Geochemical Transactions最新文献

Organic dye pollution in water has become a major source of environmental pollution. Mn(III/IV) oxides have attracted a great deal of attention to remove organic dye pollutants due to their unique structures and physicochemical properties. Numerous studies have reported the removal of dye by various Mn(III/IV) oxides through catalytic degradation and adsorption. The crystalline structures of manganese oxides and solution pH may exert substantial impact on the removal of dyes. However, few studies have focused on the oxidative degradation of RhB dye using Mn(III/IV) oxides with different crystal structures during a spontaneous reaction. In the present study, three manganese oxides with different crystal type (α-MnO₂, β-MnO₂, and δ-MnO₂) were prepared by refluxing process to decolorize RhB dye in various pH solutions.

The results showed that the decolorization efficiencies of RhB for the three manganese oxides all increase with decrease solution pH. α-MnO₂ exhibited highest activity and could efficiently degrade RhB at pH 2–6. The degradation of RhB by β-MnO₂ and δ-MnO₂ could be observed at pH 2–3, and only little adsorption RhB on manganese oxides could be found at pH 4–6. The UPLC/MS analysis suggests that the decolorization of RhB by manganese oxides consists of three main stages: (1) cleavage of the ethyl groups from RhB molecular to form Rh; (2) further destruction of –COOH and –CNH₂ from Rh to form the small molecular substances; (3) mineralization of the small molecular substances into CO₂, H₂O, NO₃ ^? and NH₄ ⁺.

Overall, these results indicate that α-MnO₂ may be envisaged as efficient oxidants for the treatment of organic dye-containing wastewater under acid conditions.

Todorokite, a 3?×?3 tectomanganate, is one of three main manganese oxide minerals in marine nodules and can be used as an active MnO₆ octahedral molecular sieve. The formation of todorokite is closely associated with the poorly crystalline phyllomanganates in nature. However, the effect of the preparative parameters on the transformation of “c-disordered” H⁺-birnessites, analogue to natural phyllomanganates, into todorokite has not yet been explored.

Synthesis of “c-disordered” H⁺-birnessites with different average manganese oxidation states (AOS) was performed by controlling the MnO₄ ^?/Mn²⁺ ratio in low-concentrated NaOH or KOH media. Further transformation to todorokite, using “c-disordered” H⁺-birnessites pre-exchanged with Na⁺ or K⁺ or not before exchange with Mg²⁺, was conducted under reflux conditions to investigate the effects of Mn AOS and interlayer cations. The results show that all of these “c-disordered” H⁺-birnessites exhibit hexagonal layer symmetry and can be transformed into todorokite to different extents. “c-disordered” H⁺-birnessite without pre-exchange treatment contains lower levels of Na/K and is preferably transformed into ramsdellite with a smaller 1?×?2 tunnel structure rather than todorokite. Na⁺ pre-exchange, i.e. to form Na-H-birnessite, greatly enhances transformation into todorokite, whereas K⁺ pre-exchange, i.e. to form K-H-birnessite, inhibits the transformation. This is because the interlayer K⁺ of birnessite cannot be completely exchanged with Mg²⁺, which restrains the formation of tunnel “walls” with 1?nm in length. When the Mn AOS values of Na-H-birnessite increase from 3.58 to 3.74, the rate and extent of the transformation sharply decrease, indicating that a key process is Mn(III) species migration from layer into interlayer to form the tunnel structure during todorokite formation.

Structural Mn(III), together with the content and type of interlayer metal ions, plays a crucial role in the transformation of “c-disordered” H⁺-birnessites with hexagonal symmetry into todorokite. This provides further explanation for the common occurrence of todorokite in the hydrothermal ocean environment, where is usually enriched in large metal ions such as Mg, Ca, Ni, Co and etc. These results have significant implications for exploring the origin and formation process of todorokite in various geochemical settings and promoting the practical application of todorokite in many fields.

We studied the annual variability of the concentration and isotopic composition of main sulfur species and sulfide oxidation intermediates in the water column of monomictic fresh-water Lake Kinneret. Sulfate concentrations in the lake are <1?mM and similar to concentrations that are proposed to have existed in the Paleoproterozoic ocean. The main goal of this research was to explore biogeochemical constrains of sulfur cycling in the modern low-sulfate fresh-water lake and to identify which processes may be responsible for the isotopic composition of sulfur species in the Precambrian sedimentary rocks.

At the deepest point of the lake, the sulfate inventory decreases by more than 20% between March and December due to microbial sulfate reduction leading to the buildup of hydrogen sulfide. During the initial stages of stratification, sulfur isotope fractionation between sulfate and hydrogen sulfide is low (11.6?‰) and sulfur oxyanions (e.g. thiosulfate and sulfite) are the main products of the incomplete oxidation of hydrogen sulfide. During the stratification and at the beginning of the lake mixing (July–December), the inventory of hydrogen sulfide as well as of sulfide oxidation intermediates in the water column increases and is accompanied by an increase in sulfur isotope fractionation to 30?±?4?‰ in October. During the period of erosion of the chemocline, zero-valent sulfur prevails over sulfur oxyanions. In the terminal period of the mixing of the water column (January), the concentration of hydrogen sulfide decreases, the inventory of sulfide oxidation intermediates increases, and sulfur isotope fractionation decreases to 20?±?2?‰.

Sulfide oxidation intermediates are present in the water column of Lake Kinneret at all stages of stratification with significant increase during the mixing of the water column. Hydrogen sulfide inventory in the water column increases from March to December, and sharply decreases during the lake mixis in January. Sulfur isotope fractionation between sulfate and hydrogen sulfide as well as concentrations of sulfide oxidation intermediates can be explained either by microbial sulfate reduction alone or by microbial sulfate reduction combined with microbial disproportionation of sulfide oxidation intermediates. Our study of sulfur cycle in Lake Kinneret may be useful for understanding the range of biogeochemical processes in low sulfate oceans over Earth history.

In this work, the geochemistry of the rare earth elements (REE) was studied in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In these samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.

Although most reported biogenic Mn oxides are hexagonal birnessites, other types of biogenic Mn oxides also commonly occur in the environment. However, sorption characteristics and underlying mechanisms of the adsorption of heavy-metal ions on these biogenic Mn oxides are still rarely addressed. In this study, the sorption mechanisms of Cu(II) on a low valence biogenic Mn oxide, poorly crystallized bixbyite-like Mn₂O₃ (α-Mn₂O₃), were investigated.

The maximum adsorption capacity of Cu(II) onto this biogenic Mn oxide at pH?6.00 was 796?mmol/kg (0.45?mol Cu mol^?1 Mn). The complex structure of adsorbed Cu(II) was constrained using Cu extended X-ray absorption fine structure (EXAFS) analysis, combined with structural parameters of the biogenic Mn oxide with alternately arranged regular and distorted MnO₆ octahedra obtained through multiple-FEFF fitting of Mn EXAFS data. The sorbed Cu(II) was found to coordinate with the biogenic Mn oxide particle edges as inner-sphere complexes. At a relatively low Cu²⁺ loading (233?mmol/kg, pH?6.00), Cu(II) adsorbed onto the biogenic Mn oxide with two types of coordinated complexes, i.e., (1) coordinated with one regular/distorted MnO₆ octahedron as a monodentate-mononuclear complex and (2) with two adjacent MnO₆ octahedra as a bidentate-binuclear complex. While, at a relatively high Cu²⁺ loading (787?mmol/kg, pH?6.00), only one type of coordinated complex was constrained, the adsorbed Cu(II) coordinated with one regular/distorted MnO₆ octahedron as a monodentate-mononuclear complex.

This research extends further insight into the bacterial Mn(II) oxidation in the environment and serves as a good reference for understanding the interactions between metal ions and biogenic low valence Mn oxides, which are still poorly explored either theoretically or practically.

Many biominerals form from amorphous calcium carbonate (ACC), but this phase is highly unstable when synthesised in its pure form inorganically. Several species of earthworm secrete calcium carbonate granules which contain highly stable ACC. We analysed the milky fluid from which granules form and solid granules for amino acid (by liquid chromatography) and functional group (by Fourier transform infrared (FTIR) spectroscopy) compositions. Granule elemental composition was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) and electron microprobe analysis (EMPA). Mass of ACC present in solid granules was quantified using FTIR and compared to granule elemental and amino acid compositions. Bulk analysis of granules was of powdered bulk material. Spatially resolved analysis was of thin sections of granules using synchrotron-based μ-FTIR and EMPA electron microprobe analysis.

The milky fluid from which granules form is amino acid-rich (≤ 136 ± 3 nmol mg^?1 (n = 3; ± std dev) per individual amino acid); the CaCO₃ phase present is ACC. Even four years after production, granules contain ACC. No correlation exists between mass of ACC present and granule elemental composition. Granule amino acid concentrations correlate well with ACC content (r ≥ 0.7, p ≤ 0.05) consistent with a role for amino acids (or the proteins they make up) in ACC stabilisation. Intra-granule variation in ACC (RSD = 16%) and amino acid concentration (RSD = 22–35%) was high for granules produced by the same earthworm. Maps of ACC distribution produced using synchrotron-based μ-FTIR mapping of granule thin sections and the relative intensity of the ν₂: ν₄ peak ratio, cluster analysis and component regression using ACC and calcite standards showed similar spatial distributions of likely ACC-rich and calcite-rich areas. We could not identify organic peaks in the μ-FTIR spectra and thus could not determine whether ACC-rich domains also had relatively high amino acid concentrations. No correlation exists between ACC distribution and elemental concentrations determined by EMPA.

ACC present in earthworm CaCO₃ granules is highly stable. Our results suggest a role for amino acids (or proteins) in this stability. We see no evidence for stabilisation of ACC by incorporation of inorganic components.

Stable Zn isotopes fractionation was studied in main biogeochemical compartments of a pristine larch forest of Central Siberia developed over continuous permafrost basalt rocks. Two north- and south-oriented watershed slopes having distinctly different vegetation biomass and active layer depth were used as natural proxy for predicting possible future climate changes occurring in this region. In addition, peat bog zone exhibiting totally different vegetation, hydrology and soil temperature regime has been studied.

The isotopic composition of soil profile from Central Siberia is rather constant with a δ⁶⁶Zn value around 0.2‰ close to the value of various basalts. Zn isotopic composition in mosses (Sphagnum fuscum and Pleurozium schreberi) exhibits differences between surface layers presenting values from 0.14 to 0.2‰ and bottom layers presenting significantly higher values (0.5 – 0.7‰) than the underlain mineral surface. The humification of both dead moss and larch needles leads to retain the fraction where Zn bound most strongly thus releasing the lighter isotopes in solution and preserving the heavy isotopes in the humification products, in general accord with previous experimental and modeling works [GCA 75:7632–7643, 2011].

The larch (Larix gmelinii) from North and South-facing slopes is enriched in heavy isotopes compared to soil reservoir while larch from Sphagnum peatbog is enriched in light isotopes. This difference may result from stronger complexation of Zn by organic ligands and humification products in the peat bog compared to mineral surfaces in North- and South-facing slope.

During the course of the growing period, Zn followed the behavior of macronutrients with a decrease of concentration from June to September. During this period, an enrichment of larch needles by heavier Zn isotopes is observed in the various habitats. We suggest that the increase of the depth of rooting zone, and the decrease of DOC and Zn concentration in soil solution from the root uptake zone with progressively thawing soil could provoke heavy isotopes to become more available for the larch roots at the end of the vegetative season compared to the beginning of the season, because the decrease of DOC will facilitate the uptake of heavy isotope as it will be less retained in strong organic complexes.

On Late Cretaceous Tethyan upwelling sediments from the Mishash/Ghareb Formation (Negev, Israel), bulk geochemical and biomarker analyses were performed to explain the high proportion of phosphates in the lower part and of organic matter (OM) preserved in upper parts of the studied section. The profile is composed of three facies types; the underlying Phosphate Member (PM), the Oil Shale Member (OSM) and the overlying Marl Member (MM).

Total organic carbon (TOC) contents are highly variable over the whole profile reaching from 0.6% in the MM, to 24.5% in the OSM. Total iron (TFe) varies from 0.1% in the PM to 3.3% in the OSM. Total sulfur (TS) ranges between 0.1% in the MM and 3.4% in the OSM, resulting in a high C/S ratio of 6.5 in the OSM section. A mean proportion of 11.5% total phosphorus (TP) in the PM changed abruptly with the facies to a mean value of only 0.9% in the OSM and the MM.

The TOC/TOC_OR ratios argue for a high bacterial sulfate reduction activity and in addition, results from fatty acid analyses indicate that the activity of sulfide-oxidizing activity of bacteria was high during deposition of the PM, while decreasing during the deposition of the OSM.

The upwelling conditions effected a high primary productivity and consequently the presence of abundant OM. This, in combination with high sulfate availability in the sediments of the PM resulted in a higher sulfide production due to the activity of sulfate-reducing bacteria. Iron availability was a limiting factor during the deposition of the whole section, affecting the incorporation of S into OM. This resulted in the preservation of a substantial part of OM against microbial degradation due to naturally-occurring sulfurization processes expressed by the high C/S ratio of 6.5 in the OSM.

Further, the abundant sulfide in the pore water supported the growth of sulfide-oxidizing bacteria promoting the deposition of P, which amounted to as much as 15% in the PM. These conditions changed drastically from the PM to the OSM, resulting in a significant reduction of the apatite precipitation and a high concentration of reactive S species reacting with the OM.

Elemental sulfur (S) persists in natural aquatic environment in a variety of forms with different size distributions from dissolved to particulate. Determination of S speciation mainly consists of the application of chromatographic and electrochemical techniques while its size determination is limited only to the application of microscopic and light scattering techniques. S biological and geochemical importance together with recent increases of S industrial applications requires the development of different analytical tools for S sizing and quantification. In recent years the use of electrochemical measurements as a direct, fast, and inexpensive technique for the different nanoparticles (NPs) characterization (Ag, Au, Pt) is increasing. In this work, electrochemical i.e. chronoamperometric measurements at the Hg electrode are performed for determination of the size distribution of the S NPs.

S NPs were synthesized in aqueous medium by sodium polysulphide acidic hydrolysis. Chronoamperometric measurements reveal the polydisperse nature of the formed suspension of S NPs. The electrochemical results were compared with dynamic light scattering measurements parallel run in the same S NPs suspensions. The two methods show fairly good agreement, both suggesting a log-normal size distribution of the S NPs sizes characterized by similar parameters.

The preliminary results highlight the amperometric measurements as a promising tool for the size determination of the S NPs in the water environment.