The nature of Cu bonding to natural organic matter
TL;DR: In this paper, the authors used XANES and EXAFS spectroscopy, along with supporting thermodynamic equilibrium calculations and structural and steric considerations, to show evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)2-like ring chelate at 100-300 ppm Cu concentration, and a six-mimbered Cu (malonate)1-2 -like ring Chelate at higher concentration.
About: This article is published in Geochimica et Cosmochimica Acta.The article was published on 2010-05-01. It has received 175 citations till now.
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TL;DR: In this paper, the impact of commercial metal oxide nanoparticles (NPs) on wheat grown in a solid matrix, sand, was investigated using dynamic light scattering and atomic force microscopy (AFM).
Abstract: Metal oxide nanoparticles (NPs) are reported to impact plant growth in hydroponic systems This study describes the impact of commercial CuO (<50 nm) and ZnO (<100 nm) NPs on wheat (Triticum aestivum) grown in a solid matrix, sand The NPs contained both metallic and non-metallic impurities to different extents Dynamic light scattering and atomic force microscopy (AFM) assessments confirmed aggregation of the NPs to submicron sizes AFM showed transformation of ZnO NPs from initial rhomboid shapes in water to elongated rods in the aqueous phase of the sand matrix Solubilization of metals occurred in the sand at similar rates from CuO or ZnO NPs as their bulk equivalents Amendment of the sand with 500 mg Cu and Zn/kg sand from the NPs significantly (p = 005) reduced root growth, but only CuO NPs impaired shoot growth; growth reductions were less with the bulk amendments Dissolved Cu from CuO NPs contributed to their phytotoxicity but Zn release did not account for the changes in plant growth Bioaccumulation of Cu, mainly as CuO and Cu(I)–sulfur complexes, and Zn as Zn-phosphate was detected in the shoots of NP-challenged plants Total Cu and Zn levels in shoot were similar whether NP or bulk materials were used Oxidative stress in the NP-treated plants was evidenced by increased lipid peroxidation and oxidized glutathione in roots and decreased chlorophyll content in shoots; higher peroxidase and catalase activities were present in roots These findings correlate with the NPs causing increased production of reactive oxygen species The accumulation of Cu and Zn from NPs into edible plants has relevance to the food chain
490 citations
01 Jan 2012
TL;DR: In this paper, the impact of metal oxide nanoparticles (NPs) on wheat grown in a solid matrix, sand, was investigated using dynamic light scattering and atomic force microscopy (AFM) assessments.
Abstract: Metal oxide nanoparticles (NPs) are reported to impact plant growth in hydroponic systems. This study describes the impact of commercial CuO (\50 nm) and ZnO (\100 nm) NPs on wheat (Triticum aestivum) grown in a solid matrix, sand. The NPs contained both metallic and non-metallic impurities to different extents. Dynamic light scattering and atomic force microscopy (AFM) assessments confirmed aggre- gation of the NPs to submicron sizes. AFM showed transformation of ZnO NPs from initial rhomboid shapes in water to elongated rods in the aqueous phase of the sand matrix. Solubilization of metals occurred in the sand at similar rates from CuO or ZnO NPs as their bulk equivalents. Amendment of the sand with 500 mg Cu and Zn/kg sand from the NPs significantly (p = 0.05) reduced root growth, but only CuO NPs impaired shoot growth; growth reductions were less with the bulk amendments. Dissolved Cu from CuO NPs contributed to their phytotoxicity but Zn release did not account for the changes in plant growth. Bioaccumula- tion of Cu, mainly as CuO and Cu(I)-sulfur complexes, and Zn as Zn-phosphate was detected in the shoots of NP-challenged plants. Total Cu and Zn levels in shoot were similar whether NP or bulk materials were used. Oxidative stress in the NP-treated plants was evidenced by increased lipid peroxidation and oxidized glutathione in roots and decreased chlorophyll content in shoots; higher peroxidase and catalase activities were present in roots. These findings correlate with the NPs causing increased production of reactive oxygen species. The accumulation of Cu and Zn from NPs into edible plants has relevance to the food chain.
457 citations
Cites background from "The nature of Cu bonding to natural..."
...Previous studies reported radiation-induced reduction of Cu in hydrated samples (Manceau and Matynia 2010; Pokrovsky et al. 2012)....
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...S coordination (Kau et al. 1987; Manceau and Matynia 2010; Pokrovsky et al. 2012)....
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...The latter features resulted from the presence of Cu(I) (Kim et al. 2003; Manceau and Matynia 2010; Pokrovsky et al. 2012)....
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...O coordination (Manceau and Matynia 2010; Pokrovsky et al. 2012) allowed the establishment of Cu(I)–...
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TL;DR: This study provides the first spectroscopic evidence for ternary complex formation between As (V) and Fe(III)-HS complexes, suggesting that this binding mechanism is of fundamental importance for the cycling of oxyanions such as As(V) in organic-rich, oxic soils and sediments.
Abstract: Formation of ternary complexes between arsenic (As) oxyanions and ferric iron (Fe) complexes of humic substances (HS) is often hypothesized to represent a major mechanism for As-HS interactions under oxic conditions. However, direct evidence for this potentially important binding mechanism is still lacking. To investigate the molecular-scale interaction between arsenate, As(V), and HS in the presence of Fe(III), we reacted fulvic and humic acids with Fe(III) (1 wt %) and equilibrated the Fe(III)-HS complexes formed with As(V) at pH 7 (molar Fe/As ∼10). The local (<5 A) coordination environments of As and Fe were subsequently studied by means of X-ray absorption spectroscopy. Our results show that 4.5–12.5 μmol As(V)/g HS (25–70% of total As) was associated with Fe(III). At least 70% of this As pool was bound to Fe(III)-HS complexes via inner-sphere complexation. Results obtained from shell fits of As K-edge extended X-ray absorption fine structure (EXAFS) spectra were consistent with a monodentate binucle...
234 citations
TL;DR: This current work presents in details the interactions of cations and NOM in the environment, the preference of cation for each functional group and the possible competition between cations for binding sites, as well as the possible impacts of the presence of cATIONS, NOM, or their complex on water treatment processes.
152 citations
Cites background from "The nature of Cu bonding to natural..."
...The size-match fit (strain energy), is a function of the bond-length and bond-angle deformation, the torsional strain of the chelate, and van der Waals interactions among non-bonded atoms (Manceau and Matynia, 2010)....
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...The remarkable affinity of Cu2þ towards NOM, compared to other cations, may probably be due to the excellent match in size between the cupric ion and one or several ligands (e.g. oxygen and sulfur) (Kinniburgh et al., 1999; Manceau and Matynia, 2010)....
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TL;DR: This review will aim at discussing the advantages and disadvantages of agronomic practices, such as liming, the use of pesticides, the application of organic matter, biochar and coal fly ashes, the inoculation with bacteria and/or mycorrhizal fungi and the intercropping, in alleviating Cu toxicity symptoms.
119 citations
Cites background from "The nature of Cu bonding to natural..."
...Manceau and Matynia (2010), exploiting XAS spectroscopy along with supporting thermodynamic equilibrium calculations and structural and steric considerations, showed evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)2-like ring chelate at 100e300 ppm Cu concentration, and a six-membered…...
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References
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Book•
01 Jan 1999
TL;DR: Cotton and Wilkinson's Advanced Inorganic Chemistry (AIC) as discussed by the authors is one of the most widely used inorganic chemistry books and has been used for more than a quarter century.
Abstract: For more than a quarter century, Cotton and Wilkinson's Advanced Inorganic Chemistry has been the source that students and professional chemists have turned to for the background needed to understand current research literature in inorganic chemistry and aspects of organometallic chemistry. Like its predecessors, this updated Sixth Edition is organized around the periodic table of elements and provides a systematic treatment of the chemistry of all chemical elements and their compounds. It incorporates important recent developments with an emphasis on advances in the interpretation of structure, bonding, and reactivity.From the reviews of the Fifth Edition:* "The first place to go when seeking general information about the chemistry of a particular element, especially when up-to-date, authoritative information is desired." -Journal of the American Chemical Society.* "Every student with a serious interest in inorganic chemistry should have [this book]." -Journal of Chemical Education.* "A mine of information . . . an invaluable guide." -Nature.* "The standard by which all other inorganic chemistry books are judged."-Nouveau Journal de Chimie.* "A masterly overview of the chemistry of the elements."-The Times of London Higher Education Supplement.* "A bonanza of information on important results and developments which could otherwise easily be overlooked in the general deluge of publications." -Angewandte Chemie.
12,231 citations
TL;DR: In this paper, the rate data for the generalized nucleophilic displacement reaction were reviewed, and the authors presented a method to estimate the rate of the generalized displacement reaction in terms of the number of nucleophiles.
Abstract: Recently (1) the rate data for the generalized nucleophilic displacement reaction were reviewed.
8,433 citations
8,158 citations
"The nature of Cu bonding to natural..." refers background in this paper
...The mean Cu(II)–Oeq distance calculated over 197 structures is r = 1.679 + 0.37ln(0.5) = 1.94 Å (Brown and Altermatt, 1985), the heuristic value for NOM....
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Book•
01 Jan 1984TL;DR: In this article, the origins of the elements, isotopes and atomic weights Chemical periodicity and the periodic table were discussed, including the following elements: Hydrogen Lithium, sodium, potassium, rubidium, caesium and francium Beryllium, magnesium, calcium, strontium, barium and radium Boron Aluminium, gallium, indium and thallium Carbon Silicon Germanium, tin and lead Nitrogen Phosphorus Arsenic, antimony and bismuth Oxygen Sulfur Selenium, tellurium
Abstract: Origin of the elements, isotopes and atomic weights Chemical periodicity and the periodic table Hydrogen Lithium, sodium, potassium, rubidium, caesium and francium Beryllium, magnesium, calcium, strontium, barium and radium Boron Aluminium, gallium, indium and thallium Carbon Silicon Germanium, tin and lead Nitrogen Phosphorus Arsenic, antimony and bismuth Oxygen Sulfur Selenium, tellurium and polonium The halogens: fluorine, chlorine, bromine, iodine and astatine The noble gases: helium, neon, argon, krypton, xenon, and radon Coordination and organometallic compounds Scandium, yttrium, lanthanum and actinium Titanium, zirconium and hafnium Vanadium, niobium and tantalum Chromium, molybdenum and tungsten Manganese, technetium and rhenium Iron, ruthenium and osmium Cobalt, rhodium and iridium Nickel, palladium, and platinum Copper, silver and gold Zinc, cadmium and mercury The lanthanide elements The actinideand transactinide elements (Z=90-112).
6,480 citations
TL;DR: In this paper, a property called absolute hardness eta is defined for neutral and charged species, atomic and molecular, for both hard and soft acids and bases, by making use of the hypothesis that extra stability attends bonding of A to B when the ionization potentials of A and B in the molecule are the same.
Abstract: For neutral and charged species, atomic and molecular, a property called absolute hardness eta is defined. Let E(N) be a ground-state electronic energy as a function of the number of electrons N. As is well-known, the derivative of E(N) with respect to N, keeping nuclear charges Z fixed, is the chemical potential ..mu.. or the negative of the absolute electronegativity chi: ..mu.. = (deltaE/deltaN)/sub Z/ = /sup -/chi. The corresponding second derivative is hardness: 2eta = (delta..mu../deltaN)/sub Z/ = (deltachi/deltaN)/sub Z/ = (delta/sup 2/E/deltaN/sup 2/)/sub Z/. Operational definitions of chi and eta are provided by the finite difference formulas (the first due to Mulliken) chi = 1/2(I+A), eta = 1/2(I-A), where I and A are the ionization potential and electron affinity of the species in question. Softness is the opposite of hardness: a low value of eta means high softness. The principle of hard and soft acids and bases is derived theoretically by making use of the hypothesis that extra stability attends bonding of A to B when the ionization potentials of A and B in the molecule (after charge transfer) are the same. For bases B, hardness is identified as the hardness of the species B/sup +/. Tables ofmore » absolute hardness are given for a number of free atoms, Lewis acids, and Lewis bases, and the values are found to agree well with chemical facts. 1 figure, 3 tables.« less
6,030 citations