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1.
Metallomics ; 12(12): 2032-2048, 2020 12 23.
Article in English | MEDLINE | ID: mdl-33165451

ABSTRACT

Low molecular weight selenium containing metabolites in the leaves of the selenium hyperaccumulator Cardamine violifolia (261 mg total Se per kg d.w.) were targeted in this study. One dimensional cation exchange chromatography coupled to ICP-MS was used for purification and fractionation purposes prior to LC-Unispray-QTOF-MS analysis. The search for selenium species in full scan spectra was assisted with an automated mass defect based filtering approach. Besides selenocystathionine, selenohomocystine and its polyselenide derivative, a total number of 35 water soluble selenium metabolites other than selenolanthionine were encountered, including 30 previously unreported compounds. High occurrence of selenium containing hexoses was observed, together with the first assignment of N-glycoside derivatives of selenolanthionine. Quantification of the most abundant selenium species, selenolanthionine, was carried out with an ion pairing LC - post column isotope dilution ICP-MS setup, which revealed that this selenoamino acid accounted for 30% of the total selenium content of the leaf (78 mg (as Se) per kg d.w.).


Subject(s)
Cardamine/metabolism , Cystathionine/analogs & derivatives , Homocystine/analogs & derivatives , Organoselenium Compounds/metabolism , Selenium/metabolism , Alanine/analogs & derivatives , Alanine/analysis , Alanine/metabolism , Cardamine/chemistry , Cystathionine/analysis , Cystathionine/metabolism , Homocystine/analysis , Homocystine/metabolism , Organoselenium Compounds/analysis , Plant Leaves/chemistry , Plant Leaves/metabolism , Selenium/analysis , Solubility , Water/chemistry
2.
Sci Total Environ ; 669: 83-90, 2019 Jun 15.
Article in English | MEDLINE | ID: mdl-30878943

ABSTRACT

Rice is an important source of selenium (Se) exposure; however, the transformation and translocation of Se in the soil-rice system remain poorly understood. Here, we investigated the speciation of Se in Se-rich soils from Enshi, Central China and assessed which Se species is bioavailable for rice grown in Enshi. Extremely high Se concentrations (0.85 to 11.46 mg/kg) were observed in the soils. The soil Se fractions, which include water-soluble Se (0.2 to 3.4%), ligand-exchangeable Se (4.5 to 15.0%), organically bound Se (57.8 to 80.0%) and residual Se (6.1 to 32.9%), are largely controlled by soil organic matter (SOM) levels. Decomposition of SOM promotes the transformation of organically bound Se to water-soluble Se and ligand-exchangeable Se, thereby increasing the bioavailability of Se. The bioaccumulation factors (BAFs) of Se decrease in the following order: roots (0.84 ±â€¯0.30) > bran (0.33 ±â€¯0.17) > leaves (0.18 ±â€¯0.09) > polished rice (0.14 ±â€¯0.07) > stems (0.12 ±â€¯0.07) > husks (0.11 ±â€¯0.07). Selenium levels in rice plants are affected by multiple soil Se fractions in the soil. Water-soluble, ligand-exchangeable and organically bound Se fractions are the major sources of Se in rice tissues.


Subject(s)
Oryza/metabolism , Selenium/metabolism , Soil Pollutants/metabolism , Soil/chemistry , Biological Availability , China
3.
Biochim Biophys Acta Gen Subj ; 1862(11): 2354-2362, 2018 Nov.
Article in English | MEDLINE | ID: mdl-29331509

ABSTRACT

BACKGROUND: Selenium hyperaccumulation in plants often involves the synthesis of non-proteinaceous methylated selenoamino acids serving for the elimination of excess selenium from plant metabolism to protect plant homeostasis. METHODS: Our study aimed at the identification of the main selenium species of the selenium hyperaccumulator plant Cardamine violifolia (Brassicaceae) that grows in the wild in the seleniferous region of Enshi, China. A sample of this plant (3.7 g Se kg-1 d.w.) was prepared with several extraction methods and the extracted selenium species were identified and quantified with liquid chromatography mass spectrometry set-ups. RESULTS: The Cardamine violifolia sample did not contain in considerable amount any of the organic selenium species that are often formed in hyperaccumulator plants; the inorganic selenium content (mostly as elemental selenium) accounted only for <20% of total Se. The most abundant selenium compound, accounting for about 40% of total Se was proved to be selenolanthionine, a selenium species that has never been unambiguously identified before from any selenium containing sample. The identification process was completed with chemical synthesis too. The molar ratio of lanthionine:selenolanthionine in the water extract was ca. 1:8. CONCLUSIONS: Finding selenolanthionine as the main organic selenium species in a plant possibly unearths a new way of selenium tolerance. This article is part of a Special Issue entitled Selenium research in biochemistry and biophysics - 200 year anniversary issue, edited by Dr. Elias Arnér and Dr. Regina Brigelius-Flohe.

4.
Environ Geochem Health ; 30(4): 307-14, 2008 Aug.
Article in English | MEDLINE | ID: mdl-18351293

ABSTRACT

In order to clarify the historic academic problem of whether or not livestock poisoning in ancient Suzhou of Northwest China, recorded by Marco Polo in 1295, was selenosis, this study deals with the biogeochemistry of selenium in Sunan County in the Hexi Corridor, which is part of ancient Suzhou in China. It was found that quite a number of farm animals had suffered from intoxication and died as a result of grazing poisonous grasses, mostly Oxytropis DC, Stellera chamaejasme, and Achnatheru inebrians. Toxic symptoms of livestock grazing on Oxytropis DC are similar to those of selenium toxicity, for instance, hair loss and hoof lesions as described by Marco Polo. Therefore, we thought that toxic grass, probably Oxytropis DC, led to the intoxication of livestock recorded by Marco Polo. Average Se concentrations in two members of this species were 0.112 +/- 0.038 mg/kg for the root of Oxytropis glabra, 0.102 +/- 0.027 mg/kg for the stem and leaf of Oxytropis glabra, and 0.066 +/- 0.009 mg/kg for Oxytropis ochrocephala. The average soil selenium concentration was 0.205 +/- 0.127 mg/kg on grassland producing Oxytropis glabra and 0.152 +/- 0.024 mg/kg on grassland producing Oxytropis ochrocephala. The average Se concentration in other plants was 0.076 mg/kg in the root of Ephedra monosperma Mey, 0.029 mg/kg in the root of Rheum palmatum, 0.031 mg/kg in the root of Stellera chamaejasme, 0.037 mg/kg in Achnatherum inebrians, and 0.067 mg/kg in forage grass (Achnatherum splendens ohwi). Selenium concentrations in soils and plants in Sunan County are far less than the thresholds causing selenium toxicity in livestock. As a result, this study concludes that the livestock poisoning recorded by Marco Polo in 1295 might not have been selenosis.


Subject(s)
Oxytropis/chemistry , Plant Poisoning/history , Plant Poisoning/veterinary , Selenium/isolation & purification , Animals , Animals, Domestic , China , History, Medieval , Horse Diseases/history , Horses , Humans , Oxytropis/poisoning , Poaceae/chemistry , Poaceae/poisoning , Rheum/chemistry , Rheum/poisoning , Selenium/history , Selenium/poisoning , Thymelaeaceae/chemistry , Thymelaeaceae/poisoning
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