Publications (11)46.54 Total impact
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Article: Speciation and biochemical transformations of sulfur and copper in rice rhizosphere and bulk soil—XANES evidence of sulfur and copper associations
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ABSTRACT: PurposeContamination of heavy metals in soil and its subsequent accumulation along the food chain is a potential risk to human health. Cu speciation in soil–plant system, particularly on the availability to plant roots, has obtained great attention. X-ray absorption near-edge structure spectroscopy (XANES) provides information about the bonding of Cu soil components at the molecular scale. In paddy soils, changes of redox conditions led to microbially mediated sulfur transformation, thus affecting heavy metal behavior. The objective of this work was to investigate how sulfur transformation in a paddy soil affected Cu biogeochemical processes. Materials and methodsThe Cu and sulfur species and their relationship in rice–soil system were investigated under flooded condition. The speciation of sulfur and copper in rice rhizosphere and bulk soil was investigated using integrated approaches including sequential extraction and XANES. Results and discussionCu speciation exhibited some differences in rhizosphere and bulk soil of rice. In flooded paddy soil, most Cu in the rhizosphere existed as Cu (II), whereas part of Cu transformed to Cu (I) in the bulk soil. Sulfur XANES showed the presence of multiple both oxidized and reduced forms of sulfur in studied soil samples, with more oxidized sulfur in the rhizosphere than in the bulk soil. Copper and sulfur speciation changed depending on redox conditions. Changes in redox potential and microbial action shifted the sulfur oxidation and reduction reaction and affected the Cu speciation. Combined action of organisms maintained Cu homeostasis through cation binding to bioactive molecules. With higher Eh in rice rhizosphere, transformation of sulfur and organic compounds together contributed to more soluble and exchangeable Cu. Cu bond to sulfur containing groups and biomineralization by microorganisms could be defenses against toxic copper. ConclusionsOur findings implied that Cu existed mainly as Cu (II) in rice rhizophere and part of Cu transformed to Cu (I) in anoxic bulk soil. With higher Eh in rice rhizosphere, transformation of sulfur and organic compounds together contributed to more soluble and exchangeable Cu. Combined action of organisms maintained Cu homeostasis through cation binding to bioactive molecules. Our results indicated the important role of sulfur in the transformation of Cu. Due to the complicated processes in soil, future work dedicating to the role of microbes is needed. KeywordsBulk soil-Copper-Rice rhizosphere-Speciation-Sulfur-XANESJournal of Soils and Sediments 04/2012; 10(5):907-914. · 1.86 Impact Factor -
Article: Imaging techniques for elements and element species in plant science.
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ABSTRACT: Revealing the uptake, transport, localization and speciation of both essential and toxic elements in plants is important for understanding plant homeostasis and metabolism, subsequently, providing information for food and nutrient studies, agriculture activities, as well as environmental research. In the last decade, emerging techniques for elemental imaging and speciation analysis allowed us to obtain increasing knowledge of elemental distribution and availabilities in plants. Chemical imaging techniques include mass spectrometric methods such as secondary ionization mass spectrometry (SIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and synchrotron-based techniques such as X-ray fluorescence spectroscopy (SRXRF), and so forth. On the other hand, X-ray absorption spectroscopy (XAS) based on synchrotron radiation is capable of in situ investigation of local atomic structure around the central element of interest. This technique can also be operated in tandem with SRXRF to image each element species of interest within plant tissue. In this review, the principles and state-of-the-art of these techniques regarding sample preparation, advantages and limitations, and improvement of sensitivity and spatial resolution are discussed. New results with respect to elemental distribution and speciation in plants revealed by these techniques are presented.Metallomics 04/2012; 4(5):403-16. · 3.90 Impact Factor -
Article: An X-ray absorption spectroscopy investigation of speciation and biotransformation of copper in Elsholtzia splendens
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ABSTRACT: Elsholtzia splendens is a Cu-tolerant plant growing in copper mine areas in the south of China. In this study, X-ray absorption spectroscopy (XAS) was used to investigate the Cu speciation and biotransformation in E. splendens with 300μM Cu treatment from 10days to 60days. The results showed that 300μM Cu was phytotoxic to E. spendens. The Cu K-edge X-ray absorption near edge structure (XANES) revealed that most copper in roots, stems and leaves exists as divalent Cu. Cu speciation changed depending on the treatment time, but there was no unidirectional trend in roots, stems, and leaves. The percentages of potential Cu ligands in all samples were estimated by fitting the XANES spectra with linear combinations. Most Cu in roots, stems and leaves was bound with cell wall and histidine (His)-like ligands, while a minor proportion of the Cu was bound to oxalate and glutathione-like ligands. The fitting results of Cu K-edge extended X-ray absorption fine structure (EAXFS) showed that nitrogen/oxygen (N/O) ligands were dominant in roots, stems and leaves of the plant, while S ligands were rare. All these results suggest that Cu bound by N/O ligands plays a key role in Cu detoxification of E. splendens, and a role for classical metal-detoxifying S ligands, such as metallothioneins and phytochelatins, in Cu detoxification of E. splendens is not supported in the present study. Due to the phytotoxicity of 300μM Cu to E. splendens, the question of whether S ligands play a significant role in Cu detoxification in E. splendens exposed to lower levels of Cu should be further studied.Plant and Soil 04/2012; 302(1):163-174. · 2.73 Impact Factor -
Article: Mass spectrometry imaging (MSI) of metals in mouse spinal cord by laser ablation ICP-MS.
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ABSTRACT: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been developed as a powerful MS imaging (MSI) tool for the direct investigation of element distributions in biological tissues. Here, this technique was adapted for the analysis of native mouse spinal cord cryosections of 3.1 mm × 1.7 mm by implementing a new conventional ablation system (NWR-213) and improving the spatial resolution from 120 μm to 65 μm in routine mode. Element images of the spinal cord are provided for the first time and the metalloarchitecture was established using a multimodal atlas approach. Furthermore, the spatial distribution of Rb was mapped for the first time in biological tissue. Metal concentrations were quantified using matrix-matched laboratory standards and normalization of the respective ion intensities to the average (13)C ion intensity of standards and samples as a surrogate of slice thickness. The "butterfly" shape of the central spinal grey matter was visualized in positive contrast by the distributions of Fe, Mn, Cu and Zn and in negative contrast by C and P. Mg, Na, K, S and Rb showed a more homogenous distribution. The concentrations averaged throughout grey matter and white matter were 8 and 4 μg g(-1) of Fe, 3 and 2 μg g(-1) of Cu, 8 and 5 μg g(-1) of Zn, 0.4 and 0.2 μg g(-1) of Mn. The carbon concentration in white matter exceeded that of grey matter by a factor of 1.44. Zn and Cu at 9 and 4 μg g(-1), respectively, were particularly enriched in the laminae I and II, in line with the high synaptic and cellular density there. Surprisingly Zn but not Cu was enriched in the central channel. Rb occurred at 0.3 μg g(-1) with a distribution pattern congruent to that of K. The coefficients of variation were 6%, 5%, 8% and 10% for Fe, Cu, Zn and Mn, respectively, throughout three different animals measured on different days. These MSI analyses of healthy wild type spinal cords demonstrate the suitability of the established techniques for investigating diseased or transgenic states in future imaging studies.Metallomics 02/2012; 4(3):284-8. · 3.90 Impact Factor -
Article: Bioimaging of metals and biomolecules in mouse heart by laser ablation inductively coupled plasma mass spectrometry and secondary ion mass spectrometry.
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ABSTRACT: Bioimaging mass spectrometric techniques allow direct mapping of metal and biomolecule distributions with high spatial resolution in biological tissue. In this study laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was used for imaging of transition metals (Fe, Cu, Zn, Mn, and Ti), alkali and alkaline-earth metals (Na, K, Mg, and Ca, respectively), and selected nonmetals (such as C, P, and S) in native cryosections of mouse heart. The metal and nonmetal images clearly illustrated the shape and the anatomy of the samples. Zinc and copper were inhomogeneously distributed with average concentrations of 26 and 11 μg g(-1), respectively. Titanium and manganese were detected at concentrations reaching 1 and 2 μg g(-1), respectively. The highest regional metal concentration of 360 μg g(-1)was observed for iron in blood present in the lumen of the aorta. Secondary ion mass spectrometry (SIMS) as an elemental and biomolecular mass spectrometric technique was employed for imaging of Na, K, and selected biomolecules (e.g., phosphocholine, choline, cholesterol) in adjacent sections. Here, two different bioimaging techniques, LA-ICPMS and SIMS, were combined for the first time, yielding novel information on both elemental and biomolecular distributions.Analytical Chemistry 10/2010; 82(22):9528-33. · 5.86 Impact Factor -
Article: Copper uptake and its effect on metal distribution in root growth zones of Commelina communis revealed by SRXRF.
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ABSTRACT: To explore the copper uptake mechanisms by the Cu-tolerant plant Commelina communis, the contents of Cu and other metals (including Fe, Zn, and Mn) in roots were detected using atomic absorption spectrometer under transporter inhibitors, partial element deficiency, or Cu excess treatments, while distribution characters of Cu and other metals in root growth zones were investigated by synchrotron radiation X-ray fluorescence spectroscopy (SRXRF). Cu uptake was inhibited by the uncoupler DNP and P-type ATPase inhibitor Na(3)VO(4), not by the Ca(2+) ion channel inhibitor LaCl(3), suggesting that Cu could probably be assimilated actively by root and be related with P-type ATPase, but not through Ca(2+) ion channel. Fe or Zn deficiency could enhance Cu uptake, while 100 μM Cu inhibited Fe, Zn, and Mn accumulation in roots significantly. Metal distribution under 100 μM Cu treatment was investigated by SRXRF. High level of Cu was found in the root meristem, and higher Cu concentrations were observed in the vascular cylinder than those in the endodermis, further demonstrating the initiative Cu transport in the root of C. communis. Under excess Cu stress, most Fe was located in the epidermis, and Fe concentrations in the endodermis were higher than those in the vascular cylinder, suggesting Cu and Fe competition not only in the epidermal cells but also for the intercellular and intracellular transport in roots. Zn was present in the meristem and the vascular cylinder similar to Cu. Cu and Zn showed a similar pattern. Mn behaves as Zn does, but not like Fe.Biological trace element research 05/2010; 141(1-3):294-304. · 1.92 Impact Factor -
Article: Biomonitoring of metal contamination in a marine prosobranch snail (Nassarius reticulatus) by imaging laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).
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ABSTRACT: An imaging mass spectrometric method using laser ablation inductively coupled plasma spectrometry (LA-ICP-MS) was developed to determine Cu, Zn, Cd, Hg and Pb and metal distribution in longitudinal tissue sections of the marine snail Nassarius reticulatus (Gastropoda, Prosobranchia). Snails were sampled in northern Brittany (France) at three stations with different contamination levels. The quantification of metal distribution (imaging or mapping) in a thin slice of the snail tissue was carried out using different strategies: by one-point calibration and via matrix-matched laboratory standards using different biological materials (BCR 278, snail tissue, and rat brain). Together with the imaging of metals the distribution of two non-metals (carbon and sulfur) was analyzed. The imaging LA-ICP-MS analysis yielded an inhomogeneous distribution for all elements investigated. The detection limits for the distribution analysis of Cu, Zn, Cd, Hg and Pb measured by LA-ICP-MS were in the low microg g(-1) range.Talanta 12/2009; 80(2):428-33. · 3.79 Impact Factor -
Article: Cerebral bioimaging of Cu, Fe, Zn, and Mn in the MPTP mouse model of Parkinson's disease using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).
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ABSTRACT: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a powerful technique for the determination of metal and nonmetal distributions within biological systems with high sensitivity. An imaging LA-ICP-MS technique for Fe, Cu, Zn, and Mn was developed to produce large series of quantitative element maps in native brain sections of mice subchronically intoxicated with 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridin (MPTP) as a model of Parkinson's disease. Images were calibrated using matrix-matched laboratory standards. A software solution allowing a precise delineation of anatomical structures was implemented. Coronal brain sections were analyzed crossing the striatum and the substantia nigra, respectively. Animals sacrificed 2 h, 7 d, or 28 d after the last MPTP injection and controls were investigated. We observed significant decreases of Cu concentrations in the periventricular zone and the fascia dentata at 2 h and 7d and a recovery or overcompensation at 28 d, most pronounced in the rostral periventricular zone (+40%). In the cortex Cu decreased slightly to -10%. Fe increased in the interpeduncular nucleus (+40%) but not in the substantia nigra. This pattern is in line with a differential regulation of periventricular and parenchymal Cu, and with the histochemical localization of Fe, and congruent to regions of preferential MPTP binding described in the rodent brain. The LA-ICP-MS technique yielded valid and statistically robust results in the present study on 39 slices from 19 animals. Our findings underline the value of routine micro-local analytical techniques in the life sciences and affirm a role of Cu availability in Parkinson's disease.Journal of the American Society for Mass Spectrometry 10/2009; 21(1):161-71. · 4.00 Impact Factor -
Article: Bioimaging of metals by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).
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ABSTRACT: The distribution analysis of (essential, beneficial, or toxic) metals (e.g., Cu, Fe, Zn, Pb, and others), metalloids, and non-metals in biological tissues is of key interest in life science. Over the past few years, the development and application of several imaging mass spectrometric techniques has been rapidly growing in biology and medicine. Especially, in brain research metalloproteins are in the focus of targeted therapy approaches of neurodegenerative diseases such as Alzheimer's and Parkinson's disease, or stroke, or tumor growth. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) using double-focusing sector field (LA-ICP-SFMS) or quadrupole-based mass spectrometers (LA-ICP-QMS) has been successfully applied as a powerful imaging (mapping) technique to produce quantitative images of detailed regionally specific element distributions in thin tissue sections of human or rodent brain. Imaging LA-ICP-QMS was also applied to investigate metal distributions in plant and animal sections to study, for example, the uptake and transport of nutrient and toxic elements or environmental contamination. The combination of imaging LA-ICP-MS of metals with proteomic studies using biomolecular mass spectrometry identifies metal-containing proteins and also phosphoproteins. Metal-containing proteins were imaged in a two-dimensional gel after electrophoretic separation of proteins (SDS or Blue Native PAGE). Recent progress in LA-ICP-MS imaging as a stand-alone technique and in combination with MALDI/ESI-MS for selected life science applications is summarized.Mass Spectrometry Reviews 07/2009; 29(1):156-75. · 10.46 Impact Factor -
Article: Imaging of nutrient elements in the leaves of Elsholtzia splendens by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).
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ABSTRACT: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of nutrient elements (such as K, Mg, Mn, Cu, P, S and B) in the leaves of Elsholtzia splendens. The plant leaves were scanned directly with a focused Nd:YAG laser in the laser ablation chamber. The ablated material was transported with argon as carrier gas to a quadrupole-based ICP-MS (ICP-QMS), and the ion intensities of (39)K(+), (24)Mg(+), (55)Mn(+), (63)Cu(+), (31)P(+), (34)S(+) and (11)B(+) were measured by ICP-QMS to study the distribution of the elements of interest. The imaging technique using LA-ICP-MS on plant leaves does not require any sample preparation. Carbon ((13)C(+)) was used as an internal standard element to compensate for the difference in the amount of material ablated. Additional experiments were performed in order to study the influence of the water content of the analyzed leaves on the intensity signal of the analyte. For quantification purposes, standard reference material (NIST SRM 1515 Apple Leaves) was selected and doped with standard solutions of the analytes within the concentration range of 0.1-2000 mg L(-1). The synthetic laboratory standards together with the samples were measured by LA-ICP-MS. The shape and structure of the leaves was clearly given by LA-ICP-MS imaging of all the elements measured. The elemental distribution varied according to the element, but with a high content in the veins for all the elements investigated. Specifically, Cu was located uniformly in the mesophyll with a slightly higher concentration in the main vein. High ion intensity was measured for S with a high amount of this element in the veins similar to the images of the metals, whereas most of the B was detected at the tip of the leaf. With synthetic laboratory standard calibration, the concentrations of elements in the leaves measured by LA-ICP-MS were between 20 microg g(-1) for Cu and 14,000 microg g(-1) for K.Talanta 05/2009; 78(1):132-7. · 3.79 Impact Factor -
Article: Study of essential element accumulation in the leaves of a Cu-tolerant plant Elsholtzia splendens after Cu treatment by imaging laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).
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ABSTRACT: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of Cu and other essential elements (such as K, Mg, Mn, P, S and B) in the leaves of a Cu-tolerant plant Elsholtzia splendens treated with the enriched (65)Cu isotope tracer (isotope abundance of 89.2%). The leaves (newly formed, fully grown and oldest) were scanned directly with a focused Nd:YAG laser in the laser ablation chamber. The ablated material was transported with argon as carrier gas to a quadrupole-based ICP-MS (ICP-QMS), and the ion intensities of (65)Cu(+), (39)K(+), (24)Mg(+), (55)Mn(+), (31)P(+), (34)S(+) and (11)B(+) were measured by ICP-QMS to study the accumulation of Cu and other elements of interest. Standard reference material NIST SRM 1515 Apple Leaves doped with known concentrations of analytes (from 0.1 to 2000mgL(-1)) was measured together with the samples by LA-ICP-MS and was used for the quantification of the analytical data. Notable accumulation of Cu in the newly formed leaves was clearly identified by imaging LA-ICP-MS. The increased isotope ratios of (65)Cu/(63)Cu measured by LA-ICP-MS demonstrated the path of Cu uptake and accumulation via the petiole and main veins in the leaves. Cu stress-induced accumulation of K, Mg, Mn, P and S in the newly formed leaves was observed, while B was not significantly affected. In the present study, the concentrations of K, Mg, Mn, P and S were not obviously changed in the fully grown leaves after short-term treatment. Along with the treatment, a visible decrease of K and P was found in the oldest leaves, while other elements were not influenced by Cu stress.Analytica chimica acta 03/2009; 633(2):165-72. · 4.31 Impact Factor
Top co-authors
Top Journals
- Metallomics (2)
- Talanta (2)
- Plant and Soil (1)
- Mass Spectrometry Reviews (1)
- Journal of Soils and Sediments (1)
Institutions
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2012
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Forschungszentrum Jülich
Düren, North Rhine-Westphalia, Germany
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2009–2012
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Zhejiang University
- Department of Environmental Engineering
Hangzhou, Zhejiang Sheng, China -
Universidade Estadual de Campinas
- Instituto de Química (IQ)
Campinas, Estado de Sao Paulo, Brazil
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