scholarly journals Impact of Zn Substitution on Fe(II)-induced Ferrihydrite 2 Transformation Pathways

2021 ◽  
Author(s):  
Jinshu Yan ◽  
Andrew Frierdich ◽  
Jeff Catalano

Iron oxide minerals are ubiquitous in soils, sediments, and aquatic systems and influence the fate and availability of trace metals. Ferrihydrite is a common iron oxide of nanoparticulate size and poor crystallinity, serving as a thermodynamically unstable precursor to more crystalline phases. While aging induces such phase transformations, these are accelerated by the presence of dissolved Fe(II). However, the impact of trace metals on Fe(II)-catalyzed ferrihydrite phase transformations at ambient temperatures and the associated effects on trace metal speciation has seen limited study. In the present work, phase transformations of ferrihydrite that contains the trace metal zinc in its structure were investigated during aging at ambient temperature in the presence of two different Fe(II) concentrations at pH 7. X-ray diffraction reveals that low Fe(II) concentration (0.2 mM) generates hematite plus minor lepidocrocite, whereas high Fe(II) concentration (1.0 mM) promotes the production of a magnetite-lepidocrocite mixture. In both cases, a substantial fraction of ferrihydrite remains after 12 days. In contrast, Zn-free ferrihydrite forms primarily lepidocrocite and goethite in the presence of 0.2 mM Fe(II), with minor hematite and a trace of ferrihydrite remaining. For 1.0 mM Fe(II), magnetite, goethite, and lepidocrocite form when Zn is absent, leaving no residual ferrihydrite. Transformations of Zn-ferrihydrite produce a transient release of zinc to solution, but this is nearly quantitatively removed into the mineral products after 1 hour. Extended X-ray absorption fine structure spectroscopy suggests that zinc partitions into the newly formed phases, with a shift from tetrahedral to a mixture of tetrahedral and octahedral coordination in the 0.2 mM Fe(II) system and taking on a spinel-like local structure in the 1.0 mM Fe(II) reaction products. This work indicates that substituting elements in ferrihydrite may play a key role in promoting the formation of hematite in low temperature systems, such as soils or sediments. In addition, the retention of zinc in the products of ferrihydrite phase transformation shows that trace metal micronutrients and contaminants may not be mobilized under circumneutral conditions despite the formation of more crystalline iron oxides. Furthermore, mass balance requires that the abundance and isotopic composition of iron oxide-associated zinc, and possibly other trace metals, in the rock record may be retained during diagenetic phase transformations of ferrihydrite if catalyzed by dissolved Fe(II).

1993 ◽  
Vol 28 (1) ◽  
pp. 83-110 ◽  
Author(s):  
Richard E. Farrell ◽  
Jae E. Yang ◽  
P. Ming Huang ◽  
Wen K. Liaw

Abstract Porewater samples from the upper Qu’Appelle River basin in Saskatchewan, Canada, were analyzed to obtain metal, inorganic ligand and amino add profiles. These data were used to compute the aqueous speciation of the metals in each porewater using the computer program GEOCHEM-PC. The porewaters were classified as slightly to moderately saline. Metal concentrations reflected both the geology of the drainage basin and the impact of anthropogenic activities. Whereas K and Na were present almost entirely as the free aquo ions, carbonate equilibria dominated the speciation of Ca. Mg and Mn (the predominant metal ligand species were of the type MCO3 (s). MCO30. and MHCO3+). Trace metal concentrations were generally within the ranges reported for non-polluted freshwater systems. Whereas the speciation of the trace metals Cr(III) and Co(II) was dominated by carbonate equilibria, Hg(II)-, Zn(II)- and Fe(II)-speciation was dominated by hydroxy-metal complexes of the type M(OH)+ and M(OH)2°. The speciation of Fe(III) was dominated by Fe(OH)3 (s). In porewaters with high chloride concentrations (> 2 mM), however, significant amounts of Hg(II) were bound as HgCl20 and HgClOH0. The aqueous speciation of Al was dominated by Al(OH)4− and Al2Si2O4(OH)6 (s). Total concentrations of dissolved free amino acids varied from 15.21 to 25.17 umole L−1. The most important metal scavenging amino acids were histidine (due to high stability constants for the metal-histidine complexes) and tryptophan (due to its relatively high concentration in the porewaters. i.e., 5.96 to 7.73 umole L−1). Secondary concentrations of various trace metal-amino add complexes were computed for all the porewaters, but metal-amino acid complexes dominated the speciation of Cu(II) in all the porewaters and Ni(II) in two of the porewaters.


2015 ◽  
Vol 2015 ◽  
pp. 1-13 ◽  
Author(s):  
Zang-Ho Shon ◽  
Ju-Hee Jeong ◽  
Yoo-Keun Kim

The effect of large-scale firework events on urban background trace metal concentrations was investigated using 24 hr data collected over 3 days at three sites in Busan Metropolitan City, Republic of Korea, during the falls (Oct.) of 2011–2013. The firework events increased local background concentrations of trace metals as follows: K (1.72 times), Sr (2.64 times), As (2.86 times), Pb (2.91 times), and Al (5.44 times). The levels of some metals did not always drop to background level one day after the firework event. The contribution of fireworks to trace metal concentration levels (and emissions) for 2011 event was negligible compared to 2012 and 2013 events due to different meteorological conditions (precipitation). In addition, the impact of firework events on the ambient concentration levels of trace metals was likely to be different depending on their chemical speciation. The impact of firework events in Busan on urban air quality (trace metal) was less intense compared to other similar festivals worldwide. The largest emission of trace metals and elements from firework burning was represented by K (128–164 kg), followed by Pb, Cd, Cu, Mg, Ba, As, Al, Ga, Co, and Na.


1989 ◽  
Vol 39 (2) ◽  
pp. 220-223 ◽  
Author(s):  
Tomás Pérez Ruiz ◽  
Manuel Hernández Córdoba ◽  
Roque Ortiz-González

2021 ◽  
Author(s):  
◽  
Annie Graham

<p>Coastal habitats are susceptible to severe contamination due to their exposure to both marine and terrestrial inputs, many of which contain toxic heavy metals. Trace metals in the marine environment can have severe impacts on the health of coastal ecosystems, as even those with essential functions can be toxic at high concentrations, and non-essential elements can cause impairment of biological functions even at low levels.  It is important to understand the chemistry of New Zealand’s marine environment, in order to successfully monitor any changes to the chemical profile of the environment from anthropogenic pollutants. Biological indicators are a useful tool for monitoring ecosystem health, and the impact of human activity on the environment. Crustaceans fulfil all the criteria of being good environmental indicators, as well as having a range of feeding strategies, and being present at multiple trophic levels. The aim of this research was to 1) investigate spatial variation and the effect of urbanisation in trace metal concentration in two native decapod species, Heterozius rotundifrons and Petrolisthes elongatus, which co-occur but feed at different trophic levels; and 2) examine how essential and non-essential trace metals are accumulated into different body tissues of the decapod Jasus edwardsii, a significant cultural and fishery species.  To assess spatial variation and trophic level differences between decapods, baseline data of the concentrations of thirty trace metals was collected and analysed from both species at three sites in the Wellington region. Little variation was found between the sites, despite their differences in proximity to urban development, but significant differences were found between species, with the consumer H. rotundifrons having higher concentrations of most trace metals than the filter feeder P. elongatus.  To assess trace metal accumulation into tissues of J. edwardsii, an experiment was run exposing juveniles to water doped with an elevated copper and neodymium treatment. Copper was preferentially accumulated into the organ tissue, as was expected for an essential element. Neodymium was accumulated differentially into organ and exoskeleton tissue depending on the treatment, with specimens in the elevated treatment taking it up into the shell rather than the organs. A second experiment was also run to investigate whether moulted exoskeletons would passively absorb copper from their environment, which was shown to be the case.  This research aids in understanding the importance of multiple species monitoring, as trace element accumulation was shown to be highly variable depending on species and metals, and contributes valuable geochemical data on native New Zealand species, which have been little studied in this context.</p>


2013 ◽  
Vol 67 (4) ◽  
pp. 817-823 ◽  
Author(s):  
Li Jing ◽  
Li Fadong ◽  
Liu Qiang ◽  
Song Shuai ◽  
Zhao Guangshuai

For this study, 34 water samples were collected along the Wei River and its tributaries. Multivariate statistical analyses were employed to interpret the environmental data and to identify the natural and anthropogenic trace metal inputs to the surface waters of the river. Our results revealed that Zn, Se, B, Ba, Fe, Mn, Mo, Ni and V were all detected in the Wei River. Compared to drinking water guidelines, the primary trace metal pollution components (B, Ni, Zn and Mn) exceeded drinking water standard levels by 47.1, 50.0, 44.1 and 26.5%, respectively. Inter-element relationships and landscape features of trace metals conducted by hierarchical cluster analysis (HCA) identified a uniform source of trace metals for all sampling sites, excluding one site that exhibited anomalous concentrations. Based on the patterns of relative loadings of individual metals calculated by principal component analysis (PCA), the primary trace metal sources were associated with natural/geogenic contributions, agro-chemical processes and discharge from local industrial sources. These results demonstrated the impact of human activities on metal concentrations in the Wei River.


Author(s):  
Renfei Li ◽  
Yuan Zhang ◽  
Hong Yu ◽  
Qiuling Dang ◽  
Hanxia Yu ◽  
...  

Wastewater irrigation is widely practiced and may cause serious environmental problems. However, current knowledge on the effects of long-term irrigation with wastewater from different sources on the biouptake of trace metals (TMs) in the rhizosphere zone by plants in farmlands is limited. Here, we analyzed wheat rhizosphere soil and wheat roots collected from a typical wastewater irrigation area in North China to evaluate the influence of wastewater irrigation from different sources on the bioavailability of trace metals in soils. Results showed that irrigation with tanning and domestic wastewater helped enhance the bioavailability of trace metals in rhizosphere soil by increasing the active organic carbon content, soil redox potential, and catalase activity, thus enhancing the proportion of the potentially bioavailable part of trace metal speciation. Conversely, irrigation with pharmaceutical wastewater can reduce the bioavailability of trace metals in rhizosphere soil by increasing total soil antibiotics and thus decreasing the proportions of bioavailable and potentially bioavailable parts of trace metal speciation. These findings can provide insights into the migration and transformation of trace metal speciation in soil rhizosphere microenvironments under the context of wastewater irrigation.


2021 ◽  
Vol 15 ◽  
Author(s):  
Ada Metaxas

Alzheimer's Disease (AD), a progressive neurodegenerative disease characterized by the buildup of amyloid-beta (Aβ) plaques, is believed to be a disease of trace metal dyshomeostasis. Amyloid-beta is known to bind with high affinity to trace metals copper and zinc. This binding is believed to cause a conformational change in Aβ, transforming Aβ into a configuration more amenable to forming aggregations. Currently, the impact of Aβ-trace metal binding on trace metal homeostasis and the role of trace metals copper and zinc as deleterious or beneficial in AD remain elusive. Given that Alzheimer's Disease is the sixth leading cause of adult death in the U.S., elucidating the molecular interactions that characterize Alzheimer's Disease pathogenesis will allow for better treatment options. To that end, the model organism C. elegans is used in this study. C. elegans, a transparent nematode whose connectome has been fully established, is an amenable model to study AD phenomena using a multi-layered, interconnected approach. Aβ-producing and non-Aβ-producing C. elegans were individually supplemented with copper and zinc. On day 6 and day 9 after synchronization, the percent of worms paralyzed, concentration of copper, and concentration of zinc were measured in both groups of worms. This study demonstrates that dyshomeostasis of trace metals copper or zinc triggers further trace metal dyshomeostasis in Aβ-producing worms, while dyshomeostasis of copper or zinc triggers a return to equilibrium in non-Aβ-producing worms. This supports the characterization of Alzheimer's Disease as a disease of trace metal dyshomeostasis.


2017 ◽  
Vol 32 (2) ◽  
pp. 289-298 ◽  
Author(s):  
Stijn J. M. Van Malderen ◽  
Brecht Laforce ◽  
Thibaut Van Acker ◽  
Laszlo Vincze ◽  
Frank Vanhaecke

In this work, a serial sectioning approach, based on polishing an epoxy-embedded sample, is used to image trace metals in cereal grains in 3D.


Minerals ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 226 ◽  
Author(s):  
Sánchez-España ◽  
Yusta

Manganese oxides are widespread in soils and natural waters, and their capacity to adsorb different trace metals such as Co, Ni, or Zn is well known. In this study, we aimed to compare the extent of trace metal coprecipitation in different Mn oxides formed during Mn(II) oxidation in highly concentrated, metal-rich mine waters. For this purpose, mine water samples collected from the deepest part of several acidic pit lakes in Spain (pH 2.7–4.2), with very high concentration of manganese (358–892 mg/L Mn) and trace metals (e.g., 795–10,394 µg/L Ni, 678–11,081 µg/L Co, 259–624 mg/L Zn), were neutralized to pH 8.0 in the laboratory and later used for Mn(II) oxidation experiments. These waters were subsequently allowed to oxidize at room temperature and pH = 8.5–9.0 over several weeks until Mn(II) was totally oxidized and a dense layer of manganese precipitates had been formed. These solids were characterized by different techniques for investigating the mineral phases formed and the amount of coprecipitated trace metals. All Mn oxides were fine-grained and poorly crystalline. Evidence from X-Ray Diffraction (XRD) and Scanning Electron Microscopy coupled to Energy Dispersive X-Ray Spectroscopy (SEM–EDX) suggests the formation of different manganese oxides with varying oxidation state ranging from Mn(III) (e.g., manganite) and Mn(III/IV) (e.g., birnessite, todorokite) to Mn(IV) (e.g., asbolane). Whole-precipitate analyses by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES), and/or Atomic Absorption Spectrometry (AAS), provided important concentrations of trace metals in birnessite (e.g., up to 1424 ppm Co, 814 ppm Ni, and 2713 ppm Zn), while Co and Ni concentrations at weight percent units were detected in asbolane by SEM-EDX. This trace metal retention capacity is lower than that observed in natural Mn oxides (e.g., birnessite) formed in the water column in a circum-neutral pit lake (pH 7.0–8.0), or in desautelsite obtained in previous neutralization experiments (pH 9.0–10.0). However, given the very high amount of Mn sorbent material formed in the solutions (2.8–4.6 g/L Mn oxide), the formation of these Mn(III/IV) oxides invariably led to the virtually total removal of Co, Ni, and Zn from the aqueous phase. We evaluate these data in the context of mine water pollution treatment and recovery of critical metals.


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