive labile Fe, Mn and Co in sediments, while other metals had much less marked structure, except for downward decreases of labile Pb, Ni, Zn and Cu in the surface sediment layers. Similar distributions were found between labile Mn and Co and among labile Ni, Cu and Zn, reflecting a close link between their geochemical behaviors. The relative mobility, defined as the ratio of metals accumulated by DGT to the total contents in a volume of sediments with a thickness of 10 mm close to the surface of DGT probe, was the greatest for Mn and Cd, followed by Zn, Ni, Cu and Co, while Pb and Fe had the lowest mobility; this order generally agreed with that defined by the modified BCR approach. Further analyses showed that the downward increases of pH values in surface sediment layer may decrease the lability of Pb, Ni, Zn and Cu as detected by DGT, while the remobilization of redox-insensitive metals in deep sediment layer may relate to Mn cycling through sulphide coprecipitation, reflected by several corresponding minima between these metals and Mn. These in situ data provided the possibility for a deep insight into the mechanisms involved in the remobilization of metals in freshwater sediments. PMID:27608033

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

Distribution and Potential Toxicity of Trace Metals in the Surface Sediments of Sundarban Mangrove Ecosystem, Bangladesh

NASA Astrophysics Data System (ADS)

Kumar, A.; Ramanathan, A.; Mathukumalli, B. K. P.; Datta, D. K.

2014-12-01

The distribution, enrichment and ecotoxocity potential of Bangladesh part of Sundarban mangrove was investigated for eight trace metals (As, Cd, Cr, Cu, Fe, Mn, Pb and Zn) using sediment quality assessment indices. The average concentration of trace metals in the sediments exceeded the crustal abundance suggesting sources other than natural in origin. Additionally, the trace metals profile may be a reflection of socio-economic development in the vicinity of Sundarban which further attributes trace metals abundance to the anthropogenic inputs. Geoaccumulation index suggests moderately polluted sediment quality w.r.t. Ni and As and background concentrations for Al, Fe, Mn, Cu, Zn, Pb, Co, As and Cd. Contamination factor analysis suggested low contamination by Zn, Cr, Co and Cd, moderate by Fe, Mn, Cu and Pb while Ni and As show considerable and high contamination, respectively. Enrichment factors for Ni, Pb and As suggests high contamination from either biota or anthropogenic inputs besides natural enrichment. As per the three sediment quality guidelines, Fe, Mn, Cu, Ni, Co and As would be more of a concern with respect to ecotoxicological risk in the Sundarban mangroves. The correlation between various physiochemical variables and trace metals suggested significant role of fine grained particles (clay) in trace metal distribution whereas owing to low organic carbon content in the region the organic complexation may not be playing significant role in trace metal distribution in the Sundarban mangroves.

Source discrimination of heavy metals in sediment and water of To Lich River in Hanoi City using multivariate statistical approaches.

PubMed

Thuong, Nguyen Thi; Yoneda, Minoru; Ikegami, Maiko; Takakura, Masato

2013-10-01

The concentrations of Mn, Fe, Ni, Cr, Cu, Pb, Zn, As, and Cd were determined to evaluate the level of contamination of To Lich River in Hanoi City. All metal concentrations in 0-10-cm water samples, except Mn, were lower than the maximum permitted concentration for irrigation water standard. Meanwhile, concentrations of As, Cd, and Zn in 0-30-cm sediments were likely to have adverse effects on agriculture and aquatic life. Sediment pollution assessment was undertaken using enrichment factor and geoaccumulation index (I geo). The I geo results indicated that the sediment was not polluted with Cr, Mn, Fe, and Ni, and the pollution level increased in the order of Cu < Pb < Zn < As < Cd. Meanwhile, significant enrichment was shown for Cd, As, Zn, and Pb. Cluster and principal component analyses suggest that As and Mn in sediment were derived from both lithogenic and anthropogenic sources, while Cu, Pb, Zn, Cr, Cd, and Ni originated from anthropogenic sources such as vehicular fumes for Pb and metallic discharge from industrial sources and fertilizer application for other metals.

Adsorption of tetracycline on Fe (hydr)oxides: effects of pH and metal cation (Cu2+, Zn2+ and Al3+) addition in various molar ratios

PubMed Central

Hsu, Liang-Ching; Liu, Yu-Ting; Syu, Chien-Hui; Huang, Mei-Hsia; Teah, Heng Yi

2018-01-01

Iron (Fe) (hydr)oxides control the mobility and bioavailability of tetracycline (TC) in waters and soils. Adsorption of TC on Fe (hydr)oxides is greatly affected by polyvalent metals; however, impacts of molar metal/TC ratios on TC adsorptive behaviours on Fe (hydr)oxides remain unclear. Results showed that maximum TC adsorption on ferrihydrite and goethite occurred at pH 5–6. Such TC adsorption was generally promoted by the addition of Cu2+, Zn2+ and Al3+. The greatest increase in TC adsorption was found in the system with molar Cu/TC ratio of 3 due to the formation of Fe hydr(oxide)–Cu–TC ternary complexes. Functional groups on TC that were responsible for the complexation with Cu2+shifted from phenolic diketone groups at Cu/TC molar ratio < 1 to amide groups at Cu/TC molar ratio ≥ 1. For the addition of Al3+, the complexation only took place with phenolic diketone groups, resulting in the enhanced TC adsorption at a molar Al/TC ratio of 1. However, TC adsorption decreased for Al/TC molar ratio > 1 as excess Al3+ led to the competitive adsorption with Al/TC complexes. For the Zn2+ addition, no significant correlation was found between TC adsorption capacity and molar Zn/TC ratios. PMID:29657795

Kinetic control on Zn isotope signatures recorded in marine diatoms

NASA Astrophysics Data System (ADS)

Köbberich, Michael; Vance, Derek

2017-08-01

Marine diatoms dominate the oceanic cycle of the essential micronutrient zinc (Zn). The stable isotopes of zinc and other metals are increasingly used to understand trace metal micronutrient cycling in the oceans. One clear feature of the early isotope data is the heavy Zn isotope signature of the average oceanic dissolved pool relative to the inputs, potentially driven by uptake of light isotopes into phytoplankton cells and export to sediments. However, despite the fact that diatoms strip Zn from surface waters across the Antarctic polar front in the Southern Ocean, the local upper ocean is not isotopically heavy. Here we use culturing experiments to quantify the extent of Zn isotope fractionation by diatoms and to elucidate the mechanisms driving it. We have cultured two different open-ocean diatom species (T. oceanica and Chaetoceros sp.) in a series of experiments at constant medium Zn concentration but at bioavailable medium Fe ranging from limiting to replete. We find that T. oceanica can maintain high growth rates and Zn uptake rates over the full range of bioavailable iron (Fe) investigated, and that the Zn taken up has a δ66Zn that is unfractionated relative to that of the bioavailable free Zn in the medium. The studied representative of the genus Chaetoceros, on the other hand, shows more significantly reduced Zn uptake rates at low Fe and records more variable biomass δ66Zn signatures, of up to 0.85‰ heavier than the medium. We interpret the preferential uptake of heavy isotopes at extremely low Zn uptake rates as potentially due to either of the following two mechanisms. First, the release of extracellular polymeric substances (EPS), at low Fe levels, may preferentially scavenge heavy Zn isotopes. Second, the Zn uptake rate may be slow enough to establish pseudo-equilibrium conditions at the transporter site, with heavy Zn isotopes forming more stable surface complexes. Thus we find that, in our experiments, Fe-limitation exerts a key control that not only limits diatom growth, but also affects the Zn uptake physiology of diatoms. Uptake of heavy isotopes occurs under Fe-limiting conditions that drive extremely low Zn uptake rates. On the other hand, more rapid Zn uptake rates result in biomass that is indistinguishable from the external bioavailable free Zn pool. These experimental results can, in principle, explain the range of Zn isotopic compositions found in the real surface ocean, given the geographically variable interplay between Fe-limitation, Zn uptake rates, and the degree of organic complexation of oceanic Zn.

Influence of variable chemical conditions on EDTA-enhanced transport of metal ions in mildly acidic groundwater

USGS Publications Warehouse

Kent, D.B.; Davis, J.A.; Joye, J.L.; Curtis, G.P.

2008-01-01

Adsorption of Ni and Pb on aquifer sediments from Cape Cod, Massachusetts, USA increased with increasing pH and metal-ion concentration. Adsorption could be described quantitatively using a semi-mechanistic surface complexation model (SCM), in which adsorption is described using chemical reactions between metal ions and adsorption sites. Equilibrium reactive transport simulations incorporating the SCMs, formation of metal-ion-EDTA complexes, and either Fe(III)-oxyhydroxide solubility or Zn desorption from sediments identified important factors responsible for trends observed during transport experiments conducted with EDTA complexes of Ni, Zn, and Pb in the Cape Cod aquifer. Dissociation of Pb-EDTA by Fe(III) is more favorable than Ni-EDTA because of differences in Ni- and Pb-adsorption to the sediments. Dissociation of Ni-EDTA becomes more favorable with decreasing Ni-EDTA concentration and decreasing pH. In contrast to Ni, Pb-EDTA can be dissociated by Zn desorbed from the aquifer sediments. Variability in adsorbed Zn concentrations has a large impact on Pb-EDTA dissociation.

Metal Sulfide Cluster Complexes and their Biogeochemical Importance in the Environment

NASA Astrophysics Data System (ADS)

Luther, George W.; Rickard, David T.

2005-10-01

Aqueous clusters of FeS, ZnS and CuS constitute a major fraction of the dissolved metal load in anoxic oceanic, sedimentary, freshwater and deep ocean vent environments. Their ubiquity explains how metals are transported in anoxic environmental systems. Thermodynamic and kinetic considerations show that they have high stability in oxic aqueous environments, and are also a significant fraction of the total metal load in oxic river waters. Molecular modeling indicates that the clusters are very similar to the basic structural elements of the first condensed phase forming from aqueous solutions in the Fe-S, Zn-S and Cu-S systems. The structure of the first condensed phase is determined by the structure of the cluster in solution. This provides an alternative explanation of Ostwald's Rule, where the most soluble, metastable phases form before the stable phases. For example, in the case of FeS, we showed that the first condensed phase is nanoparticulate, metastable mackinawite with a particle size of 2 nm consisting of about 150 FeS subunits, representing the end of a continuum between aqueous FeS clusters and condensed material. These metal sulfide clusters and nanoparticles are significant in biogeochemistry. Metal sulfide clusters reduce sulfide and metal toxicity and help drive ecology. FeS cluster formation drives vent ecology and AgS cluster formation detoxifies Ag in Daphnia magna neonates. We also note a new reaction between FeS and DNA and discuss the potential role of FeS clusters in denaturing DNA.

Combining cross flow ultrafiltration and diffusion gradients in thin-films approaches to determine trace metal speciation in freshwaters

NASA Astrophysics Data System (ADS)

Liu, Ruixia; Lead, Jamie R.; Zhang, Hao

2013-05-01

Cross flow ultrafiltration (CFUF) and diffusive gradients in thin films (DGT) with open pore gel (OP) and restricted pore gel (RP) were used to measure trace metal speciation in selected UK freshwaters. The proportions of metals present in particulate forms (>1 μm) varied widely between 40-85% Pb, 60-80% Al, 7-56% Mn, 10-49% Cu, 0-55% Zn, 20-38% Cr, 20-30% Fe, 6-25% Co, 5-22% Cd and <7% Ni. In the colloidal fraction (2 kDa-1 μm) values varied between 53-91% Pb, 33-55% Al, 21-55% Cu, 20-44% Fe, 34-36% Cr, 20-40% Cd, 7-28% Co and Ni, 2-32% Zn and <8% Mn. Wide variations were also observed in the ultrafiltered fraction (<2 kDa). These results indicated that colloids indeed influenced the occurrence and transport of Al, Fe, Cr, Co, Ni, Cu, Zn, Cr and Pb metals in rivers, while inorganic or organic colloids did not exert an important control on Mn transport in the selected freshwaters. Of total species, total labile metal measured by DGT-OP accounted for 1.4-50% for Al, Fe, Co, Ni, Cu, Cd and Pb in all selected waters. Of these metals total labile Pb concentration was the lowest with value less than 1.4% although this value slightly increased after deducting particulate fractions. In some waters, a majority of total Mn, Zn and Cr is DGT labile, in which the DGT labile Mn fraction accounted for 98-118% of the total dissolved phase. In most cases, the inorganic labile concentration measured by DGT-RP was lower than the total labile metal concentration. By the combination of CFUF and DGT techniques, the concentrations of total labile and inorganic labile metal species in CFUF-derived truly dissolved phase were measured in four water samples. 100% of ultrafiltered Mn species was found to be total DGT labile. The proportions of total labile metal species were lower than those of ultrafiltered fraction for Al, Fe, Co, Ni, Cu, Cd and Pb in all selected waters, and Cr and Zn in some cases, indicating a large amount of natural complexing ligands with smaller size for the metals to form kinetically inert species or thermodynamically stable complexes. Observed discrepancies in metal speciation between metals and within sampling sites were related to the differences in the characteristics of the metals and the nature of water sources.

Design, synthesis and photoelectrochemical properties of hexagonal metallomacrocycles based on triphenylamine: [M6(4,4'-bis(2,2':6',2''-terpyridinyl)triphenylamine)6(X)12]; [M = Fe(II), PF6- and Zn(II), BF4-].

PubMed

Hwang, Seok-Ho; Moorefield, Charles N; Wang, Pingshan; Fronczek, Frank R; Courtney, Brandy H; Newkome, George R

2006-08-07

Synthesis of a novel bis(terpyridine) ligand, 4,4'-bis(2,2':6',2''-terpyridinyl)triphenylamine, utilizing triphenylamine, as a specific angle controller, has led to the self-assembly of a unique hexagonal metallomacrocycle family, [Fe6(2)6(PF6)12] and [Zn6(2)6(BF4)12], utilizing terpyridine-metal(II)-terpyridine connectivity. The crystal structure of the novel ligand shows that the angle between the two terpyridinyl moieties is 119.69 degrees , which enabled the formation of the hexagonal-shaped macrocycles. The crystal packing architectures of this starting ligand revealed channels induced by solvent encapsulation. Following complexation of this ligand with transition metals [Fe(II) or Zn(II)] in a one-pot reaction, the resultant structures were characterized by (1)H and (13)C NMR, UV/Vis and mass spectroscopies. The expected metal-to-ligand charge transfer (MLCT; lambda(max) = 582 nm) and emission (lambda(em) = 575 nm) characteristics were exhibited by both [Fe6(2)6(PF6)12] and[Zn6(2)6(BF4)12]. The photoelectrochemical characteristics of these hexagonal metallomacrocycles demonstrate that they can be used as sensitizers in dye-sensitized solar cells.

Role of the Zn1 and Zn2 sites in metallo-β-lactamase L1

PubMed Central

Hu, Zhenxin; Periyannan, Gopalraj; Bennett, Brian; Crowder, Michael W.

2009-01-01

In an effort to probe the role of the Zn(II) sites in metallo-β-lactamase L1, mononuclear metal ion containing and heterobimetallic analogs of the enzyme were generated and characterized using kinetic and spectroscopic studies. Mononuclear Zn(II)-containing L1, which binds Zn(II) in the consensus Zn1 site, was shown to be slightly active; however, this enzyme did not stabilize a nitrocefin-derived reaction intermediate that had been previously detected. Mononuclear Co(II)- and Fe(III)-containing L1 were essentially inactive, and NMR and EPR studies suggest that these metal ions bind to the consensus Zn2 site in L1. Heterobimetallic analogs (ZnCo and ZnFe) analogs of L1 were generated, and stopped-flow kinetic studies revealed that these enzymes rapidly hydrolyze nitrocefin and that there are large amounts of the reaction intermediate formed during the reaction. The heterobimetallic analogs were reacted with nitrocefin, and the reactions were rapidly freeze quenched. EPR studies on these samples demonstrate that Co(II) is five-coordinate in the resting state, proceeds through a four-coordinate species during the reaction, and is five-coordinate in the enzyme-product complex. These studies demonstrate that the metal ion in the Zn1 site is essential for catalysis in L1 and that the metal ion in the Zn2 site is crucial for stabilization of the nitrocefin-derived reaction intermediate. PMID:18831550

Role of the Zn1 and Zn2 sites in metallo-beta-lactamase L1.

PubMed

Hu, Zhenxin; Periyannan, Gopalraj; Bennett, Brian; Crowder, Michael W

2008-10-29

In an effort to probe the role of the Zn(II) sites in metallo-beta-lactamase L1, mononuclear metal ion containing and heterobimetallic analogues of the enzyme were generated and characterized using kinetic and spectroscopic studies. Mononuclear Zn(II)-containing L1, which binds Zn(II) in the consensus Zn1 site, was shown to be slightly active; however, this enzyme did not stabilize a nitrocefin-derived reaction intermediate that had been previously detected. Mononuclear Co(II)- and Fe(III)-containing L1 were essentially inactive, and NMR and EPR studies suggest that these metal ions bind to the consensus Zn2 site in L1. Heterobimetallic analogues (ZnCo and ZnFe) analogues of L1 were generated, and stopped-flow kinetic studies revealed that these enzymes rapidly hydrolyze nitrocefin and that there are large amounts of the reaction intermediate formed during the reaction. The heterobimetallic analogues were reacted with nitrocefin, and the reactions were rapidly freeze quenched. EPR studies on these samples demonstrate that Co(II) is 5-coordinate in the resting state, proceeds through a 4-coordinate species during the reaction, and is 5-coordinate in the enzyme-product complex. These studies demonstrate that the metal ion in the Zn1 site is essential for catalysis in L1 and that the metal ion in the Zn2 site is crucial for stabilization of the nitrocefin-derived reaction intermediate.

Metallic elements occurrences within metallic fragments in the municipal waste incineration bottom ash

NASA Astrophysics Data System (ADS)

Kowalski, Piotr; Kasina, Monika; Michalik, Marek

2017-04-01

Bottom ash (BA) from municipal solid waste incineration (MSWI) is composed of grainy ash material, residual components and metallic fragments (from few µm up to 3-5 cm). Its mineral and chemical composition is related to the composition of the waste stream in the incinerator operational area. Wide use of thermal techniques in management of solid waste makes important the studies on valuable components and their distribution within the material in terms of their further processing. By using various valorization or extraction techniques it is possible to extend the range of its possible further application. To investigate metallic elements distribution within metallic fragments of the MSWI BA material produced in municipal waste incineration plant in Poland were collected in 2015 and 2016. BA and its components were investigated using spectroscopic methods of chemical analysis: ICP-OES, ICP-MS, LECO and EDS (used for microanalysis during SEM observations). BA is a material rich in Si (22.5 wt%), Ca (13.4 wt%), Fe (4 wt%), Al (5.2 wt%) and Na (3.5 wt%), composed of equal part of amorphous (silicate glass dominated) and crystalline phase (rich in silicates, aluminosilicates, oxides of non- and metallic elements and sulphates). The content of metallic elements (Al, Fe, Mg, Ti, Mn, Cr, Ni, Sc, Mo, Cu, Pb, Zn, Sn) is 11.5 wt% with domination of Al (5.2 wt%) and Fe (4 wt%) and elevated values of Mg (1 wt%), Ti (0.54 wt%), Cu (0.26 wt%) and Zn (0.27 wt%) (Kowalski et al., 2016). They were mostly concentrated in the form of metallic fragments, mainly as metallic inclusions in the size of 1-20 µm and separated metallic grains in the size of 50-300 µm. Metallic fragments present in the BA are characterized by their composition heterogeneity and various oxygen content. Fragments are rarely composed of single metallic element and usually in their composition up to few main elements dominated over others. The most common were Fe-, Al- and Zn-rich fragments forming respectively 70%, 15% and 5% of the total amount of fragments. Fe occurred mainly as component of metallic inclusions and separate grains. Al was mostly present in metallic fragments on grains boundaries and also and as separate grains (often oxidised), moreover Al was important component of aluminosilicates and amorphous phase. Zn-rich metallic fragments were mostly in the form of separate grains. In complex composition of metallic fragments some regularities in elements co-occurrences were observed: Fe often co-existed with Si, Ca, P, Al and Ti; Al co-occurred with Fe, Si and Ca; Zn co-existed with Ca, Al and Si. Forms and composition of metallic fragments allows to evaluate them as potential polymetallic resource, however an economically reasonable extraction techniques must be applied. Acknowledgment Research was funded by Polish National Science Centre (NCN). Scientific grant No. UMO-2014/15/B/ST10/04171. Reference Kowalski, P.R., Kasina, M. and Michalik M.: Metallic elements fractionation in municipal solid waste incineration residues, Energy Procedia, 97, 31-36, doi: 10.1016/j.egypro.2016.10.013, 2016.

Vertical variation of potential mobility of heavy metal in sediment to groundwater of the Kanto plain, Japan

NASA Astrophysics Data System (ADS)

Hossain, S.; Hachinohe, S.; Ishiyama, T.; Hamamoto, H.; Oguchi, C. T.

2014-12-01

Heavy metals release from sediment may occur due to sediment water interaction under different changing environmental conditions. This has substantial influence on groundwater quality. However, identification of potentially mobile fractions of metals like Cu, Cr, Ni, Pb, Zn, Fe, Mn and Ti requires for the sustainable land and groundwater development and pollution management. 44 sediment and pore water samples at 1 m interval were analyzed from a vertical profile beneath the Naka river at the bottom of Central Kanto plain, Japan. Sequential extraction method was applied to determine potentially mobile forms of metals such as water soluble, ion exchangeable, acid soluble and Fe-Mn oxide bound. Metals were determined using X-Ray Fluorescence, Inductively coupled plasma atomic emission and mass spectrometer. Analyses show that potential mobility is high in river bed, volcanic ash mix, marine and transitional clayey silt. Metal mobility was higher in lower gravelly aquifer than upper sandy aquifer. Potential mobility and bioavailability of Zn, Cu, Ni, Pb and Mn are very high in river bed sediment which may pose threat to river bottom aquatic system. Zn, Cu and Ni concentration in pore water is high in river bed and peat bearing sediment. In pore water of marine and transitional sediment ion concentration such as Ca2+ and SO42- is very high indicating high mobility of Calcium and Sulfur from sediment as no significant variation observed in total content. In vertical profile, potential mobility tendency of metal in sediment trends to be Zn > Cu > Ni > Cr > Pb > Mn > Fe > Ti. Current study indicates low potential mobility and pollution risk to groundwater due to overall low metal concentration in pore water and high portion of metals attached with sediment as Fe-Mn oxide bound. More over under strong reducing condition considerable amount of metals will release and pollute groundwater.

Changes in zinc speciation with mine tailings acidification in a semiarid weathering environment.

PubMed

Hayes, Sarah M; O'Day, Peggy A; Webb, Sam M; Maier, Raina M; Chorover, Jon

2011-09-01

High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semiarid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6000 to 450 mg kg(-1)) and plant-available (590 to 75 mg kg(-1)) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and microfocused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn(0.8)talc), Zn sorbed to ferrihydrite (Zn(adsFeOx)), and zinc sulfate (ZnSO(4) · 7H(2)O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Microscale analyses identified hetaerolite (ZnMn(2)O(4)), hemimorphite (Zn(4)Si(2)O(7)(OH)(2) · H(2)O) and sphalerite (ZnS) as minor phases. Bulk and microfocused spectroscopy complement the chemical extraction results and highlight the importance of using a multimethod approach to interrogate complex tailings systems.

Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine.

PubMed

Mohamed, Gehad G; El-Gamel, Nadia E A

2004-11-01

The ternary piroxicam (Pir; 4-hydroxy-2-methyl-N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA chelates were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

NASA Astrophysics Data System (ADS)

Mohamed, Gehad G.; El-Gamel, Nadia E. A.

2004-11-01

The ternary piroxicam (Pir; 4-hydroxy-2-methyl- N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA cheletes were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

Bioaccessibility and size distribution of metals in road dust and roadside soils along a peri-urban transect.

PubMed

Padoan, Elio; Romè, Chiara; Ajmone-Marsan, Franco

2017-12-01

Road dust (RD), together with surface soils, is recognized as one of the main sinks of pollutants in urban environments. Over the last years, many studies have focused on total and bioaccessible concentrations while few have assessed the bioaccessibility of size-fractionated elements in RD. Therefore, the distribution and bioaccessibility of Fe, Mn, Cd, Cr, Cu, Ni, Pb, Sb and Zn in size fractions of RD and roadside soils (<2.5μm, 2.5-10μm and 10-200μm) have been studied using aqua regia extraction and the Simple Bioaccessibility Extraction Test. Concentrations of metals in soils are higher than legislative limits for Cu, Cr, Ni, Pb and Zn. Fine fractions appear enriched in Fe, Mn, Cu, Pb, Sb and Zn, and 2.5-10μm particles are the most enriched. In RD, Cu, Pb, Sb and Zn derive primarily from non-exhaust sources, while Zn is found in greater concentrations in the <2.5μm fraction, where it most likely has an industrial origin. Elemental distribution across soils is dependent on land use, with Zn, Ni, Cu and Pb being present in higher concentrations at traffic sites. In addition, Fe, Ni and Cr feature greater bioaccessibility in the two finer fractions, while anthropic metals (Cu, Pb, Sb and Zn) do not. In RD, only Zn has significantly higher bioaccessibility at traffic sites compared to background, and the finest particles are always the most bioaccessible; >90% of Pb, Zn and Cu is bioaccessible in the <2.5μm fraction, while for Mn, Ni, Sb, Fe and Cr, values vary from 76% to 5%. In the 2.5-10μm fraction, the values were 89% for Pb, 67% for Zn and 60% for Cu. These results make the evaluation of the bioaccessibility of size-fractionated particles appear to be a necessity for correct estimation of risk in urban areas. Copyright © 2017 Elsevier B.V. All rights reserved.

Nicotianamine forms complexes with Zn(II) in vivo.

PubMed

Trampczynska, Aleksandra; Küpper, Hendrik; Meyer-Klaucke, Wolfram; Schmidt, Holger; Clemens, Stephan

2010-01-01

The non-proteinogenic amino acid nicotianamine (NA) is a major player in plant metal homeostasis. It is known to form complexes with different transition metals in vitro. Available evidence associates NA with translocation of Fe, and possibly other micronutrients, to and between different plant cells and tissues. To date, however, it is still extremely challenging to detect metal-ligand complexes in vivo because tissue disruption immediately changes the chemical environment and thereby the availability of binding partners. In order to overcome this limitation we used various Schizosaccharomyces pombe strains expressing a plant NAS gene to study formation of metal-NA complexes in vivo. Tolerance, accumulation and competition data clearly indicated formation of Zn(ii)-NA but not of Cu(ii)-NA complexes. Zn(ii)-NA was then identified by X-ray absorption spectroscopy (XAS). About half of the cellular Zn was found to be bound by NA in NAS-expressing cells while no NA-like ligands were detected by XAS in control cells not expressing NAS. Given the high conservation of eukaryotic metal homeostasis components, these results strongly suggest the possible existence of Zn(ii)-NA complexes also in planta. Reported observations implicating NA in plant Zn homeostasis would then indeed be attributable to direct interaction of Zn(ii) with NA rather than only indirectly to perturbations in Fe metabolism. Re-evaluation of extended X-ray absorption fine structure (EXAFS) spectra for the Zn hyperaccumulator Thlaspi caerulescens showed that NA is as expected not a major storage ligand for Zn. Instead it is hypothesized to be involved in efficient translocation of Zn to above-ground tissues in hyperaccumulators.

The role of iron(II) dilution in the magnetic and photomagnetic properties of the series [Fe(x)Zn(1-x)(bpp)₂](NCSe)₂.

PubMed

Baldé, Chérif; Desplanches, Cédric; Le Gac, Fréderic; Guionneau, Philippe; Létard, Jean-François

2014-06-07

The effects of metal dilution on the spin-crossover behavior of iron(II) in the mixed crystal series [Fe(x)Zn(1-x)(bpp)2](NCSe)2 (bpp = 2,6-bis(pyrazol-3-yl)pyridine) have been studied using magnetic susceptibility, photomagnetism and diffuse reflectivity measurements. For each mixed-crystal system, the thermal spin transition temperature, T(1/2), and the relaxation temperature of the photo-induced high-spin state, T(LIESST), have been systematically determined. It appears that T(1/2) decreases with the metal dilution while T(LIESST) remains unchanged. Dilution also tends to decrease the hysteresis width and smooth the transition curves. These effects were discussed first qualitatively and then quantitatively on the basis of a kinetic study governing the photo-induced back conversion taking into account the relative sizes of Zn(II) and Fe(II) ions. Interestingly, single crystals were obtained for [Fe(0.6)Zn(0.4)(bpp)2](NCSe)2 allowing the X-ray diffraction crystal-structure determination.

Trace metals in bulk precipitation and throughfall in a suburban area of Japan

NASA Astrophysics Data System (ADS)

Hou, H.; Takamatsu, T.; Koshikawa, M. K.; Hosomi, M.

Throughfall and bulk precipitation samples were collected monthly for 1.5 years over bare land and under canopies of Japanese cedar ( Cryptomeria japonica), Japanese red pine ( Pinus densiflora), Japanese cypress ( Chamaecyparis obtusa), and bamboo-leafed oak ( Quercus myrsinaefolia) in a suburban area of Japan. Samples were analyzed for dissolved Al, Mn, Fe, Cu, Zn, Ag, In, Sn, Sb and Bi by ICP-AES and ICP-MS. The metal concentrations were higher in throughfall, especially that of C. japonica, than bulk precipitation. Enrichment ratios (ERs: ratios of metal concentrations in throughfall to those in bulk precipitation) ranged from 2.5 (Zn) to 5.3 (Ag) (3.9 on average), and ERs for slightly soluble metals were generally higher than those for easily soluble metals. Concentrations of Mn, Fe, Cu, and Zn accounted for 99% of the total concentration of heavy metals in rainwater, whereas those of rare metals such as Ag, In, Sn, and Bi totaled <0.23%. Average concentrations of rare metals were 0.002 and 0.010 μg l -1 for Ag, 0.001 and 0.005 μg l -1 for In, 0.062 and 0.21 μg l -1 for Sn, and 0.006 and 0.023 μg l -1 for Bi in bulk precipitation and throughfall, respectively. The metal concentrations in rainwater were negatively correlated to the volume of rainwater, indicating that washout is the main mechanism that incorporates metals into rainwater. From the enrichment factors, that is, (X/Al) rain/(X/Al) crust, metals other than Fe were shown to be more enriched in rainwater than in the Earth's crust, including those present as a result of leaching from soil dust (Mn) and from anthropogenic sources (Cu, Zn, Ag, In, Sn, Sb, and Bi).

Potential human health risk from consumption of metallic elements-contaminated benthic mollusks from Don Hoi Lot sandbar, Thailand.

PubMed

Khidkhan, Kraisiri; Imsilp, Kanjana; Poapolathep, Amnart; Poapolathep, Saranya; Tanhan, Phanwimol

2017-04-15

Environmental pollutants have raised more concerns for human health risk, especially via consumption of contaminated food. Terrestrial as well as aquatic animals are capable of bioaccumulation a variety of toxic substances including metallic elements. With increasing anthropogenic activities along the coastal areas, living organisms have more chances to be exposed to released contaminants. In this study, seven metallic elements (Cd, Cu, Fe, Mn, Ni, Pb and Zn) were determined in sediments and water from Don Hoi Lot sandbar, Samutsongkharm province, Thailand. Potential human health risks via the consumption of two benthic bivalves Solen corneus (Larmarck, 1818) and Meretrix meretrix (Linnaeus, 1758) were also estimated using the target hazard quotients (THQs). The variations of metallic element concentrations were apparent between wet and dry season. Fe was the predominate metallic element in the sediment and the remaining were Mn>Pb>Zn>Ni>Cu>Cd. Whereas metallic element concentrations in water were Pb>Ni>Fe>Zn>Cu>Mn>Cd. PCA analysis confirmed that the contaminations of these metallic elements were from Mae Klong river surface water. Most Pb THQ values in both S. corneus and M. meretrix were >1 indicating that human health risk is of concern. However, the sum of THQs of an individual metallic element should also be considered since multiple metallic elements exposure is so common. Copyright © 2017 Elsevier B.V. All rights reserved.

Changes in zinc speciation with mine tailings acidification in a semi-arid weathering environment

PubMed Central

Hayes, Sarah M.; O’Day, Peggy A.; Webb, Sam M.; Maier, Raina M.; Chorover, Jon

2011-01-01

High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semi-arid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6,000 to 450 mg kg−1) and plant-available (590 to 75 mg kg−1) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and micro-focused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn0.8talc), Zn sorbed to ferrihydrite (ZnadsFeOx), and zinc sulfate (ZnSO4·7H2O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly-crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Micro-scale analyses identified hetaerolite (ZnMn2O4), hemimorphite (Zn4Si2O7(OH)2·H2O) and sphalerite (ZnS) as minor phases. Bulk and micro-focused spectroscopy complement the chemical extraction results and highlight the importance of using a multi-method approach to interrogate complex tailings systems. PMID:21761897

Relationship between gonad maturation and heavy metal accumulation in the clam, Galatea paradoxa (Born 1778) from the Volta estuary, Ghana.

PubMed

Adjei-Boateng, D; Obirikorang, K A; Amisah, S; Madkour, H A; Otchere, F A

2011-12-01

The relationship between gonadal development and the concentrations of four heavy metals Mn, Zn, Fe and Hg in the tissues of the clam Galatea paradoxa was evaluated at the Volta estuary, Ghana, over an 18-month period. Metal concentrations in the clam tissues were highly variable over the sampling period and seemed to be influenced by the reproductive cycle of the clam. Mn concentrations varied over a wide range from 49 to 867 μg/g and exhibited a significant positive correlation with gonadal development (p = 0.0146, r(2) = 0.3190). Zn and Fe concentrations ranged from 13 to 59 μg/g and 79 to 484 μg/g, respectively and both revealed negative relationships between gonad development and metal accumulation (Zn (p = 0.0554, r(2) = 0.0554) and Fe (p = 0.1040, r(2) = 0.1567)). Hg concentrations ranged from 0.026 to 0.059 μg/g over the sampling period and exhibited a slight positive relationship between gonadal development and metal accumulation (p = 0.0861, r(2) = 0.1730).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Zongchao; Wang, Fengqin, E-mail: wangfengqin@tjpu.edu.cn; Lin, Xiangyi

Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)–based metal-organic frameworks, Zn{sub 3}L{sub 3}(DMF){sub 2} (1) and Zn{sub 3}L{sub 3}(DMA){sub 2}(H{sub 2}O){sub 3} (2) (L=4,4′-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe{sup 3+} and Al{sup 3+} by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significantmore » fluorescence quenching effect for Fe{sup 3+}. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity. - Graphical abstract: Two MOFs have been selected as the fluorescence sensing materials for selectively sensing mitroaromatic compounds and metal ions. The high selectivity makes them promising fluorescence sensors for detecting and recognizing nitroaniline and Fe{sup 3+} or Al{sup 3+}.« less

Relationship between air pollution and metal levels in cancerous and non-cancerous lung tissues.

PubMed

Binkowski, Łukasz J; Rogoziński, Paweł; Błaszczyk, Martyna; Semla, Magdalena; Melia, Patrick M; Stawarz, Robert

2016-12-05

We aimed to check the relationships between levels of metals (Ca, Cd, Cu, Fe, Hg and Zn) in cancerous and non-cancerous lung tissues and their link to air pollution, expressed as particulate matter (PM) concentrations. The study also examines the influence on metal concentration in the lung tissue of patients' sex and the distance of their homes from the nearest emitter. We found that the general pattern of ascending concentrations in tumor tissue was as follows: Hg < Cd < Cu < Ca < Zn < Fe. In non-affected lung tissue the order of concentrations of Ca and Fe was reversed. With the exception of Cd and Cu, levels of metals were found in higher accumulations in non-cancerous tissue (e.g., Fe 326.423 and Ca 302.730 μg/g d.w) than in tumorous tissue (Fe 150.735 and Ca 15.025 μg/g d.w). Neither the PM10 (PM of a diameter of 10 μm) concentration nor sex revealed any connection with metal concentrations. The shorter the distance from the emitter, the higher the metal concentrations that tended to be observed for almost all metals, but a statistically significant (but weak) relationship was noted only for Cu in tumor tissue (r s : -0.4869).

CO2 and vitamin B12 interactions determine bioactive trace metal requirements of a subarctic Pacific diatom.

PubMed

King, Andrew L; Sañudo-Wilhelmy, Sergio A; Leblanc, Karine; Hutchins, David A; Fu, Feixue

2011-08-01

Phytoplankton growth can be limited by numerous inorganic nutrients and organic growth factors. Using the subarctic diatom Attheya sp. in culture studies, we examined how the availability of vitamin B(12) and carbon dioxide partial pressure (pCO(2)) influences growth rate, primary productivity, cellular iron (Fe), cobalt (Co), zinc (Zn) and cadmium (Cd) quotas, and the net use efficiencies (NUEs) of these bioactive trace metals (mol C fixed per mol cellular trace metal per day). Under B(12)-replete conditions, cells grown at high pCO(2) had lower Fe, Zn and Cd quotas, and used those trace metals more efficiently in comparison with cells grown at low pCO(2). At high pCO(2), B(12)-limited cells had ~50% lower specific growth and carbon fixation rates, and used Fe ~15-fold less efficiently, and Zn and Cd ~3-fold less efficiently, in comparison with B(12)-replete cells. The observed higher Fe, Zn and Cd NUE under high pCO(2)/B(12)-replete conditions are consistent with predicted downregulation of carbon-concentrating mechanisms. Co quotas of B(12)-replete cells were ∼5- to 14-fold higher in comparison with B(12)-limited cells, suggesting that >80% of cellular Co of B(12)-limited cells was likely from B(12). Our results demonstrate that CO(2) and vitamin B(12) interactively influence growth, carbon fixation, trace metal requirements and trace metal NUE of this diatom. This suggests the need to consider complex feedback interactions between multiple environmental factors for this biogeochemically critical group of phytoplankton in the last glacial maximum as well as the current and future changing ocean.

Trace metals in sediments of two estuarine lagoons from Puerto Rico.

PubMed

Acevedo-Figueroa, D; Jiménez, B D; Rodríguez-Sierra, C J

2006-05-01

Concentrations of As, Cd, Cu, Fe, Hg, Pb and Zn were evaluated in surface sediments of two estuaries from Puerto Rico, known as San José Lagoon (SJL) and Joyuda Lagoon. Significantly higher concentrations in microg/g dw of Cd (1.8 vs. 0.1), Cu (105 vs. 22), Hg (1.9 vs. 0.17), Pb (219 vs. 8), and Zn (531 vs. 52) were found in sediment samples from SJL when compared to Joyuda Lagoon. Average concentrations of Hg, Pb, and Zn in some sediment samples from SJL were above the effect range median (ERM) that predict toxic effects to aquatic organisms. Enrichments factors using Fe as a normalizer, and correlation matrices showed that metal pollution in SJL was the product of anthropogenic sources, while the metal content in Joyuda Lagoon was of natural origins. Sediment metal concentrations found in SJL were comparable to aquatic systems classified as contaminated from other regions of the world.

Distribution of metal concentrations in sediments of the coastal zone of the Gulf of Riga and open part of the Baltic Sea

NASA Astrophysics Data System (ADS)

Seisuma, Z.; Kulikova, I.

2012-11-01

The comparison of spatial and temporal distribution of Hg, Cd, Pb, Cu, Ni, Zn, Mn and Fe concentrations in sediments from the Gulf of Riga and open Baltic Sea along the coastal zone is presented for the first time. There were considerable differences in Pb, Zn, Mn and Fe levels in sediment at various stations of the Gulf of Riga. A significant difference of Cd, Pb, Cu, Ni, Zn levels was found in sediments of various stations in the open Baltic coast. The amount of Cd, Pb, Cu, Ni, Zn and Fe levels also differed significantly in the sediments of the Gulf of Riga in different years. A considerable yearly difference in amount of Hg, Cd, Pb, Cu, Ni and Mn levels was found in sediments in the open Baltic coast. The essential highest values of Pb and Zn in coastal sediments of the open Baltic Sea are stated in comparison with the Gulf of Riga. The concentrations of other metals have only a tendency to be higher in coastal sediments of the open Baltic Sea in comparison with the Gulf of Riga. Natural and anthropogenic factors were proved to play an important role in determining resultant metals concentrations in the regions.

Electromigration of Mn, Fe, Cu and Zn with citric acid in contaminated clay.

PubMed

Pazos, M; Gouveia, S; Sanroman, M A; Cameselle, C

2008-07-01

Metal reactivity, speciation and solubility have an important influence in its transportation through a porous matrix by electrokinetics and, therefore, they dramatically affect the removal efficiency. This work deals with the effect of solubility and transport competition among several metals (Mn, Fe, Cu and Zn) during their transport through polluted clay. The unenhancement electrokinetic treatment results in a limited removal of the tested metals because they were retained into the kaolinite sample by the penetration of the alkaline front. Metals showed a removal degree in accordance with the solubility of the corresponding hydroxide and its formation pH. In 7 days of treatment, the removal results were: 75.6% of Mn; 68.5% of Zn, 40.6% of Cu and 14.8% of Fe. In order to avoid the negative effects of the basic front generated at the cathode, two different techniques were proposed and tested: the addition of citric acid as complexing agent to the polluted kaolinite sample and the use of citric acid to control de pH on the cathode chamber. Both techniques are based on the capability of citric acid to act as a complexing and neutralizing agent. Almost complete removal of Mn, Cu and Zn was achieved when citric acid was used (as neutralizing or complexing agent). But Fe only reached 33% of removal because it formed a negatively charged complex with citrate that retarded its transportation to the cathode.

The effects of railway transportation on the enrichment of heavy metals in the artificial soil on railway cut slopes.

PubMed

Chen, Zhaoqiong; Wang, KeXiu; Ai, Ying Wei; Li, Wei; Gao, Hongying; Fang, Chen

2014-02-01

Heavy metal contamination in the artificial soils on the railway cut slopes may have great influence on the revegetation of the cut slopes. The purpose of this study was to assess the variation of heavy metal contamination levels with railway operation time and analyze their possible resources. A total of 100 soil samples from four cut slopes, which were affected by railway transportation for different years, were analyzed for metal pollution (Cd, Pb, Cr, Cu, Zn, Fe). The concentrations of Cd, Pb showed increasing trend with increasing operation time of railways, while such trend was not found in Cr, Cu, Zn, Fe. According to the soil quality standard of China, Cd was considered to have considerable contamination, while Pb has less, but Cr, Cu, Zn, Fe have none. Moreover, cadmium exhibited remarkably higher levels rather than those reported in other studies. Enrichment factors and ecological index showed that Cd and Pb showed a moderate enrichment and a considerable ecological risk in most of the soil samples. The results of descriptive statistic, principal component analysis, cluster analysis and correlation analysis were totally consistent with each other. Their results revealed that Cr, Cu, Zn and Fe had common origins, and they may come from natural resources. While Cd and Pb were significantly influenced by railway transportation, leaked cargos, fuel combustion, the use of lubricate oils and sleeper impregnation oils during railway transportation may be their main resources.

Synergistic effect of biogenic Fe3+ coupled to S° oxidation on simultaneous bioleaching of Cu, Co, Zn and As from hazardous Pyrite Ash Waste.

PubMed

Panda, Sandeep; Akcil, Ata; Mishra, Srabani; Erust, Ceren

2017-03-05

Pyrite ash, a waste by-product formed during roasting of pyrite ores, is a good source of valuable metals. The waste is associated with several environmental issues due to its dumping in sea and/or land filling. Although several other management practices are available for its utilization, the waste still awaits and calls for an eco-friendly biotechnological application for metal recovery. In the present study, chemolithotrophic meso-acidophilic iron and sulphur oxidisers were evaluated for the first time towards simultaneous mutli-metal recovery from pyrite ash. XRD and XRF analysis indicated higher amount of Hematite (Fe 2 O 3 ) in the sample. ICP-OES analysis indicated concentrations of Cu>Zn>Co>As that were considered for bioleaching. Optimization studies indicated Cu - 95%, Co - 97%, Zn - 78% and As - 60% recovery within 8days at 10% pulp density, pH - 1.75, 10% (v/v) inoculum and 9g/L Fe 2+ . The productivity of the bioleaching system was found to be Cu - 1696ppm/d (12% dissolution/d), Co - 338ppm/d (12.2% dissolution/d), Zn k 576ppm/d (9.8% dissolution/d) and As - 75ppm/d (7.5% dissolution/d). Synergistic actions for Fe 2+ - S° oxidation by iron and sulphur oxidisers were identified as the key drivers for enhanced metal dissolution from pyrite ash sample. Copyright © 2016 Elsevier B.V. All rights reserved.

Biogeochemistry of Metals in Periodic Cicada

NASA Astrophysics Data System (ADS)

Robinson, G. R.; Sibrell, P. L.; Boughton, C. J.; Yang, L. H.; Hancock, T. C.

2005-05-01

Metal concentrations were measured in three species of 17-year periodic cicadas (Magicicada spp.) to determine the bioavailability of metals from both uncontaminated and lead-arsenate-pesticide contaminated soils and evaluate whether these metal concentrations might threaten wildlife. Collections were made in Clarke and Frederick Counties, Virginia and Berkeley and Jefferson Counties, West Virginia during Brood X emergence in May and June 2004. Periodic cicadas emerge synchronously at high density after 13 or 17 years of underground development, feeding on xylem fluids, and molt into their adult form leaving a keratin exoskeleton shell. They are an important food source for birds and animals during emergence events, and influence nutrient cycles in woodland settings. Soil concentrations at the collection sites vary over one order of magnitude for Co, Cu, Fe, Hg, Mn, Mo, Se, and Zn and over two orders of magnitude for As, Au, and Pb. The concentration levels of metals in adult periodic cicadas do not pose a dietary threat to birds and other wildlife that preferentially feed upon cicadas during emergence events. The adult cicadas contain concentrations of metals similar to, or less than, other invertebrates, such as earthworms. Average adult cicada body concentrations for As, Cu, Hg, Pb, and Zn are 3, 64, 0.015, 0.4, and 160 mg/Kg (dry weight), respectively. Much of the cicada nymph body load of metals is partitioned into the molt exoskeleton. Elements, such as Al, Fe, and Pb, are strongly enriched in the exoskeleton relative to the adult body; Cu and Zn are enriched in bodies. Concentrations of Fe, Co, and Pb, when normalized to inert soil constituents such as aluminum and cerium, are similar between the molt exoskeleton and their host soil, implying that passive assimilation through prolonged soil contact (adhesion or adsorption) may control these metal concentrations. Normalized concentrations of bioessential elements, such as S, P, K, Ca, Mn, Cu, Zn, and Mo, and chalcophile (sulfur-loving) elements, such as As, Se, and Au, show strong enrichment in cicada tissues relative to soil, implying selective absorption by xylem fluids and/or cicada nymph during development. Chalcophile elements, such as As and heavy metals, accumulate in keratin-rich tissues and may bind to sulfhydryl groups. Metal concentrations in exoskeleton show a positive correlation with soil metal concentrations. Metal concentrations in adult bodies do not correlate with soil chemistry, but bioessential elements S, Mn, Fe, and Zn show differences by sex and Cu and Zn by species.

Heavy metals in bark of Pinus massoniana (Lamb.) as an indicator of atmospheric deposition near a smeltery at Qujiang, China.

PubMed

Kuang, Yuan Wen; Zhou, Guo Yi; Da Wen, Zhi; Liu, Shi Zhong

2007-06-01

Rapid urbanization and the expansion of industrial activities in the past several decades have led to large increases in emissions of pollutants in the Pearl River Delta of south China. Recent reports have suggested that industrial emission is a major factor contributing to the damages in current natural ecosystem in the Delta area. Tree barks have been used successfully to monitor the levels of atmospheric metal deposition in many areas, but rarely in China. This study aimed at determining whether atmospheric heavy metal deposition from a Pb-Zn smeltery at Qujiang, Guangdong province, could be accurately reflected both in the inner bark and the outer bark of Masson pine (Pinus massoniana L.). The impact of the emission from smeltery on the soils beneath the trees and the relationships of the concentrations between the soils and the barks were also analyzed. Barks around the bole of Pinus massoniana from a pine forest near a Pb-Zn smeltery at Qujiang and a reference forest at Dinghushan natural reserve were sampled with a stainless knife at an average height of 1.5 m above the ground. Mosses and lichens on the surface barks were cleaned prior to sampling. The samples were carefully divided into the inner bark (living part) and the outer bark (dead part) in the laboratory, and dried and ground, respectively. After being dry-ashed, the powder of the barks was dissolved in HNO3. The solutions were analyzed for iron (Fe), manganese (Mn), copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni) and cobalt (Co) by inductively coupled plasmas emission spectrometry (ICP, PS-1000AT, USA) and Cadmium (Cd) and lead (Pb) by graphite furnace atomic absorption spectrometry (GFAAS, ZEENIT 60, Germany). Surface soils (0-10 cm) beneath the sample trees were also collected and analyzed for the selected metals. Concentrations of the selected metals in soils at Qujiang were far above their environmental background values in the area, except for Fe and Mn, whilst at Dinghushan, they were far below their background values, except for Cd and Co. Levels of the metals, in particular Pb and Zn, in the soils beneath the sample trees at Qujiang were higher than those at Dinghushan with statistical significance. The result suggested that the pine forest soils at Qujiang had a great input of heavy metals from wet and dry atmospheric deposition, with the Pb-Zn smeltery most probably being the source. Levels of Cu, Fe, Mn, Zn, Ni and Pb at Qujiang, both in the inner and the outer bark, were statistically higher than those at Dinghushan. Higher concentrations of Pb, Fe, Zn and Cu may come from the stem-flow of elements leached from the canopy, soil splash on the 1.5 m height and sorption of metals in the mosses and lichens growing on the bark, which were direct or indirect results from the atmospheric deposition. Levels of heavy metals in the outer barks were associated well with the metal concentrations in the soil, reflecting the close relationships between the metal atmospheric deposition and their accumulation in the outer bark of Masson pine. The significant (p<0.01) correlations of Fe-Cu, Fe-Cr, Fe-Pb, Fe-Ni, Pb-Ni, and Pb-Zn in the outer barks at Qujiang again suggested a common source for the metals. The correlation only occurred between Pb and Ni, Cd and Co in the outer barks at Dinghushan, which suggested that those metals must possibly have other uncommon sources. Atmospheric deposition of the selected metals was great at Qujiang, based on the levels in the bark of Pinus massoniana and on the concentrations in the soils beneath the trees compared with that at Dinghushan. Bark of Pinus massoniana, especially the outer bark, was an indicator of metal loading at least at the time of sampling. The results from this study and the techniques employed constituted a new contribution to the development of biogeochemical methods for environmental monitoring particularly in areas with high frequency of pollution in China. The method would be of value for follow up studies aimed at the assessment of industrial pollution in other areas similar with the Pearl River Delta.

Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules.

PubMed

Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; Bae, Seong Hee; Hong, Seungwoo; Cho, Kyung-Bin; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

2015-07-20

Redox-inactive metal ions play important roles in tuning chemical properties of metal-oxygen intermediates. Herein we report the effect of water molecules on the redox properties of a nonheme iron(III)-peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn(2+) ion in (TMC)Fe(III) -(O2 )-Zn(CF3 SO3 )2 (1-Zn(2+) ) decreases the Lewis acidity of the Zn(2+) ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn(2+) . This further changes the reactivities of 1-Zn(2+) in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn(2+) , whereas 1-Zn(2+) coordinating two water molecules, (TMC)Fe(III) -(O2 )-Zn(CF3 SO3 )2 -(OH2 )2 [1-Zn(2+) -(OH2 )2 ], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1-Zn(2+) was converted to its corresponding iron(IV)-oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn(2+) -(OH2 )2 . The present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal-oxygen intermediates. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils.

PubMed

Kuo, S; Lai, M S; Lin, C W

2006-12-01

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.

Fahlore and Sphalerite from the Darasun Gold Deposit in the Eastern Transbaikal Region, Russia: I. Mineral Assemblages and Intergrowths, Chemical Composition, and Its Evolution

NASA Astrophysics Data System (ADS)

Lyubimtseva, N. G.; Bortnikov, N. S.; Borisovsky, S. E.; Prokofiev, V. Yu.; Vikent'eva, O. V.

2018-03-01

The mineral assemblages, mode of occurrence, and chemical compositions of coexisting fahlore and sphalerite from the Darasun gold deposit have been described. Three generations of fahlore and three generations of sphalerite have been recognized. The FeS content in sphalerite coexisting with fahlore ranges from 0.8 to 9.4 mol %. The complete solid solution series Fe-tetrahedrite-Zn-tetrahedrite-Fe-tennantite-Zn-tennantite reflected in Sb/(Sb + As) and Fe/(Fe + Zn) ratios ranging from 0 to 0.97 and from 0.07 to 1.00, respectively, with a predominant negative relationship between these ratios has been identified for the first time at the deposit. Stepped, oscillatory, and combined stepped-oscillatory growth zonings within fahlore grains and heterogeneous aggregates of fahlore have been found. Fahlore is enriched in As with respect to Sb, and Zn-tetrahedrite is followed by Fe- and Zn-tennantite from early to late generation; Zn-tetrahedrite is followed by Fe-tennantite in zoned grains and overgrown rims; sphalerite crystallized at decreased temperature and sulfur fugacity. The evolution of the chemical composition of fahlores was caused by the evolving temperature, fluid salinity, and conditions of metal migration.

Fate and Distribution of Heavy Metals in Wastewater Irrigated Calcareous Soils

PubMed Central

Stietiya, Mohammed Hashem; Duqqah, Mohammad; Udeigwe, Theophilus; Zubi, Ruba; Ammari, Tarek

2014-01-01

Accumulation of heavy metals in Jordanian soils irrigated with treated wastewater threatens agricultural sustainability. This study was carried out to investigate the environmental fate of Zn, Ni, and Cd in calcareous soils irrigated with treated wastewater and to elucidate the impact of hydrous ferric oxide (HFO) amendment on metal redistribution among soil fractions. Results showed that sorption capacity for Zarqa River (ZR1) soil was higher than Wadi Dhuleil (WD1) soil for all metals. The order of sorption affinity for WD1 was in the decreasing order of Ni > Zn > Cd, consistent with electrostatic attraction and indication of weak association with soil constituents. Following metal addition, Zn and Ni were distributed among the carbonate and Fe/Mn oxide fractions, while Cd was distributed among the exchangeable and carbonate fractions in both soils. Amending soils with 3% HFO did not increase the concentration of metals associated with the Fe/Mn oxide fraction or impact metal redistribution. The study suggests that carbonates control the mobility and bioavailability of Zn, Ni, and Cd in these calcareous soils, even in presence of a strong adsorbent such as HFO. Thus, it can be inferred that in situ heavy metal remediation of these highly calcareous soils using iron oxide compounds could be ineffective. PMID:24723833

Broiler litter as a micronutrient source for cotton: concentrations in plant parts.

PubMed

Tewolde, H; Sistani, K R; Rowe, D E

2005-01-01

Analytically, poultry litter contains nearly all essential micronutrients but the extent of phytoavailability of these nutrients and whether cotton (Gossypium hirsutum L.) and other crop plants can receive adequate amounts of these nutrients from litter is not fully known. The objective of this research was to determine whether cotton receives sufficient amounts of Fe, Cu, Mn, and Zn from litter and estimate the efficiency of cotton in extracting these metal nutrients from litter in the absence of any other source of the micronutrients. The greenhouse research used plastic pots filled with approximately 11 kg of a 2:1 (v/v) sand to vermiculite growing mix. Cotton (cv. Stoneville 474) was grown in the pots fertilized with broiler litter at rates of 30, 60, 90, or 120 g pot(-1) in a factorial combination with four supplemental nutrient solution (NS) treatments. The nutrient solutions consisted of full Hoagland's nutrient solution (NS-full); a solution of the macronutrients N, P, K, Ca, and Mg (NS-macro); a solution of the micronutrients Fe, Zn, Mn, Cu, B, and Mo (NS-micro); and water (NS-none). Based on tissue nutrient analysis, a one-time broiler litter application supplied adequate amounts of Fe, Cu, and Mn to bring the concentration of these nutrients in upper leaves within published sufficiency ranges. Zinc, with <17 mg kg(-1) concentration in the upper leaves, was the only micronutrient below the established sufficiency range regardless of the rate of applied litter. Cotton extracted Fe and Mn more efficiently than Cu or Zn, removing as much as 8.8% of Fe and 7.2% of Mn supplied by 30 g litter pot(-1). In contrast, the extraction efficiency was 1.7% for Cu and 1.9% for Zn. Roots accumulated 58% of the total absorbed Fe and 64% of Cu, and leaves accumulated 32% of the Fe and only 13% of the Cu supplied by litter. In contrast, only 16% of the total absorbed Mn and 23% of Zn accumulated in roots while leaves accumulated 64% of the total Mn and 37% of Zn. These results demonstrate that broiler litter is a valuable source of the metal nutrients supplying Fe, Cu, and Mn in full and Zn in part, but a very large fraction of the litter-supplied metal nutrients remained in the growing mix.

Diverse Reactivity of ECp* (E = Al, Ga) toward Low-Coordinate Transition Metal Amides [TM(N(SiMe3)2)2] (TM = Fe, Co, Zn): Insertion, Cp* Transfer, and Orthometalation.

PubMed

Weßing, Jana; Göbel, Christoph; Weber, Birgit; Gemel, Christian; Fischer, Roland A

2017-03-20

The reactivity of the carbenoid group 13 metal ligands ECp* (E = Al, Ga) toward low valent transition metal complexes [TM(btsa) 2 ] (TM = Fe, Co, Zn; btsa = bis(trimethylsilyl)amide) was investigated, revealing entirely different reaction patterns for E = Al and Ga. Treatment of [Co(btsa) 2 ] with AlCp* yields [Cp*Co(μ-H)(Al(κ 2 -(CH 2 SiMe 2 )NSiMe 3 )(btsa))] (1) featuring an unusual heterometallic bicyclic structure that results from the insertion of AlCp* into the TM-N bond with concomitant ligand rearrangement including C-H activation at one amide ligand. For [Fe(btsa) 2 ], complete ligand exchange gives FeCp* 2 , irrespective of the employed stoichiometric ratio of the reactants. In contrast, treatment of [TM(btsa) 2 ] (TM = Fe, Co) with GaCp* forms the 1:1 and 1:2 adducts [(GaCp*)Co(btsa) 2 ] (2) and [(GaCp*) 2 Fe(btsa) 2 ] (3), respectively. The tendency of AlCp* to undergo Cp* transfer to the TM center appears to be dependent on the nature of the TM center: For [Zn(btsa) 2 ], no Cp* transfer is observed on reaction with AlCp*; instead, the insertion product [Zn(Al(η 2 -Cp*)(btsa)) 2 ] (4) is formed. In the reaction of [Co(btsa) 2 ] with the trivalent [Cp*AlH 2 ], transfer of the amide ligands without further ligand rearrangement is observed, leading to [Co(μ-H) 4 (Al(η 2 -Cp*)(btsa)) 2 ] (5).

Synthesis of ferrites obtained from heavy metal solutions using wet method.

PubMed

Yang, Ji; Peng, Juan; Liu, Kaicheng; Guo, Rui; Xu, Dianliang; Jia, Jinping

2007-05-08

Wet method was employed to the treatment of heavy metal-contaminated wastewater, and Zn(x)Fe(3-x)O(4), Ni(x)Fe(3-x)O(4) and Cr(x)Fe(3-x)O(4) (0Cr(3+) and the influence of the three ions on sample thermostability is Zn(2+)>Ni(2+)>Cr(3+).

Mechanism of single metal exchange in the reactions of [M4(SPh)10]2- (M = Zn or Fe) with CoX2 (X = Cl or NO3) or FeCl2.

PubMed

Autissier, Valerie; Henderson, Richard A

2008-07-21

The kinetics of the reactions between [Zn4(SPh)10](2-) and an excess of MX2 (M = Co, X = NO3 or Cl; M = Fe, X = Cl), in which a Zn(II) is replaced by M(II), have been studied in MeCN at 25.0 degrees C. (1)H NMR spectroscopy shows that the ultimate product of the reactions is an equilibrium mixture of clusters of composition [Zn(n)M(4-n)(SPh)10](2-), and this is reflected in the multiphasic absorbance-time curves observed over protracted times (several minutes) using stopped-flow spectrophotometry to study the reactions. The kinetics of only the first phase have been determined, corresponding to the equilibrium formation of [Zn3M(SPh)10](2-). The effects of varying the concentrations of cluster, MX2, and ZnCl2 on the kinetics have been investigated. The rate law is consistent with the equilibrium nature of the metal exchange process and indicates a mechanism for the formation of [Zn3M(SPh)10](2-) involving two coupled equilibria. In the initial step binding of MX2 to a bridging thiolate in [Zn4(SPh)10](2-) results in breaking of a Zn-bridging thiolate bond. In the second step replacement of the cluster Zn involves transfer of the bridging thiolates from the Zn to M, with breaking of a Zn-bridged thiolate bond being rate-limiting. The kinetics for the reaction of ZnCl2 with [Zn3M(SPh)10](2-) (M = Fe or Co)} depends on the identity of M. This behavior indicates attack of ZnCl2 at a M-mu-SPh-Zn bridged thiolate. Similar studies on the analogous reactions between [Fe4(SPh)10](2-) and an excess of CoX2 (X = NO3 or Cl) in MeCN exhibit simpler kinetics but these are also consistent with the same mechanism.

Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

DOE PAGES

Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; ...

2016-05-30

Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al 2O 3 and α-Fe 2O 3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-hmore » exposure time, Pb(II) binds preferentially to the alpha-Al 2O 3 (1-102) and α-Fe 2O 3 (0001) surfaces at low Pb concentration ([Pb] = 10 –7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10 –6 to 10 –4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10 –7 to 10 –4 M). In comparison, the α-Al 2O 3 (0001) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al 2O 3 (0001) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al 2O 3 (1-102) and α-Fe 2O 3 (0001). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al 2O 3 (1-102) and α-Fe 2O 3 (0001) at [Me(II)] of 10 –7 M; at 10 –5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10 –5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb L-III-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be complexed by carboxyl groups in S. oneidensis biofilms after 3-h exposure at pH 6.0 and [Me(II)] = 10 –5 M. In contrast with Burkholderia cepacia, which was used in our previous studies of monolayer biofilm-coated metal-oxide surfaces (Templeton et al., 2001), S. oneidensis MR-1 forms relatively thick biofilm coatings (6-20 μm) that are rich in reactive functional groups and are expected to dominate metal-ion adsorption. Lastly, our results show that even thick and highly reactive biofilms like S. oneidensis do not cause much change in the intrinsic chemical reactivities of the underlying metal-oxide surfaces with respect to aqueous Pb(II) and Zn(II) and don't block reactive sites on the metal-oxide surfaces; instead they reduce the rate of Pb(II) and Zn(II) sorption onto these surfaces.« less

Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

NASA Astrophysics Data System (ADS)

Wang, Yingge; Gélabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Gescher, Johannes; Ona-Nguema, Georges; Eng, Peter J.; Bargar, John R.; Farges, Francois; Spormann, Alfred M.; Brown, Gordon E.

2016-09-01

Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al2O3 and α-Fe2O3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-h exposure time, Pb(II) binds preferentially to the α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) surfaces at low Pb concentration ([Pb] = 10-7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10-6 to 10-4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10-7 to 10-4 M). In comparison, the α-Al2O3 (0 0 0 1) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al2O3 (0 0 0 1) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) at [Me(II)] of 10-7 M; at 10-5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10-5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb LIII-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be complexed by carboxyl groups in S. oneidensis biofilms after 3-h exposure at pH 6.0 and [Me(II)] = 10-5 M. In contrast with Burkholderia cepacia, which was used in our previous studies of monolayer biofilm-coated metal-oxide surfaces (Templeton et al., 2001), S. oneidensis MR-1 forms relatively thick biofilm coatings (6-20 μm) that are rich in reactive functional groups and are expected to dominate metal-ion adsorption. Our results show that even thick and highly reactive biofilms like S. oneidensis do not cause much change in the intrinsic chemical reactivities of the underlying metal-oxide surfaces with respect to aqueous Pb(II) and Zn(II) and don't block reactive sites on the metal-oxide surfaces; instead they reduce the rate of Pb(II) and Zn(II) sorption onto these surfaces.

Heavy metal concentrations in roadside soil and street dust from Petra region, Jordan.

PubMed

Alsbou, Eid Musa Eid; Al-Khashman, Omar Ali

2017-12-28

Concentrations of Cd, Cu, Fe, Pb, and Zn were measured in the samples of street dust and surface roadside soil before Jordan switched to unleaded fuel usage. The samples were collected from Petra, the most tourist-attractive site in Jordan. The samples were analyzed for heavy metals by atomic absorption spectrophotometry. Our results show that the distribution of metals in the soil samples is affected by wind direction in the investigated area. The highest level of metals was found in the eastern parts of the roads due to the westerly-dominant wind in the studied area. The contamination levels of metals decrease as the distance from the edge of the road increases. In the roadside soil samples, the means for the concentrations of the metals at 1 m from the east side of the main road are 1.0, 19.1, 3791.4, 177.0, and 129.0 mg kg -1 for Cd, Cu, Fe, Pb, and Zn, respectively. In the samples of street dust, the means of the concentrations of the metals in the investigated area are 9.7, 11.8, 4694.4, 31.6, and 24.8 mg kg -1 for Cd, Cu, Fe, Pb, and Zn, respectively. In conclusion, the lithogenic origins (traffic emissions) are responsible for the diffusion of these metals in the studied region.

Spatio-Temporal Variability of Dissolved Metals in the Surface Waters of an Agroforestry Catchment with Low Levels of Anthropogenic Activity

NASA Astrophysics Data System (ADS)

Soto-Varela, Fátima; Rodríguez-Blanco, M. Luz; Mercedes Taboada-Castro, M.; Taboada-Castro, M. Teresa

2017-12-01

Evaluation of levels and spatial variations of metals in surface waters within a catchment are critical to understanding the extent of land-use impact on the river system. The aims of this study were to investigate the spatial and temporal variations of five dissolved metals (Al, Fe, Mn, Cu and Zn) in surface waters of a small agroforestry catchment (16 km2) in NW Spain. The land uses include mainly forests (65%) and agriculture (pastures: 26%, cultivation: 4%). Stream water samples were collected at four sampling sites distributed along the main course of the Corbeira stream (Galicia, NW Spain) between the headwaters and the catchment outlet. The headwater point can be considered as pristine environment with natural metal concentrations in waters because of the absence of any agricultural activity and limited accessibility. Metal concentrations were determined by ICP-MS. The results showed that metal concentrations were relatively low (Fe > Al > Mn > Zn > Cu), suggesting little influence from agricultural activities in the area. Mn and Zn did not show significant differences between sampling points along main stream, while for Fe and Cu significant differences were found between the headwaters and all other points. Al tended to decrease from the headwaters to the catchment outlet.

Evaluation of Trace Metal Profile in Cymbopogon validus and Hyparrhenia hirta Used as Traditional Herbs from Environmentally Diverse Region of Komga, South Africa

PubMed Central

Tembeni, Babalwa; Oyedeji, Adebola O.

2016-01-01

FAAS was used for the analysis of trace metals in fresh and dry plant parts of Cymbopogon validus and Hyparrhenia hirta species with the aim of determining the trace metals concentrations in selected traditional plants consumed in Eastern Cape, South Africa. The trace metal concentration (mg/kg) in the samples of dry Cymbopogon validus leaves (DCVL) showed Cu of 12.40 ± 1.000; Zn of 2.42 ± 0.401; Fe of 2.50 ± 0.410; Mn of 1.31 ± 0.210; Pb of 3.36 ± 0.401 mg/kg, while the samples of fresh Hyparrhenia hirta flowers (FHHF) gave Cu of 9.77 ± 0.610; Zn of 0.70 ± 0.200; Fe of 2.11 ± 0.200; Mn of 1.15 ± 0.080; Pb of 3.15 ± 0.100 mg/kg. Abundance of metal concentrations follows the order: Cu > Fe > Pb > Mn > Zn in the flower samples of Cymbopogon validus and Hyparrhenia hirta species. The concentrations of trace metals in both plant parts were below the permissible limits (PL) set by WHO. It is suggested that pharmacovigilance be carried out periodically to improve the quality, safety, and efficiency of various herbal products. PMID:27795868

Active Site Metal Identity Alters Histone Deacetylase 8 Substrate Selectivity: A Potential Novel Regulatory Mechanism.

PubMed

Castaneda, Carol Ann; Lopez, Jeffrey E; Joseph, Caleb G; Scholle, Michael D; Mrksich, Milan; Fierke, Carol A

2017-10-24

Histone deacetylase 8 (HDAC8) is a well-characterized member of the class I acetyl-lysine deacetylase (HDAC) family. Previous work has shown that the efficiency of HDAC8-catalyzed deacetylation of a methylcoumarin peptide varies depending on the identity of the divalent metal ion in the HDAC8 active site. Here we demonstrate that both HDAC8 activity and substrate selectivity for a diverse range of peptide substrates depend on the identity of the active site metal ion. Varied deacetylase activities of Fe(II)- and Zn(II)-HDAC8 toward an array of peptide substrates were identified using self-assembled monolayers for matrix-assisted laser desorption ionization (SAMDI) mass spectrometry. Subsequently, the metal dependence of deacetylation of peptides of biological interest was measured using an in vitro peptide assay. While Fe(II)-HDAC8 is generally more active than Zn(II)-HDAC8, the Fe(II)/Zn(II) HDAC8 activity ratio varies widely (from 2 to 150) among the peptides tested. These data provide support for the hypothesis that HDAC8 may undergo metal switching in vivo that, in turn, may regulate its activity. However, future studies are needed to explore the identity of the metal ion bound to HDAC8 in cells under varied conditions.

Metal forms in sediments from Arctic coastal environments in Kandalaksha Bay, White Sea, under separation processes

NASA Astrophysics Data System (ADS)

Koukina, S. E.; Vetrov, A. A.

2013-09-01

This study focuses on sediments from small restricted exchange environments along the Karelian shore of Kandalaksha Bay (White Sea, Russian Arctic), which are known as separating basins and are characterised by contrasting oxidising conditions within the water column and the occurrence of anoxia. In the basins that were studied, no significant contamination by trace heavy metals (Pb, Cu, Zn and Cr, in particular) was detected. The comparative study of the two most bioavailable metal forms, namely, labile (acid soluble) and organically bound (alkali soluble) forms, indicated that acetic acid and sodium pyrophosphate released 3-11% and 2-12%, respectively, of the total metal content from sediments. The most bioavailable parts of metals are weakly bound to organic matter and, to a greater extent, associated with easily soluble amorphous Fe-oxides. Among the studied elements, most of the bioavailable Zn and Cu was most likely bound to organic substances, whereas bioavailable Cr and Mn were controlled to a greater extent by the formation of Fe-oxyhydroxide. The elements studied could be arranged in the following decreasing order of average potential bioavailability: Cu > Zn > Mn > Fe > Cr > Pb. In the separating basins, the relative proportion of labile bioavailable metals is enhanced in relation to the neighbouring open coastal sea.

Physico-Chemical and Heavy Metal Profiles of Top Soils Sourced from Abandoned Lead-Zinc Mines at Enyigba, Ameri and Ameka Villages, Abakaliki District, Ebonyi State, South Eastern Nigeria

NASA Astrophysics Data System (ADS)

Osayande, D. A.; Azi, E. D.; Obayagbona, N.; Ovwasa, O. M.; Anegbe, B.

2016-12-01

Twenty (20) soil samples were collected from several abandoned old Pb - Zn mines located in Enyigba, Ameri, Ameka villages in the Abakaliki district of Ebonyi State, South-Eastern Nigeria. The soils were analyzed for Fe, Mn, Cu, Zn, Pb, Cd, Ni, Cr, V, pH, organic carbon and Electrical Conductivity using routine procedures. The physic-chemical analyses showed that pH values were generally low. The Electrical conductivity of the soils were high while organic carbon content in the soil was generally low. The heavy metal mean trend indicated that Pb (86) > Zn (64) > Cu (20) > Cd (15) > Ni (7) > Cr (6) > V (1). Fe and Mn values were also high. The variations observed for the heavy metal suggested both geogenic and anthropogenic activities were responsible for their distribution. Soil contamination was assessed on the basis of contamination factor (CF) and enrichment factor (EF). The CF values for the soil revealed moderate contamination for Ni, Cr, V, Zn and Mn, while Pb and Cd showed high contamination. The results of enrichment factor (EF) showed that using Fe concentration in the background value, Ni, Cr, V and Mn had moderate enrichment, Pb and Zn showed significant enrichment while Cd indicated high enrichment. The results of the principal component and cluster analyses showed that Zn, Cu, Cd, Pb metal originated from similar source but may have been significantly influenced by anthropogenic activities, while Ni, Cr, V were attributable to geogenic sources.

Structural investigations of transition metal (II) tetracyanonickelate complexes of 3-chloropyridine using Fourier transform-infrared and laser Raman spectroscopy

NASA Astrophysics Data System (ADS)

Akyüz, Sevim; Akyüz, Tanil; Eric, J.; Davies, D.

1992-01-01

The FT-IR and laser-Raman spectra of five new complexes of the formula ML 2Ni(CN) 4 (where MMn, Fe, Ni, Zn or Cd; L3-chloropyridine) are reported. The complexes are shown to have a structure consisting of two dimensional polymeric layers formed with Ni(CN) 4 ions bridged by ML 2 cations. For a given series of isomorphous complexes, the effects of metal ligand bond formation on the ligand vibrational modes are examined and the metal-sensitivity sequence of the ligand frequencies is found to be Mn≈Cd

Environmental impact of the gold mining industry in Ghana.

PubMed

Bamford, S A; Osae, E; Aboh, I; Biney, C A; Antwi, L A

1990-01-01

X-ray Fluorescence (XRF) Analysis and Atomic Absorption Spectrophotometry (AAS) have been used in assessing heavy metal pollution from some gold mines in Ghana. The presence and levels of heavy metals in gold ore, gold tailings, inland waters, and river sediments have been determined. Using these techniques, the heavy metals: Cr, Mn, Fe, Cu, Zn, As, Pb, Rb, Sr, Y, Zr, and Nb were identified in some of the solid samples within a concentration range of 0.08 ppm--4.9%. However, the inland waters showed the presence of only Fe and Zn at levels of 0.08-2.4 micrograms/mL.

Determination of heavy metal levels in water, sediment and tissues of tench (Tinca tinca L., 1758) from Beyşehir Lake (Turkey).

PubMed

Tekin-Ozan, Selda

2008-10-01

In the present study, some heavy metals (Cu, Fe, Zn and Mn) were seasonally determined in water, sediment and some tissues of fish Tinca tinca from Beyşehir Lake, which is an important bird nesting and visiting area, a water source for irrigation and drinking. In the water, Fe has the highest concentrations among the studied metals. Generally, the metal concentrations increased in the hottest period decreased in warm seasons. Results for levels in water were compared with national and international water quality guidelines, as well as literature data reported for the lakes. Fe was the highest in sediment samples, also Cu and Zn were the highest in spring, while Fe and Mn were in autumn. Among the heavy metals studied, Cu and Mn were below the detection limits in some tissues. Generally, higher concentrations of the tested metals were found in the summer and winter, compared with those during the autumn and spring seasons. High levels of heavy metals were found in liver of T. tinca, while low levels in muscle samples. Metal concentrations in the muscle of examined fish were within the safety permissible levels for human consumption. The present study shows that precautions need to be taken in order to prevent further heavy metal pollution.

Chthamalus montagui as biomonitor of metal contamination in the northwest coast of Portugal.

PubMed

Reis, Pedro A; Salgado, Maria Antónia; Vasconcelos, Vitor

2012-09-01

The concentrations of seven metals (Cd, Cr, Cu, Fe, Mn, Ni and Zn) were determined in coastal seawaters and soft and hard tissues of the barnacle Chthamalus montagui from the northwest coast of Portugal to assess the potential use of C. montagui as biomonitor of metal contamination. The results of this study showed that C. montagui soft tissues can be used for monitoring metal bioavailabilities in these coastal seawaters: (1) there were significant correlations (p < 0.05) between the metal concentrations in soft tissues and their concentrations in seawaters and (2) barnacle soft tissues were sensitive to spatial variation of metal bioavailabilities, accumulating different amounts of metals in different locations. The range of concentrations in tissues were: 0.59-1.7 mg Cd kg(-1), 0.5-3.2 mg Cr kg(-1), 0.72-3.0 mg Ni kg(-1), 1.2-6.7 mg Cu kg(-1), 9-26 mg Mn kg(-1), 214-785 mg Fe kg(-1) and 178-956 mg Zn kg(-1); (3) mean logarithmic bioaccumulation factors (log BAF) of Fe, Cr and Cd were higher, 5.49, 4.93 and 4.46, respectively, than mean log BAFs of Mn, Zn, Cu and Ni, 4.03, 3.97, 3.74 and 3.61, respectively. In contrary, C. montagui shell plates were not a good matrix to monitor metal bioavailability in these coastal seawaters, with no significant correlations (p < 0.05) between metal concentrations in the shell and in seawater. Regarding the high Zn concentrations obtained in the coastal seawaters and C. montagui soft tissues, all seawaters from northwest coast of Portugal should be classified as "moderately/remarkably polluted".

Heavy metals distribution in the coral reef ecosystems of the Northern Red Sea

NASA Astrophysics Data System (ADS)

Ali, Abdel-Hamid A. M.; Hamed, Mohamed A.; Abd El-Azim, Hoda

2011-03-01

Concentrations of seven heavy metals (Cu, Zn, Pb, Cd, Ni, Co and Fe) were measured in the seawater, sediments, common scleractinian reef-building corals and soft corals (Octocorallia : Alcyonacea) at seven reef sites in the Northern Red Sea: I (Hurghada), II (Ras Za'farana), III (El-Ain Al-Sukhna), IV (El-Tur), V (Sha'b Rashdan), VI (Sharm El-Sheikh) and VII (Dahab). Levels of heavy metals were considerably elevated in seawater, sediments and corals collected from reef sites exposed to increased environmental contamination, as a result of diversified natural and anthropogenic inputs. Soft corals of genera Lithophyton, Sarcophyton and Sinularia showed higher concentrations of Zn, Pb, Cd and Ni than hard coral genera Acropora and Stylophora. Soft coral Sarcophyton trocheliophorum collected from El Ain Al-Suhkna (Gulf of Suez) had greater concentration of Cu, followed by hard corals Acropora pharaonis and Acropora hemprichi. The elevated levels of Zn, Cd and Ni were reported in the dry tissue of soft coral Sinularia spp. On the other hand, the soft coral Lithophyton arboreum displayed the highest concentration of Pb at Sha'b Rashdan (Gulf of Suez) and elevated concentration of Zn at Sharm El-Sheikh. Sediments showed significantly higher concentration of Fe than corals. The higher levels of Fe in hard corals than soft corals reflected the incorporation of Fe into the aragonite and the chelation with the organic matrix of the skeleton. The greater abundance of soft corals in metal-contaminated reef sites and the elevated levels of metals in their tissue suggesting that the soft corals could develop a tolerance mechanism to relatively high concentrations of metals. Although the effects of heavy metals on reef corals were not isolated from the possible effects of other stresses, the percentage cover of dead corals were significantly higher as the concentrations of heavy metals increased.

Heavy metal pollution of coal mine-affected agricultural soils in the northern part of Bangladesh.

PubMed

Bhuiyan, Mohammad A H; Parvez, Lutfar; Islam, M A; Dampare, Samuel B; Suzuki, Shigeyuki

2010-01-15

Total concentrations of heavy metals in the soils of mine drainage and surrounding agricultural fields in the northern part of Bangladesh were determined to evaluate the level of contamination. The average concentrations of Ti, Mn, Zn, Pb, As, Fe, Rb, Sr, Nb and Zr exceeded the world normal averages and, in some cases, Mn, Zn, As and Pb exceeded the toxic limit of the respective metals. Soil pollution assessment was carried out using enrichment factor (EF), geoaccumulation index (I(geo)) and pollution load index (PLI). The soils show significant enrichment with Ti, Mn, Zn, Pb, As, Fe, Sr and Nb, indicating inputs from mining activities. The I(geo) values have revealed that Mn (1.24+/-0.38), Zn (1.49+/-0.58) and Pb (1.63+/-0.38) are significantly accumulated in the study area. The PLIs derived from contamination factors indicate that the distal part of the coal mine-affected area is the most polluted (PLI of 4.02). Multivariate statistical analyses, principal component and cluster analyses, suggest that Mn, Zn, Pb and Ti are derived from anthropogenic sources, particularly coal mining activities, and the extreme proximal and distal parts are heavily contaminated with maximum heavy metals.

Fe, Zn, and Cd stable isotopes from the eastern tropical South Pacific from GEOTRACES cruise GP16 - Methods and data

NASA Astrophysics Data System (ADS)

Helgoe, J. M.; Townsend, E.; John, S.

2014-12-01

A new method has been developed for the rapid analysis of metal concentrations and stable isotope ratios using a prepFAST automated sample processing robot. Although concentrations and isotopes are processed separately, similar methods are used for both. Initially all seawater is acidified to pH 2. Then Nobias resin with EDTA/IDA functional groups is added to either 10mL of sample for concentrations or ~1L samples for isotopes. Fe binds to the resin at low pH, and the pH is subsequently raised to allow Zn and Cd to bind. For concentration analyses, all subsequent chemistry is automated on the prepFAST including removal of seawater, rinsing of resin, and elution of resin into acid. For isotope samples these extraction techniques are performed manually, but the subsequent purification of Fe, Zn, and Cd by anion exchange chromatography is automated using the prepFAST. With these new methods, samples from the US GEOTRACES cruise GP16, in the eastern tropical South Pacific, are being analyzed. High concentrations of dissolved Fe are observed near the continental shelf and near submarine hydrothermal vents. Interestingly, isotope data show that dissolved Fe near the continental shelf generally has a δ56Fe close to 0 ‰. This δ56 Fe signature is suggestive of a non-reductive dissolution source for Fe, as Fe(II) released by reductive dissolution is typically closer to -2 ‰. Preliminary data show nutrient-type profiles for Zn and Cd, with Zn matching Si and Cd having a similar distribution to P. An increase in dissolved Zn near hydrothermal vents suggests a possible hydrothermal zinc source to the deep ocean. Continuing analysis of isotope data will reveal more about the source and biogeochemical cycling of these three chemically and biologically important trace metals throughout the eastern tropical Pacific Ocean.

Understanding the role of iron in the magnetism of Fe doped ZnO nanoparticles.

PubMed

Beltrán, J J; Barrero, C A; Punnoose, A

2015-06-21

The actual role of transition metals like iron in the room temperature ferromagnetism (RTFM) of Fe doped ZnO nanoparticles is still an unsolved problem. While some studies concluded that the Fe ions participate in the magnetic interaction, others in contrast do not believe Fe to play a direct role in the magnetic exchange interaction. To contribute to the understanding of this issue, we have carefully investigated the structural, optical, vibrational and magnetic properties of sol-gel synthesized Zn1-xFexO (0 < x < 0.10) nanoparticles. No Fe(2+) was detected in any sample. We found that high spin Fe(3+) ions are substitutionally incorporated at the Zn(2+) in the tetrahedral-core sites and in pseudo-octahedral surface sites in ZnO. Superficial OH(-) was observed in all samples. For x ≤ 0.03, an increment in Fe doping concentration decreased a and c lattice parameters, average Zn-O bond length, average crystallite size and band gap; while it increased the degree of distortion and quadrupole splitting. Undoped ZnO nanoparticles exhibited very weak RTFM with a saturation magnetization (Ms) of ∼0.47 memu g(-1) and this value increased to ∼2.1 memu g(-1) for Zn0.99Fe0.01O. Very interestingly, the Ms for Zn0.99Fe0.01O and Zn0.97Fe0.03O increased by a factor of about ∼2.3 by increasing annealing for 1 h to 3 h. For x ≥ 0.05, ferrimagnetic disordered spinel ZnFe2O4 was formed and this phase was found to become more ordered with increasing annealing time. Fe does not contribute directly to the RTFM, but its presence promoted the formation of additional single charged oxygen vacancies, zinc vacancies, and more oxygen-ended polar terminations at the nanoparticle surface. These defects, which are mainly superficial, altered the electronic structure and are considered as the main sources of the observed ferromagnetism.

Distribution of heavy metals in road dust along an urban-rural gradient in Massachusetts

NASA Astrophysics Data System (ADS)

Apeagyei, Eric; Bank, Michael S.; Spengler, John D.

2011-04-01

Human exposures to particulate matter emitted from on-road motor vehicles include complex mixtures of metals from tires, brakes, parts wear and resuspended road dust. The aim of this study was to assess road dust for metals associated with motor vehicle traffic, particularly those metals coming from brake and tire wears. We hypothesized that the road dust would show significant difference in both composition and concentration by traffic type, road class and by location. X-ray fluorescence (XRF) analyses of 115 parked car tires showed Zn and Ca were likely associated with tire wear dust. XRF results of three used brake pads indicated high concentrations of Fe, Ti, Cu, Ba, Mo and Zr. To assess heavy metal exposures associated with tires and brake wear adjacent to roads of varying traffic and functional classes, 85 samples of road dust were collected from road surfaces adjacent to the curb and analyzed by XRF. Median concentrations for Fe, Ca and K were greater than Ti (1619 ppm), with concentration ratios of Fe: Ca: K: Ti [16:5:3:1]. Cumulative frequency distribution graphs showed distribution of Fe, Ba, Cu, and Mo were similar regardless of road traffic rating. However, Zn, Ti, and Zr varied significantly ( p < 0.05) with traffic ratings of roadways (heavy > moderate > low traffic). Fe, Ba, Cu, and Mo also had similar distributions regardless of road class while composition of Zn, Ti, and Zr varied significantly across road class ( p < 0.05) (Major roads > Minor roads > highway). In comparing urban road dust to rural road dust, we observed Fe, Ca, K, and Ti were significantly greater in urban road dust ( p < 0.05). In urban road dust the Fe: Ca: K: Ti relationship with median Ti of 2216 ppm was 12: 6: 3.5: 1. These results indicate that roadway dust may be important sources of metals for runoff water and localized resuspended particulate matter.

Automobile shredded residue valorisation by hydrometallurgical metal recovery.

PubMed

Granata, Giuseppe; Moscardini, Emanuela; Furlani, Giuliana; Pagnanelli, Francesca; Toro, Luigi

2011-01-15

The aim of this work was developing a hydrometallurgical process to recover metals from automobile shredded residue (or car fluff). Automobile shredded residue (ASR) was characterised by particle size distribution, total metal content and metal speciation in order to guide the choice of target metals and the operating conditions of leaching. Characterisation results showed that Fe is the most abundant metal in the waste, while Zn was the second abundant metal in the fraction with diameter lower than 500 μm. Sequential extractions denoted that Zn was easily extractable by weak acid attack, while Fe and Al required a strong acid attack to be removed. In order to recover zinc from <500 μm fraction leaching tests were operated using acetic acid, sulphuric acid and sodium hydroxide at different concentrations. Sulphuric acid determined the highest zinc extraction yield, while acetic acid determined the highest zinc extractive selectivity. Sodium hydroxide promoted an intermediate situation between sulphuric and acetic acid. Zn recovery by electro winning using acetic leach liquor determined 95% of Zn electro deposition yield in 1h, while using sulphuric leach liquor 40% yield in 1h and 50% yield in 2h were obtained. Simulation results showed that the sulphuric leaching process was more attractive than acetic leaching process. Copyright © 2010 Elsevier B.V. All rights reserved.

TRACE METAL CONTENT (Cu, Zn, Mn AND Fe) IN URTICA DIOICA L. AND PLANTAGO MAJOR L.

PubMed

Krolak, Elzbieta; Raczuk, Jolanta; Borkowska, Lidia

2016-11-01

The aim of the study was to compare the contents of Cu, Zn, Mn and Fe in the washed and unwashed leaves and roots of two plant species: Urica dioica L. and Plantago major L., used in herbal medicine. These two herb species occur in the same environmental habitats, yet their morphological structure is different. The soil and plant samples for analyses were collected from an uncontaminated area in Eastern Poland. In each habitat location, the samples were taken from sandy soils with slightly acidic and neutral pH values. The obtained results showed that U. dioica and P. major accumulated similar amounts of trace metals, such as: Cu, Zn and Fe, in leaves, despite the differences in the morphological structure of their overground parts. The content of Mn in leaves U. dioica was about twice as much as in P. major. Also, no differences in the metal content were observed between washed and unwashed leaves of both species. However, in the same habitat conditions, a significantly higher content of Cu, Zn and Mn was found in the roots of P. major than U. dioica. The content of Fe in the roots was similar in both species. P. major and U. dioica may be a valuable source of microelements, if they are obtained from unpolluted habitats.

Heavy metal accumulation by Corchorus olitorius L. irrigated with wastewater.

PubMed

Ahmed, Dalia A; Slima, Dalia F

2018-05-01

Many agricultural soils in Egypt irrigated with untreated wastewater. Herein, we investigated the effect of untreated industrial wastewater irrigation on the soil and fodder plant Corchorus olittorius (Jew mallow). It also aimed to assess its effect on the growth measurements as well as analyses of soils, irrigation waters, and plants for heavy metal and nutrient concentrations. Significant differences between irrigation waters and soil irrigated with fresh and wastewater were recognized. Wastewater irrigation leads to remarkable reduction in the growth parameters and reduced its vegetative biomass. The concentration of Pb, Cd, Cr, Cu, Fe, and Zn were high significant and above phytotoxic concentrations in leaves (edible part) and roots of wastewater-irrigated plant. The present study indicated that Jew mallow plant tends to phytostabilize (Cd, Ni, and Mn) in its root and had the ability to translocate (Pb, Cu, Cr, Fe, and Zn) to its leaves. Higher concentrations of Cd, Cu, Cr, Pb, Fe, Mn, Ni, and Zn in the roots than leaves indicate that the roots are hyper-accumulators for Pb, Cr, Cu, Fe, and Zn more than the leaves. The research study recommended that there is a need to protect the soil from contamination through regular monitoring and not to cultivate Jew mallow in wastewater-irrigated soil and that it had a high capacity to accumulate heavy metals in its edible part and causes several harmful health effects for consumers.

Elemental composition of current automotive braking materials and derived air emission factors

NASA Astrophysics Data System (ADS)

Hulskotte, J. H. J.; Roskam, G. D.; Denier van der Gon, H. A. C.

2014-12-01

Wear-related PM emissions are an important constituent of total PM emissions from road transport. Due to ongoing (further) exhaust emission reduction wear emissions may become the dominant PM source from road transport in the near future. The chemical composition of the wear emissions is crucial information to assess the potential health relevance of these PM emissions. Here we provide an elemental composition profile of brake wear emissions as used in the Netherlands in 2012. In total, 65 spent brake pads and 15 brake discs were collected in car maintenance shops from in-use personal cars vehicles and analyzed with XRF for their metal composition (Fe, Cu, Zn, Sn, Al, Si, Zr, Ti, Sb, Cr, Mo, Mn, V, Ni, Bi, W, P, Pb and Co). Since car, engine and safety regulations are not nationally determined but controlled by European legislation the resulting profiles will be representative for the European personal car fleet. The brake pads contained Fe and Cu as the dominant metals but their ratio varied considerably, other relatively important metals were Sn, Zn and Sb. Overall a rather robust picture emerged with Fe, Cu, Zn and Sn together making up about 80-90% of the metals present in brake pads. Because the XRF did not give information on the contents of other material such as carbon, oxygen and sulphur, a representative selection of 9 brake pads was further analyzed by ICP-MS and a carbon and sulphur analyzer. The brake pads contained about 50% of non-metal material (26% C, 3% S and the remainder mostly oxygen and some magnesium). Based on our measurements, the average brake pad profile contained 20% Fe, 10% Cu, 4% Zn and 3% Sn as the dominant metals. The brake discs consisted almost entirely of metal with iron being the dominant metal (>95%) and only traces of other metals (<1% for individual metals). Non-metal components in the discs were 2-3% Silicon and, according to literature, ∼3% carbon. The robust ratio between Fe and Cu as found on kerbsides has been used to estimate the contribution of brake pads and brake discs to total brake wear. Based on this approach our hypothesis is that 70% of the brake wear originates from the discs and only 30% from the brake pads.

Intracellular Zn(II) Intoxication Leads to Dysregulation of the PerR Regulon Resulting in Heme Toxicity in Bacillus subtilis

PubMed Central

2016-01-01

Transition metal ions (Zn(II), Cu(II)/(I), Fe(III)/(II), Mn(II)) are essential for life and participate in a wide range of biological functions. Cellular Zn(II) levels must be high enough to ensure that it can perform its essential roles. Yet, since Zn(II) binds to ligands with high avidity, excess Zn(II) can lead to protein mismetallation. The major targets of mismetallation, and the underlying causes of Zn(II) intoxication, are not well understood. Here, we use a forward genetic selection to identify targets of Zn(II) toxicity. In wild-type cells, in which Zn(II) efflux prevents intoxication of the cytoplasm, extracellular Zn(II) inhibits the electron transport chain due to the inactivation of the major aerobic cytochrome oxidase. This toxicity can be ameliorated by depression of an alternate oxidase or by mutations that restrict access of Zn(II) to the cell surface. Conversely, efflux deficient cells are sensitive to low levels of Zn(II) that do not inhibit the respiratory chain. Under these conditions, intracellular Zn(II) accumulates and leads to heme toxicity. Heme accumulation results from dysregulation of the regulon controlled by PerR, a metal-dependent repressor of peroxide stress genes. When metallated with Fe(II) or Mn(II), PerR represses both heme biosynthesis (hemAXCDBL operon) and the abundant heme protein catalase (katA). Metallation of PerR with Zn(II) disrupts this coordination, resulting in depression of heme biosynthesis but continued repression of catalase. Our results support a model in which excess heme partitions to the membrane and undergoes redox cycling catalyzed by reduced menaquinone thereby resulting in oxidative stress. PMID:27935957

Identification of metal ion binding sites based on amino acid sequences

PubMed Central

Cao, Xiaoyong; Zhang, Xiaojin; Gao, Sujuan; Ding, Changjiang; Feng, Yonge; Bao, Weihua

2017-01-01

The identification of metal ion binding sites is important for protein function annotation and the design of new drug molecules. This study presents an effective method of analyzing and identifying the binding residues of metal ions based solely on sequence information. Ten metal ions were extracted from the BioLip database: Zn2+, Cu2+, Fe2+, Fe3+, Ca2+, Mg2+, Mn2+, Na+, K+ and Co2+. The analysis showed that Zn2+, Cu2+, Fe2+, Fe3+, and Co2+ were sensitive to the conservation of amino acids at binding sites, and promising results can be achieved using the Position Weight Scoring Matrix algorithm, with an accuracy of over 79.9% and a Matthews correlation coefficient of over 0.6. The binding sites of other metals can also be accurately identified using the Support Vector Machine algorithm with multifeature parameters as input. In addition, we found that Ca2+ was insensitive to hydrophobicity and hydrophilicity information and Mn2+ was insensitive to polarization charge information. An online server was constructed based on the framework of the proposed method and is freely available at http://60.31.198.140:8081/metal/HomePage/HomePage.html. PMID:28854211

Identification of metal ion binding sites based on amino acid sequences.

PubMed

Cao, Xiaoyong; Hu, Xiuzhen; Zhang, Xiaojin; Gao, Sujuan; Ding, Changjiang; Feng, Yonge; Bao, Weihua

2017-01-01

The identification of metal ion binding sites is important for protein function annotation and the design of new drug molecules. This study presents an effective method of analyzing and identifying the binding residues of metal ions based solely on sequence information. Ten metal ions were extracted from the BioLip database: Zn2+, Cu2+, Fe2+, Fe3+, Ca2+, Mg2+, Mn2+, Na+, K+ and Co2+. The analysis showed that Zn2+, Cu2+, Fe2+, Fe3+, and Co2+ were sensitive to the conservation of amino acids at binding sites, and promising results can be achieved using the Position Weight Scoring Matrix algorithm, with an accuracy of over 79.9% and a Matthews correlation coefficient of over 0.6. The binding sites of other metals can also be accurately identified using the Support Vector Machine algorithm with multifeature parameters as input. In addition, we found that Ca2+ was insensitive to hydrophobicity and hydrophilicity information and Mn2+ was insensitive to polarization charge information. An online server was constructed based on the framework of the proposed method and is freely available at http://60.31.198.140:8081/metal/HomePage/HomePage.html.

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

PubMed

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

Characterizing Zinc Speciation in Soils from a Smelter-Affected Boreal Forest Ecosystem.

PubMed

Hamilton, Jordan G; Farrell, Richard E; Chen, Ning; Feng, Renfei; Reid, Joel; Peak, Derek

2016-03-01

HudBay Minerals, Inc., has mined and/or processed Zn and Cu ore in Flin Flon, MB, Canada, since the 1930s. The boreal forest ecosystem and soil surrounding these facilities have been severely impacted by mixed metal contamination and HSO deposition. Zinc is one of the most prevalent smelter-derived contaminants and has been identified as a key factor that may be limiting revegetation. Metal toxicity is related to both total concentrations and speciation; therefore, X-ray absorption spectroscopy and X-ray fluorescence mapping were used to characterize Zn speciation in soils throughout the most heavily contaminated areas of the landscape. Zinc speciation was linked to two distinct soil types. Group I soils consist of exposed soils in weathered positions of bedrock outcrops with Zn present primarily as franklinite, a (ZnFeO) spinel mineral. Group II soils are stabilized by an invasive metal-tolerant grass species, with Zn found as a mixture of octahedral (Fe oxides) and tetrahedral Mn oxides) adsorption complexes with a franklinite component. Soil erosion influences Zn speciation through the redistribution of Zn and soil particulates from Group I landscape positions to Group II soils. Despite Group II soils having the highest concentrations of CaCl-extractable Zn, they support metal-tolerant plant growth. The metal-tolerant plants are probably preferentially colonizing these areas due to better soil and nutrient conditions as a result of soil deposition from upslope Group I areas. Zinc concentration and speciation appears to not influence the colonization by metal-tolerant grasses, but the overall soil properties and erosion effects prevent the revegetation by native boreal forest species. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Effects of metal ions on biomass and 5-aminolevulinic acid production in Rhodopseudomonas palustris wastewater treatment.

PubMed

Liu, Shuli; Zhang, Guangming; Li, Jianzheng; Li, Xiangkun; Zhang, Jie

2016-01-01

This work investigated the effects of eight metal ions on Rhodopseudomonas palustris growth and 5-aminolevulinic acid (ALA) yield in wastewater treatment. Results show that metal ions (Mg(2+) of 15 mmol/L, Fe(2+) of 400 μmol/L, Co(2+) of 4 μmol/L, Ni(2+) of 8 μmol/L and Zn(2+) of 4 μmol/L) could effectively improve the chemical oxygen demand (COD) removal, Rp. palustris biomass and ALA yield. The highest ALA yield of 13.1 mg/g-biomass was achieved with Fe(2+) of 400 μmol/L. ALA yields were differentially increased under different metal ions in the following order: Fe(2+) group > Mg(2+) group > Co(2+) group = Ni(2+) group > Zn(2+) group = Mo(2+) group > control. Cu(2+) and Mn(2+) inhibited Rp. palustris growth and ALA production. Mechanism analysis revealed that metal ions changed ALA yields by influencing the activities of ALA synthetase and ALA dehydratase.

PM2.5 water-soluble elements in the southeastern United States: automated analytical method development, spatiotemporal distributions, source apportionment, and implications for heath studies

NASA Astrophysics Data System (ADS)

Fang, T.; Guo, H.; Verma, V.; Peltier, R. E.; Weber, R. J.

2015-06-01

Water-soluble redox-active metals are potentially toxic due to the ability to catalytically generate reactive oxygen species (ROS) in vivo, leading to oxidative stress. As part of the Southeastern Center for Air Pollution and Epidemiology (SCAPE), we developed a method to quantify water-soluble elements, including redox-active metals, from a large number of filter samples (N = 530) in support of the Center's health studies. PM2.5 samples were collected during 2012-2013 at various sites (three urban, two rural, a near-road, and a road-side site) in the southeastern US, using high-volume samplers. Water-soluble elements (S, K, Ca, Ti, Mn, Fe, Cu, Zn, As, Se, Br, Sr, Ba, and Pb) were determined by extracting filters in deionized water and re-aerosolized for analyses by X-ray fluorescence (XRF) using an online aerosol element analyzer (Xact, Cooper Environmental). Concentrations ranged from detection limits (nominally 0.1 to 30 ng m-3) to 1.2 μg m-3, with S as the most abundant element, followed by Ca, K, Fe, Cu, Zn, and Ba. Positive Matrix Factorization (PMF) identified four factors that were associated with specific sources based on relative loadings of various tracers. These include: brake/tire wear (with tracers Ba and Cu); biomass burning (K); secondary formation (S, Se, and WSOC); and mineral dust (Ca). Of the four potentially toxic and relatively abundant metals (redox active Cu, Mn, Fe, and redox-inactive Zn), 51 % of Cu, 32 % of Fe, 17 % of Mn, and 45 % of Zn, were associated with the brake/tire factor. Mn was mostly associated with the mineral dust factor (45 %). These two factors were higher in warm (dryer) periods that favored particle re-suspension. Zn was found in a mixture of factors, with 26 % associated with mineral dust, 14 % biomass burning, and 13 % secondary formation. Roughly 50 % of Fe and 40 % of Cu was apportioned to the secondary formation factor, likely through increased solubility by sulfur-driven aerosol acidity. Linkages between sulfate and water-soluble Fe and Cu may account for some of the past observed associations between sulfate/sulfur oxide and health outcomes. For Cu, Mn, Fe, and Zn, only Fe was correlated with PM2.5 mass (r = 0.73-0.80). Overall, mobile source emissions generated through mechanical processes (re-entrained road dust, tire and break wear) and processing by secondary sulfate were major contributors to water-soluble metals known to be capable of generating ROS.

Cation Distribution and Local Configuration of Fe 2+ Ions in Structurally Nonequivalent Lattice Sites of Heterometallic Fe(II)/ M(II) ( M = Mn, Co, Ni, Cu, Zn) Diaquadiformato Complexes

NASA Astrophysics Data System (ADS)

Devillers, M.; Ladrière, J.

1993-03-01

57Fe Mössbauer investigations are carried out on a wide series of heterometallic diaquadiformato Fe(II)/ M(II) complexes with M = Mn, Co, Ni, Cu, and Zn to provide a local picture of the coordination environment of the 57Fe 2+ ions as a function of (i) the nature of the host cation and (ii) the relative amounts of both metals in the matrix (between 50 and 0.25 at.% Fe). Information is obtained on the quantitative distribution of both metals between the two structurally nonequivalent lattice sites and on the local geometry around the dopant atom in each crystal site. In the mixed Fe-Cu complexes. Fe 2+ ions are preferentially incorporated in the tetrahydrated site; in Cu-rich Fe xCu 1- x(HCO 2) 2· 2H 2O, the 57Fe 2+ ions located in the hexaformato-coordinated site are surrounded by an axially compressed octahedron of formate ligands which contrasts with the elongated configuration observed in the pure iron compound and in the other mixed systems. Semiquantitative estimations of the tetragonal field splitting and of the extent of metal-ligand interactions are proposed from the temperature dependence of the quadrupole splitting values.

Investigation of collision-induced dissociation products and structures of gas-phase [ M·GlyGlyHis-H]+ ( M = Fe, Ni, Cu, and Zn) complexes.

PubMed

Gannamani, Bharathi; Shin, Joong-Won

2017-02-01

Collision-induced dissociation is carried out for electrosprayed [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , [Cu·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + complexes. [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + yield metal-bound peptide sequence ions and dehydrated ions as primary products, whereas [Cu·GlyGlyHis-H] + generates a more extensive series of metal-bound sequence ions and a product arising from the unusual loss of a formaldehyde moiety; dehydration is significantly suppressed for this complex. Density functional theory calculations show that the copper ion-deprotonated peptide binding energy is substantially higher than those in other complexes, suggesting that there is a correlation between ion-ligand binding energy and their fragmentation behavior.

Chemical fractionation of arsenic and heavy metals in fine particle matter and its implications for risk assessment: A case study in Nanjing, China

NASA Astrophysics Data System (ADS)

Li, Huiming; Wang, Jinhua; Wang, Qin'geng; Qian, Xin; Qian, Yu; Yang, Meng; Li, Fengying; Lu, Hao; Wang, Cheng

2015-02-01

A four-step sequential extraction procedure was used to study the chemical fractionation of As and heavy metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in fine particulate matter (PM2.5) collected from Nanjing, China. The mass concentrations of most PM2.5 samples exceeded the 24 h standard (75 μg/m3) recommended by the new national ambient air quality standard of China. The most abundant elements were Fe, Zn and Pb, while As and Cd were present at the lowest concentrations. As, Cd, Cu, Mn, Pb and Zn were mostly present in the two mobile fractions, including the soluble and exchangeable fraction (F1), and carbonates, oxides and reducible fraction (F2). Fe had the highest proportion present in the residual fraction (F4). Relatively high proportions of the metals Ni and Cr were present in the oxidizable and sulfidic fraction (F3). High proportions of Zn, As and Cu and lower proportions of Cd, Cr and Fe were present in the potentially mobile phases. The enrichment factor, contamination factor and risk assessment code were calculated to analyze the main sources and assess the environmental risks of the metals in PM2.5. The carcinogenic risks of As, Cd, Ni and Pb were all lower than the accepted criterion of 10-6, whereas the carcinogenic risks of Cr for children and As and Cr for adults were higher than 10-6. The non-carcinogenic health risk of As and heavy metals because of PM2.5 exposure for children and adults were lower than but close to the safe level of 1.

Metal transport and remobilisation in a basin affected by acid mine drainage: the role of ochreous amorphous precipitates.

PubMed

Consani, Sirio; Carbone, Cristina; Dinelli, Enrico; Balić-Žunić, Tonci; Cutroneo, Laura; Capello, Marco; Salviulo, Gabriella; Lucchetti, Gabriella

2017-06-01

Metal-polluted mine waters represent a major threat to the quality of waters and sediments in a downstream basin. At the confluence between acidic mine waters and the unpolluted waters of the Gromolo Torrent (Liguria, North-West Italy), the massive formation of an ochreous amorphous precipitate takes place. This precipitate forms a soft blanket that covers the torrent bed and can be observed down to its mouth in the sea. The aim of this work is to evaluate the dispersion of metals in the Gromolo Torrent basin from the abandoned Cu-Fe sulphide mine of Libiola to the Ligurian Sea and to assess the metal remobilisation from the amorphous precipitates. The mineralogy of the superficial sediments collected in the torrent bed and the concentrations of different elements of environmental concern (Cu, Zn, Cd, Co, Cr, Mn, Ni, Pb, As, and Sb) were therefore analysed. The results showed that the precipitates contain high concentration of Fe, Al, Cu, and Zn, significantly modifying the bulk chemistry of the Gromolo Torrent sediments. In order to evaluate the possible remobilisation of ecotoxic elements from the amorphous precipitates, bulk leaching tests were performed with both deionised and seawater. Bulk leaching tests with deionised water mobilised primarily high Pb amounts, but also relatively high concentrations of Fe, Al, Cu, and Zn are released in the leachate. In seawater tests, Fe, Al, Cu, and Zn were released in smaller amounts, while other elements like Mn, Cd, Co, and Ni increased in the released fraction. Pb was still strongly released as in deionised water experiments. The results show that the interaction of precipitates and seawater can remobilise high concentrations of metals, thus affecting the surrounding environment.

The structural, magnetic and optical properties of TMn@(ZnO)42 (TM = Fe, Co and Ni) hetero-nanostructure.

PubMed

Hu, Yaowen; Ji, Chuting; Wang, Xiaoxu; Huo, Jinrong; Liu, Qing; Song, Yipu

2017-11-28

The magnetic transition-metal (TM) @ oxide nanoparticles have been of great interest due to their wide range of applications, from medical sensors in magnetic resonance imaging to photo-catalysis. Although several studies on small clusters of TM@oxide have been reported, the understanding of the physical electronic properties of TM n @(ZnO) 42 is far from sufficient. In this work, the electronic, magnetic and optical properties of TM n @(ZnO) 42 (TM = Fe, Co and Ni) hetero-nanostructure are investigated using the density functional theory (DFT). It has been found that the core-shell nanostructure Fe 13 @(ZnO) 42 , Co 15 @(ZnO) 42 and Ni 15 @(ZnO) 42 are the most stable structures. Moreover, it is also predicted that the variation of the magnetic moment and magnetism of Fe, Co and Ni in TM n @ZnO 42 hetero-nanostructure mainly stems from effective hybridization between core TM-3d orbitals and shell O-2p orbitals, and a magnetic moment inversion for Fe 15 @(ZnO) 42 is investigated. Finally, optical properties studied by calculations show a red shift phenomenon in the absorption spectrum compared with the case of (ZnO) 48 .

Selective adsorption of Pb (II) over the zinc-based MOFs in aqueous solution-kinetics, isotherms, and the ion exchange mechanism.

PubMed

Wang, Lei; Zhao, Xinhua; Zhang, Jinmiao; Xiong, Zhenhu

2017-06-01

Two series of metal-organic frameworks (MOFs) with similar formula units but different central metal ions (M) or organic linkers (L), M-BDC (BDC = terephthalate, M = Zn, Zr, Cr, or Fe), or Zn-L (L = imidazolate-2-methyl, BDC, BDC-NH 2 ), were prepared and employed as the receptors for adsorption lead ions. It was found that the Zn-BDC exhibited a much higher adsorption capacity than the other M-BDC series with various metal ions which have very closely low capacities at same conditions. Furthermore, the Zn-L (L = imidazolate-2-methyl, BDC, BDC-NH 2 ) still have highly efficient adsorption capacity of lead ions, although the adsorption capacity varies with different ligand, as well as the adsorption rate and the equilibrium pH of the solution. This significant high adsorption over Zn-L, different from other M-BDC series with various metal ions (Zr, Cr, or Fe), can be explained by ion exchange between the central metal ions of Zn-L and lead ion in solution. Based on the analysis of FT-IR, X-ray diffraction pattern, the nitrogen adsorption isotherms, the zeta potentials, and the results, a plausible adsorption mechanism is proposed. When equivalent Zn-L were added to equal volume of aqueous solution with different concentration of lead ion, the content of zinc ion in the solution increases with the increase of the initial concentration of lead ions. The new findings could provide a potential way to fabricate new metal organic frameworks with high and selective capacities of the heavy metal ions.

Synthesis of ZnFe2O4/SiO2 composites derived from a diatomite template.

PubMed

Liu, Zhaoting; Fan, Tongxiang; Zhou, Han; Zhang, Di; Gong, Xiaolu; Guo, Qixin; Ogawa, Hiroshi

2007-03-01

A novel porous ZnFe2O4/SiO2 composite product has been generated with a template-directed assembly method from porous diatomite under different synthesis conditions, such as precursor concentrations (metallic nitrates), calcination temperature and diatomite type. The phase composition and morphology of all the materials were examined by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The results indicated that an inherited hierarchical porous structure from the diatomite template can be obtained, and the synthesis conditions were found to have clear effects on the formation of the ZnFe2O4/SiO2 composite. The ideal composite of ZnFe2O4/SiO2 can be obtained through optimization of diatomite template type, precursor solution and calcination temperature. Furthermore, the adsorption abilities of two types of diatomites were analyzed in detail using FTIR spectra and nitrogen adsorption measurements etc, which proved that A-diatomite (Shengzhou-diatomite) is better than B-diatomite (Changbai-diatomite) on the aspect of adsorbing Zn and Fe ions, and of forming the ZnFe2O4.

Phase Equilibria Studies in the System ZnO-``FeO''-Al2O3-CaO-SiO2 Relevant to Imperial Smelting Furnace Slags: Part I

NASA Astrophysics Data System (ADS)

Zhao, Baojun; Hayes, Peter C.; Jak, Evgueni

2010-04-01

The phase equilibria and liquidus temperatures in the system ZnO-“FeO”-Al2O3-CaO-SiO2 in equilibrium with metallic iron have been determined experimentally in the temperature range of 1423 K to 1553 K. The experimental conditions were focused on the composition range relevant to Imperial Smelting Furnace slags. The results are presented in the form of a pseudo-ternary section ZnO-“FeO”-(CaO + SiO2 + Al2O3) in which CaO/SiO2 = 0.93 and (CaO + SiO2)/Al2O3 = 7.0. It was found that wustite and spinel are the major primary phases and that zincite and melilite are also present in the composition range investigated. Wustite (Fe2+,Zn)O and spinel (Fe2+,Zn)O (A1,Fe3+)2O3 solid solutions are formed in this system, and the ZnO concentration in the spinel phase is found to be much greater than in the liquid phase.

A synthesis of mineralization styles and geodynamic settings of the Paleozoic and Mesozoic metallic ore deposits in the Altay Mountains, NW China

NASA Astrophysics Data System (ADS)

Yang, Fuquan; Geng, Xinxia; Wang, Rui; Zhang, Zhixin; Guo, Xuji

2018-06-01

The Altay Mountains within the Xinjiang region of northwestern China hosts major metallic ore deposits. Here we review the geological characteristics, metallogenic features and tectonic settings of these deposits. The metallic ore deposits in the Altay Mountains occur mainly within four regions: North Altay, Central Altay, South Altay and Erqis. We recognize seven types of metallic ore deposits in the Altay Mountains: VMS, submarine volcanogenic iron, magmatic, skarn, pegmatite, hydrothermal vein (Cu-Zn, Fe) and orogenic gold. Among these types, the VMS, pegmatite, orogenic gold and skarn deposits are the most common. Most of the rare metal pegmatite deposits are distributed in Central Altay, with only a few in South Altay. The VMS, submarine volcanogenic type iron and skarn-type deposits are distributed in South Altay, whereas the orogenic-type gold deposits are distributed in the Erqis Fault belt. The hydrothermal vein-type deposits occur in the Erqis Fault belt and Chonghu'er Basin in South Altay. Magmatic-type deposits are mostly in the Erqis Fault belt and Central Altay. Based on isotopic age data, the VMS, submarine volcanogenic-type Fe and skarn-type Cu, Pb, Zn, Fe mineralization occurred during Early-Middle Devonian (∼410-377 Ma), orogenic-type Au, magmatic-type Cu-Ni, and a small number of skarn-type Fe, hydrothermal vein-type Cu-Zn, pegmatite-type rare-metal deposits in Early-Middle Permian (293-261 Ma), pegmatite-type rare-metal deposits, few skarn-type Fe deposit in Early-Middle Triassic (248-232 Ma), and dominantly represented by pegmatite-type rare-metal deposits in Late Triassic-Early Jurassic (223-180 Ma). The metallic ore deposits in the Altay Mountains formed in various tectonic settings, such as the Early-Middle Devonian continental arc and oceanic island arc, Early-Middle Permian post-collisional extensional setting, and Triassic-Early Jurassic intracontinental setting.

Mechanisms governing the leaching of soil metals as a result of disposal of olive mill wastewater on agricultural soils.

PubMed

Aharonov-Nadborny, R; Tsechansky, L; Raviv, M; Graber, E R

2018-07-15

Olive mill wastewater (OMWW) is an acidic, saline, and organic matter-rich aqueous byproduct of olive oil production that is usually disposed of by spreading on agricultural soils. This study tested whether spreading OMWW can release indigenous soil metals (Fe, Mn, Cu and Zn) through pH, redox, and DOM complexation-related mechanisms, using three agricultural soils having different textures and chemical properties, and controlled pH and redox conditions (pH5.6 or 8.4; ORP from -200 to +250mV). Comparison treatments included a solution having the same salt content and composition as OMWW but lacking OM, and deionized water (DW). In all three soils and under all pH and redox conditions, the model salt solution and DW treatments solubilized considerably fewer metal cations than did OMWW. Overall, the primary factor in metals release from the soils by OMWW was the DOM fraction. pH, redox and soil type played secondary but important roles in solubilization of the various metals. pH had a major impact on Mn leaching but no impact on Fe and Cu leaching. Conversely, redox did not affect Mn leaching, but lower redox conditions contributed to elevated release of both Fe and Cu. For the most part, released metals were sourced from water soluble, exchangeable, easily reducible, and moderately reducible soil metals pools. Fe, Mn and Cu released from the soils by OMWW featured mainly as metal-organic complexes, and OMWW generally caused Zn precipitation in the soils. Soils rich in clay and organic matter under reduced pH and low redox conditions released substantially more metal cations than did a sand-rich soil. Spreading OMWW may result in sequestration of essential micronutrients like Zn, and increased availability of other micronutrients such as Fe, Mn and Cu. Copyright © 2018 Elsevier B.V. All rights reserved.

Long-term variations in sediment heavy metals of a reservoir with changing trophic states: Implications for the impact of climate change.

PubMed

Wu, Qiong; Qi, Jun; Xia, Xinghui

2017-12-31

Two dated sediment cores from the Miyun Reservoir of Beijing in China were analyzed to reconstruct the pollution history of heavy metals including cadmium (Cd), chromium (Cr), iron (Fe), nickel (Ni), and zinc (Zn) as well as phosphorus (P). Enrichment factor (EF) and geoaccumulation index (I geo ) were applied to assess the enrichment status of heavy metals. Average EF and I geo values indicated that the studied heavy metals in the sediments mainly originated from non-point source pollution and soil-water erosion, showing low ecological risks. In addition, correlation analysis and principal component analysis (PCA) identified that Cd, Zn, and P were mainly from agricultural diffusion pollution caused by utilization of the phosphate fertilizer; Zn, Ni, and Cr originated from soil erosion. PCA analysis was further conducted to investigate the relationships among meteorological factors, algae-dominant total organic carbon (TOC), and heavy metals. Results showed that algae-dominant TOC had strong positive correlation with temperature, which can be explained by that increased temperature accelerated the growth of algae. Meanwhile the opposite loadings between algae-dominant TOC and heavy metal suggested that primary production played an important role in migration and transformation of metals. Moreover, stepwise multiple regression models showed that Fe was sensitive to temperature, which accounted for approximately 39.0% and 40.1% of the variations in Fe of two sediment cores, respectively. Fe showed significant decreasing trends during the past 50years. Reductive environment of water-sediment interface caused by increasing temperature probably contributed to the restoration of ferric iron, resulting in the release of soluble Fe to overlying waters. Future climate change with elevated temperature and extreme weather events will aggravate the ecological risk of heavy metals in water environment due to the enhanced leaching effect and non-point source pollution as well as the release of heavy metals from sediments to water environment. Copyright © 2017. Published by Elsevier B.V.

Portulaca grandiflora as green roof vegetation: Plant growth and phytoremediation experiments.

PubMed

Vijayaraghavan, K; Arockiaraj, Jesu; Kamala-Kannan, Seralathan

2017-06-03

Finding appropriate rooftop vegetation may improve the quality of runoff from green roofs. Portulaca grandiflora was examined as possible vegetation for green roofs. Green roof substrate was found to have low bulk density (360.7 kg/m 3 ) and high water-holding capacity (49.4%), air-filled porosity (21.1%), and hydraulic conductivity (5270 mm/hour). The optimal substrate also supported the growth of P. grandiflora with biomass multiplication of 450.3% and relative growth rate of 0.038. Phytoextraction potential of P. grandiflora was evaluated using metal-spiked green roof substrate as a function of time and spiked substrate metal concentration. It was identified that P. grandiflora accumulated all metals (Al, Cd, Cr, Cu, Fe, Ni, Pb, and Zn) from metal-spiked green roof substrate. At the end of 40 days, P. grandiflora accumulated 811 ± 26.7, 87.2 ± 3.59, 416 ± 15.8, 459 ± 15.6, 746 ± 20.9, 357 ± 18.5, 565 ± 6.8, and 596 ± 24.4 mg/kg of Al, Cd, Cr, Cu, Fe, Ni, Pb and Zn, respectively. Results also indicated that spiked substrate metal concentration strongly influenced metal accumulation property of P. grandiflora with metal uptake increased and accumulation factor decreased with increase in substrate metal concentration. P. grandiflora also showed potential to translocate all the examined metals with translocation factor greater than 1 for Al, Cu, Fe, and Zn, indicating hyperaccumulation property.

The suitability of the simplified method of the analysis of coffee infusions on the content of Ca, Cu, Fe, Mg, Mn and Zn and the study of the effect of preparation conditions on the leachability of elements into the coffee brew.

PubMed

Stelmach, Ewelina; Pohl, Pawel; Szymczycha-Madeja, Anna

2013-12-01

A fast and straightforward method of the analysis of coffee infusions was developed for measurements of total concentrations of Ca, Cu, Fe, Mg, Mn and Zn by flame atomic absorption spectrometry. Its validity was proved by the analysis of spiked samples; recoveries of added metals were found to be within 98-104% while the precision was better than 4%. The method devised was used for the analysis of re-distilled water infusions of six popular ground coffees available in the Polish market. Using the mud coffee preparation it was established that percentages of metals leached in these conditions varied a lot among analysed coffees, especially for Ca (14-42%), Mg (6-25%) and Zn (1-24%). For remaining metals, the highest extractabilities were assessed for Mn (30-52%) while the lowest for Fe (4-16%) and Cu (2-12%). In addition, it was found that the water type and the coffee brewing preparation method influence the concentration of studied metals in coffee infusions the most. Copyright © 2013 Elsevier Ltd. All rights reserved.

Heavy metals characteristics of settled particles of streets dust from Diwaniyah City- Qadisiyah Governorate - Southern Iraq

NASA Astrophysics Data System (ADS)

Al-Dabbas, Moutaz A.; Mahdi, Khalid H.; Al-Khafaji, Raad; Obayes, Kawthar H.

2018-05-01

Road-side dust samples were collected from selected areas of Diwaniyah city-Qadisiyah Governorate - Southern Iraq. The heavy metals (Fe, Co, Ni, Cu, Zn and Pb) in these streets dust samples were studied and used as indicator for pollution by using three of main indices (I-geo, CF, and PLI). Determination of heavy metal in the roadside dust is with XRD and XRF methods. I-geo for Co, Zn, Pb, and Ni in the studied sites shows relative values of class 1, which indicated the slightly polluted, while I-geo for Fe and Cu shows relative values of class 0, which indicated no pollution. The contamination factor for Co, Zn, Pb, and Ni classified as class 2, which indicate moderately contamination, while the contamination factor for Fe and Cu classified as class 1, which indicate low contamination. PLI values in the all of studied sites classified as class 2 (Deterioration on site quality) indicating local pollution, as well as denote perfection with (class 0) of no pollution. The distribution pattern of metals percentages was affected by gases emitted from transportation vehicles as well as the prevailing wind direction.

The cycling of iron, zinc and cadmium in the North East Pacific Ocean - Insights from stable isotopes

NASA Astrophysics Data System (ADS)

Conway, Tim M.; John, Seth G.

2015-09-01

Dissolved stable isotope ratios of the transition metals provide useful information, both for understanding the cycling of these bioactive trace elements through the oceans, and tracing their marine sources and sinks. Here, we present seawater dissolved Fe, Zn and Cd concentration and stable isotope ratio (δ56Fe, δ66Zn, and δ114Cd) profiles from two stations in the Pacific Ocean, the SAFe Station (30°N 140°W) in the subtropical North East Pacific from the GEOTRACES IC2 cruise, and the marginal San Pedro Basin (33.8°N 118.4°W) within the South California Bight. These data represent, to our knowledge, the first full-water column profiles for δ66Zn and δ56Fe from the open-ocean North Pacific, and the first observations of dissolved δ66Zn and δ114Cd in a low-oxygen marginal basin. At the SAFe station, δ56Fe is isotopically lighter throughout the water column (-0.6 to +0.1‰, relative to IRRM-014) compared to the North Atlantic, suggesting significant differences in Fe sources or Fe cycling between these two ocean basins. A broad minimum in δ56Fe associated with the North Pacific oxygen minimum zone (OMZ; <75 μmol kg-1 dissolved oxygen; ∼550-2000 m depth) is consistent with reductive sediments along the California margin being an important source of dissolved Fe to the North Pacific. Other processes which may influence δ56Fe at SAFe include biological cycling in the upper ocean, and input of Fe from hydrothermal vents and oxic sediments below the OMZ. Zn and Cd concentration profiles at both stations broadly match the distribution of the macronutrients silicate and phosphate, respectively. At SAFe, δ114Cd increases towards the surface, reflecting the biological preference for assimilation of lighter Cd isotopes, while negative Cd∗ (-0.12) associated with low oxygen waters supports the recently proposed hypothesis of water-column CdS precipitation. In contrast to δ114Cd, δ66Zn at SAFe decreases towards the surface ocean, perhaps due to scavenging of isotopically heavy Zn, while at intermediate depths δ66Zn provides further evidence of a mid-depth dissolved δ66Zn maximum. We suggest this may be a global feature of Zn biogeochemistry related to either regeneration of heavy adsorbed Zn, or to ZnS formation and removal within the water column. Data from San Pedro shows that anoxic sediments can be a source of isotopically light Zn to the water column (δ66Zn of ∼-0.3‰ relative to JMC Lyon), though evidence of this signal is not observed being transported to SAFe. Within North Pacific Intermediate Water at SAFe (NPIW; ∼500 m) elevated Cd∗ and Zn∗ and a focused minimum in δ56Fe suggest possible transport of Fe, Zn, and Cd over thousands of km from subpolar waters, meaning that NPIW may have a strong influence on the subsurface distribution of trace metals throughout the North Pacific.

Application of multivariate statistical analysis in the pollution and health risk of traffic-related heavy metals.

PubMed

Ebqa'ai, Mohammad; Ibrahim, Bashar

2017-12-01

This study aims to analyse the heavy metal pollutants in Jeddah, the second largest city in the Gulf Cooperation Council with a population exceeding 3.5 million, and many vehicles. Ninety-eight street dust samples were collected seasonally from the six major roads as well as the Jeddah Beach, and subsequently digested using modified Leeds Public Analyst method. The heavy metals (Fe, Zn, Mn, Cu, Cd, and Pb) were extracted from the ash using methyl isobutyl ketone as solvent extraction and eventually analysed by atomic absorption spectroscopy. Multivariate statistical techniques, principal component analysis (PCA), and hierarchical cluster analysis were applied to these data. Heavy metal concentrations were ranked according to the following descending order: Fe > Zn > Mn > Cu > Pb > Cd. In order to study the pollution and health risk from these heavy metals as well as estimating their effect on the environment, pollution indices, integrated pollution index, enrichment factor, daily dose average, hazard quotient, and hazard index were all analysed. The PCA showed high levels of Zn, Fe, and Cd in Al Kurnish road, while these elements were consistently detected on King Abdulaziz and Al Madina roads. The study indicates that high levels of Zn and Pb pollution were recorded for major roads in Jeddah. Six out of seven roads had high pollution indices. This study is the first step towards further investigations into current health problems in Jeddah, such as anaemia and asthma.

Use of ferrous iron by metallo-β-lactamases.

PubMed

Cahill, Samuel T; Tarhonskaya, Hanna; Rydzik, Anna M; Flashman, Emily; McDonough, Michael A; Schofield, Christopher J; Brem, Jürgen

2016-10-01

Metallo-β-lactamases (MBLs) catalyse the hydrolysis of almost all β-lactam antibacterials including the latest generation carbapenems and are a growing worldwide clinical problem. It is proposed that MBLs employ one or two zinc ion cofactors in vivo. Isolated MBLs are reported to use transition metal ions other than zinc, including copper, cadmium and manganese, with iron ions being a notable exception. We report kinetic and biophysical studies with the di-iron(II)-substituted metallo-β-lactamase II from Bacillus cereus (di-Fe(II) BcII) and the clinically relevant B1 subclass Verona integron-encoded metallo-β-lactamase 2 (di-Fe(II) VIM-2). The results reveal that MBLs can employ ferrous iron in catalysis, but with altered kinetic and inhibition profiles compared to the zinc enzymes. A crystal structure of di-Fe(II) BcII reveals only small overall changes in the active site compared to the di-Zn(II) enzyme including retention of the di-metal bridging water; however, the positions of the metal ions are altered in the di-Fe(II) compared to the di-Zn(II) structure. Stopped-flow analyses reveal that the mechanism of nitrocefin hydrolysis by both di-Fe(II) BcII and di-Fe(II) VIM-2 is altered compared to the di-Zn(II) enzymes. Notably, given that the MBLs are the subject of current medicinal chemistry efforts, the results raise the possibility the Fe(II)-substituted MBLs may be of clinical relevance under conditions of low zinc availability, and reveal potential variation in inhibitor activity against the differently metallated MBLs. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Phytoextraction of heavy metals by potential native plants and their microscopic observation of root growing on stabilised distillery sludge as a prospective tool for in situ phytoremediation of industrial waste.

PubMed

Chandra, Ram; Kumar, Vineet

2017-01-01

The safe disposal of post-methanated distillery sludge (PMDS) in the environment is challenging due to high concentrations of heavy metals along with other complex organic pollutants. The study has revealed that PMDS contained high amounts of Fe (2403), Zn (210), Mn (126), Cu (73.62), Cr (21.825), Pb (16.33) and Ni (13.425 mg kg -1 ) along with melanoidins and other co-pollutants. The phytoextraction pattern in 15 potential native plants growing on sludge showed that the Blumea lacera, Parthenium hysterophorous, Setaria viridis, Chenopodium album, Cannabis sativa, Basella alba, Tricosanthes dioica, Amaranthus spinosus L., Achyranthes sp., Dhatura stramonium, Sacchrum munja and Croton bonplandianum were noted as root accumulator for Fe, Zn and Mn, while S. munja, P. hysterophorous, C. sativa, C. album, T. dioica, D. stramonium, B. lacera, B. alba, Kalanchoe pinnata and Achyranthes sp. were found as shoot accumulator for Fe. In addition, A. spinosus L. was found as shoot accumulator for Zn and Mn. Similarly, all plants found as leaf accumulator for Fe, Zn and Mn except A. spinosus L. and Ricinus communis. Further, the BCF of all tested plants were noted <1, while the TF showed >1. This revealed that metal bioavailability to plant is poor due to strong complexation of heavy metals with organic pollutants. This gives a strong evidence of hyperaccumulation for the tested metals from complex distillery waste. Furthermore, the TEM observations of root of P. hysterophorous, C. sativa, Solanum nigrum and R. communis showed formation of multi-nucleolus, multi-vacuoles and deposition of metal granules in cellular component of roots as a plant adaptation mechanism for phytoextraction of heavy metal-rich polluted site. Hence, these native plants may be used as a tool for in situ phytoremediation and eco-restoration of industrial waste-contaminated site.

The effect of Fe2NiO4 and Fe4NiO4Zn magnetic nanoparticles on anaerobic digestion activity.

PubMed

Chen, Jian Lin; Steele, Terry W J; Stuckey, David C

2018-06-11

Two types of magnetic nanoparticles (MNPs), i.e. Ni ferrite nanoparticles (Fe 2 NiO 4 ) and Ni Zn ferrite nanoparticles (Fe 4 NiO 4 Zn) containing the trace metals Ni and Fe, were added to the anaerobic digestion of synthetic municipal wastewater at concentrations between 1 and 100 mg Ni L -1 in order to compare their effects on biogas (methane) production and sludge activity. Using the production of methane over time as a measure, the assays revealed that anaerobic digestion was stimulated by the addition of 100 mg Ni L -1 in Fe 2 NiO 4 NPs, while it was inhibited by the addition of 1-100 mg Ni L -1 in Fe 4 NiO 4 Zn NPs. Especially at 100 mg Ni L -1 , Fe 4 NiO 4 Zn NPs resulted in a total inhibition of anaerobic digestion. The metabolic activity of the anaerobic sludge was tested using the resazurin reduction assay, and the assay clearly revealed the negative effect of Fe 4 NiO 4 Zn NPs and the positive effect of Fe 2 NiO 4 NPs. Re-feeding fresh synthetic medium reactivated the NPs added to the anaerobic sludge, except for the experiment with 100 mg Ni L -1 addition of Fe 4 NiO 4 Zn NPs. The findings in this present study indicate a possible new strategy for NPs design to enhance anaerobic digestion. Crown Copyright © 2018. Published by Elsevier B.V. All rights reserved.

Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

2001-07-01

Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during uptake. However, Cu in Fe-Mn crusts is isotopically light (at ∼0.3 to 0.5‰) compared to the dissolved phase in seawater (at ∼0.9‰). We suggest that this is because dissolved Cu in the oceans is overwhelmingly complexed to strong organic ligands, which are better competitors for the heavy isotope.

Single and multi-layered core-shell structures based on ZnO nanorods obtained by aerosol assisted chemical vapor deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sáenz-Trevizo, A.; Amézaga-Madrid, P.; Pizá-Ruiz, P.

2015-07-15

Core–shell nanorod structures were prepared by a sequential synthesis using an aerosol assisted chemical vapor deposition technique. Several samples consisting of ZnO nanorods were initially grown over TiO{sub 2} film-coated borosilicate glass substrates, following the synthesis conditions reported elsewhere. Later on, a uniform layer consisting of individual Al, Ni, Ti or Fe oxides was grown onto ZnO nanorod samples forming the so-called single MO{sub x}/ZnO nanorod core–shell structures, where MO{sub x} was the metal oxide shell. Additionally, a three-layer core–shell sample was developed by growing Fe, Ti and Fe oxides alternately, onto the ZnO nanorods. The microstructure of the core–shellmore » materials was characterized by grazing incidence X-ray diffraction, scanning and transmission electron microscopy. Energy dispersive X-ray spectroscopy was employed to corroborate the formation of different metal oxides. X-ray diffraction outcomes for single core–shell structures showed solely the presence of ZnO as wurtzite and TiO{sub 2} as anatase. For the multi-layered shell sample, the existence of Fe{sub 2}O{sub 3} as hematite was also detected. Morphological observations suggested the existence of an outer material grown onto the nanorods and further microstructural analysis by HR-STEM confirmed the development of core–shell structures in all cases. These studies also showed that the individual Al, Fe, Ni and Ti oxide layers are amorphous; an observation that matched with X-ray diffraction analysis where no apparent extra oxides were detected. For the multi-layered sample, the development of a shell consisting of three different oxide layers onto the nanorods was found. Overall results showed that no alteration in the primary ZnO core was produced during the growth of the shells, indicating that the deposition technique used herein was and it is suitable for the synthesis of homogeneous and complex nanomaterials high in quality and purity. In addition, materials absorptance determined from the total transmittance and reflectance spectra revealed a broader absorption interval including visible light, indicating potential uses of these nanostructures on solar energy appliances. - Graphical abstract: Display Omitted - Highlights: • Uniform ZnO nanorods (core)–metal oxide (shell) were obtained sequentially by AACVD. • Shells were structured of homogeneous single or multi-layered non-mixed metal oxides. • ZnO nanorod core was preserved during the shell synthesis. • Optical absorptance revealed visible interval absorption for FeO{sub x} shell samples. • Materials can be suitable for photocatalytic or photovoltaic applications.« less

Chemical fractionation of metals in wetland sediments: Indiana Dunes National Lakeshore.

PubMed

Dollar, N L; Souch, C J; Filippelli, G M; Mastalerz, M

2001-09-15

Tessier-type (1979) sequential extractions for heavy metals (Cd, Cr, Cu, Fe, Mn, Pb, and Zn) were conducted on sediments from two wetland sites, one inundated and the other drained, within the Indiana Dunes National Lakeshore (IDNL), NW Indiana, with the objective of (i) evaluating extraction techniques on organic-rich sediments, (ii) determining the geochemistry and mobility of potentially biotoxic trace metals in a contaminated environment, and (iii) considering the implications of different restoration strategies on the potential for heavy metal remobilization. Long and repeated extractions were needed to effectively degrade the organic-rich sediments (up to 75% of the sediment by mass). Analysis of sulfur fractionation revealed that it was predominantly sequestered along with the organically bound fraction (renamed oxidizable). Metal recovery was good with the sum of the extractant steps typically within 20% of the total metal concentration determined after total microwave digestion. Results showed metal fractionation to be both metal- and site-specific, The oxidizable fraction is dominant for Cu, Cr, and Fe (>65% of the nonresidual fraction for almost all samples) and overall is most important also for Cd and Pb. The iron/manganese oxide fraction is important for Pb, Mn, and Zn, particularly at the drained site. The carbonate bound fraction is relatively insignificant at both sites, except for Cd and Mn, although it is more important at the drained site. The exchangeable fraction is significant in the uppermost sediments at the drained site, particularly for Cd (3-24%), Pb (3-14%), and Zn (36-45%); whereas, for the inundated site, it ranged only from 0 to 1% Zn, with no detectable Cd or Pb. Chromium, Cu, and Fe exist in forms not likely to be remobilized, whereas Cd, Mn, Pb, and Zn are potentially mobile if drained wetland sites are reflooded (and pH and redox potential altered). Simple mass balance calculations illustrate the potential for the removal of approximately 84,375 kg of exchangeable Zn if currently drained sites across the IDNL are reflooded, with concentrations in water draining into Lake Michigan as high as 5 ppm.

Effect of adsorbed metals ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer

USGS Publications Warehouse

Kent, D.B.; Davis, J.A.; Anderson, L.C.D.; Rea, B.A.; Coston, J.A.

2002-01-01

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales. Copyright ?? 2002 Elsevier Science Ltd.

Synthesis, characterization and antimicrobial studies of Schiff base complexes

NASA Astrophysics Data System (ADS)

Zafar, Hina; Ahmad, Anis; Khan, Asad U.; Khan, Tahir Ali

2015-10-01

The Schiff base complexes, MLCl2 [M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by the template reaction of respective metal ions with 2-acetylpyrrole and 1,3-diaminopropane in 1:2:1 M ratio. The complexes have been characterized by elemental analyses, ESI - mass, NMR (1H and 13C), IR, XRD, electronic and EPR spectral studies, magnetic susceptibility and molar conductance measurements. These studies show that all the complexes have octahedral arrangement around the metal ions. The molar conductance measurements of all the complexes in DMSO indicate their non-electrolytic nature. The complexes were screened for their antibacterial activity in vitro against Gram-positive (Streptococcus pyogenes) and Gram-negative (Klebsiella pneumoniae) bacteria. Among the metal complexes studied the copper complex [CuLCl2], showed highest antibacterial activity nearly equal to standard drug ciprofloxacin. Other complexes also showed considerable antibacterial activity. The relative order of activity against S. Pyogenes is as Cu(II) > Zn(II) > Co(II) = Fe(II) > Ni(II) and with K. Pneumonia is as Cu(II) > Co(II) > Zn(II) > Fe(II) > Ni(II).

[Heavy metals pollution and analysis of seasonal variation runoff in Xi'an].

PubMed

Yuan, Hong-Lin; Li, Xing-Yu; Wang, Xiao-Chang

2014-11-01

In order to explore heavy metals pollution situation,changes in characteristics, the correlation between each heavy mental and pollution source analysis of Xi'an various regions in different season in one year. This study collected several samples of Xi'an rainfall typical urban trunk roads throughout the year in 2013 and used inductively coupled plasma mass spectrometry (ICP-MS) to determine the level of Fe, Mn, Pb, Zn, Al, Cd of the samples, then, analyzed the seasonal change of heavy mental. Studies have shown that: the heavy metal of Xi'an road runoff pollutes seriously, the concentration of Fe over three times of the national standard and maintain the higher levels throughout the year, meanwhile the concentration with the intensity of human activities increases. The concentration of Mn and Zn in one year show a trends: winter > autumn > summer> spring. Pb concentration increases with the increase in traffic volume, while showing: winter > spring > summer > autumn. Factor analysis shows: Fe and Al was affected by the same sources-natural sources; Zn, Cd affected by anthropogenic sources of large; Mn, Pb affected by the larger traffic sources.

Field based investigation on phytoremediation potentials of Lemna minor and Azolla filiculoides in tropical, semiarid regions: Case of Ethiopia.

PubMed

Amare, Elfu; Kebede, Fassil; Berihu, Tesfay; Mulat, Worku

2017-10-16

This study investigated the concurrent accumulation of eight heavy metals by two floating aquatic macrophytes (Lemna minor and Azolla filiculoides) cultivated in ambient media and blended wastewaters in the semiarid regions of Ethiopia. Both species accumulated heavy metals in varying degrees with a significant concentration gradient within the immediate water media. Highest bioconcentration factor was determined for Mn and Fe in both plants. Results revealed that L. minor was high phytoaccumulator for Fe, Mn, Zn and Co but moderate for Cd, Cu, Ni and Cr. On the other hand, A. filiculoides was a high accumulator for Fe, Mn, Zn and Cu, but its potency was moderate for Co, Cr and Ni, but lower for Cd. Both species exhibited significant difference in accumulating Co, Zn and Mn (p < 0.05). In general, the bioconcentration factors for both plants were comparable within the same treatment. In this study, stronger associations between the heavy metal concentrations in the plant tissues and in the grown water media were observed for A. filiculoides.

Role of Metal Ions on the Activity of Mycobacterium tuberculosis Pyrazinamidase

PubMed Central

Sheen, Patricia; Ferrer, Patricia; Gilman, Robert H.; Christiansen, Gina; Moreno-Román, Paola; Gutiérrez, Andrés H.; Sotelo, Jun; Evangelista, Wilfredo; Fuentes, Patricia; Rueda, Daniel; Flores, Myra; Olivera, Paula; Solis, José; Pesaresi, Alessandro; Lamba, Doriano; Zimic, Mirko

2012-01-01

Pyrazinamidase of Mycobacterium tuberculosis catalyzes the conversion of pyrazinamide to the active molecule pyrazinoic acid. Reduction of pyrazinamidase activity results in a level of pyrazinamide resistance. Previous studies have suggested that pyrazinamidase has a metal-binding site and that a divalent metal cofactor is required for activity. To determine the effect of divalent metals on the pyrazinamidase, the recombinant wild-type pyrazinamidase corresponding to the H37Rv pyrazinamide-susceptible reference strain was expressed in Escherichia coli with and without a carboxy terminal. His-tagged pyrazinamidase was inactivated by metal depletion and reactivated by titration with divalent metals. Although Co2+, Mn2+, and Zn2+ restored pyrazinamidase activity, only Co2+ enhanced the enzymatic activity to levels higher than the wild-type pyrazinamidase. Cu2+, Fe2+, Fe3+, and Mg2+ did not restore the activity under the conditions tested. Various recombinant mutated pyrazinamidases with appropriate folding but different enzymatic activities showed a differential pattern of recovered activity. X-ray fluorescence and atomic absorbance spectroscopy showed that recombinant wild-type pyrazinamidase expressed in E. coli most likely contained Zn. In conclusion, this study suggests that M. tuberculosis pyrazinamidase is a metalloenzyme that is able to coordinate several ions, but in vivo, it is more likely to coordinate Zn2+. However, in vitro, the metal-depleted enzyme could be reactivated by several divalent metals with higher efficiency than Zn. PMID:22764307

Evaluation of heavy metals content in dietary supplements in Lebanon.

PubMed

Korfali, Samira Ibrahim; Hawi, Tamer; Mroueh, Mohamad

2013-01-18

The consumption of dietary supplements is widely spread and on the rise. These dietary supplements are generally used without prescriptions, proper counseling or any awareness of their health risk. The current study aimed at analyzing the metals in 33 samples of imported dietary supplements highly consumed by the Lebanese population, using 3 different techniques, to ensure the safety and increase the awareness of the citizen to benefit from these dietary supplements. Some samples had levels of metals above their maximum allowable levels (Fe: 24%, Zn: 33%, Mn: 27%, Se: 15%, Mo: 12% of samples), but did not pose any health risk because they were below permitted daily exposure limit and recommended daily allowance except for Fe in 6% of the samples. On the other hand, 34% of the samples had Cu levels above allowable limit where 18% of them were above their permitted daily exposure and recommended daily allowance. In contrast, all samples had concentration of Cr, Hg, and Pb below allowable limits and daily exposure. Whereas, 30% of analyzed samples had levels of Cd above allowable levels, and were statistically correlated with Ca, and Zn essential minerals. Similarly 62% of the samples had levels of As above allowable limits and As levels were associated with Fe and Mn essential minerals. Dietary supplements consumed as essential nutrients for their Ca, Zn, Fe and Mn content should be monitored for toxic metal levels due to their natural geochemical association with these essential metals to provide citizens the safe allowable amounts.

Theranostic multimodular potential of zinc-doped ferrite-saturated metal-binding protein-loaded novel nanocapsules in cancers

PubMed Central

Kamalapuram, Sishir K; Kanwar, Rupinder K; Roy, Kislay; Chaudhary, Rajneesh; Sehgal, Rakesh; Kanwar, Jagat R

2016-01-01

The present study successfully developed orally deliverable multimodular zinc (Zn) iron oxide (Fe3O4)-saturated bovine lactoferrin (bLf)-loaded polymeric nanocapsules (NCs), and evaluated their theranostic potential (antitumor efficacy, magnetophotothermal efficacy and imaging capability) in an in vivo human xenograft CpG-island methylator phenotype (CIMP)-1+/CIMP2−/chromosome instability-positive colonic adenocarcinoma (Caco2) and claudin-low, triple-negative (ER−/PR−/HER2−; MDA-MB-231) breast cancer model. Mice fed orally on the Zn-Fe-bLf NC diet showed downregulation in tumor volume and complete regression in tumor volume after 45 days of feeding. In human xenograft colon cancer, vehicle-control NC diet-group (n=5) mice showed a tumor volume of 52.28±11.55 mm3, and Zn-Fe-bLf NC diet (n=5)-treated mice had a tumor-volume of 0.10±0.073 mm3. In the human xenograft breast cancer model, Zn-Fe-bLf NC diet (n=5)-treated mice showed a tumor volume of 0.051±0.062 mm3 within 40 days of feeding. Live mouse imaging conducted by near-infrared fluorescence imaging of Zn-Fe-bLf NCs showed tumor site-specific localization and regression of colon and breast tumor volume. Ex vivo fluorescence-imaging analysis of the vital organs of mice exhibited sparse localization patterns of Zn-Fe-bLf NCs and also confirmed tumor-specific selective localization patterns of Zn-Fe-bLf NCs. Dual imaging using magnetic resonance imaging and computerized tomography scans revealed an unprecedented theranostic ability of the Zn-Fe-bLf NCs. These observations warrant consideration of multimodular Zn-Fe-bLf NCs for real-time cancer imaging and simultaneous cancer-targeted therapy. PMID:27099495

Effect of metal cation ratio on chemical properties of ZnFe2O4/AC composite and adsorption of organic contaminant

NASA Astrophysics Data System (ADS)

Meilia, Demara; Misbah Khunur, Mochamad; Setianingsih, Tutik

2018-01-01

Porous woody char is biochar prepared through pyrolisis. The biochar can be used as adsorbent. In this research, ZnFe2O4/AC composite was synthesized through imregnation of the woody biochar with ZnFe2O4 to study effect of mol ratio of Fe(III) and Zn(II) toward their physicochemistry and adsorption of drug wastewater. Paracetamol was used as adsorbate model. This research was conducted in several steps, including activation of the woody biochar using KOH activator at temperatur 500 °C for 15 min to produce the activated carbon, fungsionalization of the carbon using H2SO4 oxidator (6M) at temperature of 80 °C for 3 h, impregnation of the oxidized activated carbon with Zn-Fe-LDH (Layered Double Hydroxide) at various mol ratio of Fe(III) and Zn(III), including 1:2, 1:3 and 1:4 using NaOH solution (5M) for coprecipitation, and calcination of Zn-Fe-LDH/AC at 950 °C for 5 min to produce ZnFe2O4/AC. FTIR diffraction characterization indicated existence of M-O (M = Zn(II), Fe(III)) and OH functional groups. FTIR spectra showed increasing of bands connected to -OH by increasing of the ratio till the ratio was achieved at 1:4, then decreased again. The ratio mol showed effect on the adsorption of paracetamol. Profile of adsorption value was fit with changing of functional groups. The highest adsorption was achieved at the ratio of 1:4. After calcination it gave the adsorption value of 17,66 mg/g.

Modelling removal mechanisms of Pb, Cu, Zn and Cd in acidic groundwater during the neutralization by ambient surface and ground waters

USGS Publications Warehouse

Paulson, Anthony J.; Balistrieri, Laurie S.

1999-01-01

Removal of Pb, Cu, Zn, and Cd during neutralization of acid rock drainage is examined using model simulations of field conditions and laboratory experiments involving mixing of natural drainage and surface waters or groundwaters. The simulations consider sorption onto hydrous Fe and Al oxides and particulate organic carbon, mineral precipitation, and organic and inorganic solution complexation of metals for two physical systems where newly formed oxides and particulate organic matter are either transported or retained along the chemical pathway. The calculations indicate that metal removal is a strong function of the physical system. Relative to direct discharge of ARD into streams, lower metal removals are observed where ARD enters streamwaters during the latter stages of neutralization by ambient groundwater after most of the Fe has precipitated and been retained in the soils. The mixing experiments, which represent the field simulations, also demonstrated the importance of dissolved metal to particle Fe ratios in controlling dissolved metal removal along the chemical pathway. Finally, model calculations indicate that hydrous Fe oxides and particulate organic carbon are more important than hydrous Al oxides in removing metals and that both inorganic and organic complexation must be considered when modeling metal removal from aquatic systems that are impacted by sulfide oxidation.

Metal concentrations of wild edible mushrooms from Turkey.

PubMed

Sarikurkcu, Cengiz; Tepe, Bektas; Solak, Mehmet Halil; Cetinkaya, Serap

2012-01-01

In the present study, the contents of Zn, Fe, Cu, Mn, Co, Ni, Pb, Cd, Cr, Al, Ca, Mg, and K in Agaricus campestris, Agrocybe cylindracea, Collybia dryophila, Helvella leucopus, Russula delica, Tricholoma auratum, Amanita ovoidea, Melanoleuca excissa, Rhizopogon roseolus, Russula chloroides, Volvoriella gloiocephala, Lyophyllum decastes, Morcella angusticeps, Morchella esculenta and Morcella eximia collected from Isparta, Mugla, and Osmaniye provinces (Turkey) were determined by inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave digestion. The intake of heavy metals (Pb, Cd) and other metals (Fe, Cu, Zn) by consumption of 30 g dry weight of mushrooms daily poses no risk at all except in A. cylindracea and H. leucopus (for Cd) for the consumer.

Hydrometallurgical Treatment for Mixed Waste Battery Material

NASA Astrophysics Data System (ADS)

Ma, L. W.; Xi, X. L.; Zhang, Z. Z.; Huang, Z. Q.; Chen, J. P.

2017-02-01

Hydrometallurgical experiments are generally required to assess the appropriate treatment process before the establishment of the industrial recovery process for waste battery materials. The effects of acid systems and oxidants in metal leaching were studied. The comprehensive leaching effects of the citric acid were superior to the sulfuric acid. The potassium permanganate inhibits the dissolution of metals. Thermodynamic calculations showed that metals precipitate more easily in sulfuric acid system than in citric acid system. The Fe precipitation efficiency in sulfuric acid system was 90% at pH 3.5, but with considerable losses of Co (30%) and Ni (40%). The proper pH and organic/aqueous (O/A) ratio for Fe and Zn removal with Di-(2-ethylhexyl) phosphoric acid extraction were 2 and 0.5, respectively; while for the removal of Cu and Mn, the best pH and O/A ratio were 3 and 0.75, respectively. Crude manganese carbonate and a cobalt-nickel enriched liquid were obtained by selective precipitation in raffinate using an ammonium bicarbonate solution. In citric acid systems, the precipitation efficiency of Co, Ni, Mn, Fe, Cu and Zn were less than 20% at pH 7. The proper pH and O/A ratio for the separation of the metals in two groups (Ni/Co/Cu and Mn/Fe/Zn) were 1.5 and 2. The cobalt-nickel-copper enriched liquid was finally obtained.

Coordination polymer-derived nano-sized zinc ferrite with excellent performance in nitro-explosive detection.

PubMed

Singha, Debal Kanti; Mahata, Partha

2017-08-29

Herein, a mixed metal coordination polymer, {(H 2 pip)[Zn 1/3 Fe 2/3 (pydc-2,5) 2 (H 2 O)]·2H 2 O} 1 {where H 2 pip = piperazinediium and pydc-2,5 = pyridine-2,5-dicarboxylate}, was successfully synthesized using a hydrothermal technique. To confirm the structure and phase purity of 1, single crystals of an isomorphous pure Fe compound, {(H 2 pip)[Fe(pydc-2,5) 2 (H 2 O)]·2H 2 O} 1a, were synthesized based on similar synthetic conditions. Single crystal X-ray data of 1a confirmed the one-dimensional anionic metal-organic coordination polymer hydrogen bonded with protonated piprazine (piperazinediium) and lattice water molecules. The phase purity of 1 and 1a were confirmed via powder X-ray diffraction. Compound 1 was systematically characterized using IR, TGA, SEM, and EDX elemental mapping analysis. Compound 1 was used as a single source precursor for the preparation of nano-sized ZnFe 2 O 4 via thermal decomposition. The as-obtained ZnFe 2 O 4 was fully characterized using PXRD, SEM, TEM, and EDX elemental mapping analysis. It was found that ZnFe 2 O 4 was formed in its pure form with particle size in the nano-dimension. The aqueous dispersion of nano-sized ZnFe 2 O 4 exhibits a strong emission at 402 nm upon excitation at 310 nm. This emissive property was employed for luminescence-based detection of nitroaromatic explosives in an aqueous medium through luminescence quenching for the first time. Importantly, selective detections have been observed for phenolic nitroaromatics based on differential luminescence quenching behaviour along with a detection limit of 57 ppb for 2,4,6-trinitrophenol (TNP) in water.

Platinum-free catalysts for low temperature fuel cells

NASA Astrophysics Data System (ADS)

Lastovina, Tatiana; Pimonova, Julia; Budnyk, Andriy

2017-04-01

In this work, we have successfully prepared Zn/Co-N/C and Zn/Co-Fe/N/C composites, both derived from single zeolitic imidazolate framework (ZIF) precursor Zn/Co-ZIF containing equivalent quantities of Zn and Co metal sites. The composites were formed by pyrolysis of the precursor at 700 °C in inert gas atmosphere as such and after mixing it with Fe(II) salt and 1,10-phenontraline in ethanol. Catalytic tests for oxygen reduction reaction (ORR) in electrochemical cell demonstrated promising results allowing us to consider these composites as potential Pt-free catalysts for low temperature fuel cells.

Identification of Cerebral Metal Ion Imbalance in the Brain of Aging Octodon degus

PubMed Central

Braidy, Nady; Poljak, Anne; Marjo, Chris; Rutlidge, Helen; Rich, Anne; Jugder, Bat-Erdene; Jayasena, Tharusha; Inestrosa, Nibaldo C.; Sachdev, Perminder S.

2017-01-01

The accumulation of redox-active transition metals in the brain and metal dyshomeostasis are thought to be associated with the etiology and pathogenesis of several neurodegenerative diseases, and Alzheimer’s disease (AD) in particular. As well, distinct biometal imaging and role of metal uptake transporters are central to understanding AD pathogenesis and aging but remain elusive, due inappropriate detection methods. We therefore hypothesized that Octodon degus develop neuropathological abnormalities in the distribution of redox active biometals, and this effect may be due to alterations in the expression of lysosomal protein, major Fe/Cu transporters, and selected Zn transporters (ZnTs and ZIPs). Herein, we report the distribution profile of biometals in the aged brain of the endemic Chilean rodent O. degus—a natural model to investigate the role of metals on the onset and progression of AD. Using laser ablation inductively coupled plasma mass spectrometry, our quantitative images of biometals (Fe, Ca, Zn, Cu, and Al) appear significantly elevated in the aged O. degus and show an age-dependent rise. The metals Fe, Ca, Zn, and Cu were specifically enriched in the cortex and hippocampus, which are the regions where amyloid plaques, tau phosphorylation and glial alterations are most commonly reported, whilst Al was enriched in the hippocampus alone. Using whole brain extracts, age-related deregulation of metal trafficking pathways was also observed in O. degus. More specifically, we observed impaired lysosomal function, demonstrated by increased cathepsin D protein expression. An age-related reduction in the expression of subunit B2 of V-ATPase, and significant increases in amyloid beta peptide 42 (Aβ42), and the metal transporter ATP13a2 were also observed. Although the protein expression levels of the zinc transporters, ZnT (1,3,4,6, and 7), and ZIP7,8 and ZIP14 increased in the brain of aged O. degus, ZnT10, decreased. Although no significant age-related change was observed for the major iron/copper regulator IRP2, we did find a significant increase in the expression of DMT1, a major transporter of divalent metal species, 5′-aminolevulinate synthase 2 (ALAS2), and the proto-oncogene, FOS. Collectively, our data indicate that transition metals may be enriched with age in the brains of O. degus, and metal dyshomeostasis in specific brain regions is age-related. PMID:28405187

Density functional theory calculations on transition metal atoms adsorbed on graphene monolayers

NASA Astrophysics Data System (ADS)

Dimakis, Nicholas; Flor, Fernando Antonio; Salgado, Andres; Adjibi, Kolade; Vargas, Sarah; Saenz, Justin

2017-11-01

Transition metal atom adsorption on graphene monolayers has been elucidated using periodic density functional theory under hybrid and generalized gradient approximation functionals. More specifically, we examined the adsorption of Cu, Fe, Zn, Ru, and Os on graphene monolayers by calculating, among others, the electronic density-of-states spectra of the adatom-graphene system and the overlap populations of the adatom with the nearest adsorbing graphene carbon atoms. These calculations reveal that Cu form primarily covalent bonds with graphene atoms via strong hybridization between the adatom orbitals and the sp band of the graphene substrate, whereas the interaction of the Ru and Os with graphene also contain ionic parts. Although the interaction of Fe with graphene atoms is mostly covalent, some charge transfer to graphene is also observed. The interaction of Zn with graphene is weak. Mulliken population analysis and charge contour maps are used to elucidate charge transfers between the adatom and the substrate. The adsorption strength is correlated with the metal adsorption energy and the height of the metal adatom from the graphene plane for the geometrically optimized adatom-graphene system. Our analysis shows that show that metal adsorption strength follows the adatom trend Ru ≈ Os > Fe > Cu > Zn, as verified by corresponding changes in the adsorption energies. The increased metal-carbon orbital overlap for the Ru relative to Os adatom is attributed to hybridization defects.

Adsorptive desulfurization with metal-organic frameworks: A density functional theory investigation

NASA Astrophysics Data System (ADS)

Chen, Zhiping; Ling, Lixia; Wang, Baojun; Fan, Huiling; Shangguan, Ju; Mi, Jie

2016-11-01

The contribution of each fragment of metal-organic frameworks (MOFs) to the adsorption of sulfur compounds were investigated using density functional theory (DFT). The involved sulfur compounds are dimethyl sulfide (CH3SCH3), ethyl mercaptan (CH3CH2SH) and hydrogen sulfide (H2S). MOFs with different organic ligands (NH2-BDC, BDC and NDC), metal centers structures (M, M-M and M3O) and metal ions (Zn, Cu and Fe) were used to study their effects on sulfur species adsorption. The results revealed that, MOFs with coordinatively unsaturated sites (CUS) have the strongest binding strength with sulfur compounds, MOFs with NH2-BDC substituent group ligand comes second, followed by that with saturated metal center, and the organic ligands without substituent group has the weakest adsorption strength. Moreover, it was also found that, among different metal ions (Fe, Zn and Cu), MOFs with unsaturated Fe has the strongest adsorption strength for sulfur compounds. These results are consistent with our previous experimental observations, and therefore provide insights on the better design of MOFs for desulfurization application.

The occurrence and distribution of trace metals in the Mississippi River and its tributaries

USGS Publications Warehouse

Taylor, Howard E.; Garbarino, J.R.; Brinton, T.I.

1990-01-01

Quantitative and semiquantitative analyses of dissolved trace metals are reported for designated sampling sites on the Mississippi River and its main tributaries utilizing depth-integrated and width-integrated sampling technology to collect statistically representative samples. Data are reported for three sampling periods, including: July-August 1987, November-December 1987, and May-June 1988. Concentrations of Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Pb, Sr, Tl, U, V, and Zn are reported quantitatively, with the remainder of the stable metals in the periodic table reported semiquantitatively. Correlations between As and V, Ba and U, Cu and Zn, Li and Ba, and Li and U are significant at the 99% confidence level for each of the sampling trips. Comparison of the results of this study for selected metals with other published data show generally good agreement for Cr, Cu, Fe, and Zn, moderate agreement for Mo, and poor agreement for Cd and V.

Effect of Transport and Aging Processes on Metal Speciation in Iron Oxyhydroxide Aggregates, Tar Creek Superfund Site, Oklahoma

NASA Astrophysics Data System (ADS)

Estes, E. R.; Schaider, L. A.; Shine, J. P.; Brabander, D. J.

2010-12-01

Following the cessation of mining activity in the late 20th century, Tar Creek Superfund Site was left highly contaminated by Pb, Zn, and Cd. Tar Creek, which flows through the site and into the Neosho River, has been studied extensively because of its potential to transport metals from the mining site to downstream communities. Previous research identified aggregated iron oxyhydroxide material, which forms when mine seepage mixes with Tar Creek surface water, as a major transport vector of metals. Frequent flooding in Tar Creek deposits aggregates on downstream floodplains, where wetting and drying processes alter the speciation of iron and other metals. This study seeks to better quantify those changes and to determine how transport and aging affects the human and ecological health risk. Sequential extractions of aggregate samples collected from the creek demonstrate that Fe is present in both amorphous (10-35% of Fe extracted) and more crystalline (8-23% of Fe extracted) phases. Substantial portions of heavy metals sorb to amorphous iron oxyhydroxide phases (accounting for 10-30% of Pb and Zn extracted) but are not associated with more crystalline iron oxide phases (representing only 1% or less of the Pb and Zn extracted). Samples have a high organic matter content (18-25% mass loss on ignition), but only Fe was significantly extracted by the oxidizing step targeting organic matter (1-2% of Pb and Zn extracted, but 10-26% of Fe extracted). The majority of metals were extracted by the soluble or residual steps. If metals and organic matter inhibit transformation of amorphous iron oxyhydroxide material to nano and crystalline iron oxides, then a steady-state volume of amorphous iron oxyhydroxide material with a high total sorption capacity may exist within Tar Creek, enhancing the metal flux accommodated by this transport mechanism. Once transported downstream and deposited on floodplains, however, it is hypothesized that repeated changes in soil matrix composition and thermodynamic conditions could facilitate a transformation to more crystalline iron phases and increase metal bioavailability. While preliminary data from in-creek aggregates show no clear trend in mineralogical composition with downstream transport, only the furthest downstream samples have 2-line ferrihydrite in amounts detectable by XRD.

Detection of Labile Low-Molecular-Mass Transition Metal Complexes in Mitochondria

PubMed Central

McCormick, Sean P.; Moore, Michael J.; Lindahl, Paul A.

2015-01-01

Liquid chromatography was used with an on-line inductively coupled plasma mass spectrometer to detect low-molecular-mass (LMM) transition metal complexes in mitochondria isolated from fermenting yeast cells, human Jurkat cells, and mouse brain and liver. These complexes constituted 20 – 40% of total mitochondrial Mn, Fe, Zn, and Cu ions. The major LMM Mn complex in yeast mitochondria had a mass of ca. 1100 Da and a concentration of ~ 2 μM. Mammalian mitochondria contained a second Mn species with a mass of ca. 2000 Da at a comparable concentration. The major Fe complex in mitochondria isolated from exponentially growing yeast cells had a mass of ca. 580 Da; the concentration of Fe580 in mitochondria was ca. 100 μM. When mitochondria were isolated from fermenting cells in post-exponential phase, the mass of the dominant LMM Fe complex was ca. 1100 Da. Upon incubation, the intensity of Fe1100 declined and Fe580 increased, suggesting that the two are interrelated. Mammalian mitochondria contained Fe580 and 2 other Fe species (Fe2000 and Fe1100) at concentrations of ca. 50 μM each. The dominant LMM Zn species in mitochondria had a mass of ca. 1200 Da and a concentration of ca. 110 μM. Mammalian mitochondria contained a second major LMM Zn species at 1500 Da. The dominant LMM Cu species in yeast mitochondria had a mass of ca. 5000 Da and a concentration in yeast mitochondria of ca. 16 μM; Cu5000 was not observed in mammalian mitochondria. The dominant Co species in mitochondria, Co1200, had a concentration of 20 nM and was probably a cobalamin. Mammalian but not yeast mitochondria contained a LMM Mo species, Mo730, at ca. 1 μM concentration. Increasing Mn, Fe, Cu, and Zn concentrations 10 fold in the medium increased the concentration of the same element in the corresponding isolated mitochondria. Treatment with metal chelators confirmed that these LMM species were labile. The dominant S species at 1100 Da was not free GSH or GSSG. PMID:26018429

Heavy metal pollution assessment, source identification, and health risk evaluation in Aibi Lake of northwest China.

PubMed

Zhaoyong, Zhang; Xiaodong, Yang; Shengtian, Yang

2018-01-08

This study sought to analyze heavy metal (Pb, Zn, Cu, Ni, Mn, and Fe) pollution status in the waters of Aibi Lake in northwest China through the use of an applied comprehensive pollution index, health risk model, and multivariate statistical analyses in combination with the lake's land use types. Results showed that (1) the maximum (average) values of the heavy metals Pb, Zn, Cu, Ni, Mn, and Fe were 0.0644 (0.0123), 0.0006 (0.0002), 0.0009 (0.0032), 0.1235 (0.0242), 0.0061 (0.0025), and 0.0222 (0.0080) μg/L, respectively. Among these, in all the samples, Pb and Ni exceeded the standard and acceptable values put forth by the World Health Organization by 21.13 and 25.67%, respectively. Ni also exceeded (30.16%) the third grade of the Environmental Quality Standards for Surface Water of China. The levels of the six heavy metals were all within the fishery and irrigation water quality standard ranges in China. (2) The average values for single pollution index of heavy metals Pb, Zn, Cu, Ni, Mn, and Fe were 1.000, 0.0006, 0.0009, 3.000, 0.060, and 0.070, respectively, among which Ni levels indicated moderate to significant pollution, while others indicated healthy levels. (3) Health risk evaluation showed that the R n values for Pb, Zn, Cu, Mn, and Fe were 1.8 × 10 -4 , 5.33 × 10 -9 , 4.80 × 10 -7 , 1.08 × 10 -6 , and 2.51 × 10 -7  a -1 , respectively, of which, in all samples, Pb and Ni contents all exceeded the maximum acceptable risk levels according to the International Commission on Radiological Protection (ICRP) as well as the U.S. Environment Protection Agency. (4) Combining with multivariate statistical analyses along with the land use distribution within the lake basin, Pb, Zn, Cu, Ni, and Mn were mainly influenced by the agriculture production and emission from urban lives and traffics, and Fe mainly originated from the natural environment. The results of this research can provide reference values for heavy metal pollution prevention in Aibi Lake as well as for environmental protection of rump lakes in the arid regions of northwest China and Central Asia.

Comparative leaching of six toxic metals from raw and chemically stabilized MSWI fly ash using citric acid.

PubMed

Wang, Huawei; Fan, Xinxiu; Wang, Ya-Nan; Li, Weihua; Sun, Yingjie; Zhan, Meili; Wu, Guizhi

2018-02-15

The leaching behavior of six typical toxic metals (Pb, Zn, Cr, Cd, Cu and Ni) from raw and chemically stabilized (phosphate and chelating agent) municipal solid waste incineration (MSWI) fly ash were investigated using citric acid. Leaching tests indicated that phosphate stabilization can effectively decrease the leaching of Zn, Cd and Cr; whereas chelating agent stabilization shows a strong ability to lower the release of Pb, Cd and Cu, but instead increases the solubility of Zn and Cr at low pH conditions. Sequential extraction results suggested that the leaching of Pb, Zn and Cd in both the stabilized MSWI fly ash samples led to the decrease in Fe/Mn oxide fraction and the increase in exchangeable and carbonate fractions. The leaching of Cr was due to the decrease in exchangeable, carbonate and Fe/Mn oxide fractions in phosphate-stabilized and chelating agent-stabilized MSWI fly ash. The leaching of Cu in both stabilized MSWI fly ash was greatly ascribed to the decrease in Fe/Mn oxide and oxidisable fractions. Moreover, predicted curves by geochemical model indicated that both stabilized MSWI fly ash have the risk of releasing toxic metals under strong acid environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heavy metals in Parmelia sulcata collected in the neighborhood of a coal-fired power station.

PubMed

Freitas, M C

1994-01-01

The epiphytic lichen Parmelia sulcata was collected in the neighborhood of a Portuguese coal-fired power station (Sines coal power station) as monitor for heavy metal air pollution. A study of the metal contents variability along 1991 and 1992 was performed. The heavy metals Ag, As, Br, Co, Cr, Fe, Hg, Sb, Se, and Zn were determined by k0-based instrumental neutron activation analysis. The concentrations found in 1991 and 1992 show an accumulating process of Co and Fe (approximately 5%/mo) and of Cr and Sb (approximately 7%/mo). Low accumulation is observed for Ag, Se, and Zn (approximately 2%/mo), and no concentration variation is observed for As, Br, and Hg. It is concluded that the metal accumulation observed is the result of the nearby ash and coal deposits.

Simultaneous production of pullulan and biosorption of metals by Aureobasidium pullulans strain CH-1 on peat hydrolysate.

PubMed

Radulović, Milanka D; Cvetković, Olga G; Nikolić, Snezana D; Dordević, Dragana S; Jakovljević, Dragica M; Vrvić, Miroslav M

2008-09-01

It was demonstrated that during the growth of Aureobasidium pullulans strain CH-1 on the acid hydrolysate of peat from the Vlasina Lake, the content of metals (Cu, Fe, Zn, Mn, Pb, Cd, Ni and Cr) decreased due to biosorption. The reduction in the metal content was found to be in the range (%): 38.2-62.2, 67.7-97.3, 0.02-62.05, 0.05-23.97, 0.16-4.24, 3.45-51.72, 1.18-35.82, 0.86-44.44, for Cu, Fe, Zn, Mn, Pb, Cd, Ni and Cr, respectively. During this process, the metals were accumulated in the biomass, while pullulan, an extracellular polysaccharide produced by Aureobasidium pullulans strain CH-1, was found not to bind the above-mentioned metals.

The AMBRE project: Iron-peak elements in the solar neighbourhood

NASA Astrophysics Data System (ADS)

Mikolaitis, Š.; de Laverny, P.; Recio-Blanco, A.; Hill, V.; Worley, C. C.; de Pascale, M.

2017-04-01

Context. The pattern of chemical abundance ratios in stellar populations of the Milky Way is a fingerprint of the Galactic chemical history. In order to interpret such chemical fossils of Galactic archaeology, chemical evolution models have to be developed. However, despite the complex physics included in the most recent models, significant discrepancies between models and observations are widely encountered. Aims: The aim of this paper is to characterise the abundance patterns of five iron-peak elements (Mn, Fe, Ni, Cu, and Zn) for which the stellar origin and chemical evolution are still debated. Methods: We automatically derived iron peak (Mn, Fe, Ni, Cu, and Zn) and α element (Mg) chemical abundances for 4666 stars, adopting classical LTE spectral synthesis and 1D atmospheric models. Our observational data collection is composed of high-resolution, high signal-to-noise ratios HARPS and FEROS spectra, which were previously parametrised by the AMBRE project. Results: We used the bimodal distribution of the magnesium-to-iron abundance ratios to chemically classify our sample stars into different Galactic substructures: thin disc, metal-poor and high-α metal rich, high-α, and low-α metal-poor populations. Both high-α and low-α metal-poor populations are fully distinct in Mg, Cu, and Zn, but these substructures are statistically indistinguishable in Mn and Ni. Thin disc trends of [Ni/Fe] and [Cu/Fe] are very similar and show a small increase at supersolar metallicities. Also, both thin and thick disc trends of Ni and Cu are very similar and indistinguishable. Yet, Mn looks very different from Ni and Cu. [Mn/Fe] trends of thin and thick discs actually have noticeable differences: the thin disc is slightly Mn richer than the thick disc. The [Zn/Fe] trends look very similar to those of [α/Fe] trends. The typical dispersion of results in both discs is low (≈0.05 dex for [Mg, Mn, and Cu/Fe]) and is even much lower for [Ni/Fe] (≈0.035 dex). Conclusions: It is clearly demonstrated that Zn is an α-like element and could be used to separate thin and thick disc stars. Moreover, we show that the [Mn/Mg] ratio could also be a very good tool for tagging Galactic substructures. From the comparison with Galactic chemical evolutionary models, we conclude that some recent models can partially reproduce the observed Mg, Zn, and, Cu behaviours in thin and thick discs and metal-poor sequences. Models mostly fail to reproduce Mn and Ni in all metallicity domains, however, models adopting yields normalised from solar chemical properties reproduce Mn and Ni better, suggesting that there is still a lack of realistic theoretical yields of some iron-peak elements. The very low scatter (≈0.05 dex) in thin and thick disc sequences could provide an observational constrain for Galactic evolutionary models that study the efficiency of stellar radial migration. Based on observations collected at ESO telescopes under the AMBRE programme. Full Table 5 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/600/A22

Effect of Sulfur on Liquidus Temperatures in the ZnO-"FeO"-Al2O3-CaO-SiO2-S System in Equilibrium with Metallic Iron

NASA Astrophysics Data System (ADS)

Zhao, Baojun; Hayes, Peter C.; Jak, Evgueni

2011-10-01

The phase equilibria in the ZnO-"FeO"-Al2O3-CaO-SiO2-S system have been determined experimentally in equilibrium with metallic iron. A pseudoternary section of the form ZnO-"FeO"-(Al2O3+CaO+SiO2) for CaO/SiO2 = 0.71 (weight), (CaO+SiO2)/Al2O3 = 5.0 (weight), and fixed 2.0 wt pct S concentration has been constructed. It was found that the addition of 2.0 wt pct S to the liquid extends the spinel primary phase field significantly and decreases the size of the wustite primary phase field. The liquidus temperature in the wustite primary phase field is decreased by approximately 80 K and the liquidus temperature in the spinel primary phase field is decreased by approximately 10 K with addition of 2.0 wt pct S in the composition range investigated. It was also found that iron-zinc sulfides are present in some samples in the spinel primary phase field, which are matte appearing at low zinc concentrations and sphalerite (Zn,Fe)S at higher zinc concentrations. The presence of sulfur in the slag has a minor effect on the partitioning of ZnO between the wustite and liquid phases but no effect on the partitioning of ZnO between the spinel and liquid phases.

Magnetic moment in single crystalline BaFe2-xZnxAs2

NASA Astrophysics Data System (ADS)

Guo, Yanfeng; Wang, Xia; Li, Jun; Yamaura, Kazunari; Takayama-Muromachi, Eiji

2012-02-01

Nature of the magnetism for iron-based superconductors (FeSCs) has been actively studied since the discovery of this new family of compounds in 2008, largely owing to its significance for interpreting the paring mechanism. The approach through impurity substitution to shed light into this issue is always one of major ways. The substitution shows distinct responses to species of impurities, where partially replacement of Fe in parent FeSCs with a variety of d-metals like Co, Ni Ru, Rh, Pd, Ir, and Pt generally results in superconductivity, while recent progress in Zn doped FeSCs gives rather contrary result, where Zn severely degenerates the TC. Herein we show the magnetic and electrical studies on BaFe2-xZnxAs2 single crystals. Nonmagnetic Zn doping progressively suppresses the SDW without resulting in superconductivity, while it alternatively develops the spin-glass state, possibly suggestive of local magnetic moment around the Fe sites induced by Zn. The characterizations by X-ray diffraction, magnetic and electrical transport properties, specific heat capacity, and Hall coefficient have been done and the results will be discussed in detail.

Active Salt/Silica-Templated 2D Mesoporous FeCo-Nx -Carbon as Bifunctional Oxygen Electrodes for Zinc-Air Batteries.

PubMed

Li, Shuang; Cheng, Chong; Zhao, Xiaojia; Schmidt, Johannes; Thomas, Arne

2018-02-12

Two types of templates, an active metal salt and silica nanoparticles, are used concurrently to achieve the facile synthesis of hierarchical meso/microporous FeCo-N x -carbon nanosheets (meso/micro-FeCo-N x -CN) with highly dispersed metal sites. The resulting meso/micro-FeCo-N x -CN shows high and reversible oxygen electrocatalytic performances for both ORR and OER, thus having potential for applications in rechargeable Zn-air battery. Our approach creates a new pathway to fabricate 2D meso/microporous structured carbon architectures for bifunctional oxygen electrodes in rechargeable Zn-air battery as well as opens avenues to the scale-up production of rationally designed heteroatom-doped catalytic materials for a broad range of applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trace Metals Derived from Electronic Cigarette (ECIG) Generated Aerosol: Potential Problem of ECIG Devices That Contain Nickel

PubMed Central

Palazzolo, Dominic L.; Crow, Andrew P.; Nelson, John M.; Johnson, Robert A.

2017-01-01

Introduction: ECIGs are currently under scrutiny concerning their safety, particularly in reference to the impact ECIG liquids (E-liquids) have on human health. One concern is that aerosolized E-liquids contain trace metals that could become trapped in respiratory tissues and induce pathology. Methods: To mimic this trapping, peristaltic pumps were used to generate and transport aerosol onto mixed cellulose ester (MCE) membranes where aluminum (Al), arsenic (As), cadmium (Cd), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), and zinc (Zn) were subsequently captured and quantified. The presence of trace metals on unexposed MCE membranes and on MCE membranes exposed to mainstream smoke served as control and comparison, respectively. The presence of these metals was also determined from the E-liquid before aerosolization and untouched by the ECIG device. All metals were quantified using ICP-MS. The ECIG core assembly was analyzed using scanning electron microscopy with elemental analysis capability. Results: The contents (μg) of Al, As, Cd, Cu, Fe, Mn, Ni, Pb, and Zn on control MCE membranes were 1.2 ± 0.2, 0.050 ± 0.002, 0.047 ± 0.003, 0.05 ± 0.01, 0.001 ± 0.001, 0.16 ± 0.04, 0.005 ± 0.003, 0.014 ± 0.006, and 0.09 ± 0.02, respectively. The contents of all trace metals on MCE membranes exposed to aerosol were similar to controls, except Ni which was significantly (p < 0.01) higher (0.024 ± 0.004 μg). In contrast, contents of Al, As, Fe, Mn, and Zn on MCE membranes exposed to smoke were significantly higher (p < 0.05) than controls. The contents of Al, As, Cu, Fe, and Mn on smoke-exposed MCE membranes were also significantly higher (p < 0.05) than their content on aerosol-exposed membranes. The contents per cigarette equivalent of metals in E-liquid before aerosolization were negligible compared to amounts of aerosolized E-liquid, except for Fe (0.002 μg before and 0.001 μg after). Elemental analysis of the core assembly reveals the presence of several of these trace metals, especially Al, Fe, Ni, and Zn. Conclusions: In general, from the single ECIG-device/E-liquid combination used, the amount of trace metals from ECIG-generated aerosol are lower than in traditional mainstream smoke, Only Ni in the ECIG-generated aerosol was higher than control. The most probable source of Ni in this aerosol is the core assembly. PMID:28119618

Pollution characteristics, source apportionment, and health risk of heavy metals in street dust of Suzhou, China.

PubMed

Lin, Manli; Gui, Herong; Wang, Yao; Peng, Weihua

2017-01-01

To analyze the pollution characteristics, source apportionment, and health risk of heavy metals (HMs) in street dust of Suzhou, China, 23 sampling sites were selected and periodically sampled for 12 months. A total of 276 samples were collected, and the concentrations of selected HMs (e.g., Cr, Cu, Fe, Mn, Pb, V, and Zn) were examined with an X-ray fluorescence spectrum analyzer. Results showed that the mean concentrations of Cr, Cu, Fe, Mn, Pb, V, and Zn in the street dust of Suzhou were 112.9, 27.5, 19941.3, 410.3, 45.2, 75.6, and 225.3 mg kg -1 , respectively. Cr, Cu, Pb, and Zn exceeded their background values in local natural soils by 1.3-3.6-fold, whereas Fe, Mn, and V were all within their background values. However, enrichment factor analysis revealed that Cr, Cu, Mn, Pb, V, and Zn, especially Cr, Cu, Pb, and Zn, were enriched in Suzhou street dust. The HMs showed no significant seasonal changes overall, but spatial distribution analysis implied that the high values of Cr, Cu, Mn, Pb, V, and Zn were mainly distributed in areas with frequent human activities. Results of multivariate techniques (e.g., Pearson correlation, hierarchical cluster, and principal components analyses) suggested that Pb and Zn had complicated sources; Cu and V mainly originated from traffic sources; Fe and Mn mainly came from natural sources; and Cr was dominantly related to industrial district. Health risk assessment revealed that a single heavy metal might not cause both non-cancer and carcinogenic risks to local residents. Nevertheless, the sum of the hazard index of all selected HMs for children slightly exceeded the safety value, thereby implying that the HMs from Suzhou street dust can possibly produce significant risk to children. Cr was the priority pollutant in the study area because of its high concentration, high enrichment, and high contribution to non-cancer risk values.

Antibacterial activity of trimetal (CuZnFe) oxide nanoparticles.

PubMed

Alzahrani, Khalid E; Niazy, Abdurahman A; Alswieleh, Abdullah M; Wahab, Rizwan; El-Toni, Ahmed M; Alghamdi, Hamdan S

2018-01-01

The increasing resistance of pathogenic bacteria to antibiotics is a challenging worldwide health problem that has led to the search for new and more efficient antibacterial agents. Nanotechnology has proven to be an effective tool for the fight against bacteria. In this paper, we present the synthesis and traits of trimetal (CuZnFe) oxide nanoparticles (NPs) using X-ray diffraction, high-resolution transmission electron microscopy, and energy dispersive x-ray spectroscopy. We evaluated the antibacterial activity of these NPs against gram-negative Escherichia coli and gram-positive Enterococcus faecalis and then compared it to that of their pure single-metal oxide components CuO and ZnO. Our study showed that the antibacterial activity of the trimetal oxide NPs was greater against E . coli than against E . faecalis . Overall, the antimicrobial effect of trimetal NPs is between those of pure ZnO and CuO nanoparticles, which may mean that their cytotoxicity is also between that of pure ZnO and CuO NPs, making them potential antibiotics. However, the cytotoxicity of trimetal NPs to mammalian cells needs to be verified. The combination of three metal oxide NPs (ZnO, CuO, and Fe 2 O 3 ) in one multimetal (CuZnFe) oxide NPs will enhance the therapeutic strategy against a wide range of microbial infections. Bacteria are unlikely to develop resistance against this new NP because bacteria must go through a series of mutations to become resistant to the trimetal oxide NP. Therefore, this NP can combat existing and emerging bacterial infections.

Multivariate analysis and geochemical approach for assessment of metal pollution state in sediment cores.

PubMed

Jamshidi-Zanjani, Ahmad; Saeedi, Mohsen

2017-07-01

Vertical distribution of metals (Cu, Zn, Cr, Fe, Mn, Pb, Ni, Cd, and Li) in four sediment core samples (C 1 , C 2 , C 3 , and C 4 ) from Anzali international wetland located southwest of the Caspian Sea was examined. Background concentration of each metal was calculated according to different statistical approaches. The results of multivariate statistical analysis showed that Fe and Mn might have significant role in the fate of Ni and Zn in sediment core samples. Different sediment quality indexes were utilized to assess metal pollution in sediment cores. Moreover, a new sediment quality index named aggregative toxicity index (ATI) based on sediment quality guidelines (SQGs) was developed to assess the degree of metal toxicity in an aggregative manner. The increasing pattern of metal pollution and their toxicity degree in upper layers of core samples indicated increasing effects of anthropogenic sources in the study area.

Role of metals in free radical generation and genotoxicity induced by airborne particulate matter (PM2.5) from Pune (India).

PubMed

Yadav, Suman; Jan, Rohi; Roy, Ritwika; Satsangi, P Gursumeeran

2016-12-01

In the present study, metal-facilitated free radical generation in particulate matter (PM) and its association with deoxyribonucleic acid (DNA) damage were studied. The examined data showed that the concentration of fine PM in Pune exhibited seasonal variations. Inductively coupled plasma-atomic emission spectrometry (ICP-AES) was used to examine the metal composition, which showed the presence of metals such as Cu, Zn, Mn, Fe, Co, Cr, Pb, Cd, and Ni. Fe metal was present in the highest concentrations in both the seasons, followed by Zn. The scanning electron microscopy-energy-dispersive spectrometer (SEM-EDS) results also demonstrated that the fine PM particles deposited in summer samples were less than those of winter samples, suggesting that the PM load in winter was higher as compared to that in summer. Elemental mapping of these particles substantiates deposition of metals as Fe, Zn, etc. on particles. The electron paramagnetic species (EPR) technique was utilized for free radical detection, and plasmid DNA assay was utilized to study the genotoxicity of ambient fine PM. Obtained g values show the presence of radicals in PM samples of Pune. PM contains the C-centered radical with a vicinal oxygen atom (g = 2.003). In addition to this, the g value for Fe was also observed. Therefore, we intend that the radicals related with fine PM comprise metal-mediated radicals and produce DNA damage. The plasmid DNA assay results indicated that the TM 50 values (toxic mass of PM causing 50 % of plasmid DNA damage) of PM exhibited seasonal variations with higher TM 50 values for summer and lower TM 50 values during winter.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Huan; Zhang, Weiguo; Qian, Yu

This study investigates the distributions of Br, Ca, Cl, Cr, Cu, K, Fe, Mn, Pb, Ti, V and Zn inPhragmites australisroot system and the function of Fe nanoparticles in scavenging metals in the root epidermis using synchrotron X-ray microfluorescence, synchrotron transmission X-ray microscope measurement and synchrotron X-ray absorption near-edge structure techniques. The purpose of this study is to understand the mobility of metals in wetland plant root systems after their uptake from rhizosphere soils.Phragmites australissamples were collected in the Yangtze River intertidal zone in July 2013. The results indicate that Fe nanoparticles are present in the root epidermis and thatmore » other metals correlate significantly with Fe, suggesting that Fe nanoparticles play an important role in metal scavenging in the epidermis.« less

Coordinatively Unsaturated Metal-Organic Frameworks M3(btc)2 (M = Cr, Fe, Co, Ni, Cu, and Zn) Catalyzing the Oxidation of CO by N2O: Insight from DFT Calculations.

PubMed

Ketrat, Sombat; Maihom, Thana; Wannakao, Sippakorn; Probst, Michael; Nokbin, Somkiat; Limtrakul, Jumras

2017-11-20

The oxidation of CO by N 2 O over metal-organic framework (MOF) M 3 (btc) 2 (M = Fe, Cr, Co, Ni, Cu, and Zn) catalysts that contain coordinatively unsaturated sites has been investigated by means of density functional theory calculations. The reaction proceeds in two steps. First, the N-O bond of N 2 O is broken to form a metal oxo intermediate. Second, a CO molecule reacts with the oxygen atom of the metal oxo site, forming one C-O bond of CO 2 . The first step is a rate-determining step for both Cu 3 (btc) 2 and Fe 3 (btc) 2 , where it requires the highest activation energy (67.3 and 19.6 kcal/mol, respectively). The lower value for the iron compound compared to the copper one can be explained by the larger amount of electron density transferred from the catalytic site to the antibonding of N 2 O molecules. This, in turn, is due to the smaller gap between the highest occupied molecular orbital (HOMO) of the MOF and the lowest unoccupied molecular orbital (LUMO)  of N 2 O for Fe 3 (btc) 2 compared to Cu 3 (btc) 2 . The results indicate the important role of charge transfer for the N-O bond breaking in N 2 O. We computationally screened other MOF M 3 (btc) 2 (M = Cr, Fe, Co, Ni, Cu, and Zn) compounds in this respect and show some relationships between the activation energy and orbital properties like HOMO energies and the spin densities of the metals at the active sites of the MOFs.

Exploring the Photovoltaic Properties of Metal Bipyridine Complexes (Metal = Fe, Zn, Cr, and Ru) by Density Functional Theory

NASA Astrophysics Data System (ADS)

Irfan, Ahmad; Abbas, Ghulam

2018-03-01

The synthesis and characterisation of mononuclear Fe complexes were carried out by using bipyridine (Compound 1) at ambient conditions. Additionally, three more derivatives were designed by substituting the central Fe metal with Zn, Cr, and Ru (Compound 2, Compound 3, and Compound 4), respectively. The ground state geometry calculations were carried out by using density functional theory (DFT) at B3LYP/6-31G** (LANL2DZ) level of theory. We shed light on the frontier molecular orbitals, electronic properties, photovoltaic parameters, and structure-property relationship. The open-circuit voltage is a promising parameter that considerably affects the photovoltaic performance; thus, we have estimated its value by considering the complexes as donors whereas TiO2 and/or Si were used as acceptors. The solar cell performance behaviour was also studied by shedding light on the band alignment and energy level offset.

Crystal structure of the Entamoeba histolytica RNA lariat debranching enzyme EhDbr1 reveals a catalytic Zn 2+/Mn 2+ heterobinucleation

DOE PAGES

Ransey, Elizabeth; Paredes, Eduardo; Dey, Sourav K.; ...

2017-05-17

Here, the RNA lariat debranching enzyme, Dbr1, is a metallophosphoesterase that cleaves 2'-5' phosphodiester bonds within intronic lariats. Previous reports have indicated that Dbr1 enzymatic activity is supported by diverse metal ions including Ni 2+, Mn 2+, Mg 2+, Fe 2+, and Zn 2+. While in initial structures of the Entamoeba histolytica Dbr1 only one of the two catalytic metal-binding sites were observed to be occupied (with a Mn 2+ ion), recent structures determined a Zn 2+/Fe 2+ heterobinucleation. We solved a high-resolution X-ray crystal structure (1.8 Å) of the E. histolytica Dbr1 and determined a Zn 2+/Mn 2+ occupancy.more » ICP-AES corroborate this finding, and in vitro debranching assays with fluorescently labeled branched substrates confirm activity.« less

Crystal structure of the Entamoeba histolytica RNA lariat debranching enzyme EhDbr1 reveals a catalytic Zn 2+/Mn 2+ heterobinucleation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ransey, Elizabeth; Paredes, Eduardo; Dey, Sourav K.

Here, the RNA lariat debranching enzyme, Dbr1, is a metallophosphoesterase that cleaves 2'-5' phosphodiester bonds within intronic lariats. Previous reports have indicated that Dbr1 enzymatic activity is supported by diverse metal ions including Ni 2+, Mn 2+, Mg 2+, Fe 2+, and Zn 2+. While in initial structures of the Entamoeba histolytica Dbr1 only one of the two catalytic metal-binding sites were observed to be occupied (with a Mn 2+ ion), recent structures determined a Zn 2+/Fe 2+ heterobinucleation. We solved a high-resolution X-ray crystal structure (1.8 Å) of the E. histolytica Dbr1 and determined a Zn 2+/Mn 2+ occupancy.more » ICP-AES corroborate this finding, and in vitro debranching assays with fluorescently labeled branched substrates confirm activity.« less

Observed and modeled seasonal trends in dissolved and particulate Cu, Fe, Mn, and Zn in a mining-impacted stream.

PubMed

Butler, Barbara A; Ranville, James F; Ross, Philippe E

2008-06-01

North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with discharge directly related to snowmelt and strong seasonal storms. Additionally, conditions in the stream cause rapid precipitation of large amounts of hydrous iron oxides (HFO) that sequester metals. Because AMD-impacted systems are complex, geochemical modeling may assist with predictions and/or confirmations of processes occurring in these environments. This research used Visual-MINTEQ to determine if field data collected over a two and one-half year study would be well represented by modeling with a currently existing model, while limiting the number of processes modeled and without modifications to the existing model's parameters. Observed distributions between dissolved and particulate phases in the water column varied greatly among the metals, with average dissolved fractions being >90% for Mn, approximately 75% for Zn, approximately 30% for Cu, and <10% for Fe. A strong seasonal trend was observed for the metals predominantly in the dissolved phase (Mn and Zn), with increasing concentrations during base-flow conditions and decreasing concentrations during spring-runoff. This trend was less obvious for Cu and Fe. Within hydrologic seasons, storm events significantly influenced in-stream metals concentrations. The most simplified modeling, using solely sorption to HFO, gave predicted percentage particulate Cu results for most samples to within a factor of two of the measured values, but modeling data were biased toward over-prediction. About one-half of the percentage particulate Zn data comparisons fell within a factor of two, with the remaining data being under-predicted. Slightly more complex modeling, which included dissolved organic carbon (DOC) as a solution phase ligand, significantly reduced the positive bias between observed and predicted percentage particulate Cu, while inclusion of hydrous manganese oxide (HMO) yielded model results more representative of the observed percentage particulate Zn. These results indicate that there is validity in the use of an existing model, without alteration and with typically collected water chemistry data, to describe complex natural systems, but that processes considered optimal for one metal might not be applicable for all metals in a given water sample.

Impacts of human activity modes and climate on heavy metal "spread" in groundwater are biased.

PubMed

Chen, Ming; Qin, Xiaosheng; Zeng, Guangming; Li, Jian

2016-06-01

Groundwater quality deterioration has attracted world-wide concerns due to its importance for human water supply. Although more and more studies have shown that human activities and climate are changing the groundwater status, an investigation on how different groundwater heavy metals respond to human activity modes (e.g. mining, waste disposal, agriculture, sewage effluent and complex activity) in a varying climate has been lacking. Here, for each of six heavy metals (i.e. Fe, Zn, Mn, Pb, Cd and Cu) in groundwater, we use >330 data points together with mixed-effect models to indicate that (i) human activity modes significantly influence the Cu and Mn but not Zn, Fe, Pb and Cd levels, and (ii) annual mean temperature (AMT) only significantly influences Cu and Pb levels, while annual precipitation (AP) only significantly affects Fe, Cu and Mn levels. Given these differences, we suggest that the impacts of human activity modes and climate on heavy metal "spread" in groundwater are biased. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of processing on the proximate and metal contents in three fish species from Nigerian coastal waters

PubMed Central

Bassey, Francisca I; Oguntunde, Fehintola C; Iwegbue, Chukwujindu M A; Osabor, Vincent N; Edem, Christopher A

2014-01-01

The effects of culinary practices such as boiling, frying, and grilling on the proximate compositions and concentrations of metals (Cd, Pb, Cr, Zn, Fe, Cu, Mn, Ni, and Hg) in commonly consumed fish species from the Nigerian coastal waters were investigated. The selected fish species were Polydactylus quadratifilis, Chrysicthys nigrodigitatus and Cynoglossus senegalensis. The culinary practices lead to increased protein, fat, and ash contents and decreased moisture contents of these fish species. The culinary practices resulted significant increase in the concentrations of most of the studied metals and decrease in the concentrations of Fe, Cr, and Pb in some fish types. The concentrations and estimated dietary intakes of Cd, Pb, Cr, Zn, Fe, Cu, Mn, Ni, and Hg from consumption of the processed fish were within their statutory safe limits. The individual metal target hazard quotient (THQ) values and the total THQs were less than 1 which indicates that no health risks would arise from the long-term consumption of these fish species. PMID:24936297

A multifunctional Schiff base as a fluorescence sensor for Fe3 + and Zn2 + ions, and a colorimetric sensor for Cu2 + and applications

NASA Astrophysics Data System (ADS)

Tang, Xu; Han, Juan; Wang, Yun; Ni, Liang; Bao, Xu; Wang, Lei; Zhang, Wenli

2017-02-01

Chemosensors play important parts in the selective recognition of ions, which is widely applied in various fields of environment, industry and biological sciences. In this work, a chemosensor for multi-metal ions based on rhodamine B derivative was synthesized, which could selectively recognize various metal ions in different solvent system. The addition of Cu2 + caused the color change from colorless to pink in EtOH/H2O (v/v = 1:1) solvent system, which could be quickly identified by the naked eyes with a detection limit of 8.27 × 10- 8 M. In ethanol solution system, the addition of Fe3 + and Zn2 + caused different fluorescence changes with the detection limit of 2.12 × 10- 7 M and 6.64 × 10- 7 M respectively. The binding ratios are 1:1 (1-Cu2 +), 2:1 (1-Fe3 +) and 1:1 (1-Zn2 +), respectively. Meanwhile, the probe 1 was used to detect the trace metal ions in real water samples. Besides, the probe 1 showed sensitive fluorescence signals for Fe3 + in biological cells. The experimental results further verify the application value of the sensor.

Mineralogic sources of metals in leachates from the weathering of sedex, massive sulfide, and vein deposit mining wastes

USGS Publications Warehouse

Diehl, S.F.; Hageman, P.L.; Seal, R.R.; Piatak, N.M.; Lowers, H.

2011-01-01

Weathered mine waste consists of oxidized primary minerals and chemically unstable secondary phases that can be sources of readily soluble metals and acid rock drainage. Elevated concentrations of metals such as Cd, Cu, Fe, Mn, Ni, Pb, and Zn are observed in deionized water-based leachate solutions derived from complex sedex and Cu-Pb-Zn mine wastes. Leachate (USGS FLT) from the Elizabeth mine, a massive sulfide deposit, has a pH of 3.4 and high concentrations of Al (16700 ug/L), Cu (440 ug/L), and Zn (8620 ug/L). Leachate from the sedex Faro mine has a pH of 3.5 and high concentrations of Al (2040 ug/L), Cu (1930 ug/L), Pb (2080 ug/L), and Zn (52900 ug/L). In contrast, higher-pH leachates produced from tailings of polymetallic vein deposits have order of magnitude lower metal concentrations. These data indicate that highly soluble secondary mineral phases exist at the surface of waste material where the samples were collected. Sulfide minerals from all sites exhibit differential degrees of weathering, from dissolution etched grain rims, to rinds of secondary minerals, to skeletal remnants. These microscale mineral-dissolution textures enhance weathering and metal teachability of waste material. Besides the formation of secondary minerals, sulfide grains from dried tailings samples may be coated by amorphous Fe-Al-Si minerals that also adsorb metals such as Cu, Ni, and Zn.

Speciation and leaching of trace metal contaminants from e-waste contaminated soils.

PubMed

Cui, Jin-Li; Luo, Chun-Ling; Tang, Chloe Wing-Yee; Chan, Ting-Shan; Li, Xiang-Dong

2017-05-05

Primitive electrical and electronic waste (e-waste) recycling activities have caused serious environmental problems. However, little is known about the speciation and leaching behaviors of metal contaminants at e-waste contaminated sites. This study investigated trace metal speciation/mobilization from e-waste polluted soil through column leaching experiments involving irrigation with rainwater for almost 2.5 years. Over the experimental period, Cu and Zn levels in the porewater were 0.14±0.08mg/L, and 0.16±0.08mg/L, respectively, increasing to 0.33±0.16mg/L, and 0.69±0.28mg/L with plant growth. The amounts of Cu, Zn, and Pb released in surface soil (0-2cm) contributed 43.8%, 22.5%, and 13.8%, respectively, to the original levels. The released Cu and Zn were primarily caused by the mobilization of the carbonate species of metals, including Cu(OH) 2 , CuCO 3 , and Zn 5 (CO 3 ) 2 (OH) 6 , and amorphous Fe/Mn oxides associated fractions characterized by sequential extraction coupling with X-ray absorption spectroscopy. During the experiments, trace metals were not detected in the effluent, and the re-sequestration of trace metals was mainly attributed to the adsorption on the abundant Fe/Mn oxides in the sub-layer soil. This study quantitatively elucidated the molecular speciation of Cu and Zn in e-waste contaminated soil during the column leaching process. Copyright © 2017 Elsevier B.V. All rights reserved.

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

NASA Astrophysics Data System (ADS)

Isaure, Marie-Pierre; Laboudigue, Agnès; Manceau, Alain; Sarret, Géraldine; Tiffreau, Christophe; Trocellier, Patrick; Lamble, Géraldine; Hazemann, Jean-Louis; Chateigner, Daniel

2002-05-01

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn 2SiO 4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn 2SiO 4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.

Synthesis of metal-doped Mn-Zn ferrite from the leaching solutions of vanadium slag using hydrothermal method

NASA Astrophysics Data System (ADS)

Liu, Shiyuan; Wang, Lijun; Chou, Kuochih

2018-03-01

Using vanadium slag as raw material, Metal-doped Mn-Zn ferrites were synthesized by multi-step processes including chlorination of iron and manganese by NH4Cl, selective oxidation of Fe cation, and hydrothermal synthesis. The phase composition and magnetic properties of synthesized metal-doped Mn-Zn ferrite were characterized by X-ray powder diffraction, Raman spectroscopy, transmission electron microscopy (TEM), X-ray photon spectra (XPS) and physical property measurement. It was found that Mn/Zn mole ratio significantly affected the magnetic properties and ZnCl2 content significantly influenced the purity of the phase of ferrite. Synthesized metal-doped Mn-Zn ferrite, exhibiting a larger saturation magnetization (Ms = 60.01 emu/g) and lower coercivity (Hc = 8.9 Oe), was obtained when the hydrothermal temperature was controlled at 200 °C for 12 h with a Mn/Zn mole ratio of 4. The effect of ZnCl2 content, Mn/Zn mole ratio and temperature on magnetic properties of the synthesized metal-doped Mn-Zn ferrite were systemically investigated. This process provided a new insight to utilize resources in the aim of obtaining functional materials.

Impact of biostimulated redox processes on metal dynamics in an iron-rich creek soil of a former uranium mining area.

PubMed

Burkhardt, Eva-Maria; Akob, Denise M; Bischoff, Sebastian; Sitte, Jana; Kostka, Joel E; Banerjee, Dipanjan; Scheinost, Andreas C; Küsel, Kirsten

2010-01-01

Understanding the dynamics of metals and radionuclides in soil environments is necessary for evaluating risks to pristine sites. An iron-rich creek soil of a former uranium-mining district (Ronneburg, Germany) showed high porewater concentrations of heavy metals and radionuclides. Thus, this study aims to (i) evaluate metal dynamics during terminal electron accepting processes (TEAPs) and (ii) characterize active microbial populations in biostimulated soil microcosms using a stable isotope probing (SIP) approach. In biostimulated soil slurries, concentrations of soluble Co, Ni, Zn, As, and unexpectedly U increased during Fe(III)-reduction. This suggests that there was a release of sorbed metals and As during reductive dissolution of Fe(III)-oxides. Subsequent sulfate-reduction was concurrent with a decrease of U, Co, Ni, and Zn concentrations. The relative contribution of U(IV) in the solid phase changed from 18.5 to 88.7% after incubation. The active Fe(III)-reducing population was dominated by delta-Proteobacteria (Geobacter) in (13)C-ethanol amended microcosms. A more diverse community was present in (13)C-lactate amended microcosms including taxa related to Acidobacteria, Firmicutes, delta-Proteobacteria, and beta-Proteobacteria. Our results suggested that biostimulated Fe(III)-reducing communities facilitated the release of metals including U to groundwater which is in contrast to other studies.

Potentiometric and spectroscopic study of the interaction of 3d transition metal ions with inositol hexakisphosphate

NASA Astrophysics Data System (ADS)

Veiga, Nicolás; Macho, Israel; Gómez, Kerman; González, Gabriel; Kremer, Carlos; Torres, Julia

2015-10-01

Among myo-inositol phosphates, the most abundant in nature is the myo-inositol hexakisphosphate, InsP6. Although it is known to be vital to cell functioning, the biochemical research into its metabolism needs chemical and structural analysis of all the protonation, complexation and precipitation processes that it undergoes in the biological media. In view of its high negative charge at physiological level, our group has been leading a thorough research into the InsP6 chemical and structural behavior in the presence of the alkali and alkaline earth metal ions essential for life. The aim of this article is to extend these studies, dealing with the chemical and structural features of the InsP6 interaction with biologically relevant 3d transition metal ions (Fe(II), Fe(III), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)), in a non-interacting medium and under simulated physiological conditions. The metal-complex stability constants were determined by potentiometry, showing under ligand-excess conditions the formation of mononuclear species in different protonation states. Under metal ion excess, polymetallic species were detected for Fe(II), Fe(III), Zn(II) and Cu(II). Additionally, the 31P NMR and UV-vis spectroscopic studies provided interesting structural aspects of the strong metal ion-InsP6 interaction.

Concentration and emission sources of airborne metals in particulate matter in the industrial district of Médio Paraíba, state of Rio de Janeiro, Brazil.

PubMed

Loyola, Josiane; de Almeida, Pierre Batista; Quiterio, Simone Lorena; Sousa, Célia Regina; Arbilla, Graciela; Escaleira, Viviane; de Carvalho, Maria Isabel; dos Santos Amaral Gomes da Silva, Alzira

2006-11-01

Total suspended particles and 12 airborne metals were determined in 4 sampling sites in the industrial region of Médio Paraíba, Brazil. The geometrical means for the four sampling locals were (in units of microg/m3): 65.9 in Barra Mansa, 57.3 in Jardim Paraíba (Volta Redonda), 41.7 in Resende, and 48.9 in Volta Grande (Volta Redonda). These values are lower than levels previously determined in urban and industrial locals of the Metropolitan Area of Rio de Janeiro. For metals, the higher concentrations were obtained for Ca, Zn, Al, Fe, and Mg. Ca, Zn, and Al levels are higher than those determined in other industrial areas. These three metals are used in steel manufacturing, the main economical activity of the region. Enrichment factors for Zn, Cu, Cd, and Pb are higher than 10, suggesting an industrial input. Statistical analysis show a high correlation among Ca, Mg, Zn, Cr, Al, Mn, and Fe, all of them used as raw materials in steel manufacturing and/or accumulated as industrial blast furnace slag and steelworks slag.

Effect of citric acid on metals mobility in pruning wastes and biosolids compost and metals uptake in Atriplex halimus and Rosmarinus officinalis.

PubMed

Tapia, Y; Eymar, E; Gárate, A; Masaguer, A

2013-05-01

To assess metal mobility in pruning waste and biosolids compost (pH 6.9 and total concentration of metals in milligram per kilogram of Cd 1.9, Cu 132, Fe 8,513, Mn 192, Pb 81, and Zn 313), shrubs species Atriplex halimus and Rosmarinus officinalis were transplanted in this substrate and irrigated with citric acid (4 g L(-1), pH 2.9) and nutrient solution daily for 60 days. Citric acid significantly increased the concentrations of soluble Mn and Fe in the nutrient substrate solution measured by suction probes, while other metals did not vary in concentration (Cu and Zn) or were not observed at detectable levels (Cd and Pb). In plants, citric acid significantly increased the concentrations of Cu (2.7 ± 0.1-3.3 ± 0.1 mg kg(-1)), Fe (49.2 ± 5.2-76.8 ± 6.8 mg kg(-1)), and Mn (7.2 ± 1.1-11.4 ± 0.7 mg kg(-1)) in leaves of R. officinalis, whereas the concentration of only Mn (25.4 ± 0.3-42.2 ± 2.9 mg kg(-1)) was increased in A. halimus. Increasing Fe and Mn solubility by citric acid addition indicates the possibility of using it to improve plant nutrition. The mobility of metals in this substrate was influenced for the concentration of the metal, the degree of humification of organic matter and its high Fe content.

X-ray diffraction study of the caged magnetic compound DyFe 2 Zn 20 at low temperatures

NASA Astrophysics Data System (ADS)

Ohashi, M.; Ohashi, K.; Sawabu, M.; Miyagawa, M.; Maeta, K.; Isikawa, Y.

2018-05-01

We have carried out high-angle X-ray powder diffraction measurements of the caged magnetic compound DyFe2Zn20 at low temperature between 14 and 300 K. Even though a strong magnetic anisotropy exists in the magnetization and magnetic susceptibility due to strong exchange interaction between Fe and Dy, almost all X-ray powder diffraction peaks correspond to Bragg reflections of the cubic structural models not only at room temperature paramagnetic state but also at low temperature magnetic ordering state. The Debye temperature is obtained to be 227 K from the results of the volumetric thermal expansion coefficient, which is approximately coincident with that of CeRu2Zn20 (245 K) and that of pure Zn metal (235 K).

Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils

DOE PAGES

Boiteau, Rene M.; Shaw, Jared B.; Pasa-Tolic, Ljiljana; ...

2018-03-08

Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or howmore » they interact and compete for metal binding. Identifying these metallophores within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrices. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) of soils from native tallgrass prairies in Kansas and Iowa. Both plant and fungal metallophores were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant Fe acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamines, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2–90 pmol/g soil). In contrast, the fungal siderophore ferricrocin was specific for trivalent Fe (7–32 pmol/g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. In conclusion, small structural modifications result in significant differences in metal ligand selectivity, and likely impact metal uptake within the rhizosphere of grassland soils.« less

Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boiteau, Rene M.; Shaw, Jared B.; Pasa-Tolic, Ljiljana

Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or howmore » they interact and compete for metal binding. Identifying these metallophores within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrices. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) of soils from native tallgrass prairies in Kansas and Iowa. Both plant and fungal metallophores were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant Fe acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamines, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2–90 pmol/g soil). In contrast, the fungal siderophore ferricrocin was specific for trivalent Fe (7–32 pmol/g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. In conclusion, small structural modifications result in significant differences in metal ligand selectivity, and likely impact metal uptake within the rhizosphere of grassland soils.« less

[Long-term effects of tillage methods on heavy metal accumulation and availability in purple paddy soil].

PubMed

Chang, Tong-Ju; Cui, Xiao-Qiang; Ruan, Zhen; Zhao, Xiu-Lan

2014-06-01

A long-term experiment, conducted at Southwest University since 1990, was used to evaluate the effect of tillage methods on the total and available contents of heavy metals (Fe, Mn, Cu, Zn, Pb, Cd) in the profile of purple paddy soil and the contents of those metals in root, stem leaf and brown rice. The experiment included five tillage methods: conventional tillage, paddy-upland rotation, no-tillage and fallow in winter, ridge-no-tillage and compartments-no-tillage. The results showed that the total concentrations of Fe, Cu, Zn, Pb and Cd in the soil profile had no significant differences among five treatments, but it was found that total Mn has a significant decline in 0-20 cm under conventional tillage, paddy-upland rotation and no-tillage and fallow in winter compared with ridge-no-tillage and compartments-no-tillage. The availability of Fe, Cu, Zn, Pb and Cd decreased with the increase of soil depth in all treatments, but the availability of Mn was found to be the highest in the 20-40 cm layers except those in the paddy-upland rotation. In the ploughed layer, the contents of available Fe, Mn was the highest in paddy-upland rotation, while the contents of available Zn and Pb was the highest in conventional tillage, but tillage treatments had not significant influence to the contents of available Cu. Correlation analysis showed that available Fe was significantly negatively related to the pH values and significantly negatively related to the organic matter of soils, available Mn was significantly negatively related to the pH values and organic matter of soils, whereas the available Zn was significantly positively related to total Zn. The contents of Fe, Mn in rice root, the contents of Fe, Mn, Cu and Cd in rice straw and Cu in brown rice were higher under paddy-upland rotation, ridge-no-tillage and compartments-no-tillage than those in conventional tillage and no-tillage and fellow in winter. Paddy-upland rotation can significantly lower the migration coefficient value of Cd in brown rice, and the Pb, Cd concentration in brown rice in the treatment of paddy-upland rotation was lower than the upper limit (< 0.2 mg x kg(-1)) of the National Standard for Food Hygiene for Cd concentration. The content of Fe in root was significantly and negatively related with soil pH and significantly and positively related with soil available Fe, the content of Mn in root was significantly negatively related with soil pH and significantly positively related with soil available Mn, the content of Mn in straw was significantly negatively related with soil pH, significantly positively related with soil total Mn and significantly positively related with soil available Mn, the content of Cu in straw and brown rice was significantly negatively related with soil pH, the content of Zn was significant related with soil pH and significant related with soil CEC. The content of Fe in root, Mn in root and straw and Cd in straw was positively related with soil available Fe, Mn and Cd, respectively, but was negatively related with pH in plough layer soil, Zn in straw was also negatively related with plough layer soil pH. From the results as above, it is concluded that different tillage methods can change the values of soil pH, alter the availability of heavy metal in soils, consequently affect uptake of heavy metal by rice. Of the tillage methods, paddy-upland rotation could increase the availability of Fe and Mn, but decrease the availability of Zn, Pb and Cd in purple paddy soils. Paddy-upland rotation can also increase the contents of Fe, Mn in rice root and straw, but decrease Cd content in brown rice, and could reduce the Pb, Cd contents in brown rice in a certain extent, however, attention should be given to long-term paddy-upland rotation cause of leaching of soil surface Mn.

Speciation and precipitation of heavy metals in high-metal and high-acid mine waters from the Iberian Pyrite Belt (Portugal).

PubMed

Durães, Nuno; Bobos, Iuliu; da Silva, Eduardo Ferreira

2017-02-01

Acid mine waters (AMW) collected during high- and low-flow water conditions from the Lousal, Aljustrel, and São Domingos mining areas (Iberian Pyrite Belt) were physicochemically analyzed. Speciation calculation using PHREEQC code confirms the predominance of Me n+ and Me-SO 4 species in AMW samples. Higher concentration of sulfate species (Me-SO 4 ) than free ion species (Me n+ , i.e., Al, Fe, and Pb) were found, whereas opposite behavior is verified for Mg, Cu, and Zn. A high mobility of Zn than Cu and Pb was identified. The sulfate species distribution shows that Fe 3+ -SO 4 2- , SO 4 2- , HSO 4 - , Al-SO 4 , MgSO 4 0 , and CaSO 4 0 are the dominant species, in agreement with the simple and mixed metal sulfates and oxy-hydroxysulphates precipitated from AMW. The saturation indices (SI) of melanterite and epsomite show a positive correlation with Cu and Zn concentrations in AMW, which are frequently retained in simple metal sulfates. Lead is well correlated with jarosite and alunite (at least in very acid conditions) than with simple metal sulfates. The Pb for K substitution in jarosite occurs as increasing Pb concentration in solution. Lead mobility is also controlled by anglesite precipitation (a fairly insoluble sulfate), where a positive correlation was ascertained when the SI approaches equilibrium. The zeta potential of AMW decreased as pH increased due to colloidal particles aggregation, where water species change from SO 4 2- to OH - species during acid to alkaline conditions, respectively. The AMW samples were supersaturated in schwertmannite and goethite, confirmed by the Me n+ -SO 4 , Me n+ -Fe-O-OH, or Me n+ -S-O-Fe-O complexes identified by attenuated total reflectance infrared spectroscopy (ATR-IR). The ATR-IR spectrum of an AMW sample with pH 3.5 (sample L1) shows well-defined vibration plans attributed to SO 4 tetrahedron bonded with Fe-(oxy)hydroxides and the Me n+ sorbed by either SO 4 or Fe-(oxy)hydroxides. For samples with lower pH values (pH ~ 2.5-samples SD1 and SD4), the vibration plans attributed to Me n+ sorption are not evidenced, indicating its release in solution. The sorption of heavy metals on the first precipitated simple metal sulfates was ascertained by scanning electron microscopy coupled with X-ray spectrometry (SEM-EDX), where X-ray maps of Cu and Zn confirm a distribution of both metals in the melanterite structure.

A New Test of Copper and Zinc Abundances in Late-type Stars Using Ultraviolet Cu II and Zn II Lines

NASA Astrophysics Data System (ADS)

Roederer, Ian U.; Barklem, Paul S.

2018-04-01

We present new abundances derived from Cu I, Cu II, Zn I, and Zn II lines in six warm (5766 ≤ {T}eff} ≤ 6427 K), metal-poor (‑2.50 ≤ [Fe/H] ≤ ‑0.95) dwarf and subgiant (3.64 ≤ log g ≤ 4.44) stars. These abundances are derived from archival high-resolution ultraviolet spectra from the Space Telescope Imaging Spectrograph on board the Hubble Space Telescope and ground-based optical spectra from several observatories. Ionized Cu and Zn are the majority species, and abundances derived from Cu II and Zn II lines should be largely insensitive to departures from local thermodynamic equilibrium (LTE). We find good agreement between the [Zn/H] ratios derived separately from Zn I and Zn II lines, suggesting that departures from LTE are, at most, minimal (≲0.1 dex). We find that the [Cu/H] ratios derived from Cu II lines are 0.36 ± 0.06 dex larger than those derived from Cu I lines in the most metal-poor stars ([Fe/H] < ‑1.8), suggesting that LTE underestimates the Cu abundance derived from Cu I lines. The deviations decrease in more metal-rich stars. Our results validate previous theoretical non-LTE calculations for both Cu and Zn, supporting earlier conclusions that the enhancement of [Zn/Fe] in metal-poor stars is legitimate, and the deficiency of [Cu/Fe] in metal-poor stars may not be as large as previously thought. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained from the data archive at the Space Telescope Science Institute (STScI), which is operated by the Association of Universities for Research in Astronomy, Inc. (AURA) under NASA contract NAS 5-26555. This work is supported by NASA through grant number AR-15051 and makes use of data from programs GO-7348, GO-8197, GO-9804, GO-14161, and GO-14672. This research has also made use of the Keck Observatory Archive (KOA), which is operated by the W.M. Keck Observatory and the NASA Exoplanet Science Institute (NExScI), under contract with NASA. These data are associated with programs C314Hr, H6aH, and H283Hr. Other data have been obtained from the European Southern Observatory (ESO) Science Archive Facility. These data are associated with programs 65.L-0507(A), 67.D-0439(A), and 080.D-0347(A). This work has also made use of data collected from the McDonald Observatory of the University of Texas at Austin.

Charge-density study on layered oxyarsenides (LaO)MAs (M = Mn, Fe, Ni, Zn)

NASA Astrophysics Data System (ADS)

Takase, Kouichi; Hiramoto, Shozo; Fukushima, Tetsuya; Sato, Kazunori; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2017-12-01

Using synchrotron X-ray powder diffraction, we investigate the charge-density distributions of the layered oxypnictides (LaO)MnAs, (LaO)FeAs, (LaO)NiAs, and (LaO)ZnAs, which are an antiferromagnetic semiconductor, a parent material of an iron-based superconductor, a low-temperature superconductor, and a non-magnetic semiconductor, respectively. For the metallic samples, clear charge densities are observed in both the transition-metal pnictide layers and the rare-earth-oxide layers. However, in the semiconducting samples, there is no finite charge density between the transition-metal element and As. These differences in charge density reflect differences in physical properties. First-principles calculations using density functional theory reproduce the experimental results reasonably well.

Bioaccumulation of Heavy Metals in Water, Sediments, and Tissues and Their Histopathological Effects on Anodonta cygnea (Linea, 1876) in Kabul River, Khyber Pakhtunkhwa, Pakistan

PubMed Central

Khan, Muhammad Iftikhar; Gulfam, Naila; Siraj, Muhammad; Zaidi, Farrah; Ahmadullah; Abidullah; Fatima, Syeda Hira; Noreen, Shumaila; Hamidullah; Shah, Zafar Ali; Qadir, Fazli

2018-01-01

The present investigation aimed to assess the concentrations of selected heavy metals in water and sediments and their bioaccumulation in tissues of freshwater mussels and their histopathological effects on the digestive gland, gills, and gonads of Anodonta cygnea. Water, sediments, and freshwater mussel samples were collected at four sites, that is, reference and polluted sites, along the Kabul River, Khyber Pakhtunkhwa. The polluted sites were receiving effluents from the industrial, agricultural, municipal, and domestic sources. The order of metals in the water was Zn > Pb > Ni > Cu > Mn > Fe > Cr > Cd, in sediments the order was Fe > Zn > Cr > Ni > Mn > Pb > Cu > Cd, and in the soft tissues the order was Fe > Zn > Mn > Pb > Cu > Cr > Ni > Cd. Histopathological alterations observed in polluted sites of Kabul River were inflammation, hydropic vacuolation, and lipofuscin pigments (in digestive gland), gill lamellar fusion, dilated hemolymphatic sinus, clumping, and generation of cilia and hemocytic infiltration (in gills), and atresia, necrosis, granulocytoma, hemocytic infiltration, and lipofuscin pigments (in gonads). The histopathological alterations in the organs of Anodonta cygnea can be considered as reliable biomarkers in biomonitoring of heavy metal pollution in aquatic ecosystems. PMID:29693003

Neutralization by Metal Ions of the Toxicity of Sodium Selenide

PubMed Central

Dauplais, Marc; Lazard, Myriam; Blanquet, Sylvain; Plateau, Pierre

2013-01-01

Inert metal-selenide colloids are found in animals. They are believed to afford cross-protection against the toxicities of both metals and selenocompounds. Here, the toxicities of metal salt and sodium selenide mixtures were systematically studied using the death rate of Saccharomyces cerevisiae cells as an indicator. In parallel, the abilities of these mixtures to produce colloids were assessed. Studied metal cations could be classified in three groups: (i) metal ions that protect cells against selenium toxicity and form insoluble colloids with selenide (Ag+, Cd2+, Cu2+, Hg2+, Pb2+ and Zn2+), (ii) metal ions which protect cells by producing insoluble metal-selenide complexes and by catalyzing hydrogen selenide oxidation in the presence of dioxygen (Co2+ and Ni2+) and, finally, (iii) metal ions which do not afford protection and do not interact (Ca2+, Mg2+, Mn2+) or weakly interact (Fe2+) with selenide under the assayed conditions. When occurring, the insoluble complexes formed from divalent metal ions and selenide contained equimolar amounts of metal and selenium atoms. With the monovalent silver ion, the complex contained two silver atoms per selenium atom. Next, because selenides are compounds prone to oxidation, the stabilities of the above colloids were evaluated under oxidizing conditions. 5,5'-dithiobis-(2-nitrobenzoic acid) (DTNB), the reduction of which can be optically followed, was used to promote selenide oxidation. Complexes with cadmium, copper, lead, mercury or silver resisted dissolution by DTNB treatment over several hours. With nickel and cobalt, partial oxidation by DTNB occurred. On the other hand, when starting from ZnSe or FeSe complexes, full decompositions were obtained within a few tens of minutes. The above properties possibly explain why ZnSe and FeSe nanoparticles were not detected in animals exposed to selenocompounds. PMID:23342137

Pb2+ and Zn2+ adsorption by a natural aluminum- and iron-bearing surface coating on an aquifer sand

USGS Publications Warehouse

Coston, J.A.; Fuller, C.C.; Davis, J.A.

1995-01-01

Pb2+ and Zn2+ adsorption was studied in batch experiments with material collected from a shallow, unconfined aquifer of glacial outwash sand and gravel in Falmouth, Massachusetts, USA. The aquifer solids contain primarily quartz with minor amounts of alkali feldspars and ferromagnetic minerals. Pb2+ and Zn2+ adsorption experiments with various grain size and mineral fractions of the aquifer solids showed that: 1) Zn2+ adsorption was independent of grain size, but Pb2+ was preferentially adsorbed by the <64 ??m size fraction and 2) Pb2+ adsorption decreased after removal of the paramagnetic, Fe-bearing mineral fraction, but Zn2+ adsorption was unaffected. Pb2+ and Zn2+ adsorption on mineral separates from the aquifer material compared with metal adsorption on a purified quartz powder indicated that adsorption of both metal ions was dominated by coatings on the quartz fraction of the sediment. Characterization of the coatings by AES, SEM-EDS, and TOF-SIMS demonstrated that the natural quartz grains were extensively coated with Al- and Fe-bearing minerals of variable composition. -from Authors

Pb, Cu, and Zn distributions at humic acid-coated metal-oxide surfaces

DOE PAGES

Wang, Yingge; Michel, F. Marc; Choi, Yongseong; ...

2016-05-09

Here, mineral surfaces are often coated by natural organic matter (NOM), which has a major influence on metal-ion sorption and sequestration because of the abundance of binding sites in such coatings and the changes they cause in local nanoscale environments. The effects of NOM coatings on mineral surfaces are, however, still poorly understood at the molecular level due to the complexity of these systems. In this study, we have applied long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy to measure the partitioning of naturally present Cu(II) (0.0226%), Zn(II) (0.009%), and Pb(II) ( 0.0004%) between Elliott Soil Humic Acid (ESHA) coatings andmore » three model single-crystal metal-oxide substrates: α-Al 2O 3 (0 0 0 1), α-Al 2O 3 (1 1 0 2), and α-Fe 2O 3 (0 0 0 1). The competitive sorption effects among these metal ions for binding sites in the ESHA coatings and on the metal-oxide surfaces were investigated as a function of reaction time, calcium content, and solution pH. Pb(II) ions present in the ESHA coatings were found to redistribute to reactive α-Al 2O 3 (1 1 0 2) and α-Fe 2O 3 (0 0 0 1) surfaces after 3 h of reaction (pH = 6.0, [Ca(II)] = 2 mM). Pb(II) partitioning onto these reactive metal-oxide surfaces increased with increasing reaction time (up to 7 d). In addition, the partitioning of Cu(II) and Zn(II) from the ESHA coating to the α-Fe 2O 3 (0 0 0 1) substrate increased slightly with reaction time (2.4% and 3.7% for Cu(II) and Zn(II), respectively, after 3 h and 6.4% and 7.7% for Cu(II) and Zn(II), respectively, after 72 h of reaction time).« less

Evaluation of heavy metals content in dietary supplements in Lebanon

PubMed Central

2013-01-01

Background The consumption of dietary supplements is widely spread and on the rise. These dietary supplements are generally used without prescriptions, proper counseling or any awareness of their health risk. The current study aimed at analyzing the metals in 33 samples of imported dietary supplements highly consumed by the Lebanese population, using 3 different techniques, to ensure the safety and increase the awareness of the citizen to benefit from these dietary supplements. Results Some samples had levels of metals above their maximum allowable levels (Fe: 24%, Zn: 33%, Mn: 27%, Se: 15%, Mo: 12% of samples), but did not pose any health risk because they were below permitted daily exposure limit and recommended daily allowance except for Fe in 6% of the samples. On the other hand, 34% of the samples had Cu levels above allowable limit where 18% of them were above their permitted daily exposure and recommended daily allowance. In contrast, all samples had concentration of Cr, Hg, and Pb below allowable limits and daily exposure. Whereas, 30% of analyzed samples had levels of Cd above allowable levels, and were statistically correlated with Ca, and Zn essential minerals. Similarly 62% of the samples had levels of As above allowable limits and As levels were associated with Fe and Mn essential minerals. Conclusion Dietary supplements consumed as essential nutrients for their Ca, Zn, Fe and Mn content should be monitored for toxic metal levels due to their natural geochemical association with these essential metals to provide citizens the safe allowable amounts. PMID:23331553

Toxic Metals Enrichment in the Surficial Sediments of a Eutrophic Tropical Estuary (Cochin Backwaters, Southwest Coast of India)

PubMed Central

Martin, G. D.; George, Rejomon; Shaiju, P.; Muraleedharan, K. R.; Nair, S. M.; Chandramohanakumar, N.

2012-01-01

Concentrations and distributions of trace metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in surficial sediments of the Cochin backwaters were studied during both monsoon and pre-monsoon periods. Spatial variations were in accordance with textural charaterstics and organic matter content. A principal component analysis distinguished three zones with different metal accumulation capacity: (i) highest levels in north estuary, (ii) moderate levels in central zone, and (iii) lowest levels in southern part. Trace metal enrichments are mainly due to anthropogenic contribution of industrial, domestic, and agricultural effluents, whose effect is enhanced by settling of metals due to organic flocculation and inorganic precipitation associated with salinity changes. Enrichments factors using Fe as a normalizer showed that metal contamination was the product of anthropogenic activities. An assessment of degree of pollution-categorized sediments as moderately polluted with Cu and Pb, moderately-to-heavily polluted with Zn, and heavily-to-extremely polluted with Cd. Concentrations at many sites largely exceed NOAA ERL (e.g., Cu, Cr, and Pb) or ERM (e.g., Cd, Ni, and Zn). This means that adverse effects for benthic organisms are possible or even highly probable. PMID:22645488

Efficiency of several leaching reagents on removal of Cu, Pb, Cd, and Zn from highly contaminated paddy soil.

PubMed

Gao, Ruili; Zhu, Pengfei; Guo, Guangguang; Hu, Hongqing; Zhu, Jun; Fu, Qingling

2016-11-01

The efficiency of five different single leaching reagents (tartaric acid (TA), citric acid (CA), CaCl 2 , FeCl 3 , EDTA) and two different composite leaching reagents (CA + FeCl 3 , CA + EDTA) on removing Cu, Pb, Zn, and Cd from contaminated paddy soil in Hunan Province (in China) was studied. The results indicated that the efficiencies of CA, FeCl 3 , and EDTA on extracting Cu, Pb, Cd, and Zn from soil were greater than that of TA and CaCl 2 , and their extraction efficiencies were EDTA ≥ FeCl 3 > CA. The efficiencies of CA + FeCl 3 on extracting Cu, Pb, Cd, and Zn were higher than that of single CA or FeCl 3 . The 25 mmol L -1 CA + 20 mmol L -1 FeCl 3 was a promising composite leaching reagent for paddy soil, and it could remove Cu (57.6 %), Pb (59.3 %), Cd (84.8 %), and Zn (28.0 %), respectively. With the same amount of leaching reagent, the efficiency of continuous leaching by several times was higher than that by once. In addition, the easily reducible and oxidizable fractions of heavy metals showed significant decrease during the process of leaching.

Nanostructure ZnFe2O4 with Bacillus subtilis for Detection of LPG at Low Temperature

NASA Astrophysics Data System (ADS)

Goutham, Solleti; Kumar, Devarai Santhosh; Sadasivuni, Kishor Kumar; Cabibihan, John-John; Rao, Kalagadda Venkateswara

2017-04-01

The present study deals with the development of a chemical sensor for the detection of liquefied petroleum gas (LPG) at a low operating temperature using Zinc ferrite (ZnFe2O4)/ Bacillus subtilis ( B. subtilis) hybrid nanostructures. The nanostructure ZnFe2O4 and B. subtilis powder, taken in equal proportion was made into films using the spin coating technique. X-ray diffraction, thermal analysis, scanning electron microscopy, and transmission electron microscopy were used to study morphology, structure and crystallite size. The sensing properties of the hybrid structure were studied and excellent response was observed in the temperature range of 50-55°C for 400 ppm LPG, when compared to the individual components of the hybrid. The signal output of the proposed sensor were extremely stable for more than 30 days. This method proposes the usage of the biomolecule/metal oxide composites in electronics and helps to reduce the metal oxide usage.

Synchrotron X-ray microfluorescence measurement of metal distributions in Phragmites australis root system in the Yangtze River intertidal zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Huan; Zhang, Weiguo; Qian, Yu

2016-06-15

This study investigates the distributions of Br, Ca, Cl, Cr, Cu, K, Fe, Mn, Pb, Ti, V and Zn inPhragmites australisroot system and the function of Fe nanoparticles in scavenging metals in the root epidermis using synchrotron X-ray microfluorescence, synchrotron transmission X-ray microscope measurement and synchrotron X-ray absorption near-edge structure techniques. The purpose of this study is to understand the mobility of metals in wetland plant root systems after their uptake from rhizosphere soils.Phragmites australissamples were collected in the Yangtze River intertidal zone in July 2013. The results indicate that Fe nanoparticles are present in the root epidermis and thatmore » other metals correlate significantly with Fe, suggesting that Fe nanoparticles play an important role in metal scavenging in the epidermis.« less

Analysis of iron, zinc, selenium and cadmium in paraffin-embedded prostate tissue specimens using inductively coupled plasma mass-spectrometry

USGS Publications Warehouse

Sarafanov, A.G.; Todorov, T.I.; Kajdacsy-Balla, A.; Gray, Michael A.; MacIas, V.; Centeno, J.A.

2008-01-01

Formalin-fixed paraffin-embedded (FFPE) tissue specimens represent a valuable and abundant resource of pathologic material for various biomedical studies. In the present study, we report the application of high-resolution inductively coupled mass-spectrometry (ICP-MS) for quantification of Fe, Zn, Se and Cd in FFPE prostate tissue. These elements have a possible role in the development of prostate diseases: while Zn and Se are needed for a healthy prostate, Cd shows multiple toxic and carcinogenic effects. Excessive accumulation of Fe induces the production of highly reactive hydroxyl radical species, which may play a role in cancer etiopathogenesis. To assess whether the levels of these metals in the FFPE prostate tissue represent their original content, we compared their levels with those in the fresh tissue (on dry weight basis) in samples obtained from 15 patients. We found that in FFPE tissue, the recoveries of Se, Fe, Cd and Zn were progressively decreased, 97??11% (r=0.88), 82??22% (r=0.86), 59??23% (r=0.69) and 24??11% (r=0.38), respectively. Thus, the use of correction factors, determined as k=0.16 for Se, k=0.20 for Fe, k=0.27 for Cd and k=0.67 for Zn, is required to estimate the retrospective levels of these elements in the parental non-processed fresh (wet) prostate tissue. The technique used in this study enables the analysis of archival FFPE prostate tissue for the concentrations of Fe, Zn, Se and Cd to study association between the levels of these metals and prostate disease. ?? 2008.

Heavy metal concentration in groundwater from Besant Nagar to Sathankuppam, South Chennai, Tamil Nadu, India

NASA Astrophysics Data System (ADS)

Sridhar, S. G. D.; Sakthivel, A. M.; Sangunathan, U.; Balasubramanian, M.; Jenefer, S.; Mohamed Rafik, M.; Kanagaraj, G.

2017-12-01

The assessment of groundwater quality is an obligatory pre-requisite to developing countries like India with rural-based economy. Heavy metal concentration in groundwater from Besant Nagar to Sathankuppam, South Chennai was analyzed to assess the acquisition process. The study area has rapid urbanization since few decades, which deteriorated the condition of the aquifer of the area. Totally 30 groundwater samples were collected during pre-monsoon (June 2014) and post-monsoon (January 2015) from the same aquifer to assess the heavy metal concentration in groundwater. Groundwater samples were analyzed for heavy metals such as Fe, Pb, Zn, Cu, Ni, Cr, Co and Mn using atomic absorption spectrophotometry (AAS). Correlation matrix revealed that there is no significant correlation between heavy metals and other parameters during pre-monsoon except EC with Cr but Fe and Zn have good positive correlation during post-monsoon.

[Comparison of heavy metal elements between natural and plantation forests in a subtropical Montane forest].

PubMed

Nie, Ming; Wan, Jia-Rong; Chen, Xiao-Feng; Wang, Li; Li, Bo; Chen, Jia-Kuan

2011-11-01

Heavy metals as one of major pollutants is harmful to the health of forest ecosystems. In the present paper, the concentrations of thirteen heavy metals (Fe, Al, Ti, Cr, Cu, Mn, V, Zn, Ni, Co, Pb, Se and Cd) were compared between natural and plantation forests in the Mt. Lushan by ICP-AES and atomic absorption spectroscopy. The results suggest that the soil of natural forest had higher concentrations of Fe, Al, Ti, Cu, Mn, V, Zn, Ni, Co, Pb, Se, and Cd than the plantation forest except for Cr. The soil of natural forest had a higher level of heavy metals than that of the plantation forest as a whole. This might be due to that the natural forest has longer age than the plantation forest, and fixed soil heavy metals take a longer period of time than the plantation forest.

Secondary metabolites and metal content dynamics in Teucrium montanum L. and Teucrium chamaedrys L. from habitats with serpentine and calcareous substrate.

PubMed

Zlatić, Nenad M; Stanković, Milan S; Simić, Zoran S

2017-03-01

The purpose of this comparative analysis is the determination of the total quantity of metals (Mg, Ca, K, Ni, Fe, Mn, Zn, Cu, Cr and Pb) in soil samples, above ground plant parts and tea made of plants Teucrium montanum and T. chamaedrys from different serpentine and calcareous habitats as well as of the total quantity of phenolic compounds and antioxidant activity. The obtained results showed that the quantities of certain metals (Mg, Fe, Ni and Mn) in the soil from the serpentine habitats were greater in comparison with other metals (Ca, Zn and Pb) which were more frequently found in the soil from the calcareous habitats. The results demonstrated that the analysed plant samples from the serpentine habitats contained higher quantity of Fe, Ni and Cr as opposed to the plant samples from the calcareous habitats which contained greater quantity of Ca and Zn. Although the studied species accumulate analysed metals in different quantities, depending on the substrate type, they are not hyperaccumulators of these metals. The use of these species from serpentine habitats for tea preparation is safe to a great extent, because in spite of the determined metal absorption by plant organs, the tea does not contain dangerous quantity of heavy metals. The results showed greater total quantity of phenolic compounds and the higher level of antioxidant activity in the plant samples from serpentine habitats in comparison with the samples from calcareous habitats, which is an indicator of one of the mechanisms of adaptation to the serpentine habitat conditions.

A simple quinolone Schiff-base containing CHEF based fluorescence 'turn-on' chemosensor for distinguishing Zn2+ and Hg2+ with high sensitivity, selectivity and reversibility.

PubMed

Dong, Yuwei; Fan, Ruiqing; Chen, Wei; Wang, Ping; Yang, Yulin

2017-05-23

A new simple 'dual' chemosensor MQA ((E)-2-methoxy-N-((quinolin-2-yl)methylene)aniline) for distinguishing Zn 2+ and Hg 2+ has been designed, synthesized and characterized. The sensor showed excellent selectivity and sensitivity with a fluorescence enhancement to Zn 2+ /Hg 2+ over other commonly coexisting cations (such as Na + , Mg 2+ , Al 3+ , K + , Mn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Ga 3+ , Cd 2+ , In 3+ and Pb 2+ ) in DMSO-H 2 O solution (1/99 v/v), which was reversible with the addition of ethylenediaminetetraacetic acid (EDTA). The detection limit for Zn 2+ /Hg 2+ by MQA both reached the 10 -8 M level. The 1 : 1 ligand-to-metal coordination patterns of the MQA-Zn2+ and MQA-Hg2+ were calculated through a Job's plot and ESI-MS spectra, and were further confirmed by X-ray crystal structures of complexes MQA-Zn2+ and MQA-Hg2+. This chemosensor can recognize similar metal ions by coherently utilizing intramolecular charge transfer (ICT) and different electronic affinities of various metal ions. DFT calculations have revealed that the energy gap between the HOMO and LUMO of MQA has decreased upon coordination with Zn(ii)/Hg(ii).

Heavy metals in handloom-dyeing effluents and their biosorption by agricultural byproducts.

PubMed

Nahar, Kamrun; Chowdhury, Md Abul Khair; Chowdhury, Md Akhter Hossain; Rahman, Afzal; Mohiuddin, K M

2018-03-01

The Madhabdi municipality in the Narsingdi district of Bangladesh is a well-known area for textile, handloom weaving, and dyeing industries. These textile industries produce a considerable amount of effluents, sewage sludge, and solid waste materials every day that they directly discharge into surrounding water bodies and agricultural fields. This disposal poses a serious threat to the overall epidemic and socio-economic pattern of the locality. This research entailed the collection of 34 handloom-dyeing effluent samples from different handloom-dyeing industries of Madhabdi, which were then analyzed to determine the contents of the heavy metals iron (Fe), zinc (Zn), copper (Cu), chromium (Cr), manganese (Mn), lead (Pb), and cadmium (Cd). Average concentrations of Fe, Cr, Cu, Pb, Mn, and Zn were 3.81, 1.35, 1.70, 0.17, 0.75, and 0.73 mg L -1 , respectively, whereas Cd content was below the detectable limit of the atomic adsorption spectrophotometer. The concentrations of Fe, Cr, Cu, Pb, and Mn exceed the industrial effluent discharge standards (IEDS) for inland surface water and irrigation water guideline values. A biosorption experiment of the heavy metals (Fe, Cr, Cu, Mn, and Zn) was conducted without controlling for any experimental parameters (e.g., pH, temperature, or other compounds present in the effluent samples) by using four agricultural wastes or byproducts, namely rice husk, sawdust, lemon peel, and eggshell. Twenty grams of each biosorbent was added to 1 L of effluent samples and stored for 7 days. The biosorption capacity of each biosorbent is ranked as follows: eggshell, sawdust, rice husk, and lemon peel. Furthermore, the biosorption affinity of each metal ion was found in the following order: Cu and Cr (both had similar biosorption affinity), Zn, Fe, Mn. The effluents should not be discharged before treatment, and efficient treatment of effluents is possible with eggshell powder or sawdust at a rate of 20 g of biosorbent per liter of effluents.

Functionalization of magnetic hollow porous oval shape NiFe2O4 as a highly selective sorbent for the simultaneous determination of five heavy metals in real samples.

PubMed

Liu, Mingyang; Yang, Lijun; Zhang, Lei

2016-12-01

In this study, a functionalized magnetic hollow porous oval-shape NiFe 2 O 4 (MHPO-NiFe 2 O 4 ) was designed by a facile synthesis procedure, and employed as magnetic solid phase extraction (MSPE) material to extract several heavy metal ions. As-prepared MHPO-NiFe 2 O 4 exhibited superior adsorption capacities of 20.17, 16.64, 16.82, 9.69 and 16.58mgg -1 , for Cu(II), Cd(II), Cr(III), Co(II) and Zn(II), and was then used to detect these heavy metals elements in real samples by combining with inductively coupled plasma optical emission spectroscopy (ICP-OES). The possible mechanism of the enrichment of heavy metals ions on MHPO-NiFe 2 O 4 was proposed, which involved the dominant adsorption and desorption. The detection limits were as low as 0.015, 0.13, 0.062, 0.035 and 0.46μgL -1 for Cu(II), Cd(II), Cr(III), Co(II) and Zn(II), respectively. A good repeatability was obtained with the relative standard deviation (RSD) of 3.87%. Moreover, the method was successfully utilized for the analysis of five heavy metals in real samples (cabbage, lettuce, apple, seawater), with satisfactory recoveries in the range of 92-108%. Copyright © 2016 Elsevier B.V. All rights reserved.

Assessment of trace metal levels in size-resolved particulate matter in the area of Leipzig

NASA Astrophysics Data System (ADS)

Fomba, Khanneh Wadinga; van Pinxteren, Dominik; Müller, Konrad; Spindler, Gerald; Herrmann, Hartmut

2018-03-01

Size-resolved trace metal concentrations at four sites in Leipzig (Germany) and its surrounding were assessed between the winter of 2013 and the summer of 2015. The measurements were performed in parallel at; traffic dominated (Leipzig - Mitte, LMI), traffic and residential dominated (Eisenbahnstrasse, EIB), urban background (TROPOS, TRO) and regional background (Melpitz, MEL) sites. In total, 19 trace metals, i.e. K, Ca, Ti, Mn, Fe, Cu, Zn, As, Se, Ba, V, Pb, Ni, Cr, Sr, Sn, Sb, Co and Rb were analysed using total reflection x-ray fluorescence (TXRF). The major metals were Fe, K and Ca with concentrations ranging between; 31-440 ng/m3, 42-153 ng/m3 and 24-322 ng/m3, respectively, while the trace metals with the lowest concentrations were Co, Rb and Se with concentrations of; < 0.3 ng/m3, <0.5 ng/m3 and 0.5-0.7 ng/m3, respectively. PM10 trace metal concentrations during easterly air mass inflow especially at the background sites were in average 70% higher in the winter and 30% higher in the summer in comparison to westerly air mass inflow. Traffic at LMI contributed to about 75% of Cr, Ba, Cu, Sb, Sn, Ca, Co, Mn, Fe and Ti concentrations while regional activities contributed to more than 70% of K, Rb, Pb, Se, As and V concentrations. Traffic dominated trace metals were often observed in the coarse mode while the regional background dominated trace metals were often observed in the fine mode. Trace metal sources were related to crustal matter and road dust re-suspension for metals such as Ca, Fe, Co, Sr, and Ti, brake and tire wear (Cu, Sb, Ba, Fe, Zn, Pb), biomass burning (K, Rb), oil and coal combustion (V, Zn, As, Pb). Crustal matter contributed 5-12% in winter and 8-19% in summer of the PM10 mass. Using Cu and Zn as markers for brake and tire wear, respectively, the estimated brake and tire wear contributions to the PM10 mass were 0.1-0.8% and 1.7-2.9%, respectively. The higher contributions were observed at the traffic sites while the lower contributions were observed at the regional background site. In total, non-exhaust emissions could account for about 10-22% of the PM10 mass in the summer and about 7-15% of the PM10 mass in the winter.

Metal concentrations in the soils and native plants surrounding the old flotation tailings pond of the copper mining and smelting complex Bor (Serbia).

PubMed

Antonijević, M M; Dimitrijević, M D; Milić, S M; Nujkić, M M

2012-03-01

In this study concentrations of metals in the native plants and soils surrounding the old flotation tailings pond of the copper mine were determined. It has been established that the soil is heavily contaminated with copper, iron and arsenic, the mean concentrations being 1585.6, 29,462.5 and 171.7 mg kg(-1) respectively. All the plants, except manganese, accumulated metallic elements in concentrations which were either in the range of critical and phytotoxic values (Pb and As) or higher (Zn), and even much higher (Cu and Fe) than these values. Otherwise, the accumulation of Mn, Pb and As was considerably lower than that of Cu, Fe and Zn. In most plants the accumulation of target metals was highest in the root. Several plant species showed high bioaccumulation and translocation factor values, which classify them into species for potential use in phytoextraction. The BCF and TF values determined in Prunus persica were 1.20 and 3.95 for Cu, 1.5 and 6.0 for Zn and 1.96 and 5.44 for Pb. In Saponaria officinalis these values were 2.53 and 1.27 for Zn, and in Juglans regia L. they were 8.76 and 17.75 for Zn. The translocation factor in most plants, for most metals, was higher than one, whereas the highest value was determined in Populus nigra for Zn, amounting to 17.8. Among several tolerant species, the most suitable ones for phytostabilization proved to be Robinia pseudoacacia L. for Zn and Verbascum phlomoides L., Saponaria officinalis and Centaurea jacea L. for Mn, Pb and As. This journal is © The Royal Society of Chemistry 2012

Correlations in distribution and concentration of calcium, copper and iron with zinc in isolated extracellular deposits associated with age-related macular degeneration

USGS Publications Warehouse

Flinn, Jane M; Kakalec, Peter; Tappero, Ryan; Jones, Blair F.; Lengyel, Imre

2014-01-01

Zinc (Zn) is abundantly enriched in sub-retinal pigment epithelial (RPE) deposits, the hallmarks of age-related macular degeneration (AMD), and is thought to play a role in the formation of these deposits. However, it is not known whether Zn is the only metal relevant for sub-RPE deposit formation. Because of their involvement in the pathogenesis of AMD, we determined the concentration and distribution of calcium (Ca), iron (Fe) and copper (Cu) and compared these with Zn in isolated and sectioned macular (MSD), equatorial (PHD) and far peripheral (FPD) sub-RPE deposits from an 86 year old donor eye with post mortem diagnosis of early AMD. The sections were mounted on Zn free microscopy slides and analyzed by microprobe synchrotron X-ray fluorescence (μSXRF). Metal concentrations were determined using spiked sectioned sheep brain matrix standards, prepared the same way as the samples. The heterogeneity of metal distributions was examined using pixel by pixel comparison. The orders of metal concentrations were Ca ⋙ Zn > Fe in all three types of deposits but Cu levels were not distinguishable from background values. Zinc and Ca were consistently present in all deposits but reached highest concentration in MSD. Iron was present in some but not all deposits and was especially enriched in FPD. Correlation analysis indicated considerable variation in metal distribution within and between sub-RPE deposits. The results suggest that Zn and Ca are the most likely contributors to deposit formation especially in MSD, the characteristic risk factor for the development of AMD in the human eye.

Amyloid Plaques in PSAPP Mice Bind Less Metal than Plaques in Human Alzheimer's Disease

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leskovjan, A.; Lanzirotti, A; Miller, L

2009-01-01

Amyloid beta (A{Beta}) is the primary component of Alzheimer's disease (AD) plaques, a key pathological feature of the disease. Metal ions of zinc (Zn), copper (Cu), iron (Fe), and calcium (Ca) are elevated in human amyloid plaques and are thought to be involved in neurodegeneration. Transgenic mouse models of AD also exhibit amyloid plaques, but fail to exhibit the high degree of neurodegeneration observed in humans. In this study, we imaged the Zn, Cu, Fe, and Ca ion distribution in the PSAPP transgenic mouse model representing end-stage AD (N = 6) using synchrotron X-ray fluorescence (XRF) microprobe. In order tomore » account for differences in density in the plaques, the relative protein content was imaged with synchrotron Fourier transform infrared microspectroscopy (FTIRM) on the same samples. FTIRM results revealed a 61% increase in protein content in the plaques compared to the surrounding tissue. After normalizing to protein density, we found that the PSAPP plaques contained only a 29% increase in Zn and there was actually less Cu, Fe, and Ca in the plaque compared to the surrounding tissue. Since metal binding to A{beta} is thought to induce redox chemistry that is toxic to neurons, the reduced metal binding in PSAPP mice is consistent with the lack of neurodegeneration in these animals. These findings were in stark contrast to the high metal ion content observed in human AD plaques, further implicating the role of metal ions in human AD pathology.« less

The use of feather as an indicator for heavy metal contamination in house crow (Corvus splendens) in the Klang area, Selangor, Malaysia.

PubMed

Janaydeh, Mohammed; Ismail, Ahmad; Zulkifli, Syaizwan Zahmir; Bejo, Mohd Hair; Aziz, Nor Azwady Abd; Taneenah, Ayat

2016-11-01

The Klang area of Peninsular Malaysia has experienced rapid industrial growth with intense activities, which can increase the concentration of pollutants in the environment that significantly impact on habitats and the human health. The purpose of this study was to determine the levels of selected heavy metals (Cu, Zn, Ni, Fe, and Pb) in the heart, lung, brain, liver, kidney, muscle tissues, and feathers of house crow, Corvus splendens, in Klang, Peninsular Malaysia. House crow samples were collected from the Klang area through the Department of Public Health at Majlis Perbandaran Klang. Quantitative determination of heavy metals was carried out using atomic absorption spectrophotometer (AAS). The result shows the presence of heavy metals in all biological samples of house crows. For heavy metals in all the house crow tissues analyzed, Fe concentrations were the highest, followed by those of Zn, Cu, Pb, and Ni. The feathers and kidney accumulated high concentrations of Pb, whereas the liver accumulated high concentrations of essential heavy metals (Fe > Zn > Cu > Ni). Significant variations were also detected in the concentrations of Pb among adult and juvenile and male and female bird samples. The results also revealed significant positive correlations between Pb metal concentration in the breast feathers and all internal organs. Accumulation of toxic heavy metals in feathers reflected storing and elimination processes, while the accumulation of toxic heavy metals in the kidney can be consequential to chronic exposure. The present study clearly shows the usefulness of house crow breast feather as a suitable indicator for heavy metal accumulation in the internal organs of house crows in the Klang area.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Yong-Min; Bang, Suhee; Yoon, Heejung

Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn 2+ ion in (TMC)Fe III-(O 2)-Zn(CF 3SO 3) 2 (1-Zn 2+) decreases the Lewis acidity of the Zn 2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn 2+. This further changes the reactivities of 1-Zn 2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidantmore » (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn 2+, whereas 1-Zn 2+ coordinating two water molecules, (TMC)Fe III-(O 2)-Zn(CF 3SO 3) 2-(OH 2) 2 [1-Zn 2+-(OH 2) 2], releases the O 2 unit in the oxidation reaction. In the reduction reactions, 1-Zn 2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn 2+-(OH 2) 2. Finally, the present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.« less

Evidence for a Dual Role of an Active Site Histidine in α-Amino-β-Carboxymuconate-ε-Semialdehyde Decarboxylase†

PubMed Central

Huo, Lu; Fielding, Andrew J.; Chen, Yan; Li, Tingfeng; Iwaki, Hiroaki; Hosler, Jonathan P.; Chen, Lirong; Hasegawa, Yoshie; Que, Lawrence; Liu, Aimin

2012-01-01

The previously reported crystal structures of α-amino-β-carboxymuconate-ε-semialdehyde decarboxylase (ACMSD) show a five-coordinate Zn(II)(His)3(Asp)(OH2) active site. The water ligand is H-bonded to a conserved His228 residue adjacent to the metal center in ACMSD from Pseudomonas fluorescences (PfACMSD). Site directed mutagenesis of His228 to tyrosine and glycine in the present study results in complete or significant loss of activity. Metal analysis shows that H228Y and H228G contain iron rather than zinc, indicating that this residue plays a role in metal selectivity of the protein. As-isolated H228Y displays a blue color, which is not seen in wild-type ACMSD. Quinone staining and resonance Raman analyses indicate that the blue color originates from Fe(III)-tyrosinate ligand-to-metal-charge- transfer (LMCT). Co(II)-substituted H228Y ACMSD is brown in color and exhibits an EPR spectrum showing a high-spin Co(II) center with a well-resolved 59Co (I = 7/2) eight-line hyperfine splitting pattern. The X-ray crystal structures of the as-isolated Fe-H228Y (2.8 Å), Co- (2.4 Å) and Znsubstituted H228Y (2.0 Å resolution) support the spectroscopic assignment of metal ligation of the Tyr228 residue. The crystal structure of Zn-H228G (2.6 Å) was also solved. These four structures show that the water ligand present in WT Zn-ACMSD is either missing (Fe-H228Y, Co-H228Y, and Zn- H228G) or disrupted (Zn-H228Y) in response to His228 mutation. Together, these results highlight the importance of His228 for PfACMSD’s metal specificity as well as maintaining a water molecule as ligand of the metal center. His228 is thus proposed to play a role in activating the metal-bound water ligand for subsequent nucleophilic attack on the substrate. PMID:22746257

Influence of heavy metal leaf contaminants on the in vitro growth of urban-tree phylloplane-fungi

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, W.H.

1977-01-01

The surfaces of urban woody vegetation are contaminated with varying amounts of numerous metallic compounds, including Cd, Cu, Mn, Al, Cr, Ni, Fe, Pb, Na, and Zn. To examine the possibility that these metals may affect phylloplane fungi, the above cations were tested in vitro for their ability to influence the growth of numerous saprophytic and parasitic fungi isolated from the leaves of London plane trees. Considerable variation in growth inhibition by the metals was observed. Generally Aureobasidium pullulans, Epicoccum sp., and Phialophora verrucosa were relatively tolerant; Gnomonia platani, Cladsporium sp., and Pleurophomella sp. were intermediate; and Pestalotiopsis and Chaetomiummore » sp. were relatively sensitive to the incorporation of certain metals into solid and liquid media. If similar growth inhibitions occur in nature, competitive abilities or population structures of plant surface microbes may be altered by surface metal contamination. Metals causing the greatest and broadest spectrum growth suppression included Ni, Zn, Pb, Al, Fe, and Mn. 25 references, 4 figures.« less

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ridley, W.I.; Wolf, R.; Lamothe, P.J.; Adams, M.

2007-01-01

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in ??65Cu (- 1.41 to + 0.30???), ??56Fe (- 0.56 to + 0.34???), and ??66Zn (0.31 to 0.49???) among samples collected from different abandoned mines within a single watershed. Hence, Cu, Fe, and Zn isotopic measurements may be a powerful tool for fingerprinting specific metal sources and/or examining biogeochemical reactions within fresh water systems.

Metal pollution and ecological risk assessment in marine sediments of Karachi Coast, Pakistan.

PubMed

Mashiatullah, Azhar; Chaudhary, Muhammad Zaman; Ahmad, Nasir; Javed, Tariq; Ghaffar, Abdul

2013-02-01

Concentrations of 12 metals (Fe, Mn, Cr, Mo, Ni, Pb, Se, Sr, U, V, Zn, and Zr) in surface sediments of Karachi Coast, Pakistan were determined to evaluate their distribution and pollution assessment. The measured metals in the sediments were found to be in the range of Fe, 0.84-6.96 %; Mn, 300-1,300 μg/g; Cr, 12.0-319.84 μg/g; Mo, 0.49-2.03 μg/g; Ni, 1.53-58.86 μg/g; Pb, 9.0-49.46 μg/g; Se, 0.25-.86 μg/g; Sr, 192-1185 μg/g; U, 0.19-1.66 μg/g; V, 15.80-118.20 μg/g; Zn, 15.60-666.28 μg/g; and Zr, 44.02-175.26 μg/g. The mean contents of the metal studied were: Fe, 3.07 %, Mn, 0.05 %; Cr, 96.75 μg/g; Mo, 1.34 μg/g; Ni, 31.39 μg/g; Pb, 23.24 μg/g; Se, 0.61 μg/g; Sr, 374.83 μg/g; U, 0.64 μg/g; V, 61.75 μg/g; Zn, 204.75 μg/g; and Zr:76.27 μg/g, and arrangement of the metals from higher to lower mean content in this area is: Fe > Zn > Mn > Sr > Zn > Cr > Zr > V > Ni > Pb > Mo > U > Se. There is no significant correlation among most of these metals, indicating different anthropogenic and natural sources. To assess ecotoxic potential of marine sediments, Numerical Sediment Quality Guidelines were also applied. The concentration of Pb in all the sediments except one was lower than the threshold effect concentration (TECs) showing that there are no harmful effects to marine life from Pb. On the other hand, the concentrations of Cr, Ni, and Zn exceeded TEC in three stations, indicating their potential risk. The degree of pollution in sediments for metals was assessed by calculating enrichment factor (EF) and pollution load index (PLI). The results indicated that sediments of Layari River Mouth Area, Fish Harbour, and KPT Boat Building Area are highly enriched with Cr and Zn (EF > 5). Sediments of Layari River Outfall Zone were moderately enriched with Ni and Pb (EF > 2). The pollution load index was found in the range of 0.98 to 1.34. Lower values of PLI (≤ 1) at most of sampling locations imply no appreciable input from anthropogenic sources. However, relatively higher PLI values (>1) at Layari River Mouth Area, Fish Harbour, and KPT Boat Building Area are attributed to increased human activity in the area.

Changes of toxic metals during biological stabilization and their potential ecological risk assessment.

PubMed

Wang, Hou-cheng; Zeng, Zheng-zhong; Zhang, He-fei; Nan, Zhong-ren

2015-01-01

With various disadvantages of pollution control technologies for toxic metal-contaminated soil, we mixed contaminated soil with sludge for in situ composting to stabilize toxic metals, so plants are enriched to take up the toxic metals. When simulating the above, we added toxic metal solution into sewage sludge, and then composed it with steel slag to determine inhibition of the availability of toxic metals. When toxic metals were added into sludge, the potential ecological index and geoaccumulation index of Cd became high while Zn was low. Steel slag had an inhibited availability of Cd, and when the adjunction of steel slag was 7%, the availability of Cd was lowest. Steel slag promoted the availability of Zn, and when the adjunction of steel slag was 27%, the availability of Zn was highest. Results showed that during composting, with increasing steel slag, Cd stabilizing time was reached sooner but Zn stabilizing time was slower, and the availability of all metals became lower. In the end, composting inhibited the potential ecological index of Cd, but it promoted the potential ecological index of Zn. Steel slag promoted the stability of Cd and Zn as Fe/Mn oxide-bound and residual species. Therefore, composting sludge and steel slag could be used as an effective inhibitor of Zn and Cd pollution.

Magnetic properties of RFe2Zn20 and RCo2Zn20 (R=Y,Nd,Sm,Gd-Lu)

NASA Astrophysics Data System (ADS)

Jia, Shuang; Ni, Ni; Bud'Ko, S. L.; Canfield, P. C.

2009-09-01

Magnetization, resistivity, and specific heat measurements were performed on solution-grown single crystals of RFe2Zn20 and RCo2Zn20 (R=Y,Nd,Sm,Gd-Lu) . Whereas LuCo2Zn20 and YCo2Zn20 manifest unremarkable metallic behavior, LuFe2Zn20 and YFe2Zn20 display behaviors such as characteristic of nearly ferromagnetic Fermi liquids. When the well-defined 4f local moments (Gd3+-Tm3+) are embedded into this strongly polarizable host, they manifest enhanced ferromagnetic ordering and the values of TC for RFe2Zn20 (R=Gd-Tm) scale with the de Gennes factor. In addition, data on the RFe2Zn20 compounds indicate a small crystal electric field (CEF) effect compared with the interaction energy scale. On the other hand, the local moment bearing members of RCo2Zn20 (R=Nd,Sm,Gd-Tm) manifest weak magnetic interactions and the magnetic properties for R=Dy-Tm members are strongly influenced by the CEF effect on the R ions. The magnetic anisotropy and specific heat data for the Co series were used to determine the CEF coefficient of R ion with its cubic point symmetry. These CEF coefficients, determined for the Co series, are consistent with the magnetic anisotropy and specific heat data for the Fe series, which indicates similar CEF effects for the Fe and Co series. Such analysis, combined with specific heat and resistivity data, indicates that for R=Tb-Ho , the CEF splitting scale is smaller than their TC values, whereas for ErFe2Zn20 and TmFe2Zn20 the 4f electrons lose part of their full Hund’s rule ground state degeneracy above TC . YbFe2Zn20 and YbCo2Zn20 manifest typical but distinct heavy fermion behaviors associated with different Kondo temperatures.

Environmental effects on the aquatic system and metal discharge to the Mediterranean Sea from a near-neutral zinc-ferrous sulfate mine drainage

USGS Publications Warehouse

Frau, Franco; Medas, Daniela; Da Pelo, Stefania; Wanty, Richard B.; Cidu, Rosa

2015-01-01

After mine closure in the 1980s and subsequent shutdown of the dewatering system, groundwater rebound led to drainage outflow from the Casargiu gallery (Montevecchio mine, SW Sardinia, Italy) beginning in 1997. Mine drainage had pH 6.0 and dissolved concentrations of sulfate (5000 mg/L) and metals (e.g., 1000 mg/L Zn, 230 mg/L Fe, 150 mg/L Mn) much higher than those previously measured in groundwater under dewatering conditions. As compared with the first stages of rebound at Casargiu, a very high contamination level still persists after more than 15 years of flushing. Mine drainage (20–70 L/s; pH 6.0 ± 0.2; Zn-Mg-Ca-SO4 composition) flowed into the Rio Irvi. Abundant precipitation of amorphous Fe(III)-(oxy)hydroxides occurred. Moreover, sulfate-bearing green rust was observed to flocculate in the reach of the Rio Irvi where pH was still circumneutral. Water sampling along this stream for about 6 km almost to its mouth in the Mediterranean Sea showed a pH decrease from 6.0 to 4.0 and a significant removal of Fe (46 %) and As (96 %), while sulfate, Zn, Mn, Co, Ni, and Cd showed small variations downstream. Lead was initially adsorbed onto Fe(III)-(oxy)hydroxides, then desorbed as pH dropped below 5. The estimated amount of dissolved metals discharged into the Mediterranean Sea is significant (e.g., 900 kg/day Zn, 1.4 kg/day Cd, 5 kg/day Ni). In particular, a conservative estimation of the amount of Zn discharged to the sea is about 330 ton/year, which would correspond to 1.4 % of the global annual flux of dissolved Zn from uncontaminated rivers to the oceans.

Heavy metals seasonal variability and distribution in Lake Qaroun sediments, El-Fayoum, Egypt

NASA Astrophysics Data System (ADS)

Redwan, Mostafa; Elhaddad, Engy

2017-10-01

This study was carried out to investigate the seasonal variability and distribution of heavy metals ;HMs; (Fe, Mn, Co, Cr, Cu, Ni, Pb, Zn and V) in the bottom sediments of Lake Qaroun, in Egypt. The samples were collected from 10 sites in summer and winter seasons in 2015. Total metals concentrations were measured using inductively coupled plasma spectrometer. Multivariate techniques were applied to analyse the distribution and potential source of heavy metals. The mean seasonal concentrations follow a descending order of Fe > Mn > V > Zn > Cr > Ni > Cu > Co > Pb. The mean concentrations of HMs in sediments during summer were higher than the concentrations during winter and above the average world shale values, except for Pb, suggesting potential adverse toxicity to aquatic organisms. All metals showed enrichment during summer and winter at sites S3 and S5 in the southeastern parts of the lake due to the heavy discharge of contaminants from El-Bats and El-Wadi drains. Principal component analysis results suggested two principal components controlling HMs variability in sediments, which accounted for 63.9% (factor 1: Co, Cr, Cu, Ni, Zn, Pb and V), 15.9% (factor 2: Mn and Fe) during summer, and 76.7% (factor 1: Fe, Co, Cr, Cu, Ni, Zn, Pb and V), 13.8% (factor 2: Mn) during winter of the total variance. Geo-accumulation index (Igeo) showed some pollution risk at the southeastern and southern parts (sites S3 and S5). Dilution during winter, concentration during summer, impact of non-point sources from different agricultural, industrial, municipal sewage and fish farms in the southern part of Lake Qaroun, adsorption and salt dissolution reactions and lithogenic sources are the main controlling factors for HMs in the study area. Monitoring of contaminant discharge at Lake Qaroun should be introduced for future remediation and management strategies.

Bioaccumulation of metals in fish species from water and sediments in macrotidal Ennore creek, Chennai, SE coast of India: A metropolitan city effect.

PubMed

Jayaprakash, M; Kumar, R Senthil; Giridharan, L; Sujitha, S B; Sarkar, S K; Jonathan, M P

2015-10-01

Accumulation of trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) were investigated in water, sediment (n=20) along with six fish of diverse feeding guilds (Sillago sihama, Liza parsia, Etroplus suratensis, Oreochromis mossambicus, Arius parkii and Gerres oyena) from the Ennore creek, northern part of Chennai metropolitan megacity, southeast coast of India. Dissolved trace metals (DTMs) in surface water samples and total trace metals (TTMs) in surface sediments (top 0-10cm) indicate that concentration pattern of metals was higher in the discharge point of the river/channels entering the main creek. The maximum mean values of DTMs exhibited the following decreasing order (expressed in µg/L): Fe (1698)>Mn (24)>Zn (14.50)>Pb (13.89)>Ni (6.73)>Cu (3.53)>Co (3.04)>Cr (2.01) whereas the trend is somewhat different in sediments (µgg(-1)): Fe (4300)>Mn (640)>Cr (383)>Zn (155)>Cu (102)>Ni (35)>Pb (32)>Cd (0.51) are mainly due to the industrial complexes right on the banks of the river/channels. Species-specific heterogeneous patterns of tissue metal loads were apparent and the overall metal enrichment exhibited the following decreasing order (expressed in µgg(-1)): Cu (7.33)>Fe (6.53)>Zn (4.91)>Cr (1.67)>Pb (1.33)>Ni (0.44)>Mn (0.43)>Co (0.36)>Cd (0.11). This indicates that metals are absorbed onto the different organs, which is also endorsed by the calculated values of bioaccumulation factor (BAFs) (avg. muscle 117, gill 126, liver 123, intestine 118) in fishes. The high calculated biota sediment accumulation factor (BSAF) (0.437) for the species Arius parkii is considered to be a potential bioindicator in this region. The enrichment of trace metals is also supported by the association of metals in water, sediments and different body organs (muscle, gill, liver, intestine) of fish samples. Comparative studies with other coastal regions indicate considerable enrichment of DTMs & TTMs in sediments as well as in various organs of fish samples. Holistic spatial, temporal monitoring and comprehensive regional strategies are required to prevent health risks and ensure nutritional safety conditions. Copyright © 2015 Elsevier Inc. All rights reserved.

A bis(3-hydroxy-4-pyridinone)-EDTA derivative as a strong chelator for M3+ hard metal ions: complexation ability and selectivity.

PubMed

Gama, Sofia; Dron, Paul; Chaves, Silvia; Farkas, Etelka; Santos, M Amélia

2009-08-21

The study of chelating compounds is very important to solve problems related to human metal overload. 3-Hydroxy-3-pyridinones (HP), namely deferiprone, have been clinically used for chelating therapy of Fe and Al over the last decade. A multi-disciplinary search for alternative molecules led us to develop poly-(3-hydroxy-4-pyridinones) to increase metal chelation efficacy. We present herein a complexation study of a new bis-(3-hydroxy-4-pyridinone)-EDTA derivative with a set of M(3+) hard metal ions (M = Fe, Al, Ga), as well as Zn(2+), a biologically relevant metal ion. Thus a systematic aqueous solution equilibrium study was performed using potentiometric and spectroscopic techniques (UV-Vis, NMR methods). These set of results enables the establishment of specific models as well as the determination of thermodynamic stability constants and coordination modes of the metal complexes. The results indicate that this ligand has a higher affinity for chelating to these hard metal ions than deferiprone, and that the coordination occurs mostly through the HP moieties. Furthermore, it was also found that this ligand has a higher selectivity for chelating to M(3+) hard metal ions (M = Fe, Al, Ga) than Zn(2+).

Assessment of heavy metal accumulation in macrophyte, agricultural soil, and crop plants adjacent to discharge zone of sponge iron factory

NASA Astrophysics Data System (ADS)

Gupta, S.; Nayek, S.; Saha, R. N.; Satpati, S.

2008-08-01

The present study deals with the characterization of effluent released from sponge iron industries and distribution of heavy metals in soil and macrophytes near to effluent discharge channel. Apart from this, accumulation of heavy metals in nearby soil and vegetation system irrigated with effluent-contaminated water is also the subject of this study. Physico-chemical analysis of effluent reveals that the concentration of total suspended solids (TSS), total hardness (TH), iron (Fe2+), and oil and grease are greater than the IS (1981) norms for discharge of water into inland water body. The soil along the sides of the effluent channel also shows higher concentration of heavy metals than the background soil. The enrichment of the heavy metals are in the order of Chromium (Cr) > Iron (Fe) > Manganese (Mn) > Zinc (Zn) > Copper (Cu) > Cadmium (Cd). Macrophytes growing along the sides of the effluent channel also show significant accumulation of heavy metals almost in the same order as accumulated in soil. Higher uptake of heavy metals by these varieties reveals that these species can be used for future phytoremediation. The effluent as well as contaminated water is extensively used for irrigation for growing vegetables like tomato ( Lycopersicon esculatum) in the surrounding areas. Heavy metal accumulation in this agricultural soil are in the sequence of Cr > Fe > Mn > Zn > Cu > Cd. More or less similar type of accumulation pattern are also found in tomato plants except Fe and Zn exceeding Cr and Mn. Transfer Factor of heavy metals from soil to tomato plants (TFS) shows average value of <1, suggesting less uptake of heavy metals from soil. Among the plant parts studied, fruit shows least accumulation. Although tomato plants show some phenotypic changes, the survival of tomato plants as well as least accumulation of metals in fruit reveals their tolerance to heavy metals. Therefore it may be suggested that this plant can be grown successfully in the heavy metal contaminated soil. Further research work on in situ toxicity test will be necessary in order to identify the most resistive variety on this particular type of contaminated site.

Airborne mineral components and trace metals in Paris region: spatial and temporal variability.

PubMed

Poulakis, E; Theodosi, C; Bressi, M; Sciare, J; Ghersi, V; Mihalopoulos, N

2015-10-01

A variety of mineral components (Al, Fe) and trace metals (V, Cr, Mn, Ni, Cu, Zn, Cd, Pb) were simultaneously measured in PM2.5 and PM10 fractions at three different locations (traffic, urban, and suburban) in the Greater Paris Area (GPA) on a daily basis throughout a year. Mineral species and trace metal levels measured in both fractions are in agreement with those reported in the literature and below the thresholds defined by the European guidelines for toxic metals (Cd, Ni, Pb). Size distribution between PM2.5 and PM10 fractions revealed that mineral components prevail in the coarse mode, while trace metals are mainly confined in the fine one. Enrichment factor analysis, statistical analysis, and seasonal variability suggest that elements such as Mn, Cr, Zn, Fe, and Cu are attributed to traffic, V and Ni to oil combustion while Cd and Pb to industrial activities with regional origin. Meteorological parameters such as rain, boundary layer height (BLH), and air mass origin were found to significantly influence element concentrations. Periods with high frequency of northern and eastern air masses (from high populated and industrialized areas) are characterized by high metal concentrations. Finally, inner city and traffic emissions were also evaluated in PM2.5 fraction. Significant contributions (>50 %) were measured in the traffic site for Mn, Fe, Cr, Zn, and Cu, confirming that vehicle emissions contribute significantly to their levels, while in the urban site, the lower contributions (18 to 33 %) for all measured metals highlight the influence of regional sources on their levels.

Sediment heavy metals and benthic diversities in Hun-Tai River, northeast of China.

PubMed

Qu, Xiaodong; Ren, Ze; Zhang, Min; Liu, Xiaobo; Peng, Wenqi

2017-04-01

In aquatic ecosystems, metal contamination in sediments has become a ubiquitous environmental problem, causing serious issues. Hun-Tai River, located in northeast of China, flows through an important heavy industry region and metropolitan area. This study examined the heavy metals (Cd, Cr, Cu, Fe, Mn, Pb, Ni, and Zn) of sediments and diversities (taxa richness, Shannon diversity, and evenness) of benthic assemblages (benthic algae and macroinvertebrate) in Hun-Tai River. The results clearly described the spatial patterns of metal contamination in terms of geo-accumulation index and contamination factor, as well as the spatial patterns of benthic diversities in terms of taxa richness, Shannon index, and evenness by kriging interpolation. The sediments were largely contaminated by Cd, followed by Cu, Fe, Zn, Mn, and Ni. Cd and Zn had similar spatial patterns and similar sources. Cu, Fe, Mn, and Ni showed similar spatial patterns and similar sources. The surface sediments were unpolluted by Cr and Pb. The metal mines and the heavy industry in the major cities were the potential pollution sources. Benthic algae and macroinvertebrate responded similarly to the heterogeneous environment and metal contamination, with high taxa richness and Shannon index in middle-upper reaches of Hun-Tai River. Evenness showed complex spatial patterns. Under low contamination, both taxa richness, Shannon diversity, and evenness had a large variation range. However, under the moderate and high contamination, the taxa richness and Shannon diversity kept to a low level but the evenness had a high level. This study provided insights into the sediment heavy metal contamination in Hun-Tai River.

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn.

PubMed

Scancar, J; Milacic, R; Strazar, M; Burica, O; Bukovec, P

2001-02-01

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.

Faster extraction of heavy metals from soils using vacuum and ultrasonic energy.

PubMed

Pontes, Fernanda V M; Carneiro, Manuel C; de da Souza, Evelyn M F; da Silva, Lílian I D; Monteiro, Maria Inês C; Neto, Arnaldo A

2013-01-01

A fast vacuum- and ultrasound-assisted acid extraction of Co, Cu, Fe, Mn, Pb, and Zn from soils using a homemade system has been investigated. Preliminarily, a full factorial design with two levels and three variables (extracting agent, extraction temperature, and sonication time) was applied to optimize the extraction conditions (without vacuum) for some heavy metals (Cu, Mn, Pb, and Zn). The best results were obtained with a 3:1 HCI extraction solution, temperature of 80 degrees C, and time of 2 h. As this sonication time was too long, a vacuum pump was used to produce air bubbles in order to increase the contact between the sample and the extracting agent and to prevent the sample sedimentation. This improvement drastically reduced the sonication time to 2 min. Under these conditions, Co, Cu, Mn, and Zn were totally extracted (recoveries of 86-99%), while recoveries of 73-76 and 74% were obtained for Fe and Pb, respectively. The LOD values using flame atomic absorption spectrometry for determination of Co, Cu, Fe, Mn, Pb, and Zn were 3.2, 7.5, 37.5, 7.5, 22.5, and 3.8 micro glg, respectively. The RSDs were lower than 11% (n = 3).

Effects of Al2O3 and CaO/SiO2 Ratio on Phase Equilbria in the ZnO-"FeO"-Al2O3-CaO-SiO2 System in Equilibrium with Metallic Iron

NASA Astrophysics Data System (ADS)

Zhao, Baojun; Hayes, Peter C.; Jak, Evgueni

2011-02-01

The phase equilibria and liquidus temperatures in the ZnO-"FeO"-Al2O3-CaO-SiO2 system in equilibrium with metallic iron have been determined experimentally in the temperature range 1383 K to 1573 K (1150 °C to 1300 °C). The experimental conditions were selected to characterize lead blast furnace and imperial smelting furnace slags. The results are presented in a form of pseudoternary sections ZnO-"FeO"-(Al2O3 + CaO + SiO2) with fixed CaO/SiO2 and (CaO + SiO2)/Al2O3 ratios. It was found that wustite and spinel are the major primary phases in the composition range investigated. Effects of Al2O3 concentration as well as the CaO/SiO2 ratio on the primary phase field, the liquidus temperature, and the partitioning of ZnO between liquid and solid phases have been discussed for zinc-containing slags.

Crystal Structure and Magnetic Properties of New Cubic Quaternary Compounds RT2Sn2Zn18 (R = La, Ce, Pr, and Nd, and T = Co and Fe)

NASA Astrophysics Data System (ADS)

Isikawa, Yosikazu; Mizushima, Toshio; Ejiri, Jun-ichi; Kitayama, Shiori; Kumagai, Keigou; Kuwai, Tomohiko; Bordet, Pierre; Lejay, Pascal

2015-07-01

The new cubic quaternary intermetallic compounds RT2Sn2Zn18 (R = La, Ce, Pr, and Nd, and T = Co and Fe) were synthesized by the mixture-metal flux method using Zn and Sn. The crystal structure was investigated by powder X-ray diffraction and with a four-circle X-ray diffractometer using single crystals. The space group of the compounds is Fdbar{3}m (No. 227). The rare-earth atom is at the cubic site which is the center of a cage composed of Zn and Sn atoms. The crystal structure is the same as the CeCr2Al20-type crystal structure except the atoms at the 16c site, i.e., the Zn atoms at the 16c site are completely replaced by Sn atoms, indicating that the compounds are crystallographically new ordered quaternary compounds. The lattice parameter a and the physical properties of the magnetic susceptibility χ, the magnetization M, and the specific heat C of these cubic caged compounds were investigated. LaCo2Sn2Zn18 and LaFe2Sn2Zn18 are enhanced Pauli paramagnets that originate from the Co and Fe itinerant 3d electrons. CeCo2Sn2Zn18 and CeFe2Sn2Zn18 are also enhanced Pauli paramagnets that originate from both the 3d electrons and Ce 4f electrons. PrCo2Sn2Zn18 and PrFe2Sn2Zn18 are nonmagnetic materials with huge values of C divided by temperature, which indicates that the ground state of Pr ions is a non-Kramers' doublet. NdCo2Sn2Zn18 and NdFe2Sn2Zn18 are magnetic materials with the Néel temperatures of 1.0 and 3.8 K, respectively. All eight compounds have large magnetic moments of Co/Fe in the paramagnetic temperature region, and thus their magnetic moments are inferred to be magnetically frustrating owing to the pyrochlore lattice in the low-temperature region.

[Form tendency and bio-availability dynamics of Cu and Zn in different farm soils after application of organic fertilizer of livestock and poultry manures].

PubMed

Shang, He-ping; Li, Yang; Zhang, Tao; Su, De-chun

2015-01-01

Soil incubation experiments were conducted with different sources of manures containing heavy metals to evaluate the bioavailability of heavy metals (Cu and Zn) and their form transformation in different soils. This study may assist in developing strategies to ascertain the loads of heavy metals which entered into soils together with manures, and promote policies to evaluate the ecological risk in agriculture soils. The results showed that, during the six months of soil incubation, the pH value of acidic soil increased and the pH value of calcareous soil reduced. After adding chicken manures, the contents of available Cu in both calcareous and acid soils were significant lower than those in the equivalent inorganic salt treatments, but there was no significant difference between the treatments in the contents of available Zn in both calcareous and acid soils. Furthermore, there were also no significant differences between pig matures and the equivalent inorganic salt treatments in the contents of available Cu and Zn in both calcareous and acid soils. The results of form tendency showed that the main forms of Cu and Zn in both calcareous and acid soils, which entered into soils together with manures, were exchangeable, carbonate, Fe-Mn oxides, and organic. And the proportions of different heavy metals species in calcareous and acid soils were different with different manures sources. After six months of incubation, the contents of exchangeable and Fe-Mn oxides Cu, Zn were lower than those in the equivalent inorganic salt treatments, the contents of organics Cu and Zn were higher than those in the equivalent inorganic salt treatments, and other Cu and Zn forms in soils showed no difference with inorganic salt treatments.

Electromagnetic interference attenuation and shielding effect of quaternary Epoxy-PPy/Fe3O4-ZnO nanocomposite as a broad band microwave-absorber

NASA Astrophysics Data System (ADS)

Olad, Ali; Shakoori, Sahar

2018-07-01

An increase in the electromagnetic wave pollution generated from wireless telecommunication devices has devoted to a great request for exploiting microwave absorbing materials for themselves. The combination of inherently conducting polymers such as polypyrrole (PPy) with metal oxides has led to design ideal microwave absorbing materials which benefit both advantage effects of ICPs and metal oxide nanoparticles. Herein, the quaternary nanocomposite of Epoxy-PPy/Fe3O4-ZnO was prepared and tested for the absorption of X-band microwaves. Simultaneous application of metal oxides and conducting polypyrrole in the epoxy matrix was evaluated in order to increase the absorption intensity and broadness of microwaves in X-band region. The morphology, microstructure, and phase structure of Fe3O4, ZnO, and PPy, as well as quaternary nanocomposite were characterized and studied using FTIR, XRD, FESEM and TEM techniques. The presence of nanoparticles in the quaternary nanocomposite was confirmed by EDS. The magnetization of iron oxide was studied by VSM. The synergetic effect of iron oxide and zinc oxide nanoparticles in different weight ratios (Fe3O4/ZnO) on the electromagnetic wave absorption was evaluated. The electromagnetic parameters have been evaluated by the vector network analyzer in the frequency range of 8.2-12.4 GHz which is named as X-band region and is adequate for radar applications. The electromagnetic wave absorbing outcomes indicated that Epoxy-PPy/Fe3O4-ZnO quaternary nanocomposite has wide absorption area and high attenuation, which is believed to be due to dielectric loss properties related to the polypyrrole, magnetic loss factor of Fe3O4, and synergetic effects of components. The maximum reflection loss reached to -32.53 dB at 9.96 GHz with a nanocomposite thickness of 2 mm which is dedicated to the Epoxy-PPy/Fe3O4-ZnO with iron oxide to zinc oxide ratio of 2:1. The absorption bandwidth with the reflection loss lower than -10 dB (90% attenuation) was up to 4.2 GHz that covering a frequency range of 8.2-12.4 GHz. Results showed that absorber having %15 (w/w) polypyrrole/epoxy resin in Epoxy-PPy/Fe3O4-ZnO nanocomposite with iron oxide to zinc oxide ratio of 2:1 displays the best reflection loss properties. The loss curves illustrated the values of dielectric loss tangent and magnetic loss tangent of prepared nanocomposites which are in the range of 0.25-0.7 and -0.08 to 0.09 respectively. Therefore, microwave absorption mechanism is probably attributed to dielectric loss.

Tolerance and growth kinetics of bacteria isolated from gold and gemstone mining sites in response to heavy metal concentrations.

PubMed

Oladipo, Oluwatosin Gbemisola; Ezeokoli, Obinna Tobechukwu; Maboeta, Mark Steve; Bezuidenhout, Jacobus Johannes; Tiedt, Louwrens R; Jordaan, Anine; Bezuidenhout, Cornelius Carlos

2018-04-15

Response and growth kinetics of microbes in contaminated medium are useful indices for the screening and selection of tolerant species for eco-friendly bio-augmentative remediation of polluted environments. In this study, the heavy metal (HM) tolerance, bioaccumulation and growth kinetics of seven bacterial strains isolated from mining sites to 10 HMs (Cd, Hg, Ni, Al, Cr, Pb, Cu, Fe, Mn and Zn) at varied concentrations (25-600 mgL -1 ) were investigated. The isolates were phylogenetically (16S rRNA gene) related to Lysinibacillus macroides, Achromobacter spanius, Bacillus kochii, B. cereus, Klebsiella pneumoniae, Pseudomonas mosselii and P. nitroreducens. Metal tolerance, effects on lag phase duration and growth rates were assessed using the 96-well micro-titre method. Furthermore, metal bioaccumulation and quantities within cells were determined by transmission electron microscopy and electron dispersive x-ray analyses. Tolerance to Ni, Pb, Fe and Mn occurred at highest concentrations tested. Growth rates increased with increasing Fe concentrations, but reduced significantly (p < .05) with increasing Zn, Cu, Hg, Cd and Al. Significantly higher (p < .05) growth rates (compared to controls) was found with some isolates in Hg (25 mgL -1 ), Ni (100 mgL -1 ), Cr (150 mgL -1 ), Mn (600 mgL -1 ), Pb (100 mgL -1 ), Fe (600 mgL -1 ) and Al (50 mgL -1 ). Lag phase urations were isolate- and heavy metal-specific, in direct proportion to concentrations. A. spanius accumulated the most Mn and Zn, while B. cereus accumulated the most Cu. Metals accumulated intra-cellularly without cell morphology distortions. The isolates' multi-metal tolerance, intra-cellular metal bioaccumulation and growth kinetics suggest potentials for application in the synergetic biodegradation and bioremediation of polluted environments, especially HM-rich sites. Copyright © 2018 Elsevier Ltd. All rights reserved.

Assessment of acid leachable trace metals in sediment cores from River Uppanar, Cuddalore, Southeast coast of India.

PubMed

Ayyamperumal, T; Jonathan, M P; Srinivasalu, S; Armstrong-Altrin, J S; Ram-Mohan, V

2006-09-01

An acid leachable technique is employed in core samples (C1, C2 and C3) to develop a baseline data on the sediment quality for trace metals of River Uppanar, Cuddalore, southeast coast of India. Acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) indicate peak values at the sulphidic phase and enrichment of metals in the surface layers are due to the anthropogenic activities. Association of trace metals with Fe, Mn indicates their adsorption onto Fe-Mn oxyhydroxides and their correlation with S indicate that they are precipitated as metal sulphides. Factor analysis identified three possible types of geochemical associations and the supremacy of trace metals along with Fe, Mn, S and mud supports their geochemical associations. Factor analysis also signifies that anthropogenic activities have affected both the estuarine and fresh water regions of River Uppanar.

Synchrotron X-ray microfluorescence measurement of metal distributions in Phragmites australis root system in the Yangtze River intertidal zone

DOE PAGES

Feng, Huan; Zhang, Weiguo; Qian, Yu; ...

2016-06-15

This paper investigates the distributions of Br, Ca, Cl, Cr, Cu, K, Fe, Mn, Pb, Ti, V and Zn in Phragmites australis root system and the function of Fe nanoparticles in scavenging metals in the root epidermis using synchrotron X-ray microfluorescence, synchrotron transmission X-ray microscope measurement and synchrotron X-ray absorption near-edge structure techniques. The purpose of this study is to understand the mobility of metals in wetland plant root systems after their uptake from rhizosphere soils. Phragmites australis samples were collected in the Yangtze River intertidal zone in July 2013. The results indicate that Fe nanoparticles are present in themore » root epidermis and that other metals correlate significantly with Fe, suggesting that Fe nanoparticles play an important role in metal scavenging in the epidermis.« less

Synchrotron X-ray microfluorescence measurement of metal distributions in Phragmites australis root system in the Yangtze River intertidal zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Huan; Zhang, Weiguo; Qian, Yu

This paper investigates the distributions of Br, Ca, Cl, Cr, Cu, K, Fe, Mn, Pb, Ti, V and Zn in Phragmites australis root system and the function of Fe nanoparticles in scavenging metals in the root epidermis using synchrotron X-ray microfluorescence, synchrotron transmission X-ray microscope measurement and synchrotron X-ray absorption near-edge structure techniques. The purpose of this study is to understand the mobility of metals in wetland plant root systems after their uptake from rhizosphere soils. Phragmites australis samples were collected in the Yangtze River intertidal zone in July 2013. The results indicate that Fe nanoparticles are present in themore » root epidermis and that other metals correlate significantly with Fe, suggesting that Fe nanoparticles play an important role in metal scavenging in the epidermis.« less

[Determination of metal elements in Achyranthis bidentatae radix from various habitats].

PubMed

Tu, Wan-Qian; Zhang, Liu-Ji

2011-12-01

To establish an atomic absorption spectrometry method for determination of the contents of metal elements in Achyranthis Bidentatae Radix and analyze 21 batches of samples from different areas. Fe, Mn, Ca, Mg, K, Zn and Cu were detected by atomic absorption spectrometry with hydrogen flame detector, Pb, As and Cd were detected by graphite furnace atomic absorption, Hg was detected by cold atomic absorption. The heavy metal contents met the requirement of Chinese Pharmacopoeia. The contents of K, Mg, Cu and Mn in the samples of geo-authentic areas were higher,while the contents of Fe, Zn, Hg and Pb in the samples of non-authentic areas were higher. This method is sample, accurate, repeatable and could be used to evaluate the quality of Achyranthis Bidentatae Radix.

Binding of the Zn2+ ion to ferric uptake regulation protein from E. coli and the competition with Fe2+ binding: a molecular modeling study of the effect on DNA binding and conformational changes of Fur

NASA Astrophysics Data System (ADS)

Jabour, Salih; Hamed, Mazen Y.

2009-04-01

The three dimensional structure of Ferric uptake regulation protein dimer from E. coli, determined by molecular modeling, was docked on a DNA fragment (iron box) and Zn2+ ions were added in two steps. The first step involved the binding of one Zn2+ ion to what is known as the zinc site which consists of the residues Cys 92, Cys 95, Asp 137, Asp141, Arg139, Glu 140, His 145 and His 143 with an average metal-Nitrogen distance of 2.5 Å and metal-oxygen distance of 3.1-3.2 Å. The second Zn2+ ion is bound to the iron activating site formed from the residues Ile 50, His 71, Asn 72, Gly 97, Asp 105 and Ala 109. The binding of the second Zn2+ ion strengthened the binding of the first ion as indicated by the shortening of the zinc-residue distances. Fe2+, when added to the complex consisting of 2Zn2+/Fur dimer/DNA, replaced the Zn2+ ion in the zinc site and when a second Fe2+ was added, it replaced the second zinc ion in the iron activating site. The binding of both zinc and iron ions induced a similar change in Fur conformations, but shifted residues closer to DNA in a different manner. This is discussed along with a possible role for the Zn2+ ion in the Fur dimer binding of DNA in its repressor activity.

Synthesis and application of Fe3O4@SiO2@TiO2 for photocatalytic decomposition of organic matrix simultaneously with magnetic solid phase extraction of heavy metals prior to ICP-MS analysis.

PubMed

Habila, Mohamed A; ALOthman, Zeid A; El-Toni, Ahmed Mohamed; Labis, Joselito Puzon; Soylak, Mustafa

2016-07-01

Interference of organic compounds in the matrix of heavy metal solution could suppress their pre-concentration and detection processes. Therefore, this work aimed to develop simple and facile methods for separation of heavy metals before ICP-MS analysis. Fe3O4@SiO2@TiO2 core-double shell magnetic adsorbent was prepared and characterized by TEM, SEM, FTIR, XRD and surface area, and tested for Magnetic Solid Phase Extraction (MSPE) of Cu(II), Zn(II), Cd(II) and Pb(II). TEM micrograph of Fe3O4@SiO2@TiO2 reveals the uniform coating of TiO2 layer of about 20nm onto the Fe3O4@SiO2 nanoparticles and indicates that all nanoparticles are monodispersed and uniform. The saturation magnetization from the room-temperature hysteresis loops of Fe3O4 and Fe3O4@SiO2@TiO2 was found to be 72 and 40emug(-1), respectively, suggesting good separability of the nanoparticles. The Fe3O4@SiO2@TiO2 showed maximum adsorption capacity of 125, 137, 148 and 160mgg(-1) for Cu(II), Zn(II), Cd(II) and Pb(II) respectively, and the process was found to fit with the second order kinetic model and Langmuir isotherm. Fe3O4@SiO2@TiO2 showed efficient photocatalytic decomposition for tartrazine and sunset yellow (consider as Interfering organic compounds) in aqueous solution under the irradiation of UV light. The maximum recovery% was achieved at pH 5, by elution with 10mL of 2M nitric acid solution. The LODs were found to be 0.066, 0.049, 0.041 and 0.082µgL(-1) for Cu(II), Zn(II), Cd(II) and Pb(II), respectively while the LOQs were found to be 0.20, 0.15, 0.12 and 0.25µgL(-1) for Cu(II), Zn(II), Cd(II) and Pb(II), respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

The effect of solution pH on the electrochemical performance of nanocrystalline metal ferrites MFe2O4 (M=Cu, Zn, and Ni) thin films

NASA Astrophysics Data System (ADS)

Elsayed, E. M.; Rashad, M. M.; Khalil, H. F. Y.; Ibrahim, I. A.; Hussein, M. R.; El-Sabbah, M. M. B.

2016-04-01

Nanocrystalline metal ferrite MFe2O4 (M=Cu, Zn, and Ni) thin films have been synthesized via electrodeposition-anodization process. Electrodeposited (M)Fe2 alloys were obtained from aqueous sulfate bath. The formed alloys were electrochemically oxidized (anodized) in aqueous (1 M KOH) solution, at room temperature, to the corresponding hydroxides. The parameters controlling the current efficiency of the electrodeposition of (M)Fe2 alloys such as the bath composition and the current density were studied and optimized. The anodized (M)Fe2 alloy films were annealed in air at 400 °C for 2 h. The results revealed the formation of three ferrite thin films were formed. The crystallite sizes of the produced films were in the range between 45 and 60 nm. The microstructure of the formed film was ferrite type dependent. The corrosion behavior of ferrite thin films in different pH solutions was investigated using open circuit potential (OCP) and potentiodynamic polarization measurements. The open circuit potential indicates that the initial potential E im of ZnFe2O4 thin films remained constant for a short time, then sharply increased in the less negative direction in acidic and alkaline medium compared with Ni and Cu ferrite films. The values of the corrosion current density I corr were higher for the ZnFe2O4 films at pH values of 1 and 12 compared with that of NiFe2O4 and CuFe2O4 which were higher only at pH value 1. The corrosion rate was very low for the three ferrite films when immersion in the neutral medium. The surface morphology recommended that Ni and Cu ferrite films were safely used in neutral and alkaline medium, whereas Zn ferrite film was only used in neutral atmospheres.

A New Test of Copper and Zinc Abundances in Late-Type Stars Using Cu II and Zn II lines in the Near-Ultraviolet

NASA Astrophysics Data System (ADS)

Roederer, Ian

2017-08-01

The copper (Cu, Z = 29) and zinc (Zn, Z = 30) abundances found in late-type stars provide critical constraints on models that predict the yields of massive star supernovae, hypernovae, Type Ia supernovae, and AGB stars, which are essential ingredients in Galactic chemical evolution models. Furthermore, Zn is commonly used to compare the abundance of iron-group elements in the gas phase in high-redshift DLA systems with metallicities in Local Group stars. It is thus important that the observational Cu and Zn abundances in stars are correct. My proposed archive study will address this issue by using archive STIS spectra of 14 stars to provide the first systematic observational tests of non-LTE calculations of Cu and Zn line formation in late-type stars. The non-LTE calculations predict that all LTE [Cu/Fe] abundance ratios presently found in the literature are systematically lower than the true ratios found in stars. The non-LTE calculations for Zn predict that the LTE values in the literature may be systematically overestimated in low-metallicity stars. The LTE abundances of Cu and Zn are derived from Cu I and Zn I lines. The key advance enabled by the use of NUV spectra is the detection of several lines of Cu II and Zn II, which cannot be detected in the optical or infrared. Cu II and Zn II are largely immune to non-LTE effects in the atmospheres of late-type stars. The metallicities of the 14 stars with NUV spectra span -2.6 < [Fe/H] < -0.1, which covers the range of most Cu and Zn abundances reported in the literature. The proposed study will allow me to test the non-LTE calculations and calibrate the stellar abundances.

Impacts of geology and land use on magnetic susceptibility and selected heavy metals in surface soils of Mashhad plain, northeastern Iran

NASA Astrophysics Data System (ADS)

Karimi, Alireza; Haghnia, Gholam Hosain; Ayoubi, Shamsollah; Safari, Tayebeh

2017-03-01

Magnetic susceptibility is a fast, inexpensive and reliable technique for estimating and monitoring the anthropogenic contamination of soil with heavy metals. However, it is essential to determine the factors affecting magnetic susceptibility before applying this technique to environmental studies. The objectives of this study were to investigate i) the effect of parent materials and land use on the magnetic susceptibility and concentrations of Fe, Ni, Pb and Zn, and ii) capability of magnetic susceptibility as an indicator of anthropogenic heavy metals contamination of soil in Mashhad plain, northeastern Iran. One hundred seventy-eight composite surface soil samples (0-10 cm) were taken. The aqua-regia extractable concentrations of Fe, Ni, Zn and Pb were determined by atomic absorption spectroscopy. Magnetic susceptibility at low and high frequency (χlf and χhf) were measured and frequency dependent susceptibility (χfd) was calculated. The average concentrations of Fe, Ni, Pb and Zn were 22,812, 61.4, 74.1 and 31.6 mg kg- 1, respectively. The highest contents of Pb (69.1 mg kg- 1) and Zn (149 mg kg- 1) were observed in urban area. The highest concentration of Ni was 41,538 mg kg- 1 observed in the soils developed from ultramafic rocks. Magnetic susceptibility varied from 20.3 on marly sediments to 311.8 × 10- 8 m3 kg- 1 on ultramafic rocks. A positive strong correlation (Pvalue < 0.01, r = 0.88) was obtained between Ni and χlf. There were no significant relationships between Zn and Pb with χlf, therefore it seems that magnetic susceptibility has not been affected significantly by anthropogenic activities which enhanced Pb and Zn concentrations in urban soils. The results indicated that magnetic susceptibility was mainly controlled by Ni containing minerals with lithogenic origin. Therefore, in the soils studied, magnetic susceptibility could not be employed as indicator of anthropogenic contamination of soil with heavy metals.

Multivariate analysis of heavy metal contents in soils, sediments and water in the region of Meknes (central Morocco).

PubMed

Tahri, M; Benyaïch, F; Bounakhla, M; Bilal, E; Gruffat, J J; Moutte, J; Garcia, D

2005-03-01

Concentrations of Al, Fe, Cr, Cu, Ni, Pb and Zn in soils, sediments and water samples collected along the Oued Boufekrane river (Meknes, central Morocco) were determined. In soils, a homogeneous distribution of metal concentrations was observed throughout the study area except for Pb, which presents high enrichment at sites located at the vicinity of a main highway. In sediments, high enrichment, with respect to upstream sites, were observed downstream of the city of Meknes for Al, Cr, Fe and Ni and inside the city for Cu, Zn and Pb. In water samples, the metal contents showed to correlate with their homologues in sediments suggesting that the metal contents in water and sediments have identical origins. Descriptive statistics and multivariate analysis (principal factor method, PFM) were used to assist the interpretation of elemental data. This allowed the determination of the correlations between the metals and the identification of three main factor loadings controlling the metal variability in soils and sediments.

Trophic transfer of trace metals from the polychaete worm Nereis diversicolor to the polychaete N. virens and the decapod crustacean Palaemonetes varians

USGS Publications Warehouse

Rainbow, P.S.; Poirier, L.; Smith, B.D.; Brix, K.V.; Luoma, S.N.

2006-01-01

Diet is an important exposure route for the uptake of trace metals by aquatic invertebrates, with trace metal trophic transfer depending on 2 stages - assimilation and subsequent accumulation by the predator. This study investigated the trophic transfer of trace metals from the sediment-dwelling polychaete worm Nereis diversicolor from metal-rich estuarine sediments in southwestern UK to 2 predators - another polychaete N. virens (Cu, Zn, Pb, Cd, Fe) and the decapod crustacean Palaemonetes varians (Cu, Zn, Pb, Cd, Fe, Ag, As, Mn). N. virens showed net accumulation of Cu, Zn, Pb and Cd from the prey; accumulation increased with increasing prey concentration, but a coefficient of trophic transfer decreased with increasing prey concentration, probably because a higher proportion of accumulated metal in the prey is bound in less trophically available (insoluble) detoxified forms. The trace metal accumulation patterns of P. varians apparently restricted significant net accumulation of metals from the diet of N. diversicolor to just Cd. There was significant mortality of the decapods fed on the diets of metal-rich worms. Metal-rich invertebrates that have accumulated metals from the rich historical store in the sediments of particular SW England estuaries can potentially pass these metals along food chains, with accumulation and total food chain transfer depending on the metal assimilation efficiencies and accumulation patterns of the animal at each trophic level. This trophic transfer may be significant enough to have ecotoxicological effects. ?? Inter-Research 2006.

Fractionation of heavy metals and assessment of contamination of the sediments of Lake Titicaca.

PubMed

Cáceres Choque, Luis Fernando; Ramos Ramos, Oswaldo E; Valdez Castro, Sulema N; Choque Aspiazu, Rigoberto R; Choque Mamani, Rocío G; Fernández Alcazar, Samuel G; Sracek, Ondra; Bhattacharya, Prosun

2013-12-01

Chemical weathering is one of the major geochemical processes that control the mobilization of heavy metals. The present study provides the first report on heavy metal fractionation in sediments (8-156 m) of Lake Titicaca (3,820 m a.s.l.), which is shared by the Republic of Peru and the Plurinational State of Bolivia. Both contents of total Cu, Fe, Ni, Co, Mn, Cd, Pb, and Zn and also the fractionation of these heavy metals associated with four different fractions have been determined following the BCR scheme. The principal component analysis suggests that Co, Ni, and Cd can be attributed to natural sources related to the mineralized geological formations. Moreover, the sources of Cu, Fe, and Mn are effluents and wastes generated from mining activities, while Pb and Zn also suggest that their common source is associated to mining activities. According to the Risk Assessment Code, there is a moderate to high risk related to Zn, Pb, Cd, Mn, Co, and Ni mobilization and/or remobilization from the bottom sediment to the water column. Furthermore, the Geoaccumulation Index and the Enrichment Factor reveal that Zn, Pb, and Cd are enriched in the sediments. The results suggest that the effluents from various traditional mining waste sites in both countries are the main source of heavy metal contamination in the sediments of Lake Titicaca.

Exposure of Mn and FeSODs, but not Cu/ZnSOD, to NO leads to nitrosonium and nitroxyl ions generation which cause enzyme modification and inactivation: an in vitro study.

PubMed

Niketíc, V; Stojanović, S; Nikolić, A; Spasić, M; Michelson, A M

1999-11-01

The effect of NO treatment in vitro on structural and functional alterations of Cu/Zn, Mn, and Fe type of SODs was studied. Significant difference in response to NO of Cu/ZnSOD compared to the Mn and Fe types was demonstrated. Cu/ZnSOD was shown to be stable with respect to NO: even on prolonged exposure, NO produced negligible effect on its structure and activity. In contrast, both Mn and Fe types were found to be NO-sensitive: exposure to NO led to their fast and extensive inactivation, which was accompanied by extensive structural alterations, including (in some of the samples tested) the cleavage of enzyme polypeptide chains, presumably at His residues of the enzyme metal binding sites. The generation of nitrosonium (NO+) and nitroxyl (NO-) ions in NO treated Mn and FeSODs, which produce enzyme modifications and inactivation, was demonstrated. The physiological and biomedical significance of described findings is briefly discussed.

Controls on the Transition Metal Isotopic Composition of Seawater: Diatom Culture Experiments

NASA Astrophysics Data System (ADS)

Vance, D.; Archer, C.; Kennaway, G.; Cox, E.; Statham, P. J.

2004-12-01

Many transition metals are essential micronutrients for marine phytoplankton. As a result the expectation is that biological processes play an important, perhaps a dominant, role in their marine isotope geochemistry. These observations raise the prospect of using isotope records to trace transition metal micronutrient usage in the past oceans, an issue that is of importance to the efficiency of the biological pump and atmospheric carbon dioxide. As such, the characterisation of trace metal isotopic fractionations associated with marine primary productivity are an important scientific goal. Here we report fractionations associated with Fe, Cu and Zn sequestration by diatoms, one of the main primary producers in the oceans. Axenic unialgal cultures of Thalassiosira weissflogii and Thalassiosira pseudonana were established in artificial seawater + F/2 medium at 18° C on a 16:8 light:dark cycle. The cultures were filtered to separate diatom material from residual media and analysed for Zn, Cu and Fe concentrations and isotope composition using techniques described elsewhere1,2. Aliquots of the starting medium were also measured for each batch of cultures. The diatom organic material shows small, but consistent and resolvable, positive fractionations (0.1-0.3 per mil) for Fe, Cu and Zn relative to the starting medium. In the case of all three metals, but particularly for Zn (70-95% depending on experiment size), the diatoms had sequestered a large proportion of the available metal, suggesting that the fractionation factor for metal usage by the diatoms is much greater than 1.0001 to 1.0003. Time-series experiments are under way to determine the exact magnitude of the fractionation factor. The mass-balance is supported by the fact that the residual medium is around -0.4 per mil for Zn. The fact that diatoms incorporate trace metals that are isotopically heavier than the nutrient pool is a surprising result, the expectation having been that, as with carbon, the biological usage of trace metals would result in kinetic fractionations3. The positive fractionations necessitate an equilibrium process and, perhaps, active extra-cellular sequestration of trace metals. The second broader implication is that given the proposed role of diatoms in controlling the extreme depletion of Zn in open ocean surface waters, particularly in the Pacific where surface waters are have up to a factor of 250 less Zn than deep waters4, the depletion of the light isotope in surface waters and its enrichment in deep waters are predicted to be extreme. Zn, and other trace metal, isotopes may have an important role in recording this process in the past oceans. 1 C. Archer and D. Vance, 2004, J. Anal. Atom. Spectr. 19, 656-665. 2 J. Bermin, et al., 2004, this volume. 3 Pichat, S et al., 2003, Earth Planet. Sci. Lett. 210, 167-178. 4 Lohan, M.C. et al., 2002, Deep-Sea Res. II 49, 5793-5808.

Characterization of typical metal particles during haze episodes in Shanghai, China.

PubMed

Li, Rui; Yang, Xin; Fu, Hongbo; Hu, Qingqing; Zhang, Liwu; Chen, Jianmin

2017-08-01

Aerosol particles were collected during three heavy haze episodes at Shanghai in the winter of 2013. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy was used to study the morphology and speciation of typical metal particles at a single-particle level. In addition, time-of-flight aerosol mass spectrometry (ATOFMS) was applied to identify the speciation of the Fe-containing particles. TEM analysis indicated that various metal-containing particles were hosted by sulfates, nitrates, and oxides. Fe-bearing particles mainly originated from vehicle emissions and/or steel production. Pb-, Zn-, and Sb-bearing particles were mainly contributed by anthropogenic sources. Fe-bearing particles were clustered into six groups by ATOFMS: Fe-Carbon, Fe-Inorganic, Fe-Trace metal, Fe-CN, Fe-PO 3, and Fe-NO 3 . ATOFMS data suggested that Fe-containing particles corresponded to different origins, including industrial activities, resuspension of dusts, and vehicle emissions. Fe-Carbon and Fe-CN particles displayed significant diurnal variation, and high levels were observed during the morning rush hours. Fe-Inorganic and Fe-Trace metal particle levels peaked at night. Furthermore, Fe-Carbon and Fe-PO 3 were mainly concentrated in the fine particles. Fe-CN, Fe-Inorganic, and Fe-Trace metal exhibited bimodal distribution. The mixing state of the particles revealed that all Fe-bearing particles tended to be mixed with sulfate and nitrate. The data presented herein is essential for elucidating the origin, evolution processes, and health effects of metal-bearing particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Partitioning of Dissolved Metals (Fe, Mn, Cu, Cd, Zn, Ni, and Pb) into Soluble and Colloidal Fractions in Continental Shelf and Offshore Waters, Northern California

NASA Astrophysics Data System (ADS)

Fitzsimmons, J. N.; Parker, C.; Sherrell, R. M.

2016-02-01

The physicochemical speciation of trace metals in seawater influences their cycling as essential micronutrients for microorganisms or as tracers of anthropogenic influences on the marine environment. While chemical speciation affects lability, the size of metal complexes influences their ability to be accessed biologically and also influences their fate in the aggregation pathway to marine particles. In this study, we show that multiple trace metals in shelf and open ocean waters off northern California (IRN-BRU cruise, July 2014) have colloidal-sized components. Colloidal fractions were operationally defined using two ultrafiltration methods: a 0.02 µm Anopore membrane and a 10 kDa ( 0.003 µm) cross flow filtration (CFF) system. Together these two methods distinguished small (0.003 - 0.02 µm) and large (0.02 µm - 0.2 µm) colloids. As has been found previously for seawater in other ocean regimes, dissolved Fe had a broad size distribution with 50% soluble (<10 kDa) complexes and both small and large colloidal species. Dissolved Mn had no measurable colloidal component, consistent with its predicted chemical speciation as free Mn(II). Dissolved Cu, which like Fe is thought to be nearly fully organically bound in seawater, was only 25% colloidal, and these colloids were all small. Surprisingly Cd, Ni, and Pb also showed colloidal components (8-20%, 25-40%, and 10-50%) despite their hypothesized low organic speciation. Zn and Pb were nearly completely sorbed onto the Anopore membrane, making CFF the only viable ultrafiltration method for those elements. Zn suffered incomplete recovery ( 50-75%) through the CFF system but showed 30-85% colloidal contribution; thus, verifying a Zn colloidal phase with these methods is challenging. Conclusions will reveal links between the physical and chemical speciation for these metals and what role these metal colloids might have on trace metal exchange between the ocean margin and offshore waters.

Carbon-Coated Core-Shell Fe-Cu Nanoparticles as Highly Active and Durable Electrocatalysts for a Zn-Air Battery.

PubMed

Nam, Gyutae; Park, Joohyuk; Choi, Min; Oh, Pilgun; Park, Suhyeon; Kim, Min Gyu; Park, Noejung; Cho, Jaephil; Lee, Jang-Soo

2015-06-23

Understanding the interaction between a catalyst and oxygen has been a key step in designing better electrocatalysts for the oxygen reduction reaction (ORR) as well as applying them in metal-air batteries and fuel cells. Alloying has been studied to finely tune the catalysts' electronic structures to afford proper binding affinities for oxygen. Herein, we synthesized a noble-metal-free and nanosized transition metal CuFe alloy encapsulated with a graphitic carbon shell as a highly efficient and durable electrocatalyst for the ORR in alkaline solution. Theoretical models and experimental results demonstrated that the CuFe alloy has a more moderate binding strength for oxygen molecules as well as the final product, OH(-), thus facilitating the oxygen reduction process. Furthermore, the nitrogen-doped graphitic carbon-coated layer, formed catalytically under the influence of iron, affords enhanced charge transfer during the oxygen reduction process and superior durability. These benefits were successfully confirmed by realizing the catalyst application in a mechanically rechargeable Zn-air battery.

Mineral Composition of Wild and Cultivated Blueberries.

PubMed

Dróżdż, Paulina; Šėžienė, Vaida; Pyrzynska, Krystyna

2018-01-01

The concentrations of 13 elements (Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, and Zn) were determined in several samples of native (wild) naturally growing and cultivated blueberry fruits. The total metal contents after mineralization were analyzed by inductively coupled plasma optical emission spectrometry. Reliability of the procedure was checked by the analysis of the certified reference materials Mixed Polish Herbs (INGT-MPH-2) and Leaves of Poplar (NCS DC 73350). In the fruits collected in the forest (wild blueberries), higher contents of Ca, Na, and Mg as well as Mn and Zn were observed. Similar levels of Cu, Cr, Fe, and Ni were detected in both wild-growing and cultivated plants. The significantly higher content of Fe and Cd in cultivated blueberries was connected with the content of these metals in soil samples collected from the same places. The metal extraction efficiency by hot water varied widely for the different blueberries (wild or cultivated) as well as their form (fresh or dried).

Metal-Organic Coordination Polymer to Prepare Density Controllable and High Nitrogen-Doped Content Carbon/Graphene for High Performance Supercapacitors.

PubMed

Luo, Jinwei; Zhong, Wenbin; Zou, Yubo; Xiong, Changlun; Yang, Wantai

2017-01-11

Design and preparation of carbon-based electrode material with high nitrogen-doping ratio and appropriate density attract much interest for supercapacitors in practical application. Herein, three porous carbon/graphene (NCG Cu , NCG Fe , and NCG Zn ) with high doping ratio of nitrogen have been prepared via directly pyrolysis of graphene oxide (GO)/metal-organic coordination polymer (MOCP) composites, which were formed by reacting 4,4'-bipyridine (BPD) with CuCl 2 , FeCl 3 , and ZnCl 2 , respectively. As-prepared NCG Cu , NCG Fe and NCG Zn showed high nitrogen doping ratio of 10.68, 12.99, and 11.21 at. %; and high density of 1.52, 0.84, and 1.15 g cm -3 , respectively. When as-prepared samples were used as supercapacitor electrodes, NCG Cu , NCG Fe and NCG Zn exhibited high gravimetric specific capacitances of 369, 298.5, 309.5 F g -1 , corresponding to high volumetric specific capacitances of 560.9, 250.7, 355.9 F cm -3 at a current density of 0.5 A g -1 , as well as good cycling stability, nearly 100% of the capacitance retained after 1000 cycles even at a large current density of 10 A g -1 . It is expected that the provided novel strategy can be used to develop electrode materials in high performance energy conversion/storage devices.

Micronutrient metal speciation is driven by competitive organic chelation in grassland soils.

NASA Astrophysics Data System (ADS)

Boiteau, R.; Shaw, J. B.; Paša-Tolić, L.; Koppenaal, D.; Jansson, J.

2017-12-01

Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or how they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population.

The enhancement of heavy metal removal from polluted river water treatment by integrated carbon-aluminium electrodes using electrochemical method

NASA Astrophysics Data System (ADS)

Yussuf, N. M.; Embong, Z.; Abdullah, S.; Masirin, M. I. M.; Tajudin, S. A. A.; Ahmad, S.; Sahari, S. K.; Anuar, A. A.; Maxwell, O.

2018-01-01

The heavy metal removal enhancement from polluted river water was investigated using two types of electrodes consist of integrated carbon-aluminium and a conventional aluminium plate electrode at laboratory-scale experiments. In the integrated electrode systems, the aluminium electrode surface was coated with carbon using mixed slurry containing carbon black, polyvinyl acetate and methanol. The electrochemical treatment was conducted on the parameter condition of 90V applied voltage, 3cm of electrode distance and 60 minutes of electrolysis operational time. Surface of both electrodes was investigated for pre and post electrolysis treatment by using SEM-EDX analytical technique. Comparison between both of the electrode configuration exhibits that more metals were accumulated on carbon integrated electrode surfaces for both anode and cathode, and more heavy metals were detected on the cathode. The atomic percentage of metals distributed on the cathode conventional electrode surface consist of Al (94.62%), Zn (1.19%), Mn (0.73%), Fe (2.81%) and Cu (0.64%), while on the anode contained O (12.08%), Al (87.63%) and Zn (0.29%). Meanwhile, cathode surface of integrated electrode was accumulated with more metals; O (75.40%), Al (21.06%), Zn (0.45%), Mn (0.22), Fe (0.29%), Cu (0.84%), Pb (0.47%), Na (0.94%), Cr (0.08%), Ni (0.02%) and Ag (0.22%), while on anode contain Al (3.48%), Fe (0.49 %), C (95.77%), and Pb (0.26%). According to this experiment, it was found that integrated carbon-aluminium electrodes have a great potential to accumulate more heavy metal species from polluted water compare to the conventional aluminium electrode. Here, heavy metal accumulation process obviously very significant on the cathode surface.

Creation of Technosols to decrease metal availability in pyritic tailings with addition of biochar and marble waste

NASA Astrophysics Data System (ADS)

Moreno-Barriga, Fabián; Acosta, José A.; Ángeles Muñoz, María; Faz, Ángel; Zornoza, Raúl

2017-04-01

Creation of Technosols with the use of different materials is a sustainable strategy to reclaim mine tailings and reduce metal mobility. For this purpose, a short-term incubation experiment was designed with biochars derived from pig manure (PM), crop residues (CR) and municipal solid waste (MSW) added to tailings alone or in combination with marble waste (MaW). We aimed to assess the efficiency of the different amendments to decrease Cd, Pb and Zn availability in the Technosols and the fractions where metals were retained. Results showed that all amendments reduced metal mobility, directly related to increases in pH. Those materials with higher content of carbonates were more effective to immobilize metals ( 99%). MSW was highly effective to decrease metal mobility owing to the higher carbonate content, but addition of MaW was needed to enhance metal immobilization with PM and CR. Decreases in Cd mobility were related to retention by the carbonate, Mn/Fe oxides and oxidizable (organic compounds) fractions. Decreases in Pb mobility were related to retention in the Mn/Fe oxides and residual fractions, while decreases in Zn mobility were related to retention in Mn/Fe oxides and oxidizable fractions. The increase in the retention of metals in all fractions was directly associated to increases in pH. Association of Zn and Pb with the oxidizable fraction was also related to the recalcitrance of the organic compounds, and so dependent on biochar type. SEM/EDX showed that biochar showed great affinity to interact with iron oxides, calcium sulfates and phyllosilicates. Acknowledgements This work was supported by Fundación Séneca (Agency of Science and Technology of the Region of Murcia, Spain) [grant number 18920/JLI/13].

Health risk assessment of heavy metals in wheat using different water qualities: implication for human health.

PubMed

Khan, Zafar Iqbal; Ahmad, Kafeel; Rehman, Sidrah; Siddique, Samra; Bashir, Humayun; Zafar, Asma; Sohail, Muhammad; Ali, Salem Alhajj; Cazzato, Eugenio; De Mastro, Giuseppe

2017-01-01

In the recent years, the use of sewage water for irrigation has attracted the attention of arid and semi-arid countries where the availability of fresh water is poor. Despite the potential use of sewage water in crop irrigation as effective and sustainable strategy, the environmental and human risks behind this use need to be deeply investigated. In this regard, an experiment was carried out under field conditions in Nursery, University College of Agriculture Sargodha, to evaluate the possible health risks of undesirable metals in wheat grains. Wheat variety Sarang was cultivated and irrigated with different combinations of ground (GW) and sewage water (SW). The concentrations of heavy metals (Cr, Cd, Ni, and Pb) and trace elements (Cu, Zn, and Fe) in wheat grains as well as in soil were determined. Moreover, the pollution load index (PLI), accumulation factor (AF), daily intake of metals (DIM), and health risk index (HRI) were calculated. Results showed that the concentration trend of heavy metals was Pb

Total and labile metals in surface sediments of the tropical river-estuary system of Marabasco (Pacific coast of Mexico): Influence of an iron mine.

PubMed

Marmolejo-Rodríguez, Ana Judith; Prego, Ricardo; Meyer-Willerer, Alejandro; Shumilin, Evgueni; Cobelo-García, Antonio

2007-01-01

Marabasco is a tropical river-estuary system comprising the Marabasco river and the Barra de Navidad Lagoon. The river is impacted by the Peña Colorada iron mine, which produces 3.5 million tons of pellets per year. Thirteen surface sediment samples were collected in May 2005 (dry season) in order to establish background levels of Al, Cd, Co, Cu, Fe, Ni, Pb, and Zn in the system and to ascertain the potential mobility of metals in the sediments. Analyses were carried out in the fraction finer than 63 microm, and labile metals extracted according the BCR procedure. Certified reference materials were used for validation of methods. Total concentrations of Cd, Co, Cu, Ni, Pb, and Zn were in the range of 0.05-0.34, 6-95, 0.7-31, 9-26, 2-18, and 53-179 mgkg(-1), respectively; Al and Fe ranges of 24-127, and 26-69 mgg(-1) correspondingly. Cadmium was found to be significantly labile in the sediments (20-100%), followed by Co (0-35%), Ni (3-16%) and Zn (0-25%), whereas the labile fraction for Cu, Fe and Pb was almost negligible (<4%). According with the total metal concentrations, background levels and normalised enrichment factors (NEF) of the metals studied, the impact of the Peña Colorada iron mine on the Marabasco system is lower than expected when compared with other similar World systems influenced by mining activities.

Metabolic alterations without metal accumulation in the ovary of adult Bufo arenarum females, observed after long-term exposure to Zn(2+), followed by toxicity to embryos.

PubMed

Naab, F; Volcomirsky, M; Burlón, A; Caraballo, M E; Debray, M; Kesque, J M; Kreiner, A J; Ozafrán, M J; Schuff, J A; Stoliar, P; Vázquez, M E; Davidson, J; Davidson, M; Fonovich de Schroeder, T M

2001-08-01

Long-term exposure of aquatic organisms to metals, even those considered micronutrients, may affect their metabolism and produce sublethal effects. We evaluated the effects of long-term exposure of adult amphibian (Bufo arenarum) females to 4 microg/L of Zn(2+) (ZnSO(4) x H(2)O) in Ringer solution on the concentration of Zn and Fe, the activity of the key enzyme of the pentose phosphate pathway glucose 6-phosphate dehydrogenase, and glutathione content, both in the liver and ovary of these animals. We also performed early embryonic development studies by in vitro insemination from control and treated females. Zn exposure rendered lower Zn concentrations in the ovaries than did exposure of animals to Ringer solution without metal addition (97 +/- 50 versus 149 +/- 46 Zn microg/wet tissue g). Zn and Fe concentration correlation was positive and linear in the ovary, but was negative and nonlinear in the liver of the studied females. The activity of the enzyme glucose 6-phosphate dehydrogenase decreased (0.0599 +/- 0.0109 versus 0.0776 +/- 0.0263 micromol of NADPH/min x mg of proteins) and the endogenous glutathione content increased (0.027 +/- 0.005 versus 0.018 +/- 0.007 mg/10 mg of proteins) in the ovary but remained unaltered in the liver as a consequence of Zn treatment. Our results suggest the existence of different mechanisms of regulation of Zn and Fe concentrations in the ovary and in the liver of adult B. arenarum females. Binding of Zn to low-molecular-weight proteins, as metallothioneins, may occur in the liver, thus protecting this organ from toxic effects. In the ovary high-molecular-weight proteins, like glucose-6-phosphate dehydrogenase, should be able to bind Zn, leading to oxidative stress responsible for the observed increase in endogenous glutathione content. Inhibition of the pentose phosphate pathway in the ovary by Zn can be responsible for the reproductive failure that we detected through embryos survival studies during early life stages: 81.3 +/- 6.3% of embryos from control females survived versus 63.1 +/- 13.8% of embryos from Zn-treated females at the branchial circulation stage of development.

Combining Sequential Extractions and X-ray Absorption Spectroscopy for Quantitative and Qualitative Zinc Speciation in Soil

NASA Astrophysics Data System (ADS)

Bauer, Tatiana; Minkina, Tatiana; Batukaev, Abdulmalik; Nevidomskaya, Dina; Burachevskaya, Marina; Tsitsuashvili, Viktoriya; Urazgildieva, Kamilya

2017-04-01

The combined use of X-ray absorption spectrometry and extractive fractionation is an effective approach for studying the interaction of metal ions with soil compounds and identifying the phases-carriers of metals in soil and their stable fixation. These studies were carried out using the technique of X-ray absorption spectroscopy and chemical extractive fractionation. In a model experiment the samples taken in Calcic Chernozem were artificially contaminated with higher portion of Zn(NO3)2 (2000 mg/kg). The metal were incubated in soil samples for 2 year. The samples of soil mineral and organic phases (calcite, kaolinite, bentonite, humic acids) were saturated with Zn2+ from a solution of nitrate salts of metal. The total content of Zn in soil and soil various phases was determined using the X-ray fluorescence method. Extended X-ray absorption fine structure (EXAFS) Zn was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation. Sequential fractionation of Zn in soil conducted by Tessier method (Tessier et al., 1979) which determining 5 fractions of metals in soil: exchangeable, bound to Fe-Mn oxide, bound to carbonate, bound to the organic matter, and bound to silicate (residual). This methodology has so far more than 4000 citations (Web of Science), which demonstrates the popularity of this approach. Much Zn compounds are contained in uncontaminated soils in stable primary and secondary silicates inherited from the parental rocks (67% of the total concentrations in all fractions), which is a regional trait of soils in the fore-Caucasian plain. Extracted fractionation of metal compounds in soil samples, artificially contaminated with Zn salts, indicates the priority holding of Zn2+ ions by silicates, carbonates and Fe-Mn oxides. The Zn content significantly increases in the exchangeable fraction. Atomic structure study of the soil various phases saturated with Zn2+ ion by using (XANES) X-ray absorption spectroscopy allowed the determination of mechanism of metal ions interaction with soil phases and the resulting types of chemical bonds. Interaction with soil components modifies the electron structure of the metal ions themselves. The soil contamination with Zn is accompanied by decreasing the stable connection between metal and soil components. Interacting with humic acids in chernozem, the Zn2+ ion is coordinated by functional groups and ligands and forms unstable outer-sphere complexes. Zinc included into octahedral structures of layered minerals and hydro(oxides) can be inner-and outer-sphere adsorbed. The Zn2+ ions enable to replace Ca2+ ions in octahedral positions being coordinated with carbonate ions as ligands, thus forming absorbed complexes at the surface of mineral calcite. This work was supported by grant of the Russian Scientific Foundation № 16-14-10217.

Preferential depletion of zinc within Costa Rica upwelling dome creates conditions for zinc co-limitation of primary production

PubMed Central

Dreux Chappell, P.; Vedmati, Jagruti; Selph, Karen E.; Cyr, Heather A.; Jenkins, Bethany D.; Landry, Michael R.; Moffett, James W.

2016-01-01

The Costa Rica Dome (CRD) is a wind-driven feature characterized by high primary production and an unusual cyanobacterial bloom in surface waters. It is not clear whether this bloom arises from top-down or bottom-up processes. Several studies have argued that trace metal geochemistry within the CRD contributes to the composition of the phytoplankton assemblages, since cyanobacteria and eukaryotic phytoplankton have different transition metal requirements. Here, we report that total dissolved zinc (Zn) is significantly depleted relative to phosphate (P) and silicate (Si) within the upper water column of the CRD compared with other oceanic systems, and this may create conditions favorable for cyanobacteria, which have lower Zn requirements than their eukaryotic competitors. Shipboard grow-out experiments revealed that while Si was a limiting factor under our experimental conditions, additions of Si and either iron (Fe) or Zn led to higher biomass than Si additions alone. The addition of Fe and Zn alone did not lead to significant enhancements. Our results suggest that the depletion of Zn relative to P in upwelled waters may create conditions in the near-surface waters that favor phytoplankton with low Zn requirements, including cyanobacteria. PMID:27275028

Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts

NASA Technical Reports Server (NTRS)

Boclair, J. W.; Braterman, P. S.

1999-01-01

Solutions containing di- and trivalent metal chlorides [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+; M(III) = Al3+, Fe3+] were titrated with NaOH to yield hydrotalcite-like layered double hydroxides (LDH), [[M(II)]1-x[M(III)]x(OH)2][Cl]x yH2O, by way of M(III) hydroxide/hydrous oxide intermediates. Analysis of the resultant titration curves yields nominal solubility constants for the LDH. The corresponding LDH stabilities are in the order Mg < Mn < Co approximately Ni < Zn for M(II) and Al < Fe for M(III). The stability of LDH relative to the separate metal hydroxides/hydrous oxides is discussed.

Laser-Induced Breakdown Spectroscopy of Trace Metals

NASA Technical Reports Server (NTRS)

Simons, Stephen (Technical Monitor); VanderWal, Randall L.; Ticich, Thomas M.; West, Joseph R., Jr.

2004-01-01

An alternative approach for laser-induced breakdown spectroscopy (LIBS) determination of trace metal determination in liquids is demonstrated. The limits of detection (LOD) for the technique ranged from 10 ppb to 10 ppm for 15 metals metals (Mg, Al, Si, Ca, Ti, Cr, Fe, Co, Ni, Cu, Zn, As, Cd, Hg, Pb) tested.

Effects of metal on the biochemical properties of Helicobacter pylori HypB, a maturation factor of [NiFe]-hydrogenase and urease.

PubMed

Sydor, Andrew M; Liu, Jenny; Zamble, Deborah B

2011-03-01

The biosyntheses of the [NiFe]-hydrogenase and urease enzymes in Helicobacter pylori require several accessory proteins for proper construction of the nickel-containing metallocenters. The hydrogenase accessory proteins HypA and HypB, a GTPase, have been implicated in the nickel delivery steps of both enzymes. In this study, the metal-binding properties of H. pylori HypB were characterized, and the effects of metal binding on the biochemical behavior of the protein were examined. The protein can bind stoichiometric amounts of Zn(II) or Ni(II), each with nanomolar affinity. Mutation of Cys106 and His107, which are located between two major GTPase motifs, results in undetectable Ni(II) binding, and the Zn(II) affinity is weakened by 2 orders of magnitude. These two residues are also required for the metal-dependent dimerization observed in the presence of Ni(II) but not Zn(II). The addition of metals to the protein has distinct impacts on GTPase activity, with zinc significantly reducing GTP hydrolysis to below detectable levels and nickel only slightly altering the k(cat) and K(m) of the reaction. The regulation of HypB activities by metal binding may contribute to the maturation of the nickel-containing enzymes.

Use of Geochemical Indices in Environmental Assessment of Soil; the Predictable and the Predictably Unpredictable

NASA Astrophysics Data System (ADS)

Mikkonen, Hannah; Clarke, Bradley; van de Graaff, Robert; Reichman, Suzie

2016-04-01

Geochemical correlations between common contaminants (Pb, Ni, As, Cr, Co and Zn) and earth metals, Fe and Mn, have been recommended as empirical tools to estimate "background" concentrations of metals in soil. A limited number of studies indicate that geochemical ratios between Pb, Ni, As, Cr, Co, V and Zn with scavenger metals Fe or Mn, are consistent between soils collected from different regions (Hamon et al. 2004, Myers and Thorbjornsen 2004). These studies have resulted in the incorporation of geochemical indices into Australian guidance, for derivation of ecological investigation levels for Ni, Cr, Cu and Zn. However, little research has been undertaken to assess the variation of geochemical patterns between soils derived from different parent materials or different weathering environments. A survey of background soils derived from four different parent materials, across Victoria, Australia, was undertaken, comprising collection of samples (n=640) from the surface (0 to 0.1 m) and sub-surface (0.3 to 0.6 m). Soil samples were collected from urban and rural areas of low disturbance, away from point sources of contamination. Samples were analysed for metals/metalloids and soil physical and chemical properties. Statistical review of results included regression and multivariate analysis. The results of the soil survey were compared against geochemical relationships reported within Australia and internationally. Compilation of results from this study and international data sets, indicates that geochemical relationships for metals Cr and V (in the format of log[Cr] = alog[Fe] +c) are predictable, not only between soils derived from different parent materials, but also between soils of different continents. Conversely, relationships between Zn and Fe, Pb and Fe, Cu and Fe, Co and Mn are variable, particularly within soils derived from alluvial sediments, which may have undergone periods of reducing conditions, resulting in dissociation from metal oxides. Broad application of geochemical indices without an understanding of site specific conditions could result in significant underestimation of anthropogenic impacts to soil and potential risks to the environment. The reliability and application of geochemical indices for estimation of background concentrations will be discussed, including comment on statistical limitations, (such as management of censored results and the behaviour of composition data) and miss-use/miss-interpretation of geochemical indices within the environmental assessment industry, including inferences of causation based on empirical relationships. HAMON, R. E., MCLAUGHLIN, M. J., GILKES, R. J., RATE, A. W., ZARCINAS, B., ROBERTSON, A., COZENS, G., RADFORD, N. & BETTENAY, L. 2004. Geochemical indices allow estimation of heavy metal background concentrations in soils. Global Biogeochemical Cycles, 18, GB1014. MYERS, J. & THORBJORNSEN, K. 2004. Identifying Metals Contamination in Soil: A Geochemical Approach. Soil & Sediment Contamination, 13, 1-16.

Effects of anthropogenic activities on the heavy metal levels in the clams and sediments in a tropical river.

PubMed

Wong, Koe Wei; Yap, Chee Kong; Nulit, Rosimah; Hamzah, Mohd Suhaimi; Chen, Soo Kien; Cheng, Wan Hee; Karami, Ali; Al-Shami, Salman Abdo

2017-01-01

The present study aimed to assess the effects of anthropogenic activities on the heavy metal levels in the Langat River by transplantation of Corbicula javanica. In addition, potential ecological risk indexes (PERI) of heavy metals in the surface sediments of the river were also investigated. The correlation analysis revealed that eight metals (As, Co, Cr, Fe, Mn, Ni, Pb and Zn) in total soft tissue (TST) while five metals (As, Cd, Cr, Fe and Mn) in shell have positively and significantly correlation with respective metal concentration in sediment, indicating the clams is a good biomonitor of the metal levels. Based on clustering patterns, the discharge of dam impoundment, agricultural activities and urban domestic waste were identified as three major contributors of the metals in Pangsun, Semenyih and Dusun Tua, and Kajang, respectively. Various geochemical indexes for a single metal pollutant (geoaccumulation index (I geo ), enrichment factors (EF), contamination factor (C f ) and ecological risk (Er)) all agreed that Cd, Co, Cr, Cu, Fe, Mn, Ni and Zn are not likely to cause adverse effect to the river ecosystem, but As and Pb could pose a potential ecological risk to the river ecosystem. All indexes (degree of contamination (C d ), combined pollution index (CPI) and PERI) showed that overall metal concentrations in the tropical river are still within safe limit. River metal pollution was investigated. Anthropogenic activities were contributors of the metal pollution. Geochemical indexes showed that metals are within the safe limit.

Health risk assessment of heavy metal variability in sachet water sold in Ado-Odo Ota, South-Western Nigeria.

PubMed

Emenike, PraiseGod Chidozie; Tenebe, Theophilus Imokhai; Omeje, Maxwell; Osinubi, Damilare Samuel

2017-08-31

The sales of sachet water (SW), also known as "pure water" (PW), in Nigeria is a lucrative business. It serves many people, especially low-income earners, by providing a more affordable access to safe drinking water when compared with table water. However, some of the producers of SW do not effectively treat raw water before packaging them for sale. This study investigates the presence and concentrations of heavy metals, such as chromium (Cr), iron (Fe), manganese (Mn), copper (Cu), aluminum (Al), and zinc (Zn) in some samples of SW sold within Ota, Ogun State, Nigeria. Samples of SW from nine different producers were purchased for four consecutive weeks and analyzed to determine the concentrations of these heavy metals in them. Furthermore, health risk indicators, such as chronic daily intake (CDI) and health risk indices (HRI) for children and adults, were calculated separately. The metal concentrations were compared with allowable limits set by the World Health Organization (WHO), Nigerian Industrial Standard (NIS), and the United States Environmental Protection Agency (US EPA). High concentrations of Cr, Fe, and Al were found in all the nine samples and exceeded the maximum allowable limits (MAL) of all the standards considered. However, the concentrations of Zn, Mn, and Cu were within permissible limits. The HRIs of heavy metals were in the order of Cu > Fe > Zn > Mn > Al > Cr, but since the standard limits set for some metals were exceeded, proper and effective treatment is required to safeguard the health of consumers.

Impact of metals in surface matrices from formal and informal electronic-waste recycling around Metro Manila, the Philippines, and intra-Asian comparison.

PubMed

Fujimori, Takashi; Takigami, Hidetaka; Agusa, Tetsuro; Eguchi, Akifumi; Bekki, Kanae; Yoshida, Aya; Terazono, Atsushi; Ballesteros, Florencio C

2012-06-30

We report concentrations, enrichment factors, and hazard indicators of 11 metals (Ag, As, Cd, Co, Cu, Fe, In, Mn, Ni, Pb, and Zn) in soil and dust surface matrices from formal and informal electronic waste (e-waste) recycling sites around Metro Manila, the Philippines, referring to soil guidelines and previous data from various e-waste recycling sites in Asia. Surface dust from e-waste recycling sites had higher levels of metal contamination than surface soil. Comparison of formal and informal e-waste recycling sites (hereafter, "formal" and "informal") revealed differences in specific contaminants. Formal dust contained a mixture of serious pollutant metals (Ni, Cu, Pb, and Zn) and Cd (polluted modestly), quite high enrichment metals (Ag and In), and crust-derived metals (As, Co, Fe, and Mn). For informal soil, concentration levels of specific metals (Cd, Co, Cu, Mn, Ni, Pb, and Zn) were similar among Asian recycling sites. Formal dust had significantly higher hazardous risk than the other matrices (p<0.005), excluding informal dust (p=0.059, almost significant difference). Thus, workers exposed to formal dust should protect themselves from hazardous toxic metals (Pb and Cu). There is also a high health risk for children ingesting surface matrices from informal e-waste recycling sites. Copyright © 2012 Elsevier B.V. All rights reserved.

Development of biodegradable Zn-1X binary alloys with nutrient alloying elements Mg, Ca and Sr.

PubMed

Li, H F; Xie, X H; Zheng, Y F; Cong, Y; Zhou, F Y; Qiu, K J; Wang, X; Chen, S H; Huang, L; Tian, L; Qin, L

2015-05-29

Biodegradable metals have attracted considerable attentions in recent years. Besides the early launched biodegradable Mg and Fe metals, Zn, an essential element with osteogenic potential of human body, is regarded and studied as a new kind of potential biodegradable metal quite recently. Unfortunately, pure Zn is soft, brittle and has low mechanical strength in the practice, which needs further improvement in order to meet the clinical requirements. On the other hand, the widely used industrial Zn-based alloys usually contain biotoxic elements (for instance, ZA series contain toxic Al elements up to 40 wt.%), which subsequently bring up biosafety concerns. In the present work, novel Zn-1X binary alloys, with the addition of nutrition elements Mg, Ca and Sr were designed (cast, rolled and extruded Zn-1Mg, Zn-1Ca and Zn-1Sr). Their microstructure and mechanical property, degradation and in vitro and in vivo biocompatibility were studied systematically. The results demonstrated that the Zn-1X (Mg, Ca and Sr) alloys have profoundly modified the mechanical properties and biocompatibility of pure Zn. Zn-1X (Mg, Ca and Sr) alloys showed great potential for use in a new generation of biodegradable implants, opening up a new avenue in the area of biodegradable metals.

Development of biodegradable Zn-1X binary alloys with nutrient alloying elements Mg, Ca and Sr

PubMed Central

Li, H. F.; Xie, X. H.; Zheng, Y. F.; Cong, Y.; Zhou, F. Y.; Qiu, K. J.; Wang, X.; Chen, S. H.; Huang, L.; Tian, L.; Qin, L.

2015-01-01

Biodegradable metals have attracted considerable attentions in recent years. Besides the early launched biodegradable Mg and Fe metals, Zn, an essential element with osteogenic potential of human body, is regarded and studied as a new kind of potential biodegradable metal quite recently. Unfortunately, pure Zn is soft, brittle and has low mechanical strength in the practice, which needs further improvement in order to meet the clinical requirements. On the other hand, the widely used industrial Zn-based alloys usually contain biotoxic elements (for instance, ZA series contain toxic Al elements up to 40 wt.%), which subsequently bring up biosafety concerns. In the present work, novel Zn-1X binary alloys, with the addition of nutrition elements Mg, Ca and Sr were designed (cast, rolled and extruded Zn-1Mg, Zn-1Ca and Zn-1Sr). Their microstructure and mechanical property, degradation and in vitro and in vivo biocompatibility were studied systematically. The results demonstrated that the Zn-1X (Mg, Ca and Sr) alloys have profoundly modified the mechanical properties and biocompatibility of pure Zn. Zn-1X (Mg, Ca and Sr) alloys showed great potential for use in a new generation of biodegradable implants, opening up a new avenue in the area of biodegradable metals. PMID:26023878

Spatial distribution, ecological and health risk assessment of heavy metals in marine surface sediments and coastal seawaters of fringing coral reefs of the Persian Gulf, Iran.

PubMed

Ranjbar Jafarabadi, Ali; Riyahi Bakhtiyari, Alireza; Shadmehri Toosi, Amirhossein; Jadot, Catherine

2017-10-01

Concentrations of 13 heavy metals (Al, Fe, Mn, Zn, Cu, Cr, Co, Ni, V, As, Cd, Hg, Pb) in 360 reef surface sediments (0-5 cm) and coastal seawater samples from ten coral Islands in the Persian Gulf were analyzed to determine their spatial distribution and potential ecological risks. Different sediment quality indices were applied to assess the surface sediment quality. The mean concentrations of metals in studied sediments followed the order: Al > Fe > Ni > V > Mn > Zn > Cu > Cr > Co > As > Cd > Pb > As. Average Cd and Hg exceeded coastal background levels at most sampling sites. With the exception of As, concentrations of heavy metals decreased progressively from the west to the east of the Persian Gulf. Based on the Enrichment Factor (EF) and Potential Ecological Risk Index (RI), concentrations of V, Ni, Hg and Cd indicated moderate contamination and is of some concern. The mean values of heavy metals Toxic Units (TUs) were calculated in the following order: Hg (0.75)> Cr (0.41)> Cd (0.27)> As (0.23)> Cu (0.12)> Zn (0.05)> Pb (0.009). Furthermore, the mean contributing ratios of six heavy metals to Toxic Risk Index (TRI) values were 79% for Hg, 11.48% for Cd, 6.16% for Cr, 3.27% for Cu, 0.07% for Zn and 0.01% for Pb. Calculated values of potential ecological risk factor, revealed that the risk of the heavy metals followed the order Cd > Pb > Ni > Cr > V > Cu > Zn. The results reflected that the level of heavy metals, especially Hg and Cd, are on rise due to emerging oil exploration, industrial development, and oil refineries along the entire Gulf. Fe, Mn, Cu, Zn, V and Ni concentrations in seawater were significantly higher (p < 0.05) than the other detected dissolved heavy metals in the sampling sites. A health risk assessment using the hazard quotient index (HQ) recommended by the USEPA suggests that there is no adverse health effect through dermal exposure, and there is no carcinogenic and non-carcinogenic harm to human health. Copyright © 2017 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coussy, Samuel; Grangeon, Sylvain; Bataillard, Philippe

The prediction of the long term trace element mobility in anthropogenic soils would be a way to anticipate land management and should help in reusing slightly contaminated materials. In the present study, iron (Fe) and zinc (Zn) status evolution was investigated in a 100-year old Technosol. The site of investigation is an old brownfield located in the Nord-Pas-de-Calais region (France) which has not been reshaped since the beginning of the last century. The whole soil profile was sampled as a function of depth, and trace elements mobility at each depth was determined by batch leaching test. A specific focus onmore » Fe and Zn status was carried out by bulk analyses, such as selective dissolution, X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Fe and Zn status in the profile samples was also studied using laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE) and μ-Rutherford backscattering spectroscopy (μ-RBS). The results indicate that (i) Fe is mainly under Fe(III) form, except a minor contribution of Fe(II) in the deeper samples, (ii) some Fe species inherited from the past have been weathered and secondary minerals are constituted of metal-bearing sulphates and Fe (hydr)oxides, (iii) ferrihydrite is formed during pedogenesis (iv) 20 to 30% more Fe (hydr)oxides are present in the surface than in depth and (v) Zn has tetrahedral coordination and is sorbed to phases of increasing crystallinity when depth increases. Zn-bearing phases identified in the present study are: complex Fe, Mn, Zn sulphides, sulphates, organic matter, and ferrihydrite. Soil formation on such material does not induce a dramatic increase of Zn solubility since efficient scavengers are concomitantly formed in the system. However, Technosols are highly heterogeneous and widely differ from one place to another. The behavior examined in this study is not generic and will depend on the type of Technosol and on the secondary minerals formed as well as on the nature and amount of organic matter.« less

High density array screening to identify the genetic requirements for transition metal tolerance in Saccharomyces cerevisiae.

PubMed

Bleackley, Mark R; Young, Barry P; Loewen, Christopher J R; MacGillivray, Ross T A

2011-02-01

Biological systems have developed with a strong dependence on transition metals for accomplishing a number of biochemical reactions. Iron, copper, manganese and zinc are essential for virtually all forms of life with their unique chemistries contributing to a variety of physiological processes including oxygen transport, generation of cellular energy and protein structure and function. Properties of these metals (and to a lesser extent nickel and cobalt) that make them so essential to life also make them extremely cytotoxic in many cases through the formation of damaging oxygen radicals via Fenton chemistry. While life has evolved to exploit the chemistries of transition metals to drive physiological reactions, systems have concomitantly evolved to protect against the damaging effects of these same metals. Saccharomyces cerevisiae is a valuable tool for studying metal homeostasis with many of the genes identified thus far having homologs in higher eukaryotes including humans. Using high density arrays, we have screened a haploid S. cerevisiae deletion set containing 4786 non-essential gene deletions for strains sensitive to each of Fe, Cu, Mn, Ni, Zn and Co and then integrated the six screens using cluster analysis to identify pathways that are unique to individual metals and others with function shared between metals. Genes with no previous implication in metal homeostasis were found to contribute to sensitivity to each metal. Significant overlap was observed between the strains that were sensitive to Mn, Ni, Zn and Co with many of these strains lacking genes for the high affinity Fe transport pathway and genes involved in vacuolar transport and acidification. The results from six genome-wide metal tolerance screens show that there is some commonality between the cellular defenses against the toxicity of Mn, Ni, Zn and Co with Fe and Cu requiring different systems. Additionally, potential new factors been identified that function in tolerance to each of the six metals.

Bioleaching mechanism of Zn, Pb, In, Ag, Cd and As from Pb/Zn smelting slag by autotrophic bacteria.

PubMed

Wang, Jia; Huang, Qifei; Li, Ting; Xin, Baoping; Chen, Shi; Guo, Xingming; Liu, Changhao; Li, Yuping

2015-08-15

A few studies have focused on release of valuable/toxic metals from Pb/Zn smelting slag by heterotrophic bioleaching using expensive yeast extract as an energy source. The high leaching cost greatly limits the practical potential of the method. In this work, autotrophic bioleaching using cheap sulfur or/and pyrite as energy matter was firstly applied to tackle the smelting slag and the bioleaching mechanisms were explained. The results indicated autotrophic bioleaching can solubilize valuable/toxic metals from slag, yielding maximum extraction efficiencies of 90% for Zn, 86% for Cd and 71% for In, although the extraction efficiencies of Pb, As and Ag were poor. The bioleaching performance of Zn, Cd and Pb was independent of leaching system, and leaching mechanism was acid dissolution. A maximum efficiency of 25% for As was achieved by acid dissolution in sulfursulfur oxidizing bacteria (S-SOB), but the formation of FeAsO4 reduced extraction efficiency in mixed energy source - mixed culture (MS-MC). Combined works of acid dissolution and Fe(3+) oxidation in MS-MC was responsible for the highest extraction efficiency of 71% for In. Ag was present in the slag as refractory AgPb4(AsO4)3 and AgFe2S3, so extraction did not occur. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ion exchange treatment of rinse water generated in the galvanizing process.

PubMed

Marañón, Elena; Fernández, Yolanda; Castrillón, Leonor

2005-01-01

A study was conducted of the viability of using the cationic exchange resins Amberlite IR-120 and Lewatit SP-112 to treat rinse water generated in the galvanizing process as well as acidic wastewater containing zinc (Zn) and iron (Fe). Solutions containing either 100 mg/L of Zn at pH 5.6 (rinse water) or Fe and Zn at concentrations of 320 and 200 mg/L at pH 1.5 (acidic water), respectively, were percolated through packed beds until the resins were exhausted. Breakthrough capacities obtained ranged between 1.1 and 1.5 meq metal/mL resin. The elution of metal and the regeneration of resins were performed with hydrochloric acid. The influence of the flowrate used during the loading stage was also studied, with 0.5 bed volumes/min (3.2 cm/min) found to be the optimum flowrate.

The cosmic evolution of dust-corrected metallicity in the neutral gas

NASA Astrophysics Data System (ADS)

De Cia, Annalisa; Ledoux, Cédric; Petitjean, Patrick; Savaglio, Sandra

2018-04-01

Interpreting abundances of damped Ly-α absorbers (DLAs) from absorption-line spectroscopy has typically been a challenge because of the presence of dust. Nevertheless, because DLAs trace distant gas-rich galaxies regardless of their luminosity, they provide an attractive way of measuring the evolution of the metallicity of the neutral gas with cosmic time. This has been done extensively so far, but typically not taking proper dust corrections into account. The aims of this paper are to: (i) provide a simplified way of calculating dust corrections, based on a single observed [X/Fe], (ii) assess the importance of dust corrections for DLA metallicities and their evolution, and (iii) investigate the cosmic evolution of iron for a large DLA sample. We have derived dust corrections based on the observed [Zn/Fe], [Si/Fe], or [S/Fe], and confirmed their robustness. We present dust-corrected metallicities in a scale of [Fe/H]tot for 236 DLAs over a broad range of z, and assess the extent of dust corrections for different metals at different metallicities. Dust corrections in DLAs are important even for Zn (typically of 0.1-0.2, and up to 0.5 dex), which is often neglected. Finally, we study the evolution of the dust-corrected metallicity with z. The DLA metallicities decrease with redshift, by a factor of 50-100 from today to 12.6 billion years ago (z = 5). When including dust corrections, the average DLA metallicities are 0.4-0.5 dex higher than without corrections. The upper envelope of the relation between metallicity and z reaches solar metallicity at z ≲ 0.5, although some systems can have solar metallicity already out to z 3. Based on observations carried out at the European Organisation for Astronomical Research in the Southern Hemisphere under ESO programmes 065.P-0038, 065.O-0063, 066.A-0624, 067.A-0078, and 068.A-0600.

Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways

NASA Astrophysics Data System (ADS)

Albarede, F.; Telouk, P.; Lamboux, A.; Jaouen, K.; Balter, V.

2011-12-01

Despite its potential importance for understanding perturbations in the Fe-Cu homeostatic pathways, the natural isotopic variability of these metals in the human body remains unexplored. We measured the Fe, Cu, and Zn isotope compositions of total blood, serum, and red blood cells of ~50 young blood donors by multiple-collector ICP-MS after separation and purification by anion exchange chromatography. Zn is on average 0.2 permil heavier in erythrocytes (δ 66Zn=0.44±0.33 permil) with respect to serum but shows much less overall isotopic variability than Fe and Cu, which indicates that isotope fractionation depends more on redox conditions than on ligand coordination. On average, Fe in erythrocytes (δ 56Fe=-2.59±0.47 permil) is isotopically light by 1-2 permil with respect to serum, whereas Cu in erythrocytes (δ 65Cu=0.56±0.50 permil) is 0.8 percent heavier. Fe and Cu isotope compositions clearly separate erythrocytes of men and women. Fe and Cu from B-type men erythrocytes are visibly more fractionated than all the other blood types. Isotope compositions provide an original method for evaluating metal mass balance and homeostasis. Natural isotope variability shows that the current models of Fe and Cu erythropoiesis, which assume that erythropoiesis is restricted to bone marrow, violate mass balance requirements. It unveils unsuspected major pathways for Fe, with erythropoietic production of isotopically heavy ferritin and hemosiderin, and for Cu, with isotopically light Cu being largely channeled into blood and lymphatic circulation rather than into superoxide dismutase-laden erythrocytes. Iron isotopes provide an intrinsic measuring rod of the erythropoietic yield, while Cu isotopes seem to gauge the relative activity of erythropoiesis and lymphatics.

Recovery of zinc and cadmium from spent batteries using Cyphos IL 102 via solvent extraction route and synthesis of Zn and Cd oxide nanoparticles.

PubMed

Singh, Rashmi; Mahandra, Harshit; Gupta, Bina

2017-09-01

The overall aim of this study is to separate and recover zinc and cadmium from spent batteries. For this purpose Cyphos IL 102 diluted in toluene was employed for the extraction and recovery of Zn and Cd from Zn-C and Ni-Cd batteries leach liquor. The influence of extractant concentration for the leach liquors of Zn-C (0.01-0.05mol/L) and Ni-Cd (0.04-0.20mol/L) batteries has been investigated. Composition of the leach liquor obtained from Zn-C/Ni-Cd spent batteries is Zn - 2.18g/L, Mn - 4.59g/L, Fe - 4.0×10 -3 g/L, Ni - 0.2×10 -3 g/L/Cd - 4.28g/L, Ni - 0.896×10 -1 g/L, Fe - 0.148g/L, Co - 3.77×10 -3 g/L, respectively. Two stage counter current extraction at A/O 1:1 and 3:2 with 0.04mol/L and 0.2mol/L Cyphos IL 102 for Zn and Cd, respectively provide more than 99.0% extraction of both the metal ions with almost negligible extraction of associated metal ions. A stripping efficiency of around 99.0% for Zn and Cd was obtained at O/A 1:1 using 1.0mol/L HNO 3 in two and three counter current stages, respectively. ZnO and CdO were also synthesized using the loaded organic phase and characterized using XRD, FE-SEM and EDX techniques. XRD peaks of ZnO and CdO correspond to zincite and monteponite, respectively. The average particle size was ∼27.0nm and ∼37.0nm for ZnO and CdO, respectively. The EDX analysis of ZnO and CdO shows almost 1:1 atomic percentage. Copyright © 2017. Published by Elsevier Ltd.

Natural Variation at the FRD3 MATE Transporter Locus Reveals Cross-Talk between Fe Homeostasis and Zn Tolerance in Arabidopsis thaliana

PubMed Central

Pineau, Christophe; Loubet, Stéphanie; Lefoulon, Cécile; Chalies, Claude; Fizames, Cécile; Lacombe, Benoit; Ferrand, Marina; Loudet, Olivier; Berthomieu, Pierre; Richard, Odile

2012-01-01

Zinc (Zn) is essential for the optimal growth of plants but is toxic if present in excess, so Zn homeostasis needs to be finely tuned. Understanding Zn homeostasis mechanisms in plants will help in the development of innovative approaches for the phytoremediation of Zn-contaminated sites. In this study, Zn tolerance quantitative trait loci (QTL) were identified by analyzing differences in the Bay-0 and Shahdara accessions of Arabidopsis thaliana. Fine-scale mapping showed that a variant of the Fe homeostasis-related FERRIC REDUCTASE DEFECTIVE3 (FRD3) gene, which encodes a multidrug and toxin efflux (MATE) transporter, is responsible for reduced Zn tolerance in A. thaliana. Allelic variation in FRD3 revealed which amino acids are necessary for FRD3 function. In addition, the results of allele-specific expression assays in F1 individuals provide evidence for the existence of at least one putative metal-responsive cis-regulatory element. Our results suggest that FRD3 works as a multimer and is involved in loading Zn into xylem. Cross-homeostasis between Fe and Zn therefore appears to be important for Zn tolerance in A. thaliana with FRD3 acting as an essential regulator. PMID:23236296

Effects of sol-gel synthesis on 5Fe-15Mn-40Zn-40Ti-O mixed oxide structure and its H2S removal efficiency from industrial gas streams.

PubMed

Polychronopoulou, Kyriaki; Efstathiou, Angelos M

2009-06-15

A novel Fe-Mn-Zn-Ti-O mixed metal oxide has been developed for efficient low-temperature (25-50 degrees C) removal of H2S from a gas mixture containing 600 ppm H2S, 25 vol% H2, 7.5 vol % CO2, and 1-3 vol% H2O that simulates typical conditions experienced at the outlet of a bioreactor loaded with sulfate metal reducing bacteria (SMRB) that converts toxic Cr6+ and As5+ present in ground and surface waters and soils into nontoxic elements. During the latter conversion H2S gas is produced and has to be treated. In the present work it is demonstrated for the first time that by using the sol-gel synthesis route at given experimental conditions (e.g., metal precursor salts, solvent system, and solution pH), optimum structural properties for the Fe-Mn-Zn-Ti-O solid can be obtained for maximization of H2S uptake. In particular, at 25 degrees C an H2S uptake (0.085 g H2S/g solid) larger by at least a factor of 3 compared to a commercial Ni-based H2S absorbent material was obtained.

Electrocatalytic oxidation of Epinephrine and Norepinephrine at metal oxide doped phthalocyanine/MWCNT composite sensor

PubMed Central

Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Ebenso, Eno E.

2016-01-01

Glassy carbon electrode (GCE) was modified with metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, and the electrocatalytic properties were studied. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using FTIR, Raman and SEM techniques. The electrodes were characterized using cyclic voltammetry (CV) technique. The electrocatalytic behaviour of the electrode towards epinephrine (EP) and norepinephrine (NE) oxidation was investigated using CV and DPV. Result showed that GCE-MWCNT/Fe3O4/2,3-Nc, GCE-MWCNT/Fe3O429H,31H-Pc, GCE-MWCNT/ZnO/2,3-Nc and GCE-MWCNT/ZnO/29H,31H-Pc electrodes gave enhanced EP and NE current response. Stability study indicated that the four GCE-MWCNT/MO/Pc modified electrodes were stable against electrode fouling effect with the percentage NE current drop of 5.56–5.88% after 20 scans. GCE-MWCNT/Fe3O4/29H,31H-Pc gave the lowest limit of detection (4.6 μM) towards EP while MWCNT/ZnO/29H,31H-Pc gave the lowest limit of detection (1.7 μM) towards NE. The limit of detection and sensitivity of the electrodes compared well with literature. Electrocatalytic oxidation of EP and NE on GCE-MWCNT/MO/Pc electrodes was diffusion controlled with some adsorption of electro-oxidation reaction intermediates products. The electrodes were found to be electrochemically stable, reusable and can be used for the analysis of EP and NE in real life samples. PMID:27245690

Bioremoval of trace metals from rhizosediment by mangrove plants in Indian Sundarban Wetland.

PubMed

Chowdhury, Ranju; Favas, Paulo J C; Jonathan, M P; Venkatachalam, Perumal; Raja, P; Sarkar, Santosh Kumar

2017-11-30

The study accentuated the trace metal accumulation and distribution pattern in individual organs of 13 native mangrove plants along with rhizosediments in the Indian Sundarban Wetland. Enrichment of the essential micronutrients (Mn, Fe, Zn, Cu, Co, Ni) was recorded in all plant organs in comparison to non-essential ones, such as Cr, As, Pb, Cd, Hg. Trunk bark and root/pneumatophore showed maximum metal accumulation efficiency. Rhizosediment recorded manifold increase for most of the trace metals than plant tissue, with the following descending order: Fe>Mn>Zn>Cu>Pb>Ni>Cr>Co>As>Cd>Hg. Concentrations of Cu, Ni, Pb and Hg were found to exceed prescribed sediment quality guidelines (SQGs) indicating adverse effect on adjacent biota. Both index of geoaccumulation (I geo ) and enrichment factor (EF) also indicated anthropogenic contamination. Based on high (>1) translocation factor (TF) and bioconcentration factor (BCF) values Sonneratiaapetala and Avicenniaofficinalis could be considered as potential accumulators, of trace metals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heavy metal, pH, and total solid content of maple sap and syrup produced in eastern Canada.

PubMed

Robinson, A R; MacLean, K S; MacConnell, H M

1989-01-01

Maple sap and syrups in eastern Canada were analyzed for pH, total solids, and the heavy metals Cu, Fe, Pb, and Zn. The levels of heavy metals found were within the range normally contained in food and water samples except for Pb. The concentration factor found in reducing sap to syrup did not reflect the same concentration change for the measured parameters. This indicates removal or conversion of heavy metals and organic acids with the sugar sands. There was no statistical difference among provinces with respect to the heavy metal, pH, and total solids content of sap. The only significant difference in syrup occurred with Cu and this appeared to be the result of the processing procedure. As the season progressed, the Cu, Pb, pH, and total solids content of the sap decreased while Zn increased and Fe showed little change. Syrups reflected a similar change. Statistical differences occurred in sap composition among sites within each province.

Trace elements in tourmalines from massive sulfide deposits and tourmalinites: Geochemical controls and exploration applications

USGS Publications Warehouse

Griffin, W.L.; Slack, J.F.; Ramsden, A.R.; Win, T.T.; Ryan, C.G.

1996-01-01

Trace element contents of tourmalines from massive sulfide deposits and tourmalinites have been determined in situ by proton microprobe; >390 analyses were acquired from 32 polished thin sections. Concentrations of trace elements in the tourmalines vary widely, from <40 to 3,770 ppm Mn, <4 to 1,800 ppm Ni, <2 to 1,430 ppm Cu, <9 to 4,160 ppm Zn, 3 to 305 ppm Ga, <6 to 1,345 ppm Sr, <10 to 745 ppm Sn, <49 to 510 ppm Ba, and <3 to 4,115 ppm Pb. Individual grains and growth zones are relatively homogeneous, suggesting that these trace elements are contained within the crystal structure of the tourmaline, and are not present in inclusions. The highest base metal contents are in ore-related tourmaline samples from Kidd Creek (Ontario), Broken Hill (Australia), and Sazare (Japan). Tourmaline data from these and many other massive sulfide deposits cluster by sample and display broadly linear trends on Zn vs. Fe plots, suggesting chemical control by temperature and hydrothermal and/or metamorphic fluid-mineral equilibria. Significant Ni occurs only in samples from the Kidd Creek Cu-Zn-Pb-Ag deposit, which is associated with a large footwall ultramafic body. An overall antithetic relationship between Zn and Ni probably reflects fluid source controls. Mn is correlated with Fe in tourmalines from barren associations, and possibly in some tourmalines associated with sulfide vein deposits. Sn increases systematically with Fe content irrespective of association; the highest values are found in schorls from granites. Other trace elements are generally uncorrelated with major element concentrations (e.g., Sr-Ca). Base metal proportions in the tourmalines show systematic patterns on ternary Cu-Pb-Zn diagrams that correlate well with the major commodity metals in the associated massive sulfide deposits. For example, data for tourmalines from Cu-Zn deposits (e.g., Ming mine, Newfoundland) fall mainly on the Cu-Zn join, whereas those from Pb-Zn deposits (e.g., Broken Hill, Australia) plot on the Pb-Zn join; no data fall on the Cu-Pb join, consistent with the lack of this metal association in massive sulfide deposits. The systematic relationship between base metal proportions in the tourmalines and the metallogeny of the host massive sulfide deposits indicates that the analyzed tourmalines retain a strong chemical signature of their original hydrothermal formation, in spite of variable metamorphic recrystallization. Such trace element patterns in massive sulfide tourmalines may be useful in mineral exploration, specifically for the evaluation of tourmaline concentrations in rocks, soils, and stream sediments.

Metal loading assessment of a small mountainous sub-basin characterized by acid drainage -- Prospect Gulch, upper Animas River watershed, Colorado

USGS Publications Warehouse

Wirt, Laurie; Leib, Kenneth J.; Melick, Roger; Bove, Dana J.

2001-01-01

strongly affected by natural acidity from pyrite weathering. Metal content in the water column is a composite of multiple sources affected by hydrologic, geologic, climatic, and anthropogenic conditions. Identifying sources of metals from various drainage areas was determined using a tracer injection approach and synoptic sampling during low flow conditions on September 29, 1999 to determine loads. The tracer data was interpreted in conjunction with detailed geologic mapping, topographic profiling, geochemical characterization, and the occurrence and distribution of trace metals to identify sources of ground-water inflows. For this highly mineralized sub-basin, we demonstrate that SO4, Al, and Fe load contributions from drainage areas that have experienced historical mining?although substantial?are relatively insignificant in comparison with SO4, Al, and Fe loads from areas experiencing natural weathering of highlyaltered, pyritic rocks. Regional weathering of acid-sulfate mineral assemblages produces moderately low pH waters elevated in SO4, Al, and Fe; but generally lacking in Cu, Cd, Ni, and Pb. Samples impacted by mining are also characterized by low pH and large concentrations of SO4, Al, and Fe; but contained elevated dissolved metals from ore-bearing vein minerals such as Cu, Zn, Cd, Ni, and Pb. Occurrences of dissolved trace metals were helpful in identifying ground-water sources and flow paths. For example, cadmium was greatest in inflows associated with drainage from inactive mine sites and absent in inflows that were unaffected by past mining activities and thus served as an important indicator of mining contamination for this environmental setting. The most heavily mine-impacted reach (PG153 to PG800), contributed 8% of the discharge, and 11%, 9%, and 12% of the total SO4, Al, and Fe loads in Prospect Gulch. The same reach yielded 59% and 37% of the total Cu and Zn loads for the subbasin. In contrast, the naturally acidic inflows from the Red Chemotroph iron spring yielded 39% of the discharge and 54%, 73%, and 87% of the SO4, Al, and Fe loads; but only 4% of the total Cu and 30% of the total Zn loads in Prospect Gulch. Base flow from the Prospect Gulch sub-basin contributes about 4.8 percent of the total discharge at the mouth of Cement Creek; compared with sampled instream loads of 1.8%, 8.8%, 15.9%, 28%, and 8.6% for SO4, Al, Fe, Cu and Zn, respectively. Water-shed scale remediation efforts targeted at reducing loads of SO4, Al, and Fe at inactive mine sites are likely to fail because the major sources of these constituents in Prospect Gulch are predominantly discharged from natural sources. Remediation goals aimed at reducing acidity and loads of Cu and other base metals, may succeed, however, because changes in pH and loads are disproportionately greater than increases in discharge over the same reach, and a substantial fraction of the metal loading is from mining-impacted reaches. Whether remediation of abandoned mines in Prospect Gulch can be successful depends on how goals are defined?that is, whether the objective is to reduce loads of SO4, Al, and Fe; or whether loads of Cu and other base metals and pH are targeted.

Flexible porous coordination polymer of Ni(II) for developing nanoparticles through acid formation and redox activity of the framework

NASA Astrophysics Data System (ADS)

Agarwal, Rashmi A.

2017-10-01

Immobilization of the nanoparticles (NPs) in a two dimensional porous coordination polymer (PCP) is currently an emerging field for a number of applications. But still it is a great challenge to fabricate any specified metal NPs in a single network. Herein the synthesis of Au, Pd, Mn, Fe, Cu, Zn, Mg, Li, Fe/Cu, Zn/Mg etc, NPs in a highly flexible PCP of Ni(II); {[Ni3(TBIB)2(BTC)2(H2O)6]·5C2H5OH·9H2O}n [TBIB = 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene, H3BTC = 1,3,5-benzenetricarboxylic acid] have been reported. This universal host is able to grow mixed metal NPs from mixed metal precursors. Monodentate carboxylate groups of BTC linker act as anchoring sites for the metal ions of the metal precursors. This is the main driving force to grow NPs within the cavities along with the high flexibility of this polymer at room temperature. Mechanism involves acid formation followed by redox reaction to synthesize metal NPs explained by EPR and FTIR. Paramagnetic properties have been shown by as-synthesized Fe NPs integrated framework at room temperature under applied magnetic field up to 17,500 Oe.

The flotation tailings of the former Pb-Zn mine of Touiref (NW Tunisia): mineralogy, mine drainage prediction, base-metal speciation assessment and geochemical modeling.

PubMed

Othmani, Mohamed Ali; Souissi, Fouad; Bouzahzah, Hassan; Bussière, Bruno; da Silva, Eduardo Ferreira; Benzaazoua, Mostafa

2015-02-01

The underground extraction of Pb-Zn mineralization in the Touiref area stopped in 1958. A large volume of flotation tailings (more than 500 Mt) containing sulfides were deposited in a tailings impoundment. The goals of this study are to evaluate the neutralization capacity of the unoxidized and oxidized tailings, to assess the speciation of metals between the different components of the tailings material, and to assess the mobility of metals and the secondary minerals' precipitation in pore waters using geochemical modeling. To accomplish these objectives, representative samples from both fresh and oxidized zones were collected along a vertical profile through the tailings pile. Physical, chemical (ICP-MS), and mineralogical characterization (X-ray diffraction (XRD), reflected light microscopy, scanning electron microscope (SEM)) of these samples was performed. Grain size analysis shows that the tailings are dominated by silt- to sand-sized fractions. The microscopic observation highlights the presence of pyrite, marcasite, galena, and sphalerite as primary minerals in a carbonated matrix. The study reveals also the presence of secondary minerals represented by cerussite, smithsonite, anglesite, and Fe oxi-hydroxides as important scavengers for trace elements. The static tests show that the presence of calcite in the tailing samples ensures acid-neutralizing capacity (ANC), which is significantly greater than the acidity potential (PA). The geochemical characterization of the unoxidized samples shows higher Cd, Pb, and Zn concentrations than the oxidized samples containing the highest values for Fe and SO4. Sequential extraction tests show that significant percentages of metals are distributed between the acid-soluble fractions (Cd, Pb, and Zn) and the reducible one (Zn). Pore water analysis indicates that Ca is the dominant cation (8,170 and 6,200 mg L(-1), respectively), whereas sulfate is the principal anion (6,900 and 5,100 mg L(-1), respectively). Saturation index (SI) calculations of minerals in pore water extracted from both the oxidized and unoxidized samples are indicative of gypsum (SI >0) and Fe(III) oxides (SI ≫0) precipitation. The latter controls the Fe concentration in solution.

Synchrotron micro-scale measurement of metal distributions in Phragmites australis and Typha latifolia root tissue from an urban brownfield site

DOE PAGES

Feng, Huan; Qian, Yu; Gallagher, Frank J.; ...

2015-11-01

Liberty State Park in New Jersey, USA, is a “brownfield” site containing various levels of contaminants. To investigate metal uptake and distributions in plants on the brownfield site, Phragmites australis and Typha latifolia were collected in Liberty State Park during the growing season (May–September) in 2011 at two sites with the high and low metal loads, respectively. The objective of this study was to understand the metal (Fe, Mn, Cu, Pb and Zn) concentration and spatial distributions in P. australis and T. latifolia root systems with micro-meter scale resolution using synchrotron X-ray microfluorescence (μXRF) and synchrotron X-ray computed microtomography (μCMT)more » techniques. The root structure measurement by synchrotron μCMT showed that high X-ray attenuation substance appeared in the epidermis. Synchrotron μXRF measurement showed that metal concentrations and distributions in the root cross-section between epidermis and vascular tissue were statistically different. Significant correlations were found between metals (Cu, Mn, Pb and Zn) and Fe in the epidermis, implying that metals were scavenged by Fe oxides. The results from this study suggest that the expression of metal transport and accumulation within the root systems may be element specific. The information derived from this study can improve our current knowledge of the wetland plant ecological function in brownfield remediation.« less

Phase Equilibria in the ZnO-"FeO"-SiO2 System in Reducing Atmosphere and in the ZnO-"FeO"-SiO2-"Cu2O" System in Equilibrium with Liquid Copper Metal at 1250 °C (1523 K)

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

2018-05-01

Recent experimental studies in the ZnO-"FeO"-SiO2 system in reducing atmosphere demonstrated significant discrepancies with the current FactSage thermodynamic model developed using previous experimental data in this system in equilibrium with metallic iron and air. The present experimental study on phase equilibria in the ZnO-"FeO"-SiO2-"Cu2O" system in equilibrium with liquid copper at 1250 °C (1523 K) at low copper oxide concentrations in slag was initiated and undertaken to resolve these discrepancies. A high-temperature equilibration-rapid quenching-electron-probe X-ray microanalysis (EPMA) technique using a primary phase substrate support and closed system approach with Cu metal introduced to determine effective equilibrium oxygen partial pressure from the Cumetal/Cu2Oslag equilibria was applied to provide accurate information on the liquidus and corresponding solid compositions in the spinel, willemite, and tridymite primary phase fields. The present results confirmed the accuracy of the FactSage model, resolved discrepancies, and demonstrated significant uncertainties in the recent studies by other authors on the system in the open reducing atmosphere. The present study shows how this closed system approach can be used to obtain key thermodynamic data on phase equilibria in systems containing volatile metal species, overcoming the limitations and uncertainties encountered in conventional open gas/condensed phase equilibration with these systems. The study highlights the importance of the focus on obtaining accurate experimental data and the risks of misleading information from inadequate experimental control and analysis. The study also demonstrates that continuing in-depth critical review and analysis of the elemental reactions taking place in complex systems is an essential step in phase equilibrium research.

Do fattening process and biological parameters affect the accumulation of metals in Atlantic bluefin tuna?

PubMed

Milatou, Niki; Dassenakis, Manos; Megalofonou, Persefoni

2015-01-01

The objective of this study was to determine the current levels of heavy metals and trace elements in Atlantic bluefin tuna muscle tissues and how they are influenced by the fattening process and various life history parameters to ascertain whether the concentrations in muscle tissue exceed the maximum levels defined by the European Commission Decision and to evaluate the health risk posed by fish consumption. A total of 20 bluefin tuna reared in sea cages, ranging from 160 to 295 cm in length and from 80 to 540 kg in weight, were sampled from a bluefin tuna farm in the Ionian Sea. The condition factor K of each specimen was calculated and their age was estimated. Heavy metal and trace element (Hg, Zn, Fe and Cu) contents were determined in muscle tissue using cold vapour atomic absorption spectrometry and flame and graphite furnace atomic absorption spectrometry. The total Hg concentrations ranged from 0.28 to 1.28 mg kg(-1) w/w, Zn from 5.81 to 76.37 mg kg(-1) w/w, Fe from 12.14 to 39.58 mg kg(-1) w/w, and Cu from 0.36 to 0.94 mg kg(-1) w/w. Only 5% of the muscle samples of tuna contained Hg above the maximum level laid down by the European Commission Decision. Moreover, 15% of the muscle samples contained Zn above the maximum level, while Fe and Cu concentrations were within the acceptable tolerable guideline values. The reared bluefin tuna had lower concentrations of Hg than the wild ones from the Mediterranean Sea. Hg and Fe concentrations showed a positive relationship with size and age of bluefin tuna, whereas negative relationships were found for the concentrations of Zn and Cu. The estimated dietary intake values of the analysed metals were mostly below the derived guidelines.

Distribution of Bioactive Trace Metals (Fe, Co, Ni, Cu and Zn) in the semiarid Kuwait Bay, stressed by natural and anthropogenic processes

NASA Astrophysics Data System (ADS)

Al-Said, T. F.; Pokavanich, T.; Al-Hashem, A.; Kedila, R.

2016-02-01

Kuwait is in the northwestern part of the Arabian Gulf and receives flow from Shatt Al-Arab River as the main fresh water input to the Gulf. Kuwait's waters can be described as eutrophic, euphotic, and highly saline waters. The main objective of the study is to assess spatial and temporal distribution of Cu, Co, Zn, Fe and Ni, nutrients such as nitrate and phosphate, chlorophyll-a and physical variables along transects in Kuwait's Waters. No systematic research on bioactive metals has been studied in the region. Concentration of trace metal in the shallow Kuwait Bay was relatively high and decreased towards the southern water. This is attributed to higher sewage input, domestic and industrial effluents, dust storms and human activities. Cu, Ni, Fe, Zn and Co levels were measured using proven tested methodology i.e., Adsorptive Cathodic Stripping Voltammetry (Ad-CSV) and Flow Injection Analyzer (FIA). Surface seawater samples were collected from 26 stations using clean polyethylene sampling devices from four transects during two seasons in 2015. Average concentrations of Copper, Nickel, Cobalt, Zinc and chlorophyll-a corresponded to 14.99, 22.32, 0.74, 14.56 nM and 3.05µg/L during June 2015. These values indicated lower concentrations compared to previously published values from Kuwait's waters: Cu 48.52, Ni 26.12, Co 4.69, Zn 93.86 nM. Two transects conducted during summer 2015 showed positive relationship between metals (Cu, Co and Ni) and chlorophyll. Strong and apparent correlation was observed between cobalt and chlorophyll-a in Kuwait Bay indicating that these micronutrient are abundant and higher than phytoplankton essential requirements. Recent measured Fe concentration 7.95nM in Kuwait Bay was comparable to values found in similar coastal water. Latest results obtained during the transactional surveys and processes involved in Kuwait's waters will be shown and discussed during the presentation.

Intercalation of Coordinatively Unsaturated Fe(III) Ion within Interpenetrated Metal-Organic Framework MOF-5.

PubMed

Holmberg, Rebecca J; Burns, Thomas; Greer, Samuel M; Kobera, Libor; Stoian, Sebastian A; Korobkov, Ilia; Hill, Stephen; Bryce, David L; Woo, Tom K; Murugesu, Muralee

2016-06-01

Coordinatively unsaturated Fe(III) metal sites were successfully incorporated into the iconic MOF-5 framework. This new structure, Fe(III) -iMOF-5, is the first example of an interpenetrated MOF linked through intercalated metal ions. Structural characterization was performed with single-crystal and powder XRD, followed by extensive analysis by spectroscopic methods and solid-state NMR, which reveals the paramagnetic ion through its interaction with the framework. EPR and Mössbauer spectroscopy confirmed that the intercalated ions were indeed Fe(III) , whereas DFT calculations were employed to ascertain the unique pentacoordinate architecture around the Fe(III) ion. Interestingly, this is also the first crystallographic evidence of pentacoordinate Zn(II) within the MOF-5 SBU. This new MOF structure displays the potential for metal-site addition as a framework connector, thus creating further opportunity for the innovative development of new MOF materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Maternal Cadmium, Iron and Zinc Levels, DNA Methylation and Birth Weight

EPA Science Inventory

BACKGROUND:Cadmium (Cd) is a ubiquitous and environmentally persistent toxic metal that has been implicated in neurotoxicity, carcinogenesis and obesity and essential metals including zinc (Zn) and iron (Fe) may alter these outcomes. However mechanisms underlying these relationsh...

Highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste with amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent.

PubMed

Bao, Shuangyou; Tang, Lihong; Li, Kai; Ning, Ping; Peng, Jinhui; Guo, Huibin; Zhu, Tingting; Liu, Ye

2016-01-15

Amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent was used as a novel sorbent to highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste in the presence of Fe(II). These hot-dip galvanizing pickling waste mainly contain ZnCl2 and FeCl2 in aqueous HCl media. The properties of this magnetic adsorbent were examined by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), infrared spectrometer (FT-IR) and BET surface area measurements. Various factors influencing the adsorption of Zn(II) ion such as initial concentration of metal ions, the amount of adsorbent, pH value of the solutions, the concentration of coexisting iron ion were investigated by batch experiments. The results indicated that the adsorption equilibrium data obeyed the Freundlich model with maximum adsorption capacities for Zn(II) to 169.5mg/g. The maximum adsorption occurred at pH 5±0.1 and Fe(II) interferences had no obvious influence. This work provides a potential and unique technique for zinc ion removal from hot-dip galvanizing pickling waste. Copyright © 2015 Elsevier Inc. All rights reserved.

Substrate Profile and Metal-ion Selectivity of Human Divalent Metal-ion Transporter-1*

PubMed Central

Illing, Anthony C.; Shawki, Ali; Cunningham, Christopher L.; Mackenzie, Bryan

2012-01-01

Divalent metal-ion transporter-1 (DMT1) is a H+-coupled metal-ion transporter that plays essential roles in iron homeostasis. DMT1 exhibits reactivity (based on evoked currents) with a broad range of metal ions; however, direct measurement of transport is lacking for many of its potential substrates. We performed a comprehensive substrate-profile analysis for human DMT1 expressed in RNA-injected Xenopus oocytes by using radiotracer assays and the continuous measurement of transport by fluorescence with the metal-sensitive PhenGreen SK fluorophore. We provide validation for the use of PhenGreen SK fluorescence quenching as a reporter of cellular metal-ion uptake. We determined metal-ion selectivity under fixed conditions using the voltage clamp. Radiotracer and continuous measurement of transport by fluorescence assays revealed that DMT1 mediates the transport of several metal ions that were ranked in selectivity by using the ratio Imax/K0.5 (determined from evoked currents at −70 mV): Cd2+ > Fe2+ > Co2+, Mn2+ ≫ Zn2+, Ni2+, VO2+. DMT1 expression did not stimulate the transport of Cr2+, Cr3+, Cu+, Cu2+, Fe3+, Ga3+, Hg2+, or VO+. 55Fe2+ transport was competitively inhibited by Co2+ and Mn2+. Zn2+ only weakly inhibited 55Fe2+ transport. Our data reveal that DMT1 selects Fe2+ over its other physiological substrates and provides a basis for predicting the contribution of DMT1 to intestinal, nasal, and pulmonary absorption of metal ions and their cellular uptake in other tissues. Whereas DMT1 is a likely route of entry for the toxic heavy metal cadmium, and may serve the metabolism of cobalt, manganese, and vanadium, we predict that DMT1 should contribute little if at all to the absorption or uptake of zinc. The conclusion in previous reports that copper is a substrate of DMT1 is not supported. PMID:22736759

Enhanced Al and Zn removal from coal-mine drainage during rapid oxidation and precipitation of Fe oxides at near-neutral pH

USGS Publications Warehouse

Burrows, Jill E.; Cravotta, Charles A.; Peters, Stephen C.

2017-01-01

Net-alkaline, anoxic coal-mine drainage containing ∼20 mg/L FeII and ∼0.05 mg/L Al and Zn was subjected to parallel batch experiments: control, aeration (Aer 1 12.6 mL/s; Aer 2 16.8 mL/s; Aer 3 25.0 mL/s), and hydrogen peroxide (H2O2) to test the hypothesis that aeration increases pH, FeII oxidation, hydrous FeIII oxide (HFO) formation, and trace-metal removal through adsorption and coprecipitation with HFO. During 5.5-hr field experiments, pH increased from 6.4 to 6.7, 7.1, 7.6, and 8.1 for the control, Aer 1, Aer 2, and Aer 3, respectively, but decreased to 6.3 for the H2O2 treatment. Aeration accelerated removal of dissolved CO2, Fe, Al, and Zn. In Aer 3, dissolved Al was completely removed within 1 h, but increased to ∼20% of the initial concentration after 2.5 h when pH exceeded 7.5. H2O2 promoted rapid removal of all dissolved Fe and Al, and 13% of dissolved Zn.Kinetic modeling with PHREEQC simulated effects of aeration on pH, CO2, Fe, Zn, and Al. Aeration enhanced Zn adsorption by increasing pH and HFO formation while decreasing aqueous CO2 available to form ZnCO30 and Zn(CO3)22− at high pH. Al concentrations were inconsistent with solubility control by Al minerals or Al-containing HFO, but could be simulated by adsorption on HFO at pH < 7.5 and desorption at higher pH where Al(OH)4− was predominant. Thus, aeration or chemical oxidation with pH adjustment to ∼7.5 could be effective for treating high-Fe and moderate-Zn concentrations, whereas chemical oxidation without pH adjustment may be effective for treating high-Fe and moderate-Al concentrations.

Regulating cellular trace metal economy in algae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blaby-Haas, Crysten E.; Merchant, Sabeeha S.

As indispensable protein cofactors, Fe, Mn, Cu and Zn are at the center of multifaceted acclimation mechanisms that have evolved to ensure extracellular supply meets intracellular demand. In starting with selective transport at the plasma membrane and ending in protein metalation, metal homeostasis in algae involves regulated trafficking of metal ions across membranes, intracellular compartmentalization by proteins and organelles, and metal-sparing/recycling mechanisms to optimize metal-use efficiency. Overlaid on these processes are additional circuits that respond to the metabolic state as well as to the prior metal status of the cell. Here, we focus on recent progress made toward understanding themore » pathways by which the single-celled, green alga Chlamydomonas reinhardtii controls its cellular trace metal economy. We also compare these mechanisms to characterized and putative processes in other algal lineages. Photosynthetic microbes continue to provide insight into cellular regulation and handling of Cu, Fe, Zn and Mn as a function of the nutritional supply and cellular demand for metal cofactors. We found that new experimental tools such as RNA-Seq and subcellular metal imaging are bringing us closer to a molecular understanding of acclimation to supply dynamics in algae and beyond.« less

Regulating cellular trace metal economy in algae

DOE PAGES

Blaby-Haas, Crysten E.; Merchant, Sabeeha S.

2017-06-30

As indispensable protein cofactors, Fe, Mn, Cu and Zn are at the center of multifaceted acclimation mechanisms that have evolved to ensure extracellular supply meets intracellular demand. In starting with selective transport at the plasma membrane and ending in protein metalation, metal homeostasis in algae involves regulated trafficking of metal ions across membranes, intracellular compartmentalization by proteins and organelles, and metal-sparing/recycling mechanisms to optimize metal-use efficiency. Overlaid on these processes are additional circuits that respond to the metabolic state as well as to the prior metal status of the cell. Here, we focus on recent progress made toward understanding themore » pathways by which the single-celled, green alga Chlamydomonas reinhardtii controls its cellular trace metal economy. We also compare these mechanisms to characterized and putative processes in other algal lineages. Photosynthetic microbes continue to provide insight into cellular regulation and handling of Cu, Fe, Zn and Mn as a function of the nutritional supply and cellular demand for metal cofactors. We found that new experimental tools such as RNA-Seq and subcellular metal imaging are bringing us closer to a molecular understanding of acclimation to supply dynamics in algae and beyond.« less

Mass-size distribution and concentration of metals from personal exposure to arc welding fume in pipeline construction: a case report.

PubMed

Yang, Show-Yi; Lin, Jia-Ming; Young, Li-Hao; Chang, Ching-Wen

2018-04-07

We investigate exposure to welding fume metals in pipeline construction, which are responsible for severe respiratory problems. We analyzed air samples obtained using size-fractioning cascade impactors that were attached to the welders performing shielded metal and gas tungsten arc welding outdoors. Iron, aluminum, zinc, chromium, manganese, copper, nickel, and lead concentrations in the water-soluble (WS) and water-insoluble (WI) portions were determined separately, using inductively coupled plasma mass spectrometry. The mass-size distribution of welding fume matches a log-normal distribution with two modes. The metal concentrations in the welding fume were ranked as follows: Fe > Al > Zn > Cr > Mn > Ni > Cu > Pb. In the WS portion, the capacities of metals dissolving in water are correlated with the metal species but particle sizes. Particularly, Zn, Mn, and Pb exhibit relatively higher capacities than Cu, Cr, Al, Fe, and Ni. Exposure of the gas-exchange region of the lungs to WS metals were in the range of 4.9% to 34.6% of the corresponding metals in air by considering the particle-size selection in lungs, metal composition by particle size, and the capacities of each metal dissolving in water.

Structural effects in the interstitial solid solution system (La,Ce)(Fe,Si)13Cx-H: Correlation with hydrogenation kinetics

NASA Astrophysics Data System (ADS)

Hai, X.; Porcher, F.; Mayer, C.; Miraglia, S.

2018-02-01

Steady state and in-situ neutron powder diffraction on selected compositions of the magneto-caloric (La,Ce)(Fe,Si)13CxHy compounds has been used to locate the sites accommodated by the interstitial species and to reveal the structural modifications (breathing) that occur upon metal substitution and/or interstitial insertion. The latter type of measurement in which the sequential filling of interstitial sites is followed allows one to extract some useful hydrogenation kinetics data. This structural investigation has allowed to precise the deformations undergone by the complex metallic alloys La(Fe,Si)13 when subjected to light interstitial insertion or rare earth substitution at the cation site of the NaZn13-structure type. We attempt to correlate hydrogenation kinetics variations (depression or enhancement of the hydrogen absorption rate) with a particular inhomogeneous cell variation (breathing) and bonding of the NaZn13 structure-type.

Trace metals in liver from bluefish, tautog, and tilefish in relation to body length

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mears, H.C.; Eisler, R.

1977-09-01

Livers from bluefish, tilefish and tautog collected during the summer of 1971 off the New Jersey coast were analyzed for Cd, Cr, Cu, Fe, Mn, Ni, and Zn by atomic absorption spectrophotometry. Liver ash from male and female tautog contained decreasing concentrations of Ni with increasing body length. Smaller males also contained greater levels of Cr and Cu in liver than larger tautogs. Larger tilefish contained proportionately more Cd, Cu, and Fe in liver than smaller tilefish. Decreasing levels of Mn and Zn with body length were apparent only for females. Livers from larger male bluefish were associated with highermore » concentrations of Fe than those from smaller males, while those from larger females contained lower concentrations of Cr than those from smaller females. The data suggest that future comparisons for trace metals which vary as a function of size be made only among fish of the same length.« less

Assessment of spatial variability of heavy metals in Metropolitan Zone of Toluca Valley, Mexico, using the biomonitoring technique in mosses and TXRF analysis.

PubMed

Zarazúa-Ortega, Graciela; Poblano-Bata, Josefina; Tejeda-Vega, Samuel; Ávila-Pérez, Pedro; Zepeda-Gómez, Carmen; Ortiz-Oliveros, Huemantzin; Macedo-Miranda, Guadalupe

2013-01-01

This study is aimed at assessing atmospheric deposition of heavy metals using the epiphytic moss genera Fabronia ciliaris collected from six urban sites in the Metropolitan Zone of the Toluca Valley in Mexico. The concentrations of K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Sr, and Pb were determined by total reflection X-ray fluorescence technique. Results show that the average metal concentration decrease in the following order: Fe (8207 mg/Kg) > Ca (7315 mg/Kg) > K (3842 mg/Kg) > Ti (387 mg/Kg) > Mn, Zn (191 mg/Kg) > Sr (71 mg/Kg) > Pb (59 mg/Kg) > Cu, V (32 mg/Kg) > Cr (24 mg/Kg) > Rb (13 mg/Kg) > Ni (10 mg/Kg). Enrichment factors show a high enrichment for Cr, Cu, Zn, and Pb which provides an evidence of anthropogenic impact in the industrial and urban areas, mainly due to the intense vehicular traffic and the fossil fuel combustion. Monitoring techniques in mosses have proved to be a powerful tool for determining the deposition of heavy metals coming from diverse point sources of pollution.

Evaluation of heavy metal concentrations of edible wild-grown mushrooms from China.

PubMed

Wang, Xuemei; Liu, Honggao; Zhang, Ji; Li, Tao; Wang, Yuanzhong

2017-03-04

The heavy metal contents (Co, Cu, Fe, Mn, Ni, and Zn) of eight species of wild edible mushrooms from China were determined. The analyses were performed using inductively coupled plasma atomic emission spectrophotometry after microwave digestion. The contents of Co, Cu, Fe, Mn, Ni, and Zn in caps of mushroom samples were 0.7-7.2, 16.2-70.4, 371-1315, 12.5-29.8, 7.1-58.5, and 77.8-187.4 mg kg -1 dry matter (dm), respectively, while considerable differences were found to be 1.8-25.9, 9.8-36.3, 288-6762, 13.3-103.9, 5.9-78.7, and 38.7-118 mg kg -1 dm for stipes. The results indicated that higher levels of Co, Fe, and Ni were found in the mushrooms samples analyzed. Zinc and manganese levels were similar to previous reports, whereas Cu was lower than literature values. Correlation analysis suggested that significant correlations were found between the minerals determined and the greatest amount of contamination is associated with Co, Mn, Ni, and Fe. The results of this study indicate that heavy metal contents in mushroom species are mainly related to the mineral resources of sampling sites.

Acid Mine Drainage and Metal Sulfate Minerals in the Shasta Mining District, California

NASA Astrophysics Data System (ADS)

Livingston, J. D.; Murphy, W. M.; Miller, R. M.; Ayars, E. J.

2005-12-01

Metal sulfate minerals were collected at four surface water drainage sites during September and October of 2004 in the Shasta Mining District, southern Klamath Mountains, Shasta County, California and analyzed by X-ray fluorescence, atomic absorption spectroscopy, and X-ray diffraction to determine elements present, quantities of Fe, Cu, and Zn, and mineralogy. The Shasta Mining District produced major quantities of Cu, Zn, and pyrite (S) with minor amounts of Au, Ag, and Fe from massive sulfide bodies (Kinkel et al., 1956). Three study sites are located on Iron Mountain and one study site is at Bully Hill. Although mining occurred during a period of just over 100 years, it is estimated that acid mine drainage (AMD) will continue from Iron Mountain for over 3,200 years (Nordstrom and Alpers, 1998). AMD at the study sites produces blooms of metal sulfates during California's Mediterranean climate summer. The minerals readily dissolve in the "first flush" of seasonal rain creating runoff water of low pH with high amounts of dissolved metals (Bayless and Olyphant, 1993; Jambor et al., 2000). Data were examined for mineralogical changes in time and space and for zoning of minerals on a scale of centimeters. Sulfate mineral samples are complex with some samples composed of over a dozen different minerals. Site 1 is located on Spring Creek downstream from the Iron Mountain superfund remediation site, so levels of Fe, Cu, and Zn in the sulfates at this site are lower than at the other sites. Two site 1 samples from the same location taken a month apart show Ca, Fe, Cu, Sr, Y, and Sn, and the first sample also has detectable Br. The metal sulfates identified from the first visit are celestine, cesanite, chessexite, hectorfloresite, and ungemachite, and the mineralogy of the second visit is bilinite, epsomite, millosevichite, and anhydrite. The Fe bearing sulfate mineral during the first visit is ungemachite, but bilinite was the Fe bearing mineral at the time of the second visit. Analyses indicate a dynamic evolution of sulfate minerals at individual locations over time, mineralogical and chemical differences among individual locations at a site, and mineralogical zonations in individual samples.

Trace metal levels, sources, and ecological risk assessment in a densely agricultural area from Saudi Arabia.

PubMed

Al-Wabel, Mohammad I; Sallam, Abd El-Azeem S; Usman, Adel R A; Ahmad, Mahtab; El-Naggar, Ahmed Hamdy; El-Saeid, Mohammed Hamza; Al-Faraj, Abdulelah; El-Enazi, Khaled; Al-Romian, Fahad A

2017-06-01

The present study was conducted in one of the most densely cultivated area of Al-Qassim region in Kingdom of Saudi Arabia to (i) monitor trace metal (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) contents in surface and subsurface soils, (ii) assess the pollution and potential ecological risk levels of trace metals, and (iii) identify trace metal sources using enrichment factor (EF), correlation matrix, and principal component analysis (PCA). The pollution levels of the analyzed trace metals calculated by the geoaccumulation index (I geo ) and contamination factor (C f ) suggested that the soils were highly contaminated with Cd and moderately contaminated with Pb. Based on the average values of EF, soil samples were found to present extremely high enrichment for Cd, significant enrichment for Pb, moderate enrichment for Zn, and deficient to minimal enrichment for other trace metals. Among the analyzed trace metals, a very high ecological risk was observed only in the case of Cd at some sampling sites. Meanwhile, other investigated trace metals had a low ecological risk. The results of PCA combined with correlation matrix suggested that Fe, Mn, Zn, Cu, Cr Ni, Cu, and Co represent natural abundance in soil, but Cd, Pb, and Cu are of anthropogenic inputs, mainly due to agrochemical and fertilizer applications. It could be generally concluded that the obtained results can be useful for assessing and conducting a future program for trace metal monitoring in agricultural areas of Saudi Arabia.

Bioremediation of industrially contaminated soil using compost and plant technology.

PubMed

Taiwo, A M; Gbadebo, A M; Oyedepo, J A; Ojekunle, Z O; Alo, O M; Oyeniran, A A; Onalaja, O J; Ogunjimi, D; Taiwo, O T

2016-03-05

Compost technology can be utilized for bioremediation of contaminated soil using the active microorganisms present in the matrix of contaminants. This study examined bioremediation of industrially polluted soil using the compost and plant technology. Soil samples were collected at the vicinity of three industrial locations in Ogun State and a goldmine site in Iperindo, Osun State in March, 2014. The compost used was made from cow dung, water hyacinth and sawdust for a period of twelve weeks. The matured compost was mixed with contaminated soil samples in a five-ratio pot experimental design. The compost and contaminated soil samples were analyzed using the standard procedures for pH, electrical conductivity (EC), organic carbon (OC), total nitrogen (TN), phosphorus, exchangeable cations (Na, K, Ca and Mg) and heavy metals (Fe, Mn, Cu, Zn and Cr). Kenaf (Hibiscus cannabinus) seeds were also planted for co-remediation of metals. The growth parameters of Kenaf plants were observed weekly for a period of one month. Results showed that during the one-month remediation experiment, treatments with 'compost-only' removed 49 ± 8% Mn, 32 ± 7% Fe, 29 ± 11% Zn, 27 ± 6% Cu and 11 ± 5% Cr from the contaminated soil. On the other hand, treatments with 'compost+plant' remediated 71 ± 8% Mn, 63 ± 3% Fe, 59 ± 11% Zn, 40 ± 6% Cu and 5 ± 4% Cr. Enrichment factor (EF) of metals in the compost was low while that of Cu (EF=7.3) and Zn (EF=8.6) were high in the contaminated soils. Bioaccumulation factor (BF) revealed low metal uptake by Kenaf plant. The growth parameters of Kenaf plant showed steady increments from week 1 to week 4 of planting. Copyright © 2015 Elsevier B.V. All rights reserved.

Assessment of heavy metal contamination in the sediments of Nansihu Lake Catchment, China.

PubMed

Liu, Enfeng; Shen, Ji; Yang, Liyuan; Zhang, Enlou; Meng, Xianghua; Wang, Jianjun

2010-02-01

At present, anthropogenic contribution of heavy metals far exceeds natural input in some aquatic sediment, but the proportions are difficult to differentiate due to the changes in sediment characters. In this paper, the metal (Al, Fe, K, Mg, Ca, Cr, Cu, Ni, and Zn) concentrations, grain size, and total organic carbon (TOC) content in the surface and core sediments of Nansihu Lake Catchment (the open lake and six inflow rivers) were determined. The chemical speciations of the metals (Al, Fe, Cr, Cu, Ni, and Zn) in the surface sediments were also analyzed. Approaches of factor analysis, normalized enrichment factor (EF) and the new non-residual fractions enrichment factor (K(NRF)) were used to differentiate the sources of the metals in the sediments, from detrital clastic debris or anthropogenic input, and to quantify the anthropogenic contamination. The results indicate that natural processes were more dominant in concentrating the metals in the surface and core sediments of the open lake. High concentration of Ca and deficiency of other metals in the upper layers of the sediment core were attributed to the input of carbonate minerals in the catchment with increasing human activities since 1980s. High TOC content magnified the deficiency of the metals. Nevertheless, the EF and K(NRF) both reveal moderate to significant anthropogenic contamination of Cr, Cu, Ni, and Zn in the surface sediments of Laoyun River and the estuary and Cr in the surface sediments of Baima River. The proportion of non-residual fractions (acid soluble, reducible, and oxidizable fractions) of Cr, Cu, Ni, and Zn in the contaminated sediments increased to 37-99% from the background levels less than 30%.

Assessment of metal pollution in a former mining area in the NW Tunisia: spatial distribution and fraction of Cd, Pb and Zn in soil.

PubMed

Othmani, Mohamed Ali; Souissi, Fouad; Durães, Nuno; Abdelkader, Moussi; da Silva, Eduardo Ferreira

2015-08-01

This study aims to evaluate the impact of the former mining Touiref district (NW Tunisia) on the spatial distribution of metal contamination. In order to characterize the metal content of the tailings and to assess how far the soils from the district could be impacted by metals, a sampling campaign was conducted. According to the spatial distribution concentration maps of potential toxic elements (PTE), the highest concentrations occur near the flotation tailings and in mining facilities and decrease abruptly with distance. These results confirm that wind is the main agent capable of dispersing metals in a W-E direction, with concentrations exceeding the standards of soil quality for Cd, Pb and Zn over several hundred metres away from the source, facilitated by the small-size fraction and low cohesion of tailings particles. Chemical fractionation showed that Pb and Cd were mainly associated with the acid-soluble fraction (carbonates) and Fe-(oxy) hydroxides, while Zn was mainly associated with Fe-(oxy) hydroxides but also with sulphides. Thus, the immobilization of metals in solution may be favoured by the alkaline conditions, promoted by carbonates dissolution. However, being carbonate important-bearing phases of Cd and Pb (but also for Zn), the dissolution facility of these minerals may enhance the release of metals, particularly far away from the mine where the physicochemical conditions can be different. Also, the metal uptake by plants in these alkaline conditions may be favoured, especially if secondary phases with high sorption ability are reduced at this site. A remediation plan to this area is needed, with particularly attention in the confinement of the tailings.

[Design and synthesis of imine compound for metal cation logical gates recognition and setup of double-control fluorescent molecule switch].

PubMed

Huang, Tao; Zhu, Yu-lian; Dai, Xue-qin; Zhang, Qi; Huang, Yan

2011-07-01

The Schiff base's reduced product N,N-bis(4-methoxybenzyl) ethane-1,2-diamine, which was used as a receptor L, was designed and synthesized for the first time in the present article. It was found that Cu2+ and Fe3+ could quench L in fluorescence observably and Zn2+ and Cd2+ could enhance L remarkably. So the two pair metal cation could set up "OR" logical gate relation with the receptor molecule L, then a logical recognition system be formed. The data of resolved ZnL's single crystal indicated that ZnL belonged to monoclinic (CCDC No. 747994). Integrated spectrum instrument was used to characterize the structure of its alike series of complex compound. According to ZnL's excellent fluorescence character and the ability to exchange with contiguous metal cation, ZnZ+/ZnL/Co2+, Zn2+/ZnL/Nit+ fluorescent molecule switch was designed. It is hoped that the work above could be positive for the development of molecule computer, bio-intellectualized inspection technology (therapy) and instrument.

High temperature dissolution of oxides in complexing media

NASA Astrophysics Data System (ADS)

Sathyaseelan, Valil S.; Rufus, Appadurai L.; Subramanian, Hariharan; Bhaskarapillai, Anupkumar; Wilson, Shiny; Narasimhan, Sevilimedu V.; Velmurugan, Sankaralingam

2011-12-01

Dissolution of transition metal oxides such as magnetite (Fe 3O 4), mixed ferrites (NiFe 2O 4, ZnFe 2O 4, MgFe 2O 4), bonaccordite (Ni 2FeBO 5) and chromium oxide (Cr 2O 3) in organic complexing media was attempted at higher temperatures (80-180 °C). On increasing the temperature from 80 to 180 °C, the dissolution rate of magnetite in nitrilo triacetic acid (NTA) medium increased six folds. The trend obtained for the dissolution of other oxides was ZnFe 2O 4 > NiFe 2O 4 > MgFe 2O 4 > Cr 2O 3, which followed the same trend as the lability of their metal-oxo bonds. Other complexing agents such as ethylene diamine tetra acetic acid (EDTA), pyridine dicarboxylic acid (PDCA), citric acid and reducing agents viz., oxalic acid and ascorbic acid were also evaluated for their oxide dissolution efficiency at 160 °C. EDTA showed maximum dissolution rate of 21.4 μm/h for magnetite. Addition of oxalic acid/ascorbic acid to complexing media (NTA/EDTA) showed identical effect on the dissolution of magnetite. Addition of hydrazine, another reducing agent, to NTA decreased the rate of dissolution of magnetite by 50%.

Long-Term Exposure of Tropical Soils to Pressure Treated Lumber, Barro Colorado Island, Panama: Impacts on Soil Metal Mobility and Microbial Community Structure

NASA Astrophysics Data System (ADS)

Marietta, M. L.; Fowle, D. A.; Roberts, J. A.

2008-12-01

Pressure treated lumber (CCA) has been used in a variety of structures for over seven decades, but recent concerns have been raised about leaching of metals such as chromium (Cr) and arsenic (As) into proximal soils and water supplies. Pressure treated lumber abundance and its continued use necessitate a thorough understanding of metal release and sequestration in the subsurface. To date, no long-term, in situ study on the migration of CCA compounds from lumber has been performed. Barro Colorado Island, Panama is the site of several previous CCA studies and provides an opportunity to investigate the long-term (>70 years) effects of pressure treated lumber in oxisols, where high rainfall and warm temperatures may represent an end-member condition for the leaching and mobility of these metals. Soil samples from CCA and control sites were measured for Cr, As, Cu, Zn, and Fe abundances, microbial biomass and community structure via phospholipid fatty acid analysis, along with basic soil properties. CCA lumber samples were also characterized for their metal abundance. Lumber treated with zinc meta-arsenite displayed advanced decay with elevated As, Cu, and Zn concentrations observed in the adjacent soil. Increased soil organic matter and microbial biomass correlate to decreases in Fe and Fe-associated metals compared to the control. High As concentrations persist to <1 m of the source. Lumber treated with potassium dichromate contained high chromium concentrations and displayed little decay, however, soil concentrations of Cr, Fe, and Cu were generally less than control soils. Over these same intervals, soil organic matter and microbial biomass increased, particularly the fraction of metal reducing bacteria (MRB). We hypothesize that organic carbon loading from lumber stimulates MRB, leading to mobilization of Fe and Fe-associated metals from these oxide-rich soils. Principal component analysis of PLFA data confirms a distinction between controls and samples with elevated metal abundance at each site. This study provides fundamental insight into the long-term persistence of CCA compounds in Fe-rich soils and could serve in practical applications related to CCA contamination.

Assessment of trace metals using lichen transplant from automobile mechanic workshop in Ile-Ife metropolis, Nigeria.

PubMed

Odiwe, Anthony I; Adesanwo, Adeyemi T J; Olowoyo, Joshua O; Raimi, Idris O

2014-04-01

The level of air pollution around the automobile mechanic workshops has been generally overlooked. This study, examined the level of trace metals in automobile mechanic workshops and the suitability of using transplanted lichen thalli of Lepraria incana for measuring air pollution in such areas. Samples of the lichen thalli were transplanted into seven different sites and were attached to the bark of trees at each site. The samples were harvested from the sites after 3-month exposure. Concentrations of Pb, Cu, Cd, Fe, Zn, and S content were determined using an atomic absorption spectrophotometer. Results showed that there was a significant difference in the trace metals concentrations across the sites (p < 0.05). The analyzed lichen samples showed a range of 91.26-119.35 ppm for Fe, 30.23-61.32 ppm for Zn, 1.25-2.45 ppm for Cu, 0.017-0.043 ppm for Cd, 0.018-0.051 ppm, and 0.37-0.42 ppm for S. From the study, sites 6 and 7 presented higher concentrations of Cd, Pb, and Zn than other sites. The enrichment factor calculated showed that Zn, Cd, and Pb were greatly enriched from the workshops. The trend in the concentration of these heavy metals suggests that activities in these workshops might become a major source of certain heavy metals in the environment and if the pollution activities persist, it might become worrisome over time.

Fractionation and mobility of Cu, Fe, Mn, Pb and Zn in the road dust retained on noise barriers along expressway - a potential tool for determining the effects of driving conditions on speciation of emitted particulate metals.

PubMed

Świetilik, Ryszard; Trojanowska, Marzena; Strzelecka, Monika; Bocho-Janiszewska, Anita

2015-01-01

Road dust (RD) retained on noise barriers was used as a monitor of emission of traffic-related metals from expressway. By using SEM/EDX analysis it has been revealed that the main components of this particulate were irregular fine aggregates and tire debris with a ragged porous structure and with inclusions derived from the road surface. The results of chemical fractionation showed that driving conditions influence strongly a distribution pattern of Cu, whereas the atmospheric corrosion process affects a distribution pattern of Zn. The distribution pattern of Cu originating only from vehicle braking emission was “isolated” from the distribution pattern of road traffic copper. The predicted comparative mobilities of the emitted metals form the order: Zn > Cu ≈ Mn > Pb > Fe. The high mobility of zinc (K = 0.61)may create a current inhalation hazard and may be a source of future environmental hazard in the areas adjacent to heavily trafficked roads.

Seasonal study of concentration of heavy metals in waters from lower São Francisco River basin, Brazil.

PubMed

Souza, A M; Salviano, A M; Melo, J F B; Felix, W P; Belém, C S; Ramos, P N

2016-01-01

In this study we determined the concentration of metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in the water lower São Francisco River basin, to evaluate the influence of urbanization and industrialization on environmental changes in the water resource. All samples were analyzed using the IUPAC adapted method and processed in an atomic absorption spectrophotometer. The sampling stations located near the industrial areas were influenced by industrialization because they presented higher concentrations of Cd, Cr, Ni and Cu. The other sampled locations showed changes with regard the trace elements probably originating in the soil, like Fe, Zn and Pb. There was a gradual increase in the concentrations of metals, in general, in the period of highest rainfall of the hydrographic network. Overall, except for Zn and Mn, the trace elements exceeded the maximum allowed value established by national legislation (CONAMA). Lower São Francisco River basin has suffered interference from urbanization and industrialization, so awareness programs should be developed so as to control and lessen future problems.

Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boiteau, Rene M.; Shaw, Jared B.; Pasa-Tolic, Ljiljana

Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or howmore » they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. Even small structural differences result in significant differences in their environmental metal speciation, and likely impact metal uptake within the rhizosphere of calcareous soils.« less

Histone Deacetylase 8: Characterization of Physiological Divalent Metal Catalysis.

PubMed

Nechay, Michael R; Gallup, Nathan M; Morgenstern, Amanda; Smith, Quentin A; Eberhart, Mark E; Alexandrova, Anastassia N

2016-07-07

Histone deacetylases (HDACs) are responsible for the removal of acetyl groups from histones, resulting in gene silencing. Overexpression of HDACs is associated with cancer, and their inhibitors are of particular interest as chemotherapeutics. However, HDACs remain a target of mechanistic debate. HDAC class 8 is the most studied HDAC, and of particular importance due to its human oncological relevance. HDAC8 has traditionally been considered to be a Zn-dependent enzyme. However, recent experimental assays have challenged this assumption and shown that HDAC8 is catalytically active with a variety of different metals, and that it may be a Fe-dependent enzyme in vivo. We studied two opposing mechanisms utilizing a series of divalent metal ions in physiological abundance (Zn(2+), Fe(2+), Co(2+), Mn(2+), Ni(2+), and Mg(2+)). Extensive sampling of the entire protein with different bound metals was done with the mixed quantum-classical QM/DMD method. Density functional theory (DFT) on an unusually large cluster model was used to describe the active site and reaction mechanism. We have found that the reaction profile of HDAC8 is similar among all metals tested, and follows one of the previously published mechanisms, but the rate-determining step is different from the one previously claimed. We further provide a scheme for estimating the metal binding affinities to the protein. We use the quantum theory of atoms in molecules (QTAIM) to understand the different binding affinities for each metal in HDAC8 as well as the ability of each metal to bind and properly orient the substrate for deacetylation. The combination of this data with the catalytic rate constants is required to reproduce the experimentally observed trend in metal-depending performance. We predict Co(2+) and Zn(2+) to be the most active metals in HDAC8, followed by Fe(2+), and Mn(2+) and Mg(2+) to be the least active.

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

NASA Astrophysics Data System (ADS)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

Decontamination of coal mine effluent generated at the Rajrappa coal mine using phytoremediation technology.

PubMed

Lakra, Kalpana C; Lal, B; Banerjee, T K

2017-06-03

Toxicity of the effluent generated at the Rajrappa coal mine complex under the Central Coalfields Limited (CCL, a subsidiary of Coal India Limited) in Jharkhand, India was investigated. The concentrations (mg L -1 ) of all the toxic metals (Fe, Mn, Ni, Zn, Cu, Pb, Cr, and Cd) in the coal mine effluent were above the safe limit suggested by the Environmental Protection Agency (EPA 2003). Among these, Fe showed the highest concentration (18.21 ± 3.865), while Cr had the lowest effluent concentration (0.15 ± 0.014). Efforts were also made to detoxify the effluent using two species of aquatic macrophytes namely "'Salvinia molesta and Pistia stratiotes." After 10 days of phytoremediation, S. molesta removed Pb (96.96%) > Ni (97.01%) > Cu (96.77%) > Zn (96.38%) > Mn (96.22%) > Fe (94.12%) > Cr (92.85%) > Cd (80.99%), and P. stratiotes removed Pb (96.21%) > Fe (94.34%) > Ni (92.53%) > Mn (85.24%) > Zn (79.51%) > Cr (78.57%) > Cu (74.19%) > Cd (72.72%). The impact of coal mine exposure on chlorophyll content showed a significant decrease of 42.49% and 24.54% from control values in S. molesta and P. stratiotes, respectively, perhaps due to the damage inflicted by the toxic metals, leading to the decay of plant tissues.

Selective ion exchange governed by the Irving-Williams series in K2Zn3[Fe(CN)6]2 nanoparticles: toward a designer prodrug for Wilson's disease.

PubMed

Kandanapitiye, Murthi S; Wang, Fan Jennifer; Valley, Benjamin; Gunathilake, Chamila; Jaroniec, Mietek; Huang, Songping D

2015-02-16

The principle of the Irving-Williams series is applied to the design of a novel prodrug based on K2Zn3[Fe(CN)6]2 nanoparticles (ZnPB NPs) for Wilson's disease (WD), a rare but fatal genetic disorder characterized by the accumulation of excess copper in the liver and other vital organs. The predetermined ion-exchange reaction rather than chelation between ZnPB NPs and copper ions leads to high selectivity of such NPs for copper in the presence of the other endogenous metal ions. Furthermore, ZnPB NPs are highly water-dispersible and noncytotoxic and can be readily internalized by cells to target intracellular copper ions for selective copper detoxification, suggesting their potential application as a new-generation treatment for WD.

Developmental phytotoxicity of metal oxide nanoparticles to Arabidopsis thaliana.

PubMed

Lee, Chang Woo; Mahendra, Shaily; Zodrow, Katherine; Li, Dong; Tsai, Yu-Chang; Braam, Janet; Alvarez, Pedro J J

2010-03-01

Phytotoxicity is an important consideration to understand the potential environmental impacts of manufactured nanomaterials. Here, we report on the effects of four metal oxide nanoparticles, aluminum oxide (nAl(2)O(3)), silicon dioxide (nSiO(2)), magnetite (nFe(3)O(4)), and zinc oxide (nZnO), on the development of Arabidopsis thaliana (Mouse-ear cress). Three toxicity indicators (seed germination, root elongation, and number of leaves) were quantified following exposure to each nanoparticle at three concentrations: 400, 2,000, and 4,000 mg/L. Among these particles, nZnO was most phytotoxic, followed by nFe(3)O(4), nSiO(2), and nAl(2)O(3), which was not toxic. Consequently, nZnO was further studied to discern the importance of particle size and zinc dissolution as toxicity determinants. Soluble zinc concentrations in nanoparticle suspensions were 33-fold lower than the minimum inhibitory concentration of dissolved zinc salt (ZnCl(2)), indicating that zinc dissolution could not solely account for the observed toxicity. Inhibition of seed germination by ZnO depended on particle size, with nanoparticles exerting higher toxicity than larger (micron-sized) particles at equivalent concentrations. Overall, this study shows that direct exposure to nanoparticles significantly contributed to phytotoxicity and underscores the need for eco-responsible disposal of wastes and sludge containing metal oxide nanoparticles.

Phytoremediation potential of weeds in heavy metal contaminated soils of the Bassa Industrial Zone of Douala, Cameroon.

PubMed

Lum, A Fontem; Ngwa, E S A; Chikoye, D; Suh, C E

2014-01-01

Phytoremediation is a promising option for reclaiming soils contaminated with toxic metals, using plants with high potentials for extraction, stabilization and hyperaccumulation. This study was conducted in Cameroon, at the Bassa Industrial Zone of Douala in 2011, to assess the total content of 19 heavy metals and 5 other elements in soils and phytoremediation potential of 12 weeds. Partial extraction was carried out in soil, plant root and shoot samples. Phytoremediation potential was evaluated in terms of the Biological Concentration Factor, Translocation Factor and Biological Accumulation Coefficient. The detectable content of the heavy metals in soils was Cu:70-179, Pb:8-130, Zn:200-971, Ni:74-296, Co:31-90, Mn:1983-4139, V:165-383, Cr:42-1054, Ba:26-239, Sc:21-56, Al:6.11-9.84, Th:7-22, Sr:30-190, La:52-115, Zr:111-341, Y:10-49, Nb:90-172 in mg kg(-1), and Ti:2.73-4.09 and Fe:12-16.24 in wt%. The contamination index revealed that the soils were slightly to heavily contaminated while the geoaccumulation index showed that the soils ranged from unpolluted to highly polluted. The concentration of heavy metals was ranked as Zn > Ni > Cu > V > Mn > Sc > Co > Pb and Cr in the roots and Mn > Zn > Ni > Cu > Sc > Co > V > Pb > Cr > Fe in the shoots. Dissotis rotundifolia and Kyllinga erecta had phytoextraction potentials for Pb and Paspalum orbicularefor Fe. Eleusine indica and K. erecta had phytostabilisation potential for soils contaminated with Cu and Pb, respectively.

Effects of freshwater leaching on potential bioavailability of heavy metals in tidal flat soils.

PubMed

Li, Hui; Lu, Jun; Li, Qu-Sheng; He, Bao-Yan; Mei, Xiu-Qin; Yu, Dan-Ping; Xu, Zhi-Min; Guo, Shi-Hong; Chen, Hui-Jun

2016-02-01

Leaching experiments were conducted to investigate the effects of desalination levels and sediment depths on potential bioavailability of heavy metal (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in tidal flat soils. The data showed that both the desalination levels (p < 0.001) and soil depths (p < 0.001) had significant effects on the concentrations of acid-volatile sulfide (AVS). AVS concentrations generally exhibited increasing trends with an increase in depth and decreasing trends with enhanced desalination levels. The desalination levels had significant (p < 0.05) effects on the concentrations of simultaneously extracted metal (SEM; Cd, Cr, Cu, Fe, Mn, Pb, and Zn). Moreover, the concentrations of SEM (Cd, Cr, Cu, Fe, Mn, Pb, and Zn) generally tended to decrease with an increase in the desalination level. The desalination treatment significantly reduced the ratios of SEM/AVS compared with control. However, the ratios of SEM/AVS increased with enhanced desalination levels in treatments. Results reveal that low desalination treatment is better for reducing toxicity to benthic organisms than high desalination treatment. Since these reclaimed tidal flats with low desalinisation are suitable for saline water aquaculture, transforming the present land use of reclaimed tidal flats from fresh water aquaculture into saline water aquaculture may reduce health risk of heavy metals remained in sediments. These results will also contribute to our understanding of the dynamic behavior of heavy metals in the reclamation of tidal flats during leaching and the role of the ratio of SEM/AVS predictions on assessing the ecological risks of reclaimed tidal flats.

Transition metals and water-soluble ions in deposits on a building and their potential catalysis of stone decay

NASA Astrophysics Data System (ADS)

McAlister, J. J.; Smith, B. J.; Török, A.

Atmospheric particulates (dust) deposited on buildings are a complex chemical and mineralogical mixture including transition metal oxide matrices that act as a significant medium for further surface reactions and provide efficient sinks for pollutants, especially in urban environments. Once deposited, their transformation by reaction with specific and often highly localised environmental conditions across building facades is related to their degree of exposure to rain-wash. These transformations are central to the soiling of buildings and the availability of salts that lead to stone decay. To investigate these relationships, samples were collected at high and low elevations and under highly and moderately sheltered conditions from a building located on a busy arterial route in Budapest. Selective extraction analysis highlights the mobility/availability of Fe, Mn, Zn, Cu, Cr, Pb and Ni, plus water-soluble Ca 2+, Mg 2+, Na +, K +, Cl -, SO 42- and NO 3- and their potential to take part in surface reactions that could enhance stone decay. Concentrations of water-soluble Fe, Mn and Zn in sheltered dust reach 126 mg kg -1, 80 mg kg -1 and 220 mg kg -1 respectively and under acidic environmental conditions and high humidity, similar levels of Mn and significantly higher concentrations of Fe, Zn, Cu and Pb may be released from the exchangeable/carbonate phase making these metals potentially available to catalyse surface reactions. Sulphate and nitrate coatings plus sufficient moisture increase metal solubility and active sites may be regenerated allowing mobile transition metals to become available and possibly catalyse further surface reactions.

Removal of metals from lead-zinc mine tailings using bioleaching and followed by sulfide precipitation.

PubMed

Ye, Maoyou; Li, Guojian; Yan, Pingfang; Ren, Jie; Zheng, Li; Han, Dajian; Sun, Shuiyu; Huang, Shaosong; Zhong, Yujian

2017-10-01

Mine tailings often contain significant amounts of metals and sulfide, many traditional operations used to minerals was not as good as those currently available. This study investigated metals removal from lead-zinc mine tailings using bioleaching and followed by sulfide precipitation. Metals were dissolved from the tailings by the bacteria in a bioleaching reactor. During a 10% pulp density bioleaching experiment, approximately 0.82% Pb, 97.38% Zn, and 71.37% Fe were extracted after 50 days. With the pulp density of 10% and 20%, the dissolution of metals followed shrinking core kinetic model. Metals (Pb, Zn, and Fe) present in the pregnant bioleaching leachate. Metals were next precipitated as a sulfide phase using sodium sulfide (Na 2 S). Metal precipitations were selectively and quantitatively produced from the bioleaching leachate by adding Na 2 S. More than 99% of the zinc and 75% of the iron was precipitated using 25 g/L Na 2 S in the bioleaching leachate. The results in the study were to provide useful information for recovering or removing metals from lead-zinc mine tailings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Distribution of rare-earth (Y, La, Ce) and other heavy metals in the profiles of the podzolic soil group

NASA Astrophysics Data System (ADS)

Vodyanitskii, Yu. N.; Goryachkin, S. V.; Savichev, A. T.

2011-05-01

Along with Fe and Al, many heavy metals (Mn, Cr, Zn, Cu, and Ni) show a markedly pronounced eluvial-illuvial redistribution in the profiles of soils of the podzolic group. The intensity of the redistribution of the bulk forms of these metals is comparable with that of Fe and exceeds that of Al. Although the podzolic soils are depleted of rare-earth metals, the latter respond readily to soil podzolization. The inactive participation of Al is explained by an insignificant portion of the active reaction-capable fraction. Podzolization does not influence the profile distribution of Sr and Ba. The leaching degree of heavy metals such as Mn, Cr, Zn, Ni, and Zr is noticeably higher in the sandy podzols than in the loamy podzolic soils. Leaching of heavy metals from the podzolic horizons is of geochemical importance, whereas the depletion of metals participating in plant nutrition and biota development is of ecological importance. The leaching of heavy metals is related to the destruction of clay particles in the heavy-textured podzolic soils; the effect of the soil acidity on the leaching of heavy metals is less significant.

First-principles studies on 3d transition metal atom adsorbed twin graphene

NASA Astrophysics Data System (ADS)

Li, Lele; Zhang, Hong; Cheng, Xinlu; Miyamoto, Yoshiyuki

2018-05-01

Twin graphene is a new two-dimensional semiconducting carbon allotrope which is proposed recently. The structural, magnetic and electronic properties are investigated for 3d transition metal (TM) atom adsorbed twin graphene by means of GGA+U calculations. The results show most of single 3d transition metal atom except Zn can make twin graphene magnetization. The adsorption of single TM atom can also make the twin graphene systems turn to half metal (V adsorption), half-semiconductor (Fe adsorption) or metal (Sc, Cr, Mn, Co and Cu adsorption). The semiconducting nature still exists for Ti, Ni and Zn adsorption. All the 3d TM adatoms belong to n-type doping for transferring charge to the neighboring C atoms and have strong covalent bond with these C atoms. The influence of Hubbard U value on half-metallic V adsorbed system is also considered. As the U increases, the system can gradually transform from metal to half metal and metal. The effect of the coverage is investigated for two TM atoms (Sc-Fe) adsorption, too. We can know TM atoms adsorbed twin graphene have potentials to be spintronic device and nanomagnets from the results.

Does fish reproduction and metabolic activity influence metal levels in fish intestinal parasites, acanthocephalans, during fish spawning and post-spawning period?

PubMed

Filipović Marijić, Vlatka; Vardić Smrzlić, Irena; Raspor, Biserka

2014-10-01

Application of fish intestinal parasites, acanthocephalans, as bioindicators in metal exposure assessment usually involves estimation of their metal levels and bioconcentration factors. Metal levels in parasite final host, fishes, are influenced by fish physiology but there is no data for acanthocephalan metal levels. Gastrointestinal Zn, Fe, Mn, Cd, Ag levels in European chub (Squalius cephalus L.) from the Sava River were significantly higher during chub spawning (April/May) compared to the post-spawning period (September). In acanthocephalans (Pomphorhynchus laevis and Acanthocephalus anguillae) significantly higher metal levels during chub spawning were observed only for Zn in P. laevis. Bioconcentration factors were twice as high for Fe, Mn, Ag, Pb in the post-spawning period, probably as a consequence of lower gastrointestinal metal levels in fish rather than metal exposure. Therefore, bioconcentration factors should be interpreted with caution, due to their possible variability in relation to fish physiology. In addition, gastrointestinal Cu, Cd and Pb levels were lower in infected than uninfected chub, indicating that metal variability in fishes might be affected by the presence of acanthocephalans. Copyright © 2014 Elsevier Ltd. All rights reserved.

Non-destructive pollution exposure assessment in the European hedgehog (Erinaceus europaeus): II. Hair and spines as indicators of endogenous metal and As concentrations.

PubMed

D'Havé, Helga; Scheirs, Jan; Mubiana, Valentine Kayawe; Verhagen, Ron; Blust, Ronny; De Coen, Wim

2006-08-01

The role of hair and spines of the European hedgehog as non-destructive monitoring tools of metal (Ag, Al, Cd, Co, Cr, Cu, Fe, Ni, Pb, Zn) and As pollution in terrestrial ecosystems was investigated. Our results showed that mean pollution levels of a random sample of hedgehogs in Flanders are low to moderate. Yet, individual hedgehogs may be at risk for metal toxicity. Tissue distribution analyses (hair, spines, liver, kidney, muscle and fat tissue) indicated that metals and As may reach considerable concentrations in external tissues, such as hair and spines. Positive relationships were observed between concentrations in hair and those in liver, kidney and muscle for Al, Co, Cr, Cu, and Pb (0.43 < r < 0.85). Spine concentrations were positively related to liver, kidney and muscle concentrations for Cd, Co, Cr, Cu and Pb (0.37 < r < 0.62). Hair Ag, As, Fe and Zn and spine Ag, Al, As and Fe were related to metal concentrations in one or two of the investigated internal tissues (0.31 < r < 0.45). The regression models presented here may be used to predict metal and As concentrations in internal tissues of hedgehogs when concentrations in hair or spines are available. The present study demonstrated the possibility of using hair and spines for non-destructive monitoring of metal and As pollution in hedgehogs.

Spatial and temporal characterization of trace elements and nutrients in the Rawal Lake Reservoir, Pakistan using multivariate analysis techniques.

PubMed

Malik, Riffat Naseem; Nadeem, Muhammad

2011-12-01

Rawal Lake Reservoir is renowned for its ecological significance and is the sole source of drinking water of the third largest city of Pakistan. However, fish kill in recent years and anthropogenic impacts from human-related activities in its catchment area have resulted in deterioration of its surface water quality. This study aims to characterize spatial and temporal variations in surface water quality, identify contaminant sources, and compare their levels with quality guidelines. Surface water samples were collected from 10 sites and analyzed for 27 physicochemical parameters for a period of 2 years on a seasonal basis. Concentration of metals in surface water in pre-monsoon were in the order: Fe > Mg > Ca > Mn > Zn > Ni > Cr > Cu > Co > Pb, whereas in post-monsoon, the order of elemental concentrations was: Ca > Mg > Na > Fe > K > Zn > Cr > Li > Pb > Co > Ni > Cu > Mn > Cd. Metals (Ni, Fe, Zn, and Ca), pH, electrical conductivity (EC), dissolved oxygen (DO), chemical oxygen demand (COD), and nutrients (PO (4) (3-) , NO(3)-N, and SO (4) (2-) ) were measured higher in pre-monsoon, whereas concentration of Cu, Mn, Cr, Co, Pb, Cd, K, Na, Mg, Li, Cl(-), and NH(4)-N were recorded higher in post-monsoon. Results highlighted serious metal pollution of surface water. Mean concentration of Zn, Cd, Ni, Cu, Fe, Cr, and Pb in both seasons and Mn in post-monsoon were well above the permissible level of surface water quality criteria. Results stress the dire need to reduce heavy-metal input into the lake basin and suggest that heavy-metal contamination should be considered as an integral part of future planning and management strategies for restoration of water quality of the lake reservoir.

Electrodeposition of quaternary alloys in the presence of magnetic field

PubMed Central

2010-01-01

Electrodeposition of Ni-Co-Fe-Zn alloys was done in a chloride ion solution with the presence and absence of a Permanent Parallel Magnetic Field (PPMF). The PPMF was applied parallel to the cathode surface. The deposition profile was monitored chronoamperometrically. It was found that the electrodeposition current was enhanced in the presence of PPMF (9 T) compared to without PPMF. The percentage of current enhancement (Γ%) was increased in the presence of PPMF, with results of Γ% = 11.9%, 16.7% and 18.5% at -1.1, -1.2 and -1.3 V respectively for a 2400 sec duration. In chronoamperometry, the Composition Reference Line (CRL) for Ni was around 57%, although the nobler metals (i.e. Ni, Co) showed anomalous behaviour in the presence of Zn and Fe. The anomalous behaviour of the Ni-Co-Fe-Zn electrodeposition was shown by the Energy Dispersive X-Ray (EDX) results. From Atomic Force Microscopy (AFM) measurements, it was found that the surface roughness of the Ni-Co-Fe-Zn alloy films decreased in the presence of a PPMF. PMID:20604934

The 3D Distribution of Dissolved and Colloidal Fe, Mn, Zn, Cu, Ni, Cd and Pb in the Western Antarctic Peninsula Shelf Region; Implications for Natural Fe Fertilization

NASA Astrophysics Data System (ADS)

Sherrell, R. M.; Fitzsimmons, J. N.; Roccanova, J.; Schofield, O.; Meredith, M. P.

2016-02-01

The Western Antarctic Peninsula (WAP) shelf region is is a natural Fe fertilization zone where primary production exceeds that of the adjacent open Southern Ocean. Until recently, however, distributions of Fe and of other bioactive metals were completely lacking for the WAP, and the sources and delivery mechanisms of Fe to the euphotic zone were only speculated upon. We have previously presented surface water (2m) dissolved (dTM, <0.2µm) and particulate (pTM, >0.45µm) distributions for Fe and a suite of other bioactive metals over the WAP shelf, covering the Palmer LTER sampling grid for Jan. 2010, 2011 and 2012. We now report the first complete 3D distribution of dissolved and colloidal Fe (and Mn, Zn, Cu, Ni, Cd and Pb) over the LTER grid in Jan. 2015, allowing assessment of dFe size speciation, sources and transport pathways in this dynamic shelf system. Dissolved metals were analyzed by automated offline preconcentration (seaFAST-pico, ESI) followed by sector-field ICP-MS. We confirm previous findings of low ( 0.1nM) dFe in surface waters on the mid-outer shelf in the northern portion of the grid, and now find that concentrations at this level or below persist through the euphotic zone. However, dFe increases rapidly with depth, with low surface values underlain by substantially higher concentrations even at 50m. Inner shelf surface waters are generally substantially > 0.1nM, suggesting Fe replete conditions in this region. Vertical profiles reveal that dFe generally increases with depth, much moreso in the inner shelf (dFe up to 5.0nM) than the outer shelf. A general N-S gradient in dFe is also evident, with concentrations higher in the southern WAP, especially in Marguerite Bay. In addition, shelf stations often show a dFe maximum suggesting remineralization from sinking biogenic particles. These findings for dFe and for the other metals, will be used to help unravel the biogeochemical workings of natural Fe fertilization in this region.

Localization and distribution of Zn and Fe in grains of biofortified bread wheat lines through micro- and triaxial-X-ray fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Cardoso, P.; Mateus, T. C.; Velu, G.; Singh, R. P.; Santos, J. P.; Carvalho, M. L.; Lourenço, V. M.; Lidon, F.; Reboredo, F.; Guerra, M.

2018-03-01

X-ray fluorescence analysis has been performed in wheat grains from a field trial where some biofortified and non-biofortified wheat varieties were subjected to Zn biofortification through soil fertilizer application. A set of ten biofortified and non-biofortified wheat varieties developed at the International Maize and Wheat Improvement Center, Mexico, were used for this study. Two analytical methods were employed to investigate the contents and localization of the trace metals Zn and Fe within the grains, one with polarized monochromatic X-rays for lower limits of detection, and another featuring polycapillary lenses for micrometric beam size (μ-EDXRF). Elemental maps were obtained with μ-EDXRF allowing for the study of Zn and Fe localization in plants grown in normal and Zn-enriched soil. It is acknowledged that the biofortification procedures result in around 30% average increase in overall Zn concentration when compared to other high Zn genotypes grown in normal soil. A genotypic ranking was performed taking into account the influence of the measurement methods and field conditions and the obtained results show that two of the top three varieties regarding zinc contents also rank among the top three in terms of Fe concentration. Elemental mapping analysis seems to favor the use of integral flour for the manufacture of bread and pasta products, as the bran retains most of the minerals.

Assessing trace metal pollution through high spatial resolution of surface sediments along the Tunis Gulf coast (southwestern Mediterranean).

PubMed

Ennouri, Rym; Zaaboub, Noureddine; Fertouna-Bellakhal, Mouna; Chouba, Lassad; Aleya, Lotfi

2016-03-01

Tunis Gulf (northern Tunisia, Mediterranean Sea) is of great economic importance due to its abundant fish resources. Rising urbanization and industrial development in the surrounding area have resulted in an increase in untreated effluents and domestic waste discharged into the gulf via its tributary streams. Metal (Cd, Pb, Hg, Cu, Zn, Fe, and Mn) and major element (Mg, Ca, Na, and K) concentrations were measured in the grain fine fraction <63 μm by atomic absorption spectrophotometry. Results showed varying spatial distribution patterns for metals, indicating complex origins and controlling factors such as anthropogenic activities. Sediment metal concentrations are ranked as follows: Fe > Mg > Zn > Mn > Pb > Cu > Cd > Hg. Metals tend to be concentrated in proximity to source points, suggesting that the mineral enrichment elements come from sewage of coastal towns and pollution from industrial dumps and located along local rivers, lagoons, and on the gulf shore itself. This study showed that trace metal and major element concentrations in surface sediments along the Tunis Gulf shores were lower than those found in other coastal areas of the Mediterranean Sea.

In Vitro Antioxidant versus Metal Ion Chelating Properties of Flavonoids: A Structure-Activity Investigation

PubMed Central

Cherrak, Sabri Ahmed; Mokhtari-Soulimane, Nassima; Berroukeche, Farid; Bensenane, Bachir; Cherbonnel, Angéline; Merzouk, Hafida; Elhabiri, Mourad

2016-01-01

Natural flavonoids such as quercetin, (+)catechin and rutin as well as four methoxylated derivatives of quercetin used as models were investigated to elucidate their impact on the oxidant and antioxidant status of human red blood cells (RBCs). The impact of these compounds against metal toxicity was studied as well as their antiradical activities with DPPH assay. Antihemolytic experiments were conducted on quercetin, (+)catechin and rutin with excess of Fe, Cu and Zn (400 μM), and the oxidant (malondialdehyde, carbonyl proteins) and antioxidant (reduced glutathione, catalase activity) markers were evaluated. The results showed that Fe and Zn have the highest prooxidant effect (37 and 33% of hemolysis, respectively). Quercetin, rutin and (+)catechin exhibited strong antioxidant properties toward Fe, but this effect was decreased with respect to Zn ions. However, the Cu showed a weak antioxidant effect at the highest flavonoid concentration (200 μM), while a prooxidant effect was observed at the lowest flavonoid concentration (100 μM). These results are in agreement with the physico-chemical and antiradical data which demonstrated that binding of the metal ions (for FeNTA: (+)Catechin, KLFeNTA = 1.6(1) × 106 M-1 > Rutin, KLFeNTA = 2.0(9) × 105 M-1 > Quercetin, KLFeNTA = 1.0(7) × 105 M-1 > Q35OH, KLFeNTA = 6.3(8.7) × 104 M-1 > Quercetin3’4’OH and Quercetin 3OH, KLFeNTA ~ 2 × 104 M-1) reflects the (anti)oxidant status of the RBCs. This study reveals that flavonoids have both prooxidant and antioxidant activity depending on the nature and concentration of the flavonoids and metal ions. PMID:27788249

Effects of wastewater irrigation on chemical and physical properties of Petroselinum crispum.

PubMed

Keser, Gonca; Buyuk, Gokhan

2012-06-01

The present study was carried out to assess the impact of wastewater on parsley (Petroselinum crispum). The parameters determined for soil were pH, electrical conductivity (EC), soil organic matter (SOM), nutrient elements (Ca, Mg, Na, K, Mn, Cu, Zn, and Fe), and heavy metals (Cd, Cr, Ni, and Pb), while the parameters determined for the plant included pigment content, dry matter, nutrient element, and heavy metals. SOM, EC, and clay contents were higher, and pH was slightly acidic in soil treated with wastewater compared to control soil. The enrichment factors (EF) of the nutrient elements in contaminated soil are in the sequence of Na (2) > Ca (1.32) > Mn = Mg (1.17) > Cu (1.11) > Zn (1.08) > Fe (1.07) > K (0.93), while EF in parsley are Na (6.63) > Ca (1.60) > Mg (1.34) > Zn (1.15) > Fe (0.95) > Cu = K (0.90) > Mn (0.85). Application of wastewater significantly decreased dry matter, while photosynthetic pigment content increased in parsley. The enrichment of the heavy metals is in the sequence: Cd (1.142) > Pb (1.131) > Ni (1.112) > Cr (1.095). P. crispum shows a high transfer factor (TF > 1) for Cd signifying a high mobility of Cd from soil to plant. Thus, although the wastewater irrigation in parsley production aims to produce socioeconomic benefits, study results indicated that municipal wastewater is not suitable for irrigation of parsley because it has negative effects on plant and causes heavy metal accumulation.

Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

DOE PAGES

Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; ...

2015-06-19

Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn 2+ ion in (TMC)Fe III-(O 2)-Zn(CF 3SO 3) 2 (1-Zn 2+) decreases the Lewis acidity of the Zn 2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn 2+. This further changes the reactivities of 1-Zn 2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidantmore » (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn 2+, whereas 1-Zn 2+ coordinating two water molecules, (TMC)Fe III-(O 2)-Zn(CF 3SO 3) 2-(OH 2) 2 [1-Zn 2+-(OH 2) 2], releases the O 2 unit in the oxidation reaction. In the reduction reactions, 1-Zn 2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn 2+-(OH 2) 2. Finally, the present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.« less

Toxicity of a metal(loid)-polluted agricultural soil to Enchytraeus crypticus changes under a global warming perspective: Variations in air temperature and soil moisture content.

PubMed

González-Alcaraz, M Nazaret; van Gestel, Cornelis A M

2016-12-15

This study aimed to assess how the current global warming perspective, with increasing air temperature (20°C vs. 25°C) and decreasing soil moisture content (50% vs. 30% of the soil water holding capacity, WHC), affected the toxicity of a metal(loid)-polluted agricultural soil to Enchytraeus crypticus. Enchytraeids were exposed for 21d to a dilution series of the agricultural soil with Lufa 2.2 control soil under four climate situations: 20°C+50% WHC (standard conditions), 20°C+30% WHC, 25°C+50% WHC, and 25°C+30% WHC. Survival, reproduction and bioaccumulation of As, Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn were obtained as endpoints. Reproduction was more sensitive to both climate factors and metal(loid) pollution. High soil salinity (electrical conductivity~3dSm -1 ) and clay texture, even without the presence of high metal(loid) concentrations, affected enchytraeid performance especially at drier conditions (≥80% reduction in reproduction). The toxicity of the agricultural soil increased at drier conditions (10% reduction in EC10 and EC50 values for the effect on enchytraeid reproduction). Changes in enchytraeid performance were accompanied by changes in As, Fe, Mn, Pb and Zn bioaccumulation, with lower body concentrations at drier conditions probably due to greater competition with soluble salts in the case of Fe, Mn, Pb and Zn. This study shows that apart from high metal(loid) concentrations other soil properties (e.g. salinity and texture) may be partially responsible for the toxicity of metal(loid)-polluted soils to soil invertebrates, especially under changing climate conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Impact of metal binding on the antitumor activity and cellular imaging of a metal chelator cationic imidazopyridine derivative.

PubMed

Roy, Mithun; Chakravarthi, Balabhadrapatruni V S K; Jayabaskaran, Chelliah; Karande, Anjali A; Chakravarty, Akhil R

2011-05-14

A new water soluble cationic imidazopyridine species, viz. (1E)-1-((pyridin-2-yl)methyleneamino)-3-(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2(3H)-yl)propan-2-ol (1), as a metal chelator is prepared as its PF(6) salt and characterized. Compound 1 shows fluorescence at 438 nm on excitation at 342 nm in Tris-HCl buffer giving a fluorescence quantum yield (φ) of 0.105 and a life-time of 5.4 ns. Compound 1, as an avid DNA minor groove binder, shows pUC19 DNA cleavage activity in UV-A light of 365 nm forming singlet oxygen species in a type-II pathway. The photonuclease potential of 1 gets enhanced in the presence of Fe(2+), Cu(2+) or Zn(2+). Compound 1 itself displays anticancer activity in HeLa, HepG2 and Jurkat cells with an enhancement on addition of the metal ions. Photodynamic effect of 1 at 365 nm also gets enhanced in the presence of Fe(2+) and Zn(2+). Fluorescence-based cell cycle analysis shows a significant dead cell population in the sub-G1 phase of the cell cycle suggesting apoptosis via ROS generation. A significant change in the nuclear morphology is observed from Hoechst 33258 and an acridine orange/ethidium bromide (AO/EB) dual nuclear staining suggesting apoptosis in cells when treated with 1 alone or in the presence of the metal ions. Apoptosis is found to be caspase-dependent. Fluorescence imaging to monitor the distribution of 1 in cells shows that 1 in the presence of metal ions accumulates predominantly in the cytoplasm. Enhanced uptake of 1 into the cells within 12 h is observed in the presence of Fe(2+) and Zn(2+).

Anthropogenic sources and environmentally relevant concentrations of heavy metals in surface water of a mining district in Ghana: a multivariate statistical approach.

PubMed

Armah, Frederick A; Obiri, Samuel; Yawson, David O; Onumah, Edward E; Yengoh, Genesis T; Afrifa, Ernest K A; Odoi, Justice O

2010-11-01

The levels of heavy metals in surface water and their potential origin (natural and anthropogenic) were respectively determined and analysed for the Obuasi mining area in Ghana. Using Hawth's tool an extension in ArcGIS 9.2 software, a total of 48 water sample points in Obuasi and its environs were randomly selected for study. The magnitude of As, Cu, Mn, Fe, Pb, Hg, Zn and Cd in surface water from the sampling sites were measured by flame Atomic Absorption Spectrophotometry (AAS). Water quality parameters including conductivity, pH, total dissolved solids and turbidity were also evaluated. Principal component analysis and cluster analysis, coupled with correlation coefficient analysis, were used to identify possible sources of these heavy metals. Pearson correlation coefficients among total metal concentrations and selected water properties showed a number of strong associations. The results indicate that apart from tap water, surface water in Obuasi has elevated heavy metal concentrations, especially Hg, Pb, As, Cu and Cd, which are above the Ghana Environmental Protection Agency (GEPA) and World Health Organisation (WHO) permissible levels; clearly demonstrating anthropogenic impact. The mean heavy metal concentrations in surface water divided by the corresponding background values of surface water in Obuasi decrease in the order of Cd > Cu > As > Pb > Hg > Zn > Mn > Fe. The results also showed that Cu, Mn, Cd and Fe are largely responsible for the variations in the data, explaining 72% of total variance; while Pb, As and Hg explain only 18.7% of total variance. Three main sources of these heavy metals were identified. As originates from nature (oxidation of sulphide minerals particularly arsenopyrite-FeAsS). Pb derives from water carrying drainage from towns and mine machinery maintenance yards. Cd, Zn, Fe and Mn mainly emanate from industry sources. Hg mainly originates from artisanal small-scale mining. It cannot be said that the difference in concentration of heavy metals might be attributed to difference in proximity to mining-related activities because this is inconsistent with the cluster analysis. Based on cluster analysis SN32, SN42 and SN43 all belong to group one and are spatially similar. But the maximum Cu concentration was found in SN32 while the minimum Cu concentration was found in SN42 and SN43.

Assessment of oxidative stress and bioaccumulation of the metals Cu, Fe, Zn, Pb, Cd in the polychaete Perinereis gualpensis from estuaries of central Chile.

PubMed

Gaete, Hernán; Álvarez, Manuel; Lobos, Gabriela; Soto, Eulogio; Jara-Gutiérrez, Carlos

2017-11-01

The estuaries of the Aconcagua and Maipo Rivers of central Chile are receptors of residues that contain metals from anthropic activities including agriculture, mining and smelters, which have different levels in the two basins. This study postulates that the exposition to metals is different in the two estuaries and that their sediments contain bioavailable chemical agents that produce oxidative stress. The aim of the study was to evaluate the effect of estuarine sediments on the polychaete Perinereis gualpensis using oxidative stress biomarkers and to determine the metal concentrations in sediments and their accumulation in P. gualpensis. Sediments and organisms were collected in December 2015 and January 2016 in the estuaries. The Catapilco estuary was used as control, since its basin has little anthropic activity. The metal concentrations of Fe Cu, Pb, Zn and Cd were determined in tissues of the organisms and in sediments. The granulometry, conductivity, redox potential, pH and organic matter in sediments were determined, as well as catalase activity and lipid peroxidation. The results show that the concentrations of metals in sediments were higher in the estuary of the Aconcagua River: Cu: 48 ± 2μgg -1 ; Fe: 154 ± 19mgg -1 , Pb: 20 ± 3μgg -1 and Zn: 143 ± 20μgg -1 . In tissues, Pb and Fe were higher in the estuary of the Maipo River, while Cd was detected only in the Catapilco River mouth. Catalase activity was greater in the estuary of the Aconcagua River and lipid peroxidation in the estuary of the Catapilco River. Significant regressions were found between biomarkers of oxidative stress and metal concentrations in tissues of P. gualpensis. In conclusion, the sediments of the studied estuaries contain bioavailable chemical agents that provoke oxidative stress in P. gualpensis, which may be a risk for the benthic communities of these ecosystems. This species is proposed to monitor metals bioavailability and oxidative stress in estuarine sediments. Copyright © 2017 Elsevier Inc. All rights reserved.

Metal pollution in Al-Khobar seawater, Arabian Gulf, Saudi Arabia.

PubMed

Alharbi, Talal; Alfaifi, Hussain; El-Sorogy, Abdelbaset

2017-06-15

In order to assess heavy metals pollution along the Al-Khobar coastline, 30 seawater samples and 15 sediment ones were collected for Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Hg and Pb analysis by Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). The analysis indicated a southward decreasing pattern in most heavy metal concentrations and the average values of Zn, Fe, Mn, Cu, As and Cr were higher than the ones reported from some worldwide seas and gulfs. Most of the highest levels were recorded within the bays and were related with in situ under sediments especially that composed of clays and very fine sands, and in localities characterized with anthropogenic activities like landfilling, desalination plants, fishing boats, oil spills and solid rubbish. The results of the present study provide useful background for further marine investigation and management in the Arabian Gulf region. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Determination of inorganic elements in different parts of Sonchus oleraceus L by flame atomic absorption spectrometry].

PubMed

Wang, Nai-Xing; Cui, Xue-Gui; Du, Ai-Qin; Mao, Hong-Zhi

2007-06-01

Flame atomic absorption spectrometry with air-acetylene flame was used for the determination of inorganic metal elements in different parts ( flower, leaf, stem and root) of Sonchus oleraceus L. The contents of Ca, Mg, K, Na, Fe, Mn, Cu, Zn, Cr, Co, Ni, Pb and Cd in the flower, leaf, stem and root of Sonchus oleraceus L were compared. The order from high to low of the additive weight (microg x g(-1)) for the 13 kinds of metal elements is as follows: leaf (77 213.72) > flower (47 927.15) > stem(42 280.99) > root (28 131.18). From the experimental results it was found that there were considerable differences in the contents of the metal elements in different parts, and there were richer contents of Fe, Zn, Mn and Cu in root and flower, which are necessary to human health, than in other parts.

Three-dimensional atlas of iron, copper, and zinc in the mouse cerebrum and brainstem.

PubMed

Hare, Dominic J; Lee, Jason K; Beavis, Alison D; van Gramberg, Amanda; George, Jessica; Adlard, Paul A; Finkelstein, David I; Doble, Philip A

2012-05-01

Atlases depicting molecular and functional features of the brain are becoming an integral part of modern neuroscience. In this study we used laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS) to quantitatively measure iron (Fe), copper (Cu), and zinc (Zn) levels in a serially sectioned C57BL/6 mouse brain (cerebrum and brainstem). Forty-six sections were analyzed in a single experiment of approximately 158 h in duration. We constructed a 46-plate reference atlas by aligning quantified images of metal distribution with corresponding coronal sections from the Allen Mouse Brain Reference Atlas. The 46 plates were also used to construct three-dimensional models of Fe, Cu, and Zn distribution. This atlas represents the first reconstruction of quantitative trace metal distribution through the brain by LA-ICPMS and will facilitate the study of trace metals in the brain and help to elucidate their role in neurobiology.

Cu, Fe, and Zn Isotope Variations Within a High-Temperature Mid-Ocean Ridge Sulfide Structure

NASA Astrophysics Data System (ADS)

Ewing, S. M.; Nelson, B. K.; Kelley, D. S.; Nielsen, D. C.

2006-12-01

Hydrothermal processes at mid-ocean ridges play an important role in controlling the transition metal budget of seawater and the crust through which it circulates. Preliminary work has shown stable metal isotope variations accompany these processes. We report Cu, Zn, and Fe isotope analyses of transects through a high temperature sulfide structure ("Fin") collected during the 1998 Edifice Rex Sulfide Recovery Project. We analyzed two horizontal transects through the sulfide edifice, from inner conduit to outer surface. Transects A and F are 9 and 6 cm in length, respectively. Each displays radially zoned mineralogy progressing from a chalcopyrite (ccp) zone through zones of zinc sulfide, pyrite-anhydrite (pyr-anh) matrix, zinc sulfide-anhydrite (zns-anh) matrix, to an outer well-cemented silica (Si) zone. Additional ccp and pyr-anh zones appear in transect A resulting from a smaller breakout conduit. In transect A, Cu displays the most isotopic variation, with little variation in Fe and Zn isotopes. From the inner ccp zone outward, the Cu isotope profile shows a 0.4‰ (±0.05‰ 2σ) increase in the first pyr-anh zone over the coarse-grained ccp zone. The δ65Cu drops by 0.6‰ in the secondary ccp zone and recovers to values of the innermost wall in the following zone where it is constant until the outermost portion of the Si rich zone, which shows a 1.3‰ increase over inner zone values. The Zn isotope profile has a total variation of 0.27‰ (±0.05‰ 2σ), with a 0.2‰ increase in the first pyr- anh zone followed by a .27‰ decrease in the adjacent zone, and recovering to its heaviest values in the second pyr-anh zone. The Zn profile lacks any significant increase of the δ^{64}Zn in the outermost zones. The Fe isotope profile shows very little variation across the chimney wall, but does have a sharp 0.7‰ (±0.1‰ 2σ) increase in the δ56Fe in the well-cemented Si rich zone. In transect F, the Cu isotope profile again shows the most variation, but displays a more pronounced jump of 1.3‰ at the zinc sulfide boundary and no obvious increase of the δ65Cu in the Si rich zone. Similarly with Zn, there is a 0.35‰ increase of the δ^{64}Zn, but no outer wall increase. Fe, on the other hand, has variation of the same order as transect A, and shows a 0.6‰ increase of the δ56Fe in both the zns-anh and Si rich zones. These profiles are likely the result of a combination of diffusion and advection processes, fluid mineral equilibria, and mineral-mineral equilibria. High δ values of the outer zones likely reflect oxidation reactions with seawater. Processes responsible for isotopic variations within interior zones of the structure are ambiguous. Kinetic effects and biological activity may play a role, as Zn, which is not redox sensitive and only minimally coordination sensitive, has profiles that are qualitatively similar to Cu and Fe, but less analytically pronounced. Our findings are within the range of other published results, and further illustrate such measurable metal isotope variation exists not only on the vent field scale among chimneys, but systematically within chimney walls.

Copper and zinc uptake by rice and accumulation in soil amended with municipal solid waste compost

NASA Astrophysics Data System (ADS)

Bhattacharyya, P.; Chakraborty, A.; Chakrabarti, K.; Tripathy, S.; Powell, M. A.

2006-04-01

Effect of addition of municipal solid waste compost (MSWC) on two metals viz. copper (Cu) and zinc (Zn) contents of submerged rice paddies were studied. Experiments were conducted during the three consecutive wet seasons from 1997 to 1999 on rice grown under submergence, at the Experimental Farm of Calcutta University, India. A sequential extraction method was used to determine the metal (Cu and Zn) fractions in MSWC and cow dung manure (CDM). Both metals were significantly bound to the organic matter and Fe and Mn oxides in MSWC and CDM. Metal content in rice straw was higher than in rice grain. Metal bound with Fe and Mn oxides in MSWC and CDM best correlated with straw and grain metal followed by exchangeable and water soluble fractions. Carbonate, organic matter bound and residual fractions in MSWC and CDM did not significantly correlate with rice straw and grain metal. The MSWC would be a valuable resource for agriculture if it can be used safely, but long-term field experiments with MSWC are needed to assess by regular monitoring of the metal loads and accumulation in soil and plants.

Distribution of Ca, Fe, Cu and Zn in primary colorectal cancer and secondary colorectal liver metastases

NASA Astrophysics Data System (ADS)

Al-Ebraheem, A.; Mersov, A.; Gurusamy, K.; Farquharson, M. J.

2010-07-01

A microbeam synchrotron X-ray fluorescence (μSRXRF) technique has been used to determine the localization and the relative concentrations of Zn, Cu, Fe and Ca in primary colorectal cancer and secondary colorectal liver metastases. 24 colon and 23 liver samples were examined, all of which were formalin fixed tissues arranged as microarrays of 1.0 mm diameter and 10 μm thickness. The distribution of these metals was compared with light transmission images of adjacent sections that were H and E stained to reveal the location of the cancer cells. Histological details were provided for each sample which enable concentrations of all elements in different tissue types to be compared. In the case of liver, significant differences have been found for all elements when comparing tumour, normal, necrotic, fibrotic, and blood vessel tissues (Kruskal Wallis Test, P<0.0001). The concentrations of all elements have also been found to be significantly different among tumour, necrotic, fibrotic, and mucin tissues in the colon samples (Kruskal Wallis Test, P<0.0001). The concentrations of all elements have been compared between primary colorectal samples and colorectal liver metastases. Concentration of Zn, Cu, Fe and Ca are higher in all types of liver tissues compared to those in the colon tissues. Comparing liver tumour and colon tumour samples, significant differences have been found for all elements (Mann Whitney, P<0.0001). For necrotic tissues, significant increase has been found for Zn, Ca, Cu and Fe (Mann Whitney, P<0.0001 for Fe and Zn, 0.014 for Ca, and 0.001 for Cu). The liver fibrotic levels of Zn, Ca, Cu and Fe were higher than the fibrotic colon areas (independent T test, P=0.007 for Zn and Mann Whitney test P<0.0001 for Cu, Fe and Ca). For the blood vessel tissue, the analysis revealed that the difference was only significant for Fe ( P=0.009) from independent T test.

Evaluation of metal content in perch of the Ob River basin

NASA Astrophysics Data System (ADS)

Osipova, N. A.; Stepanova, K. D.; Matveenko, I. A.

2015-11-01

The geochemical features of river perch in the River Ob basin have been studied (the upper and middle reaches of the Ob River and the lower reach of the Tom River). The contents of Ag, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sn, W, Zn, Hg in perch's soft tissue are defined by the methods of ICP AES and stripping voltammetry, that of mercury in bones - by the atomic absorption method using mercury analyzer PA-915+. The distribution series of metal absolute concentrations in perch's soft tissue from the Ob River basin are plotted: Fe > Zn > Cu > Mn, typical for uncontaminated or slightly metal contaminated water bodies. In soft tissue of the studied samples the metal content does not exceed the permissible values. The mercury content in bones of studied samples is in the range 0,036-0,556 mg/kg. The mercury concentration is higher in bones in comparison with soft tissue in all samples.

Biomonitoring of heavy metals contamination by mosses and lichens around Slovinky tailing pond (Slovakia).

PubMed

Demková, Lenka; Bobul'ská, Lenka; Árvay, Július; Jezný, Tomáš; Ducsay, Ladislav

2017-01-02

Three moss (Pleurozium spp., Polytrichum spp., and Rhytidiadelphus spp.) and two lichen (Hypogymnia physodes and Pseudevernia furfuracea) taxons covered in the bags were used to monitor air quality. Bags were exposed at the different distances from the tailing pond because of insufficient security and source of heavy metal pollution. Moss/lichen bags were exposed for six weeks at 0-, 50-, 100-, 150- and 200-m distances from Slovinky tailing pond, in the main wind direction (down the valley). Accumulation ability of heavy metals expressed by relative accumulation factor (RAF) increases in the order of Polytrichum spp.

Too much is bad--an appraisal of phytotoxicity of elevated plant-beneficial heavy metal ions.

PubMed

Anjum, Naser A; Singh, Harminder P; Khan, M Iqbal R; Masood, Asim; Per, Tasir S; Negi, Asha; Batish, Daizy R; Khan, Nafees A; Duarte, Armando C; Pereira, Eduarda; Ahmad, Iqbal

2015-03-01

Heavy metal ions such as cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), and zinc (Zn) are considered essential/beneficial for optimal plant growth, development, and productivity. However, these ions readily impact functions of many enzymes and proteins, halt metabolism, and exhibit phytotoxicity at supra-optimum supply. Nevertheless, the concentrations of these heavy metal ions are increasing in agricultural soils worldwide via both natural and anthropogenic sources that need immediate attention. Considering recent breakthroughs on Co, Cu, Fe, Mn, Mo, Ni, and Zn in soil-plant system, the present paper: (a) overviews the status in soils and their uptake, transport, and significance in plants; (b) critically discusses their elevated level-mediated toxicity to both plant growth/development and cell/genome; (c) briefly cross talks on the significance of potential interactions between previous plant-beneficial heavy metal ions in plants; and (d) highlights so far unexplored aspects in the current context.

Age-dependent accumulation of heavy metals in a pod of killer whales (Orcinus orca) stranded in the northern area of Japan.

PubMed

Endo, Tetsuya; Kimura, Osamu; Hisamichi, Yohsuke; Minoshima, Yasuhiko; Haraguchi, Koichi

2007-02-01

Mercury (Hg), cadmium (Cd), iron (Fe) manganese (Mn), zinc (Zn) and copper (Cu) concentrations in the liver, kidney and muscle of nine killer whales (including three calves) that stranded together in the northern area of Japan were determined. The Hg and Cd concentrations were found at trace levels in the calf organs, and increased with age. The Fe concentration in the muscle was significantly lower in the calves than in the mature whales and also increased with age. In contrast, Mn and Cu concentrations in the muscle were significantly higher in the calves than in the mature whales, and changes in the Zn concentration relative to age were unclear. These results suggest minimal mother-to-calf transfer of the toxic metals Hg and Cd and accumulation of these metals in the organs with age, while the essential metals Mn and Cu were found at higher concentrations in the muscle of calves than in mature whales.

Thermosynechococcus elongatus DpsA binds Zn(II) at a unique three histidine-containing ferroxidase center and utilizes O2 as iron oxidant with very high efficiency, unlike the typical Dps proteins.

PubMed

Alaleona, Flaminia; Franceschini, Stefano; Ceci, Pierpaolo; Ilari, Andrea; Chiancone, Emilia

2010-02-01

The cyanobacterium Thermosynechococcus elongatus is one the few bacteria to possess two Dps proteins, DpsA-Te and Dps-Te. The present characterization of DpsA-Te reveals unusual structural and functional features that differentiate it from Dps-Te and the other known Dps proteins. Notably, two Zn(II) are bound at the ferroxidase center, owing to the unique substitution of a metal ligand at the A-site (His78 in place of the canonical aspartate) and to the presence of a histidine (His164) in place of a hydrophobic residue at a metal-coordinating distance in the B-site. Only the latter Zn(II) is displaced by incoming iron, such that Zn(II)-Fe(III) complexes are formed upon oxidation, as indicated by absorbance and atomic emission spectroscopy data. In contrast to the typical behavior of Dps proteins, where Fe(II) oxidation by H(2)O(2) is about 100-fold faster than by O(2), in DpsA-Te the ferroxidation efficiency of O(2) is very high and resembles that of H(2)O(2). Oxygraphic experiments show that two Fe(II) are required to reduce O(2), and that H(2)O(2) is not released into solution at the end of the reaction. On this basis, a reaction mechanism is proposed that also takes into account the formation of Zn(II)-Fe(III) complexes. The physiological significance of the DpsA-Te behavior is discussed in the framework of a possible localization of the protein at the thylakoid membranes, where photosynthesis takes place, with the consequent increased formation of reactive oxygen species.

Mobilization of Trace Metals in an Experimental Carbon Sequestration Scenario

NASA Astrophysics Data System (ADS)

Marcon, V.; Kaszuba, J. P.

2012-12-01

Mobilizing trace metals with injection of supercritical CO2 into deep saline aquifers is a concern for geologic carbon sequestration. The potential for leakage from these systems requires an understanding of how injection reservoirs interact with the overlying potable aquifers. Hydrothermal experiments were performed to evaluate metal mobilization and mechanisms of release in a carbonate storage reservoir and at the caprock-reservoir boundary. Experiments react synthetic Desert Creek limestone and/or Gothic Shale, formations in the Paradox Basin, Utah, with brine that is close to equilibrium with these rocks. A reaction temperature of 1600C accelerates the reaction kinetics without changing in-situ water-rock reactions. The experiments were allowed to reach steady state before injecting CO2. Changes in major and trace element water chemistry, dissolved carbon and sulfide, and pH were tracked throughout the experiments. CO2 injection decreases the pH by 1 to 2 units; concomitant mineral dissolution produces elevated Ba, Cu, Fe, Pb, and Zn concentrations in the brine. Concentrations subsequently decrease to approximately steady state values after 120-330 hours, likely due to mineral precipitation as seen in SEM images and predicted by geochemical modeling. In experiments that emulate the caprock-reservoir boundary, final Fe (0.7ppb), an element of secondary concern for the EPA, and Pb (0.05ppb) concentrations exceed EPA limits, whereas Ba (0.140ppb), Cu (48ppb), and Zn (433ppb) values remain below EPA limits. In experiments that simulate deeper reservoir conditions, away from the caprock boundary, final Fe (3.5ppb) and Pb (0.017ppb) values indicate less mobilization than seen at the caprock-reservoir boundary, but values still exceed EPA limits. Barium concentrations always remain below the EPA limit of 2ppb, but are more readily mobilized in experiments replicating deeper reservoir conditions. In both systems, transition elements Cd, Cr, Cu, Pb and Zn behave in a similar manner, increasing in concentration with injection but continually decreasing after about 830 hours until termination of the experiment. SEM images and geochemical models indicate initial dissolution of all rocks and minerals, re-precipitation of Ca-Mg-Fe carbonates and Fe-sulfides, and precipitation of anhydrite in both systems. Calcite dissolves more readily than dolomite in these experiments, but re-precipitates in veins on dolomite. If brines leak from a storage reservoir and mix with a potable aquifer, the experimental results suggest that Ba, Cu, and Zn will not be contaminants of concern. Pb, Fe and As (still under consideration) initially exceed the EPA threshold and may require careful attention in a sequestration scenario. However, experimentally observed trends of decreasing trace metal concentration suggest that these metals could become less of a concern during the life of a carbon repository. Finally, the caprock plays an active role in trace metal mobilization in the system. The caprock provides a source of metals, although subsequent precipitation may remove metals from solution.

Pollution in the urban soils of Lianyungang, China, evaluated using a pollution index, mobility of heavy metals, and enzymatic activities.

PubMed

Li, Yu; Li, Hong-Guan; Liu, Fu-Cheng

2017-01-01

Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had significant negative correlations with total Cu, Pb, Cr, Zn, Cd, and heavy metal fractions. This showed that alkaline phosphatase activity was sensitive to heavy metals in heavily contaminated regions, whereas urease and invertase were less affected. The combination of the various methods may offer a powerful analytical technique in the study of heavy metal pollution in street soil.

Role of hydrous iron oxide formation in attenuation and diel cycling of dissolved trace metals in a stream affected by acid rock drainage

USGS Publications Warehouse

Parker, S.R.; Gammons, C.H.; Jones, Clain A.; Nimick, D.A.

2007-01-01

Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column. ?? 2006 Springer Science+Business Media B.V.

From which soil metal fractions Fe, Mn, Zn and Cu are taken up by olive trees (Olea europaea L., cv. 'Chondrolia Chalkidikis') in organic groves?

PubMed

Chatzistathis, T; Papaioannou, A; Gasparatos, D; Molassiotis, A

2017-12-01

Organic farming has been proposed as an alternative agricultural system to help solve environmental problems, like the sustainable management of soil micronutrients, without inputs of chemical fertilizers. The purposes of this study were: i) to assess Fe, Mn, Zn and Cu bioavailability through the determination of sequentially extracted chemical forms (fractions) and their correlation with foliar micronutrient concentrations in mature organic olive (cv. 'Chondrolia Chalkidikis') groves; ii) to determine the soil depth and the available forms (fractions) by which the 4 metals are taken up by olive trees. DTPA extractable (from the soil layers 0-20, 20-40 and 40-60 cm) and foliar micronutrient concentrations were determined in two organic olive groves. Using the Tessier fractionation, five fractions, for all the metals, were found: exchangeable, bound to carbonates (acid-soluble), bound to Fe-Mn oxides (reducible), organic (oxidizable), as well as residual form. Our results indicated that Fe was taken up by the olive trees as organic complex, mainly from the soil layer 40-60 cm. Manganese was taken up from the exchangeable fraction (0-20 cm); Zinc was taken up as organic complex from the layers 0-20 and 40-60 cm, as well as in the exchangeable form from the upper 20 cm. Copper was taken up from the soil layers 0-20 and 40-60 cm as soluble organic complex, and as exchangeable ion from the upper 20 cm. Our data reveal the crucial role of organic matter to sustain metal (Fe, Zn and Cu) uptake -as soluble complexes-by olive trees, in mature organic groves grown on calcareous soils; it is also expected that these data will constitute a thorough insight and useful tool towards a successful nutrient and organic C management for organic olive groves, since no serious nutritional deficiencies were found. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dietary exposure to toxic and essential trace elements by consumption of wild and farmed carp (Cyprinus carpio) and Caspian kutum (Rutilus frisii kutum) in Iran.

PubMed

Heshmati, Ali; Karami-Momtaz, Javad; Nili-Ahmadabadi, Amir; Ghadimi, Sabah

2017-04-01

This study was conducted to determine and compare the concentrations of mercury (Hg), cadmium (Cd), arsenic (As), lead (Pb), nickel (Ni), iron (Fe), zinc (Zn), copper (Cu), manganese (Mn), cobalt (Co), and selenium (Se) in the muscle of wild and farmed carp (Cyprinus carpio) and wild and farmed Caspian kutum (Rutilus frisii kutum) collected from south-western Caspian Sea areas of Iran between December 2014 and March 2015. In addition, risk assessment of consumers to exposure to metals through fish consumption was estimated. In all the samples, the arsenic concentration was lower than the detection limit. The Pb, Cd, Hg and Mn concentrations were significantly higher in the wild fish samples compared to the farmed fish samples. There was no significant difference in the Fe, Zn, Cu, Co, Ni and Se concentrations of the wild and farmed carp and the wild and farmed Caspian kutum. Iron displayed the highest concentration of all the analysed metals in both the wild and farmed fish, followed by Zn and Cu. The highest Hg, Cd, Pb, Ni, Fe, Zn, Cu, Mn, Co and Se concentrations were 0.056, 0.011, 0.065, 0.120, 4.151, 3.792, 2.948, 2.690, 0.037 and 0.162 μg g -1 , respectively. The estimated daily intake of all metals was acceptable, and the hazard quotient values showed that consumption of the analysed fish posed no health risk to consumers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Major- and minor-metal composition of three distinct solid material fractions associated with Juan de Fuca hydrothermal fluids (northeast Pacific), and calculation of dilution fluid samples

USGS Publications Warehouse

Hinkley, T.K.; Seeley, J.L.; Tatsumoto, M.

1988-01-01

Three distinct types of solid material are associated with each sample of the hydrothermal fluid that was collected from the vents of the Southern Juan de Fuca Ridge. The solid materials appear to be representative of deposits on ocean floors near mid-ocean ridges, and interpretation of the chemistry of the hydrothermal solutions requires understanding of them. Sr isotopic evidence indicates that at least two and probably all three of these solid materials were removed from the solution with which they are associated, by precipitation or adsorption. This occurred after the "pure" hydrothermal fluid was diluted and thoroughly mixed with ambient seawater. The three types of solid materials, are, respectively, a coarse Zn- and Fe-rich material with small amounts of Na and Ca; a finer material also rich in Zn and Fe, but with alkali and alkaline-earth metals; and a scum composed of Ba or Zn, with either considerable Fe or Si, and Sr. Mineral identification is uncertain because of uncertain anion composition. Only in the cases of Ba and Zn were metal masses greater in solid materials than in the associated fluids. For all other metals measured, masses in fluids dwarf those in solids. The fluids themselves contain greater concentrations of all metals measured, except Mg, than seawater. We discuss in detail the relative merits of two methods of determining the mixing proportions of "pure" hydrothermal solution and seawater in the fluids, one based on Sr isotopes, and another previously used method based on Mg concentrations. Comparison of solute concentrations in the several samples shows that degree of dilution of "pure" hydrothermal solutions by seawater, and amounts of original solutes that were removed from it as solid materials, are not related. There is no clear evidence that appreciable amounts of solid materials were not conserved (lost) either during or prior to sample collection. ?? 1988.

Effects of Oral Administration of CrCl3 on the Contents of Ca, Mg, Mn, Fe, Cu, and Zn in the Liver, Kidney, and Heart of Chicken.

PubMed

Liu, Yanhan; Zhao, Xiaona; Zhang, Xiao; Zhao, Xuejun; Liu, Yongxia; Liu, Jianzhu

2016-06-01

This study aimed to investigate the effects of oral administration of trivalent chromium on the contents of Ca, Mg, Mn, Fe, Cu, and Zn in the heart, liver, and kidney. Different levels of 1/8, 1/4, and 1/2 LD50 (LD50 = 5000 mg/kg body mass) CrCl3 milligrams per kilogram body mass daily were added into the water to establish the chronic poisoning model. Ca, Mg, Mn, Fe, Cu, and Zn were detected with the flame atomic absorption spectrometry in the organs exposed 14, 28, and 42 days to CrCl3, respectively. Results showed that Cr was accumulated in the heart, liver, and kidney significantly (P < 0.05) with extended time and dose. The contents of Ca and Fe increased, whereas those of Mg, Mn, Cu, and Zn decreased in the heart, liver, and kidney of each treated group, which had a dose- and time-dependent relationship, but the contents of Mg and Zn in the heart took on a fluctuated change. These particular observations were different from those in the control group. In conclusion, the oral administration of CrCl3 could change the contents of Ca, Mg, Mn, Fe, Cu, and Zn in the heart, liver, and kidney, which may cause disorders in the absorption and metabolism of the metal elements of chickens.

Effects of Fe plaque and organic acids on metal uptake by wetland plants under drained and waterlogged conditions.

PubMed

Li, W C; Deng, H; Wong, M H

2017-12-01

This study aims to assess the role of Fe plaque in metal uptake and translocation by different wetland plants and examine the effects of organic acids on metal detoxification in wetland plants. It was found that although exposed to a similar level of metals in rhizosphere soil solution, metal uptake by shoots of Cypercus flabelliformis and Panicum paludosum was greatly reduced, consequently leading to a better growth under flooded than under drained conditions. This may be related to the enhanced Fe plaque in the former, but due to the decreased root permeability in the latter under anoxic conditions. The Fe plaque on root surface has potential to sequester metals and then reduce metal concentrations and translocation in shoot tissues. However, whether the Fe plaque acts as a barrier to metal uptake and translocation may also be dependent on the root anatomy. Although metal tolerance in wetland plants mainly depends upon their metal exclusion ability, the higher-than-toxic-level of metal concentrations in some species indicates that internal metal detoxification might also exist. It was suggested that malic or citric acid in shoots of P. paludosum and C. flabelliformis may account for their internal detoxification for Zn. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparative study on the physical properties of transition metal-doped (Co, Ni, Fe, and Mn) ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Azab, A. A.; Ateia, Ebtesam E.; Esmail, S. A.

2018-07-01

Nano-crystalline of TM-doped ZnO with general formula Zn0.97TM0.03O (TM: Mn, Fe, Co, and Ni) was prepared using sol-gel method. The dependence of crystal structure, morphology, and optical and magnetic properties on the type of transition metals was investigated. The XRD investigation of pure and TM-doped ZnO nanoparticles samples confirms the formation of single-phase hexagonal wurtzite structure. The estimated crystallite sizes are found in the range of 17 and 38 nm for the doped and pure samples, respectively. The obtained data suggest that the dopant type plays a vital role in the physical properties of the investigated samples. The optical band-gap energy Eg has been calculated from near infrared (NIR) and visible (VIS) reflectance spectra using the Kubelka-Munk function. Minimum value of 2.398 eV and maximum one of 3.29 eV were obtained for Manganese-doped ZnO and pure ZnO, respectively. The analysis of XRD and VSM of the samples confirms that the observed room-temperature (RT) ferromagnetism can be attributed to an intrinsic property of doped material sample and not due to formation of any secondary phase. The magnetic results show that Mn is the most effective dopant for producing ferromagnetism in nanoparticles of ZnO.

The Samarco mine tailing disaster: A possible time-bomb for heavy metals contamination?

PubMed

Queiroz, Hermano M; Nóbrega, Gabriel N; Ferreira, Tiago O; Almeida, Leandro S; Romero, Thais B; Santaella, Sandra T; Bernardino, Angelo F; Otero, Xosé L

2018-05-10

In November 2015, the largest socio-environmental disaster in the history of Brazil occurred when approximately 50 million m 3 of mine tailings were released into the Doce River (SE Brazil), during the greatest failure of a tailings dam worldwide. The mine tailings passed through the Doce River basin, reaching the ecologically important estuary 17 days later. On the arrival of the mine wastes to the coastal area, contamination levels in the estuarine soils were measured to determine the baseline level of contamination and to enable an environmental risk assessment. Soil and tailings samples were collected and analyzed to determine the redox potential (Eh), pH, grain size and mineralogical composition, total metal contents (Fe, Mn, Cr, Zn, Ni, Cu, Pb and Co) and organic matter content. The metals were fractionated to elucidate the mechanisms governing the trace metal dynamics. The mine tailings are mostly composed of Fe (mean values for Fe: 45,200 ± 2850; Mn: 433 ± 110; Cr: 63.9 ± 15.1; Zn: 62.4 ± 28.4; Ni: 24.7 ± 10.4; Cu: 21.3 ± 4.6; Pb: 20.2 ± 4.6 and Co: 10.7 ± 4.8 mg kg -1 ), consisting of Fe-oxyhydroxides (goethite, hematite); kaolinite and quartz. The metal contents of the estuarine soils, especially the surface layers, indicate trace metal enrichment caused by the tailings. However, the metal contents were below threshold levels reported in Brazilian environmental legislation. Despite the fact that only a small fraction (<2%) of the metals identified are readily bioavailable (i.e. soluble and exchangeable fraction), trace metals associated with Fe oxyhydroxides contributed between 69.8 and 87.6% of the total contents. Control of the trace metal dynamics by Fe oxyhydroxides can be ephemeral, especially in wetland soils in which the redox conditions oscillate widely. Indeed, the physicochemical conditions (Eh < 100 mV and circumneutral pH) of estuarine soils favor Fe reduction microbial pathways, which will probably increase the trace metal bioavailability and contamination risk. Copyright © 2018 Elsevier B.V. All rights reserved.

Generalized green synthesis and formation mechanism of sponge-like ferrite micro-polyhedra with tunable structure and composition

NASA Astrophysics Data System (ADS)

Tong, Guoxiu; Du, Fangfang; Xiang, Lingjing; Liu, Fangting; Mao, Lulu; Guan, Jianguo

2013-12-01

This paper describes a green versatile glucose-engineered precipitation-sintering process that allows for the selective and mass preparation of spongy porous ferrite (M = Fe, Zn, Co, Ni, Mn, etc.) micro-polyhedra with tunable morphology, texture, and composition. Some kinetic factors, such as the molar ratio of glucose to metal nitrates, reaction temperature, sintering temperature and time, and type of metal nitrates, can be expediently employed to modulate their aspect ratio, shape, size, composition, and textural properties. In this protocol, glucose functions as a reductant, protecting agent, structure-directing agent, and a sacrificial template to guide the assembly of sheet-like nuclei into polyhedral precursors and the formation of spongy porous structures. Owing to larger EM parameters, multiresonant behavior, and dissipative current, spongy porous Fe3O4 polyhedra exhibited enhanced microwave-absorbing properties. This endows them with important potential applications in magnetic devices, catalysis, sorption, photoluminescence, electromagnetic wave absorbing materials, anode materials, and so on. Meanwhile, this general approach can be extended to synthesize other porous sponges with regular geometric configuration because it is simple, inexpensive, environmentally benign, and suitable for extensive production.This paper describes a green versatile glucose-engineered precipitation-sintering process that allows for the selective and mass preparation of spongy porous ferrite (M = Fe, Zn, Co, Ni, Mn, etc.) micro-polyhedra with tunable morphology, texture, and composition. Some kinetic factors, such as the molar ratio of glucose to metal nitrates, reaction temperature, sintering temperature and time, and type of metal nitrates, can be expediently employed to modulate their aspect ratio, shape, size, composition, and textural properties. In this protocol, glucose functions as a reductant, protecting agent, structure-directing agent, and a sacrificial template to guide the assembly of sheet-like nuclei into polyhedral precursors and the formation of spongy porous structures. Owing to larger EM parameters, multiresonant behavior, and dissipative current, spongy porous Fe3O4 polyhedra exhibited enhanced microwave-absorbing properties. This endows them with important potential applications in magnetic devices, catalysis, sorption, photoluminescence, electromagnetic wave absorbing materials, anode materials, and so on. Meanwhile, this general approach can be extended to synthesize other porous sponges with regular geometric configuration because it is simple, inexpensive, environmentally benign, and suitable for extensive production. Electronic supplementary information (ESI) available: Nitrogen adsorption-desorption isotherms, the corresponding pore size distribution curves, TG-DSC curves, XRD pattern, and IR spectra for the precursors; XRD patterns of the samples obtained at various temperatures under N2; XRD pattern, reduction rate, and reactive oxygen species production of ZnO-ZnFe2O4 XRD patterns, SEM images, EDX patterns, nitrogen adsorption-desorption isotherms, and the corresponding pore size distribution curves of CoFe2O4-NiFe2O4-Co1.29Ni1.71O4 polyhedra and NiO-ZnFe2O4. See DOI: 10.1039/c3nr03745b

A probable risk factor of female breast cancer: study on benign and malignant breast tissue samples.

PubMed

Rehman, Sohaila; Husnain, Syed M

2014-01-01

The study reports enhanced Fe, Cu, and Zn contents in breast tissues, a probable risk factor of breast cancer in females. Forty-one formalin-fixed breast tissues were analyzed using atomic absorption spectrophotometry. Twenty malignant, six adjacent to malignant and 15 benign tissues samples were investigated. The malignant tissues samples were of grade 11 and type invasive ductal carcinoma. The quantitative comparison between the elemental levels measured in the two types of specimen (benign and malignant) tissues (removed after surgery) suggests significant elevation of these metals (Fe, Cu, and Zn) in the malignant tissue. The specimens were collected just after mastectomy of women aged 19 to 59 years from the hospitals of Islamabad and Rawalpindi, Pakistan. Most of the patients belong to urban areas of Pakistan. Findings of study depict that these elements have a promising role in the initiation and development of carcinoma as consistent pattern of elevation for Fe, Cu, and Zn was observed. The results showed the excessive accumulation of Fe (229 ± 121 mg/L) in malignant breast tissue samples of patients (p < 0.05) to that in benign tissues samples (49.1 ± 11.4 mg/L). Findings indicated that excess accumulation of iron in malignant tissues can be a risk factor of breast cancer. In order to validate our method of analysis, certified reference material muscle tissue lyophilized (IAEA) MA-M-2/TM was analyzed for metal studied. Determined concentrations were quite in good agreement with certified levels. Asymmetric concentration distribution for Fe, Cu, and Zn was observed in both malignant and benign tissue samples.

Assessment of metal contents in spices and herbs from Saudi Arabia.

PubMed

Seddigi, Z S; Kandhro, G A; Shah, F; Danish, E; Soylak, Mustafa

2016-02-01

In the recent years, there has been a growing interest in monitoring heavy metal contamination of spices/herbs. Spices and herbs are sources of many bioactive compounds that can improve the tastes of food as well as influence digestion and metabolism processes. In the present study, the levels of some essential and toxic elements such as iron (Fe), zinc (Zn), copper (Cu), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), lead (Pb), and cadmium (Cd), present in common spices/herbs that were purchased from the local market in Saudi Arabia, were analyzed by atomic absorption spectroscopy after digestion with nitric acid/hydrogen peroxide mixture. Samples from the following spices/herbs were used: turmeric, cloves, black pepper, red pepper, cumin, legume, cinnamon, abazir, white pepper, ginger, and coriander. The concentration ranges for the studied elements were found as 48.8-231, 4.7-19.4, 2.5-10.5, below detection level (BDL)-1.0, 8.8-490, 1.0-2.6, and BDL-3.7 µg g(-1) for Fe, Zn, Cu, Cr, Mn, Ni, and Pb, respectively, while Cd and Co levels were below the detection limit. Consumers of these spices/herbs would not be exposed to any risk associated with the daily intake of 10 g of spices per day as far as metals Fe, Zn, Cu, Cr, Mn, Ni, and Pb are concerned. © The Author(s) 2013.

Effects of different concentrations of metal ions on degradation of adenosine triphosphate in common carp (Cyprinus carpio) fillets stored at 4°C: An in vivo study.

PubMed

Li, Dapeng; Qin, Na; Zhang, Longteng; Lv, Jian; Li, Qingzheng; Luo, Yongkang

2016-11-15

The impact of different concentrations of Na(+), K(+), Ca(2+), Mg(2+), Fe(2+), and Zn(2+) on the degradation of adenosine triphosphate (ATP) and the influence of these ions on the activity of adenosine monophosphate deaminase (AMP-deaminase) and acid phosphatase (ACP) in common carp fillets (in vivo) during 4°C storage was examined. The content of ATP, inosine monophosphate (IMP), and hypoxanthine (Hx), and the activity of AMP-deaminase and ACP were determined. Results indicated that the effects of different concentrations of six kinds of metal ions on AMP-deaminase and ACP were not the same. Na(+), K(+), Fe(2+), and Zn(2+) enhanced AMP-deaminase activity, which led to the rapid degradation of ATP and to the generation of a large quantity of IMP within a short time. Ca(2+) and Mg(2+) delayed the change in AMP-deaminase and ACP activity in carp and caused a further delay in the degradation of ATP. Fe(2+) and Zn(2+) inhibited ACP activity, which reduced the decomposition of IMP and the formation of Hx. Copyright © 2016 Elsevier Ltd. All rights reserved.

Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

USGS Publications Warehouse

Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

2012-01-01

Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation of ZnS by O 2, an estimated 8% of sulfate-oxygen was derived from O 2, which is enriched in 18O relative to water, thus resulting in a larger apparent ?? 18OSO 4-H 2O value of 9.5???. Based on the data presented we hypothesize that the similar ?? 18OSO 4-H 2O values of ~8??? from all of the aerobic and anaerobic experiments result from a common rate-limiting step that involves oxygen isotopic exchange between a sulfite (SO3-) intermediate and H 2O. Our results indicate that the ??18OSO4 values cannot be used to distinguish biological and abiotic, nor aerobic versus anaerobic, pathways of sphalerite oxidation. However, the ?? 18OSO 4-H 2O values of ~8??? measured here are distinctly higher than ?? 18OSO 4-H 2O values of ~4??? previously reported for pyrite oxidation indicating the influence of sulfide mineralogy on measured ?? 18OSO 4 values. ?? 2011 Elsevier Ltd.

A general approach for MFe2O4 (M = Zn, Co, Ni) nanorods and their high performance as anode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Nana; Xu, Huayun; Chen, Liang; Gu, Xin; Yang, Jian; Qian, Yitai

2014-02-01

MFe2O4 (M = Zn, Co, Ni) nanorods are synthesized by a template-engaged reaction, with β-FeOOH nanorods as precursors which are prepared by a hydrothermal method. The final products are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). The electrochemical properties of the MFe2O4 (M = Zn, Co, Ni) nanorods are tested as the anode materials for lithium ion batteries. The reversible capacities of 800, 625 and 520 mAh g-1 are obtained for CoFe2O4, ZnFe2O4 and NiFe2O4, respectively, at the high current density of 1000 mA g-1 even after 300 cycles. The superior lithium-storage performances of MFe2O4 (M = Zn, Co, Ni) nanorods can be attributed to the one-dimensional (1D) nanostructure, which can shorten the diffusion paths of lithium ions and relax the strain generated during electrochemical cycling. These results indicate that this method is an effective, simple and general way to prepare good electrochemical properties of 1D spinel Fe-based binary transition metal oxides. In addition, the impact of different reaction temperatures on the electrochemical properties of MFe2O4 nanorods is also investigated.

Investigations on structural, vibrational and dielectric properties of nanosized Cu doped Mg-Zn ferrites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yadav, Anand; Department of Physics, MEDICAPS Institute of Science and Technology, Pithampur 453331; Rajpoot, Rambabu

2016-05-23

Transition metal Cu{sup 2+} doped Mg-Zn ferrite [Mg{sub 0.5}Zn{sub 0.5-x}Cu{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 0.5)] were prepared by sol gel auto combustion (SGAC) method to probe the structural, vibrational and electrical properties. X-ray diffraction (XRD) pattern reveals a single-phase cubic spinel structure without the presence of any secondary phase corresponding to other structure. The average particle size of the parent Mg{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} is found to be ~29.8 nm and is found to increase with Cu{sup 2+} doping. Progressive reduction in lattice parameter of Mg{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} has been observed due to difference inmore » ionic radii of cations with improved Cu doping. Spinel cubic structure is further confirmed by Raman spectroscopy. Small shift in Raman modes towards higher wave number has been observed in doped Mg-Zn ferrites. The permittivity and dielectric loss decreases at lower doping and increases at higher order doping of Cu{sup 2+}.« less

Pb, Cu, and Zn distributions at humic acid-coated metal-oxide surfaces

NASA Astrophysics Data System (ADS)

Wang, Yingge; Michel, F. Marc; Choi, Yongseong; Eng, Peter J.; Levard, Clement; Siebner, Hagar; Gu, Baohua; Bargar, John R.; Brown, Gordon E.

2016-09-01

Mineral surfaces are often coated by natural organic matter (NOM), which has a major influence on metal-ion sorption and sequestration because of the abundance of binding sites in such coatings and the changes they cause in local nanoscale environments. The effects of NOM coatings on mineral surfaces are, however, still poorly understood at the molecular level due to the complexity of these systems. In this study, we have applied long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy to measure the partitioning of naturally present Cu(II) (0.0226%), Zn(II) (0.009%), and Pb(II) (∼0.0004%) between Elliott Soil Humic Acid (ESHA) coatings and three model single-crystal metal-oxide substrates: α-Al2O3 (0 0 0 1), α-Al2O3 (1 -1 0 2), and α-Fe2O3 (0 0 0 1). The competitive sorption effects among these metal ions for binding sites in the ESHA coatings and on the metal-oxide surfaces were investigated as a function of reaction time, calcium content, and solution pH. Pb(II) ions present in the ESHA coatings were found to redistribute to reactive α-Al2O3 (1 -1 0 2) and α-Fe2O3 (0 0 0 1) surfaces after 3 h of reaction (pH = 6.0, [Ca(II)] = 2 mM). Pb(II) partitioning onto these reactive metal-oxide surfaces increased with increasing reaction time (up to 7 d). In addition, the partitioning of Cu(II) and Zn(II) from the ESHA coating to the α-Fe2O3 (0 0 0 1) substrate increased slightly with reaction time (2.4% and 3.7% for Cu(II) and Zn(II), respectively, after 3 h and 6.4% and 7.7% for Cu(II) and Zn(II), respectively, after 72 h of reaction time). However, no changes in the partitioning of Cu(II) and Zn(II) onto the α-Al2O3 (1 -1 0 2) surface were observed with increasing reaction time, suggesting that these ions strongly complex with functional groups in the ESHA coatings. Similar results were obtained for Cu(II) and Zn(II) on the ESHA-coated α-Al2O3 (1 -1 0 2) surfaces in samples without the addition of calcium. However, the amounts of Pb(II) mobilized from the ESHA coatings onto the α-Al2O3 (1 -1 0 2) surfaces increased from 40% (no added Ca) to 58% (with 2 mM Ca) after 72 h of reaction time, possibly due to displacement of Pb(II) by Ca(II) from binding sites in the ESHA coatings. In contrast, Pb(II), Cu(II), and Zn(II) present in the ESHA coatings were found to be unreactive with the α-Al2O3 (0 0 0 1) surface. The observed reactivities of the three ESHA-coated metal-oxide surfaces with respect to metal-ion sorption are consistent with the trend observed for the uncoated metal-oxide surfaces: α-Fe2O3 (0 0 0 1) > α-Al2O3 (1 -1 0 2) > α-Al2O3 (0 0 0 1). In addition, Pb(II) partitioning onto α-Al2O3 (1 -1 0 2) surfaces increased with increasing pH from 4.0 to 9.0 as a result of the increasingly negative surface charge. These results show that intrinsic properties (nature of binding sites, binding affinities, and surface charge) of the ESHA coatings and metal-oxide surfaces, as well as external parameters such as pH and competing ions, are key factors governing the distribution and speciation of metal ions at complex NOM/mineral interfaces.

Heavy metals in soils of cocoa plantation (Theobroma cacao L.)

USDA-ARS?s Scientific Manuscript database

Cocoa has experienced significant growth in recent years in Peru and the presence of heavy metals in the soils of these plantations is a potential problem for the export of this product. Contents of heavy metals (Cd, Ni, Pb, Fe, Cu, Zn, Mn) in soils from 19 plantations that have been in production f...

Speciations of trace metals in the Danube alluvial sediments within an oil refinery.

PubMed

Relić, Dubravka; Dordević, Dragana; Popović, Aleksandar; Blagojević, Tamara

2005-07-01

A sequential extraction procedure was applied to identify forms of Ni, Zn, Pb and Cu with Fe- and Mn-oxides associated in alluvial sediments of the River Danube within Pancevo Oil Refinery (Serbia). The five steps of the sequential extraction procedure partitioned metals into: CH(3)COONH(4) extractable (S1); NH(2)OH.HCl carbonate extractable and easily reducible (S2); (NH(4))(2)C(2)O(2)/H(2)C(2)O(2) moderately reducible (S3); H(2)O(2)-HNO(3) organic extractable (S4); and HCl acid soluble residue (S5). Extracted concentrations of trace metals, analyzed after all five steps, were found to be (mg kg(-1)) for Mn: 656, Fe: 26734, Ni: 32.3, Zn: 72.8, Pb: 13.4 and Cu: 27.0. Most of the elements were found in acid soluble residue, characterizing stable compounds in sediments. Non-residual fractions of trace metals (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were used to understand and visualize the associations between the non-residual fractions of trace metals and certain forms, more or less crystalline of Fe- and Mn-oxides within the analyzed sediments, since Fe- and Mn-oxides play an important role in trace metal sorption within aquatic systems, especially within the Danube alluvium where the fluctuations of groundwater are very frequent and the level of groundwater could come close to surface.

Chromate reduction and heavy metal fixation in soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwitzgebel, K.

In situ reduction of chromates and the fixation of the metals Cr, Pb, Zn, Cu, Cd and Ni in soil was investigated using Fe II and soluble silica. Fe II fulfills two functions. It reduces chromates (CrVI) at soil pH to CrIII and the reaction products, Fe(OH)[sub 3] and Cr(OH)[sub 3], coprecipitate/adsorb heavy metals. In the absence of CrVI iron is added as FeIII. Destabilized silica also fulfills two functions. It reacts with the metal and metal hydroxides and reduces the soil permeability. The leaching rate (mg/m[sup 2]s) of a metal is the product of leachate flow rate ([ell]/M[sup 2]s)more » and the leachate concentration (mg/[ell]). The leachate flow rate is directly proportional to the hydraulic coefficient (Darcy's Law). Treatment with destabilized silica reduces the hydraulic coefficient of virgin soil (K[sub h] = 10[sup [minus]2]...10[sup [minus]4]) to K[sub h]=10[sup [minus]7] (cm/s) resulting in a flow rate reduction of 3--5 orders of magnitude. Iron plus silica treatment results in a leachate concentration reduction of up to 2 orders of magnitude (Cr:95--99%;Pb:99%;Zn 95--99%; Cd:93--99%; Ni:75--94%). Combined effect of flow rate reduction and leachate concentration reduction results in a potential leaching rate reduction of five to seven orders of magnitude. Iron-silica treatment may be developed into an efficient containment technology, provided the silica gel integrity does not change with time.« less

Chromate reduction and heavy metal fixation in soil. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwitzgebel, K.

In situ reduction of chromates and the fixation of the metals Cr, Pb, Zn, Cu, Cd and Ni in soil was investigated using Fe II and soluble silica. Fe II fulfills two functions. It reduces chromates (CrVI) at soil pH to CrIII and the reaction products, Fe(OH){sub 3} and Cr(OH){sub 3}, coprecipitate/adsorb heavy metals. In the absence of CrVI iron is added as FeIII. Destabilized silica also fulfills two functions. It reacts with the metal and metal hydroxides and reduces the soil permeability. The leaching rate (mg/m{sup 2}s) of a metal is the product of leachate flow rate ({ell}/M{sup 2}s)more » and the leachate concentration (mg/{ell}). The leachate flow rate is directly proportional to the hydraulic coefficient (Darcy`s Law). Treatment with destabilized silica reduces the hydraulic coefficient of virgin soil (K{sub h} = 10{sup {minus}2}...10{sup {minus}4}) to K{sub h}=10{sup {minus}7} (cm/s) resulting in a flow rate reduction of 3--5 orders of magnitude. Iron plus silica treatment results in a leachate concentration reduction of up to 2 orders of magnitude (Cr:95--99%;Pb:99%;Zn 95--99%; Cd:93--99%; Ni:75--94%). Combined effect of flow rate reduction and leachate concentration reduction results in a potential leaching rate reduction of five to seven orders of magnitude. Iron-silica treatment may be developed into an efficient containment technology, provided the silica gel integrity does not change with time.« less

Characterization of trace metal removal products in vertical flow bioreactor substrates at the Mayer Ranch Passive Treatment System in the Tar Creek Superfund Site.

PubMed

LaBar, Julie A; Nairn, Robert W

2018-05-01

A passive treatment system (PTS), including two parallel vertical flow bioreactors (VFBR), was constructed in 2008 for the treatment of unabated net-alkaline ferruginous mine drainage in the Tar Creek Superfund Site in northeastern Oklahoma. Water quality data collected since the PTS began operation indicate significant removal of trace metals in the VFBR. Results of a sequential extraction procedure (SEP) performed on substrate samples showed that the majority of Cd, Co, Fe, Ni, Pb, and Zn were retained in the refractory organic/sulfide fraction. Subsequent acid volatile sulfide/simultaneously extracted metals (AVS/SEM) analyses confirmed the retention of Cd, Fe, Pb, and Zn as sulfides, but Co and Ni results were less certain. The majority of trace metals were retained as insoluble products in the VFBR, while up to 20% of most of the trace metals were retained in soluble, bioavailable fractions. Nearly 70% of Mn was retained in the soluble and bioavailable exchangeable, carbonate, and labile organic fractions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Metal speciation in agricultural soils adjacent to the Irankuh Pb-Zn mining area, central Iran

NASA Astrophysics Data System (ADS)

Mokhtari, Ahmad Reza; Roshani Rodsari, Parisa; Cohen, David R.; Emami, Adel; Dehghanzadeh Bafghi, Ali Akbar; Khodaian Ghegeni, Ziba

2015-01-01

Mining activities are a significant potential source of metal contamination of soils in surrounding areas, with particular concern for metals dispersed into agricultural area in forms that are bioavailable and which may affect human health. Soils in agricultural land adjacent to Pb-Zn mining operations in the southern part of the Irankuh Mountains contain elevated concentrations for a range of metals associated with the mineralization (including Pb, Zn and As). Total and partial geochemical extraction data from a suite of 137 soil samples is used to establish mineralogical controls on ore-related trace elements and help differentiate spatial patterns that can be related to the effects of mining on the agricultural land soils from general geological and environmental controls. Whereas the patterns for Pb, Zn and As are spatially related to the mining operations they display little correlation with the distribution of secondary Fe + Mn oxyhydroxides or carbonates, suggesting dispersion as dust and in forms with limited bioavailability.

Effects of iron(III)chelates on the solubility of heavy metals in calcareous soils.

PubMed

Ylivainio, Kari

2010-10-01

In this study I evaluated the effects of complexing agents on the solubility of heavy metals in an incubation experiment up to 56 days when complexing agents were applied as Fe-chelates (Fe-EDDS(S,S), Fe-EDDS(mix), Fe-EDTA and Fe-EDDHA) on calcareous soils at a level sufficient to correct Fe chlorosis (0.1 mmol kg(-1)). Of these ligands, EDDHA was the most efficient in keeping Fe in water-soluble form, and EDDS increased the solubility of Cu and Zn most, and only EDTA increased the solubility of Cd and Pb. EDTA increased the solubility of Ni steadily during the incubation period, equalling about 5-8% of the added EDTA concentration. [S,S]-EDDS was biodegraded within 56 days, whereas EDDS(mix) was less biodegradable. Ni-chelates were the most recalcitrant against biodegradation. The study shows that even a moderate input of chelates to soil increases the solubility of toxic heavy metals and their risk of leaching. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Spatial distribution of arsenic and heavy metals in willow roots from a contaminated floodplain soil measured by X-ray fluorescence spectroscopy.

PubMed

Zimmer, Dana; Kruse, Jens; Baum, Christel; Borca, Camelia; Laue, Michael; Hause, Gerd; Meissner, Ralph; Leinweber, Peter

2011-09-01

Under changing redox conditions some plants create plaques at their root surface, which may affect the mobility and uptake of As and heavy metals but it is unknown to what extent this also holds true for willows in contaminated floodplain soils. Therefore, willow roots were sampled from a phytoremediation trial in the contaminated floodplain of the river Elbe (Germany), cryofixed, freeze-dried, and cross sections were mapped for the distribution of As, Ca, Cu, Fe, K, Mn, Ni, S and Zn by synchrotron based X-ray fluorescence spectroscopy. The elements Ca, Cu, Ni, S and Zn were concentrated in the aerenchymatic tissue, and not associated with Fe and Mn. Mixed Fe-Mn plaques covered the surface of the willow roots and As was accumulated in these plaques. The observed association pattern between As and Fe was explained by the different sorption/desorption properties of As(III) and As(V). The Cu and Zn intensities were not associated with the intensity of Fe in the plaque, which seems to be a willow-specific difference compared to other wetland plants. These results suggested that willows are especially suited to stabilize low-phytoextractable elements like Cu and As in their roots and rhizosphere. Thus, short rotation coppicing of willows may be a practical approach to mitigate the adverse effects of floodplain soil contamination. Copyright © 2011 Elsevier B.V. All rights reserved.

Metal discharges by Sinaloa Rivers to the coastal zone of NW Mexico.

PubMed

Frías-Espericueta, M G; Mejía-Cruz, R; Osuna López, I; Muy-Rangel, M D; Rubio-Carrasco, W; Aguilar-Juárez, M; Voltolina, D

2014-02-01

The aim of this work was to survey the discharges of dissolved and particulate Cd, Cu, Fe, Mn, Pb and Zn of the eight main rivers of Sinaloa State to the Mexican coastal environment. Zn was the most abundant dissolved metal and Fe was the most abundant particulate (8.02-16.90 and 51.8-1,140.3 μg/L, respectively). Only particulate Mn had significantly (p = 0.028) higher values in summer-fall (rainy season), whereas the significantly (p = 0.036) higher values of dissolved Zn were observed in winter and spring. The highest annual total discharges to Sinaloa coastal waters were those of the rivers San Lorenzo and Piaxtla (>2 × 10(3) m.t.) and the lowest those of rivers Baluarte and El Fuerte (349 and 119 m.t., respectively). Pb concentrations may become of concern, because they are higher than the value recommended for the welfare of aquatic communities of natural waters.

NiFe (Oxy) Hydroxides Derived from NiFe Disulfides as an Efficient Oxygen Evolution Catalyst for Rechargeable Zn-Air Batteries: The Effect of Surface S Residues.

PubMed

Wang, Tanyuan; Nam, Gyutae; Jin, Yue; Wang, Xingyu; Ren, Pengju; Kim, Min Gyu; Liang, Jiashun; Wen, Xiaodong; Jang, Haeseong; Han, Jiantao; Huang, Yunhui; Li, Qing; Cho, Jaephil

2018-05-21

A facile H 2 O 2 oxidation treatment to tune the properties of metal disulfides for oxygen evolution reaction (OER) activity enhancement is introduced. With this method, the degree of oxidation can be readily controlled and the effect of surface S residues in the resulted metal (oxy)hydroxides for the OER is revealed for the first time. The developed NiFe (oxy)hydroxide catalyst with residual S demonstrates an extraordinarily low OER overpotential of 190 mV at the current density of 10 mA cm -2 after coupling with carbon nanotubes, and outstanding performance in Zn-air battery tests. Theoretical calculation suggests that the surface S residues can significantly reduce the adsorption free energy difference between O* and OH* intermediates on the Fe sites, which should account for the high OER activity of NiFe (oxy)hydroxide catalysts. This work provides significant insight regarding the effect of surface heteroatom residues in OER electrocatalysis and offers a new strategy to design high-performance and cost-efficient OER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, structural and magnetic behavior studies of Zn-Al substituted cobalt ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Zare, Samad; Ati, Ali A.; Dabagh, Shadab; Rosnan, R. M.; Othaman, Zulkafli

2015-06-01

A series of nano-sized Zn-Al substituted cobalt ferrite Co(1-x)Zn(x)Fe2-xAlxO4 with 0.0 ⩽ x ⩽ 1.0 have been synthesized by chemical co-precipitation technique. The XRD spectra revealed the single phase spinel structure of Co(1-x)Zn(x)Fe2-xAlxO4 with average size of nanoparticles are estimated to be 17-30 nm. These are small enough to achieve the suitable signal to noise ratio, which is important in the high-density recording media. The FTIR spectra show the characteristic of two strong absorption bands at 560-600 cm-1 corresponds to the intrinsic stretching vibrations of the metal at the tetrahedral site and lowest band is observed at 370-410 cm-1 corresponds to octahedral site. The crystalline structures of nanoparticles composite were characterized by Field Emission Scanning Electron Microscopy (FE-SEM). The magnetic properties such as saturation magnetization, remanence magnetization, and coercivity were calculated from the hysteresis loops. Saturation magnetization were found to increase up to x = 0.4 while remanence magnetization and coercivity continuously decrease with increasing Zn-Al concentration. The stability in coercivity while increase in saturation magnetization confirms that the Co0.6Zn0.4Fe1.6Al0.4O4 ferrite sample is suitable for applications in high-density recording media.

Electroplating wastewater treatment by the combined electrochemical and ozonation methods.

PubMed

Orescanin, Visnja; Kollar, Robert; Mikelic, Ivanka Lovrencic; Nad, Karlo

2013-01-01

This article presents a pilot-plant study of the electroplating wastewater treatment by the processes of electroreduction with iron electrode plates, and electrocoagulation/ozonation with aluminum electrode set, followed by the process of ozonation. The initial effluent was found to be highly enriched in heavy metals and to possess the elevated levels of organic contaminants. The values of Cr(VI), Fe, Ni, Cu, Zn, Pb, TOC, and COD exceeded the upper permissible limits of 63, 220.2, 1.1, 7, 131.3, 1.7, 12.3, and 11.4 times, respectively. The heavy metal removal was forced either by the coagulation/flocculation using Fe(II), Fe(III), and Al(III) ions released into the treated solution by the electrochemical corrosion of the sacrificial iron and aluminum electrodes, or the precipitation of the metal hydroxides as well as co-precipitation with iron and aluminum hydroxides. The principle organic matter destruction mechanisms were ozone oxidation and the indirect oxidation with chlorine/hypochlorite formed by the anodic oxidation of chloride already present in the wastewater. Following the combined treatment, the removal efficiencies of Cr(VI), Fe, Ni, Cu, Zn, Pb, TOC, and COD were 99.94%, 100.00%, 95.86%, 98.66%, 99.97%, 96.81%, 93.24%, and 93.43%, respectively, thus complying with the regulated values.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phumying, Santi; Labuayai, Sarawuth; Swatsitang, Ekaphan

Graphical abstract: This figure shows the specific magnetization curves of the as-prepared MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders obtained from room temperature VSM measurement. These curves are typical for a soft magnetic material and indicate hysteresis ferromagnetism in the field ranges of ±500 Oe, ±1000 Oe, and ±2000 Oe for the CoFe{sub 2}O{sub 4}, MgFe{sub 2}O{sub 4} and MnFe{sub 2}O{sub 4} respectively, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} show a superparamagnetic behavior. Highlights: ► Nanocrystalline MFe{sub 2}O{sub 4} powders were synthesized by a novel hydrothermal method. ► Metal acetylacetonates andmore » aloe vera plant-extracted solution are used. ► This biosynthetic route is very simple and provides high-yield oxide nanomaterials. ► XRD and TEM results indicate that the prepared samples have only spinel structure. ► The maximum M{sub s} of 68.9 emu/g at 10 kOe were observed for the samples of MnFe{sub 2}O{sub 4}. - Abstract: Nanocrystalline spinel ferrite MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders were synthesized by a novel hydrothermal method using Fe(acac){sub 3}, M(acac){sub 3} (M = Ni, Co, Mn, Mg, Zn) and aloe vera plant extracted solution. The X-ray diffraction and selected-area electron diffraction results indicate that the synthesized nanocrystalline have only spinel structure without the presence of other phase impurities. The crystal structure and morphology of the spinel ferrite powders, as revealed by TEM, show that the NiFe{sub 2}O{sub 4} and CoFe{sub 2}O{sub 4} samples contain nanoparticles, whereas the MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples consist of many nanoplatelets and nanoparticles. Interestingly, the ZnFe{sub 2}O{sub 4} sample contains plate-like structure of networked nanocrystalline particles. Room temperature magnetization results show a ferromagnetic behavior of the CoFe{sub 2}O{sub 4}, MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} exhibit a superparamagnetic behavior.« less

Silicic Acid and Beer Consumption Reverses the Metal Imbalance and the Prooxidant Status Induced by Aluminum Nitrate in Mouse Brain.

PubMed

González-Muñoz, María José; Garcimartán, Alba; Meseguer, Isabel; Mateos-Vega, Carmen José; Orellana, José María; Peña-Fernández, Antonio; Benedí, Juana; Sánchez-Muniz, Francisco J

2017-01-01

Emerging evidence suggests that by affecting mineral balance, aluminum (Al) may enhance some events associated with neurodegenerative diseases. To examine the effect of Al(NO3)3 exposure on brain Al, cooper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), silicon (Si), and zinc (Zn) levels, and the metal-change implication in brain oxidant and inflammatory status. Four groups of six-week-old male NMRI mice were treated for three months: i) controls, administrated with deionized water; ii) Al, which received Al(NO3)3; iii) Al+silicic acid, which were given Al(NO3)3 plus silicic acid; and iv) Al+beer, which received Al(NO3)3 plus beer. Brain Al and TBARS levels and TNFα and GPx expressions increased, while Cu, Mn, and Zn levels, and catalase and CuZn-SOD expression decreased (at least, p < 0.05) in Al versus control animals. Al, Si, and TBARS levels and TNFα expression decreased (p < 0.05) in Al+silicic acid and Al+beer specimens while Cu, Mn, and Zn levels and antioxidant expression increased versus the Al group. Brain Al levels correlated negatively with those of Cu, Fe, Mn, and Zn, and catalase, CuZn-SOD, and GPx enzyme expressions but positively with Si and TBARS levels and TNFα expression. Two components of the principal component analysis (PCA) explained 71.2% of total data variance (p < 0.001). PCA connected the pro-oxidant markers with brain Al content, while brain Zn and Cu levels were closer to antioxidant enzyme expression. Administration of Al(NO3)3 induced metal imbalance, inflammation, and antioxidant status impairment in the brain. Those effects were blocked to a significant extent by silicic acid and beer administration.

Bioaccumulation of trace metals in octocorals depends on age and tissue compartmentalization

PubMed Central

Hwang, Jiang-Shiou; Huang, Ke Li; Huang, Mu-Yeh; Liu, Xue-Jun; Khim, Jong Seong; Wong, Chong Kim

2018-01-01

Trace metal dynamics have not been studied with respect to growth increments in octocorals. It is particularly unknown whether ontogenetic compartmentalization of trace metal accumulation is species-specific. We studied here for the first time the intracolonial distribution and concentrations of 18 trace metals in the octocorals Subergorgia suberosa, Echinogorgia complexa and E. reticulata that were retrieved from the northern coast of Taiwan. Levels of trace metals were considerably elevated in corals collected at these particular coral habitats as a result of diverse anthropogenic inputs. There was a significant difference in the concentration of metals among octocorals except for Sn. Both species of Echinogorgia contained significantly higher concentrations of Cu, Zn and Al than Subergorgia suberosa. We used for the first time exponential growth curves that describe an age-specific relationship of octocoral trace metal concentrations of Cu, Zn, Cd, Cr and Pb where the distance from the grip point was reflecting younger age as linear regressions. The larger colony (C7) had a lower accumulation rate constant than the smaller one (C6) for Cu, Zn, Cd, Cr and Pb, while other trace metals showed an opposite trend. The Cu concentration declined exponentially from the grip point, whereas the concentrations of Zn, Cd, Cr and Pb increased exponentially. In S. suberosa and E. reticulata, Zn occurred primarily in coenosarc tissues and Zn concentrations increased with distance from the grip point in both skeletal and coenosarc tissues. Metals which appeared at high concentrations (e.g. Ca, Zn and Fe) generally tended to accumulate in the outer coenosarc tissues, while metals with low concentrations (e.g. V) tended to accumulate in the soft tissues of the inner skeleton. PMID:29684058

Analysis of Zn, Cd, As, Cu, Pb, and Fe in snails as bioindicators and soil samples near traffic road by ICP-OES.

PubMed

Massadeh, Adnan M; Alomary, Ahmed A; Mir, Sayeeda; Momani, Fouad A; Haddad, Hazem I; Hadad, Yazen A

2016-07-01

Snails are used as biological indicators of the environment pollution for heavy metals. Living snail samples were collected from different sites at the city of Irbid-Jordan and classified according to their morphological features including Helix pelasga, Eobania vermiculata, Xeropicta derbentina, Oychilus, Xerocrassa seetzenii, Xerocrassa simulata, and Pila. Zn, Cd, As, Cu, Pb, and Fe levels were measured by inductively coupled plasma-optical emission spectroscopy. Results indicated that metal concentrations in all snail shell samples were with an average and range for Zn 22.4 (6.5-105.5) μg g(-1), Cd 7.8 (0.4-48.1) μg g(-1), As 25.9 (0.7-248.5) μg g(-1), Cu 15.1 (1.6-69.0) μg g(-1), Pb 0.4 (0.2-1.7) μg g(-1), and Fe 119.6 (14.0-1102.0) μg g(-1), whereas, in soil samples, the average and range for Zn 204.0 (12.0-709.0) μg g(-1), Cd 5.7 (0.2-39.5) μg g(-1), As 3.2 (1.8-5.2) μg g(-1), Cu 22.1 (2.3-77.4) μg g(-1), Pb 0.2 (0.1-0.3) μg g(-1), and Fe 242.4 (25.0-680.0) μg g(-1).

Assessment of total soil and plant trace elements in rice-based production systems in NE Italy

NASA Astrophysics Data System (ADS)

Bini, Claudio; Nadimi-Goki, Mandana; Kato, Yoichi; Vianello, Gilmo; Vittori, Livia; Wahsha, Mohammad; Spiandorello, Massimo

2014-05-01

Macro- and micronutrients concentrations, and PTEs contents in soils and plants (rice) from the rice district in the Venetian territory (NE Italy) have been determined by ICP-MS spectrometry, with the following aims: - to determine the background levels of macro- and microelements in the study area; - to assess possible contamination of soils and plants; - to calculate the Translocation Factor (TF) of metals from soil to plant, and the possible hazard for human health. Four rice plots with different rotation systems were investigated from seedling time to harvesting; sampling of soils (0-30cm) and plants was carried out 4 times during growing season (three replicates). Rice plants were separated into roots, stems, leaves and grains, and then oven-dried. Chemical and physical analyses were carried out at the Soil Science Lab of the University of Bologna and Venice, respectively. The results obtained point to a land with moderate soil contamination by trace elements (namely Li, Sn, Tl, Sr, Ti, Fe). Heavy metal (Sb, As, Be, Cd, Co, Cr, Ni, Pb, Cu, V, Zn ) concentrations in soils are below the threshold indicated by the Italian legislation (DM 152/2006). Cd, Sn, and Ti contents in soils are positively correlated with soil pH, while As, Fe, Li, Ti, Tl and Zn are negatively correlated with organic matter content. With the exception of Strontium, soil metal contents are always correlated between variable couples. HMs in plants vary according to the sampling season, texture and moisture, and soil pH. Most non-essential trace elements are accumulated in rice roots and, only in cases of essential micronutrients, in leaves. Therefore, rice can be assumed as an accumulator plant of As, Pb, Cr, Ba, and Ti, whereas it is as an indicator plant for Cu, Fe, Ni, Mn and Zn. The results of multiple linear regression analysis showed that soil pH has a larger effect on Ba, Cr, Cu, Fe, Mn, Ni, Ti and Zn concentrations in grain than other soil parameters. The average translocation of metals from soil to root was found to be >1, irrespective of the essential/not essential function; conversely, only essential elements ((Cu, Fe, Mn, Zn) are translocated rather easily from roots to leaves (TF ≤1) via phloem (TF< <1), and very little translocated to grains (TF< <1). Therefore, it is suggested that rice could be useful in contaminated-sites restoration projects by the phytostabilization technique. Moreover, there is very limited hazard for human population consuming rice crops. Key Words: Macro- and micronutrients concentrations, heavy metals, trace elements, rice plant, Italy, accumulator plant, indicator plant * Corresponding author. Tel.: +39 3891356251 E-mail address: mandy.nadimi@gmail.com

Studies on the growth and flowering of a short-day plant, Wolffia microscopica : II. Role of metal ions and chelates.

PubMed

Seth, P N; Venkataraman, R; Maheshwari, S C

1970-12-01

As found earlier, supply of EDTA was obligatory for both flowering and satisfactory vegetative growth in Wolffia microscopica. It is now shown that the metal affecting growth and flowering is most probably iron. Omission of Fe but not of Cu, Zn, Mn and B from the medium markedly affects vegetative growth. There exists also a strong interaction between EDTA and Fe, one being largely inactive in the absence of the other. When Fe-EDDHA is substituted for Fe-citrate and EDTA in the medium, no great effect is seen in vegetative growth, but flowering takes place even under continuous light. Studies with (59)Fe show that, in the medium containing Fe-EDDHA, Fe uptake is stimulated several-fold; this is apparently associated with the flowering condition.

THE EFFECTS OF ELEVATED METALS ON BENTHIC COMMUNITY METABOLISM IN A ROCKY MOUNTAIN STREAM

EPA Science Inventory

The effects of elevated metals (dissolved Zn, Mn and/or Fe) in a Rocky Mountain stream were assessed using measures of primary productivity, community respiration and water-column toxicity. Primary productivity was measured as rates of O2 evolution from natural substrates incubat...

Metal analysis of cotton

USDA-ARS?s Scientific Manuscript database

Seven varieties of cotton were investigated for 8 metal ions (K, Na, Mg, Ca, Fe, Cu, Zn, and Mn) using Inductively Coupled Plasma-Optical Emission Spectroscopy. All of the varieties were grown at the same location. Half of the samples were dry (rain fed only) and the other were well-watered (irrigat...

Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) centers.

PubMed

Shim, Yurina; Young, Ryan M; Douvalis, Alexios P; Dyar, Scott M; Yuhas, Benjamin D; Bakas, Thomas; Wasielewski, Michael R; Kanatzidis, Mercouri G

2014-09-24

Naturally abundant enzymes often feature active sites comprising transition metal cluster units that catalyze chemical processes and reduce small molecules as well as protons. We introduce a family of new chalcogenide aerogels (chalcogels), aiming to model the function of active sites and the structural features of a larger protective framework. New metal incorporated iron sulfur tin sulfide chalcogels referred to as ternary chalcogels and specifically the chalcogels M-ITS-cg3, fully integrate biological redox-active Fe4S4 clusters into a semiconducting porous framework by bridging them with Sn4S10 linking units. In the M-ITS-cg3 system we can tailor the electro- and photocatalytic properties of chalcogels through the control of spatial distance of redox-active Fe4S4 centers using additional linking metal ions, M(2+) (Pt, Zn, Co, Ni, Sn). The presence of a third metal does not change the structural properties of the biomimetic chalcogels but modifies and even enhances their functional performance. M-ITS-cg3s exhibit electrocatalytic activity in proton reduction that arises from the Fe4S4 clusters but is tuned inductively by M(2+). The metal ions alter the reduction potential of Fe4S4 in a favorable manner for photochemical hydrogen production. The Pt incorporated ITS-cg3 shows the greatest improvement in the overall hydrogen yield compared to the binary ITS-cg3. The ability to manipulate the properties of biomimetic chalcogels through synthetic control of the composition, while retaining both structural and functional properties, illustrates the chalcogels' flexibility and potential in carrying out useful electrochemical and photochemical reactions.

The effects of copper, manganese and zinc on plant growth and elemental accumulation in the manganese-hyperaccumulator Phytolacca americana.

PubMed

Zhao, Huijun; Wu, Liangqi; Chai, Tuanyao; Zhang, Yuxiu; Tan, Jinjuan; Ma, Shengwen

2012-09-01

Synchrotron radiation X-ray fluorescence (SRXRF) and inductively coupled plasma mass spectrometry were used to estimate major, minor and trace elements in Cu-, Zn- and Mn-treated Phytolacca americana. The effects of the addition of Cu, Zn and Mn on morphological parameters, such as root length, shoot height, and fresh and dry weights of shoots and roots, were also examined. In addition, the activities of superoxide dismutase (SOD), ascorbate peroxidase (APX), guaiacol peroxidases (GPX) and catalase (CAT) and the expression of Fe-SOD, Cu/Zn-SOD, metallothionein-2 and glutathione S-transferase (GST) exposed to the highest amounts of Cu, Zn or Mn were detected. Our results confirmed the following: (1) Zn supplementation leads to chlorosis, disturbed elemental homeostasis and decreased concentrations of micro- and macroelements such as Fe, Mg, Mn, Ca and K. Cu competed with Fe, Mn and Zn uptake in plants supplemented with 25 μM Cu. However, no antagonistic interactions took place between Cu, Zn, Mn and Fe uptake in plants supplemented with 100 μM Cu. Mn supplementation at various concentrations had no negative effects on elemental deficits. Mn was co-located with high concentrations of Fe and Zn in mature leaves and the concentrations of macro elements were unchanged. (2) P. americana supplemented with increased concentrations of Zn and Cu exhibited lower biomass production and reduced plant growth. (3) When plants were supplemented with the highest Zn and Cu concentrations, symptoms of toxicity corresponded to decreased SOD or CAT activities and increased APX and GPX activities. However, Mn tolerance corresponded to increased SOD and CAT activities and decreased POD and APX activities. Our study revealed that heavy metals partially exert toxicity by disturbing the nutrient balance and modifying enzyme activities that induce damage in plants. However, P. americana has evolved hyper accumulating mechanisms to maintain elemental balance and redox homeostasis under excess Mn. Copyright © 2012 Elsevier GmbH. All rights reserved.