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This study presents the latest results of the groundwater monitoring of a research project, which tested an innovative pump and treat method in combination with an in-situ remediation. This technique was assessed on an abandoned site in Austria, where two hot spots of hexavalent chromium (Cr(VI)) were located. For the in-situ remediation, a strong reducing agent (sodium dithionite) was injected into the underground to reduce Cr(VI) to Cr(III) by using different injection strategies. Throughout this treatment, part of the Cr(VI) is mobilized and not instantly reduced. To prevent a further spreading of the mobilized Cr(VI), the pump and treat method, which uses zero-valent iron to clean the groundwater, was installed downgradient of the hot spots. Based on the groundwater sample analyses, it was possible to distinguish different remediation phases, characterized by excess chromate and excess sulfite. During the excess sulfite conditions, Cr(VI) was successfully removed from the system, but after terminating the sodium dithionite injection, the Cr(VI) rebounded.

Determining the topology of membrane-inserted proteins and peptides often relies upon indirect fluorescent measurements. One such technique uses NBD, an environmentally sensitive fluorophore that can be covalently linked to proteins. Relative to a hydrophilic environment, NBD in a hydrophobic environment shows an increase in emission intensity and a shift to shorter wavelengths. To gain further insight, NBD fluorescence can be chemically quenched using dithionite. As dithionite is an anion, it is only expected to penetrate the outer leaflet interfacial region and should be excluded from the hydrocarbon core, the inner leaflet, and the lumen of LUV. This assumption holds at neutral pH, where a large number of NBD/dithionite experiments are carried out. Here, we report control experiments in which LUV were directly labeled with NBD-PE to assess dithionite quenching in acidic conditions. Results showed that at acidic pH, dithionite moved more freely across the bilayer to quench the inner leaflet. For the buffer conditions used, dithionite exhibited a sharp change in behavior between pH 5.5 and 6.0. Therefore, in acidic conditions, dithionite could not differentiate in which leaflet the NBD resided.

The tremendous reservoir of soil organic carbon (SOC) in wetlands is being threatened by water-table decline (WTD) globally. However, the SOC response to WTD remains highly uncertain. Here we examine the under-investigated role of iron (Fe) in mediating soil enzyme activity and lignin stabilization in a mesocosm WTD experiment in an alpine wetland. In contrast to the classic ‘enzyme latch’ theory, phenol oxidative activity is mainly controlled by ferrous iron [Fe(II)] and declines with WTD, leading to an accumulation of dissolvable aromatics and a reduced activity of hydrolytic enzyme. Furthermore, using dithionite to remove Fe oxides, we observe a significant increase of Fe-protected lignin phenols in the air-exposed soils. Fe oxidation hence acts as an ‘iron gate’ against the ‘enzyme latch’ in regulating wetland SOC dynamics under oxygen exposure. This newly recognized mechanism may be key to predicting wetland soil carbon storage with intensified WTD in a changing climate. The response of soil organic carbon in wetlands to water-table decline remains uncertain. Here, the authors examine the role of iron in mediating soil enzyme activity and lignin stabilization and find that iron protecting lignin phenols in soils exposed to air acts as an iron gate against the enzyme latch.

Boreal peatlands store abundant carbon (C) belowground because of saturated conditions and cold temperatures, which inhibit the enzymatic release of dissolved organic carbon (DOC) from organic matter. However, metals may also bind DOC, as well as nitrogen (N) and phosphorus (P), and their impact may vary among peatlands with differing hydrology. To assess variation of metal-C-nutrient interactions within and among peatlands and with depth, we sampled cores from seven peatlands in the Marcell Experimental Forest, Minnesota, including bogs, poor fens, and a rich fen. We extracted peat with sodium sulfate to release elements bound with exchangeable metals such as calcium (Ca) or aluminum (Al), and with sodium dithionite to release elements bound with the redox-active metals iron (Fe) and manganese (Mn). We compared extracted elements to long-term peat porewater measurements. Mean DOC extracted by sulfate or dithionite in the bogs and poor fens was 5 or 8 times greater, respectively, than porewater DOC, and in the rich fen it was 8 or 38 times greater. Similarly, N and P extracted by sulfate and dithionite were 10–24 times higher than porewater in the bogs and poor fens and 7–55 times higher in the rich fen. The ratio and absolute values of redox-sensitive and ion-exchangeable elements varied by element among peatland types and with peat depth and values were not always greater in fens than bogs. We conclude that both redox-active (Fe) and non-redox-active (Ca and Al) metals bind important pools of peatland C and nutrients regardless of peatland hydrologic type and despite the very low total mineral content of these boreal peats.

Fe-OC is crucial for SOC preservation in the global ecosystem. However, there is still significant uncertainty in the determination methods of Fe-OC, and these methods are often not calibrated to each other, making the Fe-OC content by different methods impossible to compare. Here, Fe-OC is analyzed by the CBD method and the SD method from 45 soils from different land types (e.g., wetland, grassland, and forest) to compare and analyze the uncertainty and influencing factors between the two methods. Our results showed that the Fe-OC contributions to SOC (fFe-OC) measured by CBD and SD methods were significantly lower in the wetland ecosystem than in grassland and forest ecosystems. The Fe-OC content and fFe-OC in the grassland ecosystem was significantly higher using the CBD method compared to the SD method, with no significant difference between the methods in wetland and forest ecosystems. The random forest model revealed that Fe-OCCBD content was mainly affected by C/N, Clay%, and TC, whereas SOC, total nitrogen, and soil inorganic carbon were the main influences on Fe-OCSD. Taken together, our findings highlight the importance of incorporating ecosystem types and soil properties into soil carbon estimation models when predicting and estimating Fe-OC and its contribution to SOC.

A new method for hemoglobin (Hb) deoxygenation, in suspension or within red blood cells (RBCs) is described using the commercial enzyme product, EC-Oxyrase®. The enzymatic deoxygenation method has several advantages over established deoxygenation methodologies, such as avoiding side reactions that produce methemoglobin (metHb), thus eliminating the need for an inert deoxygenation gas and airtight vessel, and facilitates easy re-oxygenation of Hb/RBCs by washing with a buffer that contains dissolved oxygen (DO). The UV-visible spectra of deoxyHb and metHb purified from human RBCs using three different preparation methods (sodium dithionite [to produce deoxyHb], sodium nitrite [to produce metHb], and EC-Oxyrase® [to produce deoxyHb]) show the high purity of deoxyHb prepared using EC-Oxyrase® (with little to no metHb or hemichrome production from side reactions). The oxyHb deoxygenation time course of EC-Oxyrase® follows first order reaction kinetics. The paramagnetic characteristics of intracellular Hb in RBCs were compared using Cell Tracking Velocimetry (CTV) for healthy and sickle cell disease (SCD) donors and oxygen equilibrium curves show that the function of healthy RBCs is unchanged after EC-Oxyrase® treatment. The results confirm that this enzymatic approach to deoxygenation produces pure deoxyHb, can be re-oxygenated easily, prepared aerobically and has similar paramagnetic mobility to existing methods of producing deoxyHb and metHb.

Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts of metal reductant and the requirement of installing a directing group into alkenes to suppress the inherent β-H elimination bring great limitations to this type of reaction. We demonstrate herein that the difunctionalization of alkenes with two different alkyl halides is accessible via a radical-anion relay with Na 2 S 2 O 4 as both reductant and sulfone-source. The Na 2 S 2 O 4 together with the electron-shuttle catalyst is crucial to divert the mechanistic pathway toward the formation of alkyl sulfone anion instead of the previously reported alkylmetal intermediates. Mechanistic studies allow the identification of carbon-centered alkyl radical and sulfur-centered alkyl sulfone radical, which are in equilibrium via capture or extrusion of SO 2 and could be converted to alkyl sulfone anion accelerated by iron electron-shuttle catalysis, leading to the observed high chemoselectivity. Stoichiometric amounts of metal reductant and the requirement of a directing group limit the application of transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides. Here, the authors report a reductive difunctionalization of alkenes via a radical-anion relay with Na 2 S 2 O 4 as both reductant and sulfone-source.

Developing mild decolorization technology is critical for accomplishing clean pulping to overcome issues of the severe degradation of cellulose during the preparation of cotton pulp from waste cotton textiles and the high energy consumed in this preparation. The sodium hydroxide (NaOH)-sodium dithionite (Na2S2O4) system is widely used for decolorizing cotton fabrics. However, previous reports have only studied decolorizing cotton fabrics using this hybrid system and did not clarify the decolorization mechanism of NaOH and Na2S2O4 on fabric dyed with different types of reactive dyes. Therefore, in this work, according to the chromophore groups and active groups of the reactive dyes, the decolorization of cotton fibers dyed with azo monochlorotriazine reactive dyes, anthraquinone vinyl sulfone reactive dyes and diazobismonochlorotriazine reactive dyes was studied. The decolorization mechanism of NaOH and Na2S2O4 on cotton fabrics dyed with different types of reactive dyes was clarified by employing NaOH and Na2S2O4 separately and in combination. Fourier transform infrared spectroscopy, X-ray diffractometer and extension testing were used to explore the effects of decolorization on the chemical structure, crystalline structure, and physical and mechanical properties of cotton fabrics. This work provides a theoretical basis for the decolorization of cotton fabrics dyed using different reactive dyes.Graphic abstract

The chemical reduction within a family of organic selenocyanates, as masked selenols, using reducing agents, such as Rongalite, sodium dithionite, and sodium thiosulfate is investigated. Using Rongalite, the corresponding diselenides were obtained quantitatively and selectively in very good to excellent yields (51–100 %) starting from alkyl, aryl, and benzyl selenocyanates. The scope of the reaction is unaffected by the electronic nature of the substituents. Furthermore, the reducing agent, Rongalite, is compatible with hydrolysable and reducing‐sensitive functional groups. Additionally, a simple methodology employing the in‐situ generated benzyl selenolate anion (PhCH2Se−) to promote aliphatic nucleophilic substitution, epoxide ring opening, and Michael addition reactions has been developed; thus, extending the structural diversity of the synthesized selenium derivatives. The chemical reduction of alkyl, aryl, and benzyl selenocyanates, as masked selenols, using Rongalite is investigated. As a result, the corresponding diselenides were obtained selectively in very good to excellent yields. Additionally, a simple methodology is described using the in‐situ generated benzyl selenolate anion to promote nucleophilic substitution, epoxide ring opening, and Michael addition reactions.

Hydrogen production from microalgae has attracted considerable attention due to its high energy content and as a renewable and environmentally friendly energy source. Various strains of microalgae have been reported to produce “biohydrogen”, but screening for new strains is still necessary to discover strains with higher hydrogen yields. A newly isolated hydrogen-producing green alga was screened and labeled Chlorella sp. KLSc59. The effect of extracellular pH, light intensity, external carbon sources, reducing agents, and nutrient deprivation on biohydrogen production of Chlorella sp. KLSc59 were investigated. Hydrogen yield was higher under anaerobic conditions. Under external pH 7.2 with 53.2 μmol photons m−2 s−1 light intensity and using acetate as a carbon source, the optimum hydrogen yield was 281 μmol H2 mg−1 Chl. Nutrient deprivation reduced the hydrogen yield. Several reducing agents were assessed, and 1 mM ethanol enhanced yield by 3 times for 850 μmol H2 mg−1 Chl, and 1 mM sodium dithionite increased yield by 2.7 times for 750 μmol H2 mg−1 Chl. Significantly, our new strain showed higher hydrogen yields ranging from 1.5 to 68 times compared with other microalgae. Thus, Chlorella sp. KLSc59 showed valuable potential for biohydrogen production.