Thlaspi arvense binds Cu(ii) as a bis-(l-histidinato) complex on root cell walls in an urban ecosystem

Manceau, Alain; Simionovici, Alexandre; Lanson, Martine; Perrin, Jonathan; Tucoulou, R.; Bohic, Sylvain; Fakra, Sirine C.; Marcus, Matthew A.; Bedell, Jean Philippe; Nagy, Kathryn L.

doi:10.1039/c3mt00215b

Cited by 17 publications

(13 citation statements)

References 99 publications

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“…A case in point is the bis-chelate of histidine with Cu, in which the two chelates fold in sequence as pH increases leading to coexisting conformers. [8][9][10] Bond lengths are in angstroms, and bond angles are in black. Atomic charges, in units of elementary charge e and calculated by natural population analysis (NPA), 11 are in blue.…”

Section: Associated Content Supporting Informationmentioning

confidence: 99%

“…8 Occupational exposure is mainly to gaseous or dust forms of mercury. [8][9][10] Mercury intake is monitored by measurement of Hg concentration in urine, blood, or scalp hair with hair being the common matrix analyzed for methylmercury. These measurements assess the total burden of mercury in individuals to diagnose poisoning and provide data for epidemiological studies, but cannot indicate the source of mercury essential for treatment and forensic investigation.Recently, progress in identifying source was achieved with mercury isotopic analyses that show mass independent and mass dependent fractionations in hair indicative of exposure to methylmercury via coastal vs. freshwater fish consumption 11,12 and to inorganic mercury via artisanal gold mining.…”

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confidence: 99%

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Chemical Forms of Mercury in Human Hair Reveal Sources of Exposure

Manceau

Enescu

Simionovici

et al. 2016

Environ. Sci. Technol.

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Humans are contaminated by mercury in different forms from different sources. In practice, contamination by methylmercury from fish consumption is assessed by measuring hair mercury concentration, whereas exposure to elemental and inorganic mercury from other sources is tested by analysis of blood or urine. Here, we show that diverse sources of hair mercury at concentrations as low as 0.5 ppm can be individually identified by specific coordination to C, N, and S ligands with high energy-resolution X-ray absorption spectroscopy. Methylmercury from seafood, ethylmercury used as a bactericide, inorganic mercury from dental amalgams, and exogenously derived atmospheric mercury bind in distinctive intermolecular configurations to hair proteins, as supported by molecular modeling. A mercury spike located by X-ray nanofluorescence on one hair strand could even be dated to removal of a single dental amalgam. Chemical forms of other known or putative toxic metals in human tissues could be identified by this approach with potential broader applications to forensic, energy, and materials science.

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Section: Associated Content Supporting Informationmentioning

confidence: 99%

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confidence: 99%

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Chemical Forms of Mercury in Human Hair Reveal Sources of Exposure

Manceau

Enescu

Simionovici

et al. 2016

Environ. Sci. Technol.

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“…Copper and iron, as redox metals, directly induce ROS creation through Fenton and Haber–Weiss reactions [ 9 ]. Furthermore, copper ions form complexes with metalloproteins and can be bound by L-histidine-Cu(II) [ 10 ], L-cysteine-Cu(I) [ 11 ] and methionine-Cu(I) [ 12 ]. Thus, disturbances in the ETC and impaired ATP production may influence the Yang cycle and synthesis of the S-adenosyl-L-methionine (SAM) metabolite [ 13 ], which is the universal methyl-group donor in the cell [ 14 , 15 , 16 ].…”

Section: Introductionmentioning

confidence: 99%

Triticale Green Plant Regeneration Is Due to DNA Methylation and Sequence Changes Affecting Distinct Sequence Contexts in the Presence of Copper Ions in Induction Medium

Orłowska

Pachota

Androsiuk

et al. 2021

Cells

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Metal ions in the induction medium are essential ingredients allowing green plant regeneration. For instance, Cu(II) and Ag(I) ions may affect the mitochondrial electron transport chain, influencing the Yang cycle and synthesis of S-adenosyl-L-methionine, the prominent donor of the methylation group for all cellular compounds, including cytosines. If the ion concentrations are not balanced, they can interfere with the proper flow of electrons in the respiratory chain and ATP production. Under oxidative stress, methylated cytosines might be subjected to mutations impacting green plant regeneration efficiency. Varying Cu(II) and Ag(I) concentrations in the induction medium and time of anther culture, nine trials of anther culture-derived regenerants of triticale were derived. The methylation-sensitive AFLP approach quantitative characteristics of tissue culture-induced variation, including sequence variation, DNA demethylation, and DNA de novo methylation for all symmetric-CG, CHG, and asymmetric-CHH sequence contexts, were evaluated for all trials. In addition, the implementation of mediation analysis allowed evaluating relationships between factors influencing green plant regeneration efficiency. It was demonstrated that Cu(II) ions mediated relationships between: (1) de novo methylation in the CHH context and sequence variation in the CHH, (2) sequence variation in CHH and green plant regeneration efficiency, (3) de novo methylation in CHH sequences and green plant regeneration, (4) between sequence variation in the CHG context, and green plant regeneration efficiency. Cu(II) ions were not a mediator between de novo methylation in the CG context and green plant regeneration. The latter relationship was mediated by sequence variation in the CG context. On the other hand, we failed to identify any mediating action of Ag(I) ions or the moderating role of time. Furthermore, demethylation in any sequence context seems not to participate in any relationships leading to green plant regeneration, sequence variation, and the involvement of Cu(II) or Ag(I) as mediators.

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“…To synthesize metal-cysteine, metal-histidine, and metal-glutathione complexes, solutions with a 1:10 ratio of metal to ligand were reacted based on published methods (Kelly et al, 2002;Beauchemin et al, 2004;Montargès-Pelletier et al, 2008;Dokken et al, 2009;Manceau et al, 2013;Van Der Ent et al, 2017). All solutions were prepared in the anaerobic chamber and using deoxygenated ultrapure water.…”

Section: Synthesis Of Reference Standardsmentioning

confidence: 99%

Consistent Controls on Trace Metal Micronutrient Speciation in Wetland Soils and Stream Sediments

Yan¹,

Sharma²,

Flynn³

et al. 2022

Preprint

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Trace metal are essential for microbially-mediated biogeochemical processes occurring in anoxic wetland soils and stream bed sediments, but low availability of these elements may inhibit anaerobic element cycling and transformations. Solid-phase speciation is likely a critical control on trace metal availability but has seen limited study in anoxic systems having concentrations similar to geological background levels, where metal limitations may be most prevalent. We have investigated trace metal concentrations and solid-phase speciation in three freshwater subsurface aquatic systems: marsh wetland soils, riparian wetland soils, and the sediments of a streambed. These systems displayed low solid-phase trace metal concentrations, generally at or below geological background levels, which generally followed the trend Zn > Cu ≈ Ni > Co and showed no correlation with major element compositions. All soils and sediments were dominated by quartz but varied in clay mineralogy as well as the organic matter, total sulfur, and total iron contents. X-ray absorption near-edge structure (XANES) spectroscopy shows that sulfur speciation in both wetlands is dominated by organic sulfur. Elemental sulfur and iron sulfides together made up <25% of the sulfur in the wetland soils, but the distribution between inorganic and organic forms was reversed in the stream sediments. Ferrous and ferric iron in clay minerals were common species identified by both XANES and extended X-ray absorption fine structure (EXAFS) spectroscopies at all sites. Iron(III) oxides were substantial components in all but the marsh wetland soils. Quantitative analysis of copper, nickel, and zinc XANES spectra revealed similar metal speciation across all sites. Copper speciation was dominated by sulfides, adsorbed species, and minor amounts of copper bound to organic matter; no metallic copper was detected. Nickel speciation also varied little and was dominated by nickel in clay mineral octahedral sheets and nickel sulfide, with adsorbed species also present. Zinc speciation was slightly more varied, with the marsh wetland soils and stream bed sediments containing adsorbed species, zinc associated with clay mineral structures, and zinc bound to reduced sulfur groups on organic matter, whereas the riparian wetland soils lacked clay-associated zinc but contained zinc sulfide. Trace metals bound to reduced sulfur occurred at every site, with a greater sulfur-bound fraction for copper. The fractional abundance of sulfur-bound species showed no relationship with soil or sediment total sulfur content, which varied by two orders of magnitude. More broadly, the observations in this study suggest that trace metal speciation in freshwater wetland soils and stream sediments is consistently dominated by a small set of recurring components which are distinct for each metal. This may represent a general geochemical phenomenon in anoxic soils and sediments containing trace metals at background concentrations (as low as 3 µg g-1) that was not predicted from systems that are contaminated with or naturally-enriched in copper, nickel, or zinc.

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Thlaspi arvense binds Cu(ii) as a bis-(l-histidinato) complex on root cell walls in an urban ecosystem

Cited by 17 publications

References 99 publications

Chemical Forms of Mercury in Human Hair Reveal Sources of Exposure

Chemical Forms of Mercury in Human Hair Reveal Sources of Exposure

Triticale Green Plant Regeneration Is Due to DNA Methylation and Sequence Changes Affecting Distinct Sequence Contexts in the Presence of Copper Ions in Induction Medium

Consistent Controls on Trace Metal Micronutrient Speciation in Wetland Soils and Stream Sediments

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