Zn Speciation in the Organic Horizon of a Contaminated Soil by Micro-X-ray Fluorescence, Micro- and Powder-EXAFS Spectroscopy, and Isotopic Dilution

Sarret, Géraldine; Balesdent, Jérôme; Bouziri, Lamia; Garnier, Jean‐Marie; Marcus, Matthew A.; Geoffroy, Nicolas; Panfili, Frédéric; Manceau, Alain

doi:10.1021/es035171t

Cited by 93 publications

(89 citation statements)

References 32 publications

(81 reference statements)

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“…Spectra ZnCa3, ZnCa4, and Zn1 are somehow intermediate between the two previous sets of spectra, suggesting a mixture of Zn species. Data analysis was done by linear combination fits using an extended database of Zn reference compounds containing Zn-bearing and Zn-sorbed minerals, Zn precipitates, and Zn complexed to simple organic acids and complex biopolymers (Sarret et al, 2004;Guiné et al, 2006). One-to three-component simulations were tested.…”

Section: Calcite (Inset Inmentioning

confidence: 99%

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Trichomes of Tobacco Excrete Zinc as Zinc-Substituted Calcium Carbonate and Other Zinc-Containing Compounds

et al. 2006

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(S.F., M.A.M.) Tobacco (Nicotiana tabacum L. cv Xanthi) plants were exposed to toxic levels of zinc (Zn). Zn exposure resulted in toxicity signs in plants, and these damages were partly reduced by a calcium (Ca) supplement. Confocal imaging of intracellular Zn using Zinquin showed that Zn was preferentially accumulated in trichomes. Exposure to Zn and Zn 1 Ca increased the trichome density and induced the production of Ca/Zn mineral grains on the head cells of trichomes. These grains were aggregates of submicrometer-sized crystals and poorly crystalline material and contained Ca as major element, along with subordinate amounts of Zn, manganese, potassium, chlorine, phosphorus, silicon, and magnesium. Micro x-ray diffraction revealed that the large majority of the grains were composed essentially of metal-substituted calcite (CaCO 3 ). CaCO 3 polymorphs (aragonite and vaterite) and CaC 2 O 4 (Ca oxalate) mono-and dihydrate also were identified, either as an admixture to calcite or in separate grains. Some grains did not diffract, although they contained Ca, suggesting the presence of amorphous form of Ca. The presence of Zn-substituted calcite was confirmed by Zn K-edge micro-extended x-ray absorption fine structure spectroscopy. Zn bound to organic compounds and Zn-containing silica and phosphate were also identified by this technique. The proportion of Zn-substituted calcite relative to the other species increased with Ca exposure. The production of Zn-containing biogenic calcite and other Zn compounds through the trichomes is a novel mechanism involved in Zn detoxification. This study illustrates the potential of laterally resolved x-ray synchrotron radiation techniques to study biomineralization and metal homeostasis processes in plants.Smoking of tobacco (Nicotiana tabacum) leaves is one of the principal routes of exposure to heavy metals. Metals contained in tobacco leaves originate from root uptake and transfer to the shoots and also from deposition of aerosol particles on the leaves (Fleisher and Parungo, 1974). Efforts have been made to minimize toxic metal contents in the leaves (LugonMoulin et al., 2004). However, this is not the case for counterfeit tobacco products, which contain higher concentrations of metals than their genuine equivalents (Stephens et al., 2005). Besides its primary application for leaf production, tobacco is also a candidate for phytoextraction. Although this plant species is not a hyperaccumulator, it has several advantages, including a high biomass, moderate soil requirements, fast growth rate, and ease of harvesting. For this particular application, research is conducted with the aim of enhancing metal accumulation in the shoots (Song et al., 2003).Little is known about the mechanisms of metals accumulation and detoxification in tobacco. The exposure of plants to high concentrations of metals generally induces a stress, whose visible symptoms include an inhibition of root elongation, a decrease in shoot growth, leaf chlorosis, and necrosis of the tissues. This stress is ge...

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Section: Calcite (Inset Inmentioning

confidence: 99%

“…EXAFS spectra were extracted using the standard procedure and then simulated by linear combinations of reference spectra from an extended spectral library (Sarret et al, 2004;Guiné et al, 2006). The spectrum for Znsubstituted calcite was provided by R.J. Reeder (Reeder et al, 1999;Elzinga and Reeder, 2002).…”

Section: Xrd and Exafs Data Treatmentmentioning

confidence: 99%

Trichomes of Tobacco Excrete Zinc as Zinc-Substituted Calcium Carbonate and Other Zinc-Containing Compounds

et al. 2006

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“…Alternatively, the size of the X-ray probe can be adapted to a particular scale dependent on the heterogeneity of the sample. For soils and sediments, the micrometer scale of resolution is appropriate because fine particles of similar composition and structure formed by biotic and abiotic natural processes tend to aggregate Isaure et al, 2002Isaure et al, , 2005Manceau et al, 2002b;Kirpichtchikova et al, 2003;Manceau et al, 2004;Sarret et al, 2004). This second approach is preferable because it is less invasive than chemical extraction (Ostergren et al, 1999;Calmano et al, 2001).…”

Section: Introductionmentioning

confidence: 99%

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

Panfili

Manceau

Sarret

et al. 2005

Geochimica et Cosmochimica Acta

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122

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Running Title: Effect of phytostabilzation on Zn speciation in dredged sediment 2 ABSTRACTThe maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies, such as phytoremediation. In the present work, the mineralogical transformations of Zn Seven Zn species were identified at the micrometer-scale : sphalerite, gahnite, franklinite, Zncontaining ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted, kerolite-like, trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra.In the untreated and unvegetated sediment, Zn was distributed as ~50 % (mole ratio of total Zn) sphalerite, ~40 % Zn-ferrihydrite, and ~10-20 % (Zn-Al)-hydrotalcite plus Znphyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20 % and were replaced by Zn-phosphate (~30-40 %). In the presence of plants, ZnS was almost completely dissolved and the released Zn bound to phosphate (~40-60 %) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite (~20-40 %). Neither the plant species 3 nor the co-addition of mineral amendment affected the Zn speciation in the vegetated sediment.The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near-saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)-hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result from heterogenous precipitation on mineral surface. 4

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“…In soil, Zn is present in various forms. Among the total soil Zn content, Zn primary minerals constitute around 15%, Zn organic matter complexes around 45%, outer-sphere complexes around 20%, Zn-sorbed phosphate around 10%, and Zn-sorbed iron oxyhydroxides around 10% (Sarret et al 2004). The solubility and availability of Zn is determined by various factors like high CaCO3, high pH, high clay soils, low organic matter, low soil moisture, and high iron and aluminum oxides (Cakmak 2008).In low Zn soils, the Zn uptake may be enhanced by the exudation of low-molecular-weight compounds like malate and mugineic acid family phytosiderophores (Arnold et al 2010;Cakmak et al 1994;Peng et al 2009;Suzuki et al 2006;Walter et al 1994;Widodo et al 2010;Zhang et al 1989).…”

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Zn Uptake and Translocation in Rice Plants

Ishimaru

Bashir

Nishizawa

2011

Rice

157

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Zinc (Zn) is an essential micronutrient with numerous cellular functions in plants, and its deficiency represents one of the most serious problems in human nutrition worldwide. Zn deficiency causes a decrease in plant growth and yield. On the other hand, Zn could be toxic if excess amounts are accumulated. Therefore, the uptake and transport of Zn must be strictly regulated. In this review, the dominant fluxes of Zn in soil-root-shoot translocation in rice plants (Oryza sativa) are described, including Zn uptake from soils in the form of Zn 2+ and Zn-DMA at the root surface, and Zn translocation to shoots. Knowledge of these fluxes could be helpful to formulate genetic and physiologic strategies to address the widespread problem of Zn-limited crop growth.

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Zn Speciation in the Organic Horizon of a Contaminated Soil by Micro-X-ray Fluorescence, Micro- and Powder-EXAFS Spectroscopy, and Isotopic Dilution

Cited by 93 publications

References 32 publications

Trichomes of Tobacco Excrete Zinc as Zinc-Substituted Calcium Carbonate and Other Zinc-Containing Compounds

Trichomes of Tobacco Excrete Zinc as Zinc-Substituted Calcium Carbonate and Other Zinc-Containing Compounds

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

Zn Uptake and Translocation in Rice Plants

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