Isotopic fractionation
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We studied the key geochemical and mineralogical factors that could affect the fractionation of stable thallium (Tl) isotopes in soil. A set of grassland soil samples enriched in geogenic Tl in combination with selected Tl-containing mineral materials from the Czech Republic (Kluky) were investigated for this purpose. The results demonstrate significant incorporation of Tl in pedogenic (specific) Mn-oxide, which led to a large accumulation of the heavy 205Tl isotope (∼+14 ε205Tl units), presumably resulting from oxidative Tl sorption. Consequently, we concluded that the Mn-oxide-controlled Tl uptake is the primary cause of the observed 205Tl enrichment in the middle profile zone, at the A/B soil horizon interface, with up to +4 of ε205Tl. Furthermore, our results displayed a clear relationship between the Tl isotopic fractionation degree and the Mn-oxide soil concentration (R2 = 0.6), as derived from the oxalate-extractable data. A combination of soil and mineralogical considerations suggests that 205Tl enrichment in respective soil samples is also partly due to the Tl present in micaceous clay minerals, mainly illite, which is the predominant pedogenic Tl host phase. In line with our previous results, this Tl behavior can be inferred from systematic Mn-oxide degradation and the associated Tl (enriched in 205Tl) cycling in the studied soils and thus, presumably in the redoximorphic soils in general.
- MeSH
- izotopy MeSH
- látky znečišťující půdu analýza MeSH
- půda * MeSH
- thallium analýza MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
This work investigates the mechanisms behind Cr(VI) biosorption/reduction on three biomaterials (brewers draff, grape waste and synthetic humic acid). Coupled Cr isotope analysis with ICP-OES, XPS and SEM was tested as a novel approach to study the reduction of Cr(VI) by the biomaterials. The Cr(VI) biosorption process was accompanied with heavier Cr isotopes enrichment in the remaining Cr(VI) fraction. A significant fractionation of Cr stable isotopes was observed with no significant pH effect; δ(53)Cr of the remaining fraction ranged from 0.2‰ to 1.9‰ while δ(53)Cr of the product (sorbed Cr) ranged from -1.2‰ to -2.8‰. The Rayleigh fractionation model fitted well the measured data and Cr isotope analysis provides thus an efficient tool to quantify Cr(VI) reduction by different biomaterials. In general, the sorption/reduction potential of the three studied biomaterials decreased in the following order: grape waste>humic acids>brewers draff.
In a controlled growth experiment we found that the cyanobacterium Nostoc punctiforme has a bulk cell 26Mg/24Mg ratio (expressed as δ26Mg) that is -0.27‰ lower than the growth solution at a pH of ca. 5.9. This contrasts with a recently published δ26Mg value that was 0.65‰ higher than growth solution for the black fungus Knufia petricola at similar laboratory conditions, interpreted to reflect loss of 24Mg during cell growth. By a mass balance model constrained by δ26Mg in chlorophyll extract we inferred the δ26 Mg value of the main Mg compartments in a cyanobacteria cell: free cytosolic Mg (-2.64‰), chlorophyll (1.85‰), and the nonchlorophyll-bonded Mg compartments like ATP and ribosomes (-0.64‰). The lower δ26Mg found in Nostoc punctiforme would thus result from the absence of significant Mg efflux during cell growth in combination with either (a) discrimination against 26Mg during uptake by desolvation of Mg or transport across protein channels or (b) discrimination against 24Mg in the membrane transporter during efflux. The model predicts the preferential incorporation of 26Mg in cells and plant organs low in Mg and the absence of isotope fractionation in those high in Mg, corroborated by a compilation of Mg isotope ratios from fungi, bacteria, and higher plants.
- MeSH
- chemická frakcionace MeSH
- hořčík * MeSH
- izotopy MeSH
- Nostoc * MeSH
- rostliny MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
A116Cd-106Cd double-spike method in combination with thermal ionization mass spectrometry (TIMS) was applied to obtain cadmium (Cd) mass fractions and stable isotope compositions in seven biogenic certified reference materials (pine needles, tomato leaves, spinach leaves, lichen, mussel tissue, oyster tissue, and pig kidney). This sample set was supplemented by the analysis of two manganese nodules and one soil reference material for which the Cd isotopic data has already been reported. The intermediate measurement precision of the whole protocol as determined for the NIST SRM 3108 Cd standard solution yields an excellent value of δ114/110Cd of -0.005 ± 0.029‰ (2SD, n = 47). The Cd isotopic compositions of the biogenic materials, reported as δ114/110Cd relative to NIST SRM 3108, range from -0.52 to +0.50‰. Plants show δ114/110Cd mean values ranging from -0.09 to +0.45‰ whereas the δ114/110Cd value of -0.17‰ was detected in the lichen and the values of -0.51, -0.52, and +0.47‰ were gathered for the oyster, mussel, and pig kidney tissues, respectively. The observed large variation of the δ114/110Cd values in the biogenic reference materials indicates a potential to use the natural mass-dependent Cd isotope fractionation in environmental, biogeochemical, and physiological studies.
Feedstock type influences bacterial and methanogenic communities in anaerobic digestion. These two communities work tightly to maintain the stability of anaerobic digestion. How to quick report the changes of microbial community structure especially methanogenesis is the key issue for optimizing anaerobic digestion process. In this study, 13C isotope fractionations of CH4 and CO2 in biogas and microbial community composition were analyzed in 5 different feedstocks. Our results showed that grass silage, maize silage and swine manure fed reactors had similar δ 13C values and methanogenic community composition, dominated by Methanosarcinaceae. The lowest δ 13CH4 values were detected in straw and chicken manure fed reactors, reflecting reduced microbial degradation of material or the presence of toxic components in these feedstocks. The straw fed bioreactor lead to low δ 13CH4 values, probably reflecting relatively high levels of the syntrophic acetate oxidizing bacteria, Synergistaceae and Syntrophaceae, which might work collectively with hydrogenotrophic methanogens, resulting in the low δ 13CH4 values in this bioreactor. Significantly, all core microbes in the 5 different feedstock fed bioreactors were either Clostridia species or related to the Synergistaceae (syntrophic acetate oxidizing bacteria).
- MeSH
- anaerobióza MeSH
- biopaliva * MeSH
- bioreaktory MeSH
- hnůj MeSH
- izotopy MeSH
- methan MeSH
- mikrobiota * MeSH
- prasata MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
We studied thallium (Tl) isotope fractionation in white mustard grown hydroponically at different Tl doses. Thallium isotope signatures in plants indicated preferential incorporation of the light 203Tl isotope during Tl uptake from the nutrient solution. Negative isotope fractionation was even more pronounced in dependence on how much the available Tl pool decreased. This finding corresponds to the concept of isotope overprinting related to a high contamination level in the growing media (solution or soil). Regarding Tl translocation in plants, we observed a large Tl isotope shift with an enrichment in the heavy 205Tl isotope in the shoots relative to the roots in treatments with low/moderate solution Tl concentrations (0.01/0.05 mg Tl/L), with the corresponding α205/203Tl fractionation factors of ˜1.007 and 1.003, respectively. This finding is probably a consequence of specific (plant) reactions of Tl replacing K in its cycle. The formation of the S-coordinated Tl(I) complexes, potentially affecting both Tl accumulation and Tl isotope fractionation in plants, however, was not proven in our plants, since we did not have indication for that on the basis of X-ray absorption spectroscopy, suggesting that Tl was mainly present as free/hydrated Tl+ ion or chemically bound to O-containing functional groups.
- MeSH
- algoritmy MeSH
- biomasa MeSH
- Brassica metabolismus MeSH
- hořčice rodu Brassica metabolismus MeSH
- kořeny rostlin metabolismus MeSH
- kovy metabolismus MeSH
- listy rostlin metabolismus MeSH
- radioaktivní znečišťující látky MeSH
- radioizotopy thallia chemie metabolismus MeSH
- stonky rostlin metabolismus MeSH
- thallium chemie metabolismus MeSH
- výhonky rostlin metabolismus MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM10). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ(60)Ni (-0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ(65)Cu (-0.06 ± 0.06‰ to -3.94 ± 0.3‰) values which exceeds the range of δ(60)Ni and δ(65)Cu values determined in the smelter, i.e. in feeding material and slag (δ(60)Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ(65)Cu from -1.67 ± 0.04‰ to -1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ(60)Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ(65)Cu up to -0.06 ± 0.06‰ and -0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment.
High Cs-137 concentrations in plants growing on peatland inspired us to investigate the quantity of its bioavailable fraction in natural peat. Our investigation aims to: a) estimate the quantity of bioavailable Cs-137 and Pu present in peat, b) verify the similarity of Cs-137 and K-40 behaviours, and c) perform a quantification of Cs-137 and Pu transfer from peat to plants. We analysed the vertical distribution of Cs-137 and Pu isotopes in the peat and their concentrations in plants growing on these places. Bioavailability of radionuclides was investigated by sequential extraction. Sequential analyses revealed that it was the upper layer which contained the majority of Cs-137 in an available form while deeper layers retained Cs-137 in immobile fractions. We can conclude that 18% of all Cs-137 in the peat is still bioavailable. Despite of the low quantity of bioavailable fraction of Cs-137 its transfer factor reached extremely high values. In the case of Pu, 64% of its total amount was associated with fulvic/humic acids which resulted in the high transfer factor from peat to plants. 27 years after the Chernobyl nuclear accident, the significant part of radionuclides deposited in peatland is still bioavailable.
Here, for the first time, we report the thallium (Tl) isotope record in moderately contaminated soils with contrasting land management (forest and meadow soils), which have been affected by emissions from coal-fired power plants. Our findings clearly demonstrate that Tl of anthropogenic (high-temperature) origin with light isotope composition was deposited onto the studied soils, where heavier Tl (ε(205)Tl ∼ -1) naturally occurs. The results show a positive linear relationship (R(2) = 0.71) between 1/Tl and the isotope record, as determined for all the soils and bedrocks, also indicative of binary Tl mixing between two dominant reservoirs. We also identified significant Tl isotope variations within the products from coal combustion and thermo-desorption experiments with local Tl-rich coal pyrite. Bottom ash exhibited the heaviest Tl isotope composition (ε(205)Tl ∼ 0), followed by fly ash (ε(205)Tl between -2.5 and -2.8) and volatile Tl fractions (ε(205)Tl between -6.2 and -10.3), suggesting partial Tl isotope fractionations. Despite the evident role of soil processes in the isotope redistributions, we demonstrate that Tl contamination can be traced in soils and propose that the isotope data represent a possible tool to aid our understanding of postdepositional Tl dynamics in surface environments for the future.
- MeSH
- elektrárny MeSH
- látky znečišťující půdu MeSH
- monitorování životního prostředí MeSH
- půda * MeSH
- thallium * MeSH
- uhlí MeSH
- Publikační typ
- časopisecké články MeSH
We studied arid desert soils from Namibia (Rosh Pinah) that were contaminated with up to 7 mg kg-1 of thallium (Tl) via dust emitted from a local flotation tailing dam. Chemical extractions of waste and soil materials indicated that most of the Tl is strongly bound, in accordance with X-ray diffraction and X-ray absorption spectroscopy data that point to the predominant association of Tl with metal sulfides and phyllosilicates. The isotope fractionation factor ε205Tl of the soil samples (from -0.4 to +3.8) shows a positive linear relationship (R2 = 0.62) with 1/Tl, indicative for the mixing of two major Tl pools, presumably anthropogenic Tl and geogenic Tl. The ε205Tl value for the topmost soil samples (∼+3) closely matches the ε205Tl value for post-flotation waste particles with a diameter of <0.05 mm, whereas the bulk flotation waste exhibits a significantly larger ε205Tl value (∼+6). These variations are in accordance with predominant atmospheric transfer of Tl from the tailings to the adjacent soils via fine (dust) particles. The identified minimal Tl alteration in soils indicates that only a small part of the Tl could be potentially released and passively enter the vegetation, local population and/or food chain in the long term. From this viewpoint, Tl does not represent such an important environmental concern as other (abundant) contaminants at the locality. Furthermore, there could be a relevance for other alkaline desert soils, including those where Tl pollution plays a major role.
- MeSH
- izotopy MeSH
- látky znečišťující půdu analýza MeSH
- monitorování životního prostředí metody MeSH
- potravní řetězec MeSH
- pouštní klima MeSH
- půda chemie MeSH
- thallium analýza MeSH
- znečištění životního prostředí MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Namibie MeSH
