Reducing Conditions Research Articles

Volcanism and turbidity current events as drivers of the evolution of benthic redox conditions: Organic matter enrichment in the Chang 7 member, Upper Triassic Yanchang formation, Ordos Basin, North China

Depositional events have a significant impact on the terrestrial redox conditions and provide evidence for studying the organic matter enrichment. The objective of this study was to evaluate the influence of volcanic and turbidity current events on benthic redox conditions during the Upper Triassic Chang 7 member (Ch7) of the Ordos Basin. To address these issues, the varying sedimentological settings, paleoredox conditions, and relationships between the redox environment and depositional events were investigated via sedimentary analysis of the profiles, microscopic analysis, organic geochemical analysis, and elemental geochemical data. The fine-grained sediments in the Chang 73 submember (Ch73) consist of abundant organic matter, collophanite, and framboidal pyrite. However, in the upper part of the Ch7 member, there was a decrease in organic matter, a decrease in the number of microorganisms, and an increase in pyrite size, indicating that the oxic environment is not favorable for organic matter enrichment. The element and geochemical proxies show similar vertical variations and redox changes. Volcanic activity can bring substantial amounts of material or elements to the basin. The enrichment of Hg and S exhibited considerable variation, ranging from 8.7 to 274.4 ppb and from 0.16 to 4.53 wt%, respectively, which influenced the organic matter accumulation through the flourishing and death of microorganisms and redox changes in the benthic environment of the terrestrial basin. As the lake basin shrinks, the Ti and Al contents increase with increasing frequency of turbidity current events, and the terrestrial debris transported to the lake basin gradually increases while carrying large amounts of oxygen and affecting sedimentation rates, contributing to the destruction of the reducing conditions of the benthic environment, subsequently, influencing organic matter accumulation. These results will be helpful in understanding the effect of multiple depositional events on organic matter enrichment in lacustrine basins.

Nickel-Catalyzed Desulfurative Cross-Coupling of Aryl Iodides with Heteroaromatic Thioethers via C-S Bond Cleavage.

Herein, we present a Ni-catalyzed direct cross-coupling of heteroaromatic thioethers with aryl iodides via selective C(sp2)-S bond cleavage under reductive conditions, thereby providing various biaryl frameworks with high efficiency. Mechanistic studies suggested Mo(CO)6 played a crucial role in facilitating the activation of the C(sp2)-S bond. This protocol demonstrated a wide substrate scope, operational simplicity, and good functional group compatibility. Furthermore, the utility of this reaction was highlighted by facile scale-up and sequential modification of heteroaryl frameworks.

Results and Conclusions | On Policy-Based Papers: Large Scale. Strategic Visioning & Design

The theme of this international research project and scientific journal issue is Re- Inventing Phoeniciae (Finiq): New Inter- sections of Tradition, Innovation, Land- scapes and Tourism. The respective International PhD workshop of Polis Uni- versity and Ferrara University took place from 09-20 January 2023. This phase concluded with a series of presentations, lectures, and graphical-conceptual dia- grams. After that, the researchers worked independently for the rest of the year to elaborate further scientific specula- tions and write down articles. Tutors of the workshop and the project have been: Prof. Besnik Aliaj, Prof. Pantelis Skayan- nis, Dr. Sotir Dhamo, Dr. Skender Luarasi, Dr. Llazar Kumaraku, Dr. Malvina Istrefaj, Dr. Doriana Musaj and Sadmira Malaj. Fi- niq Municipality is located in the South of Albania, cross-bordering Greece. It is in- cluded in the Vlora’s County and it is just 9 kilometers from the port & tourism City of Saranda; not far from the UNESCO City of Gjirokastra; and adjacent to the UNESCO Archeological Site of Butrint. The settle- ment of Finiq has been the main munici- pal center since the last administrative reform. The municipality looks “poor” and neglected, but indeed is rich in all aspects. It is particularly important because of the presence of the Foinikea Archaeologi- cal Park at the top of a hill (received this status in 2005). Inside the Municipal terri- tory, there are lots of attractive sites, such as the water springs Blue Eye; main riv- ers and lakes; the Monastery of St. Nikolla (in Mesopotam village), and many other amazing churches, etc. This makes the municipality dominated by nature (e.g. flat fields; a continuous layer of hills, rivers, and lakes, etc.) and monuments that rep- resent a rich cultural heritage. Within this context, some villages arise up in moun- tains or hills, characterized mostly either by forgotten historic houses and churches or by new infrastructures and civil struc- tures built in reinforced concrete. This is due to the fact that the new buildings were built irregularly during the late post- communist decades, instead of what was built historically. Therefore the local villag- es are losing gradually their own original spirit, which could be better observed in the case of UNESCO heritage settlements like the city of Gjirokaster, or in the villages of Dropull municipality (another Greek mi- nority area as Finiq). Most of the commu- nity, especially young people left due to a massive emigration mainly in Greece and the USA, or migration to the capital region of Tirana. This means that the municipal- ity suffers now from poor human capaci- ties, poor budgets, and low tax collection baseline, while the remaining people are getting older. However, the natural and historical potential, and the nearby port and touristic cities of Saranda and Gjiro- kastra (Albania), as well as Igoumentisa and Janina (Greece) make the area highly possible to be developed soon as a sup- port territory for agricultural, historic and hospitality services. Under the conditions of massive emigration and reduction of population, the researchers put emphasis on the use of new technologies and alternative municipal planning and urban- landscape design methodologies.

Revolutionizing CO2‐to‐C2 Conversion: Unleashing the Potential of CeO2 Nanocores for Self‐ Supported Electrocatalysts with Cu2O Nanoflakes on 3D Graphene Aerogel

AbstractCu serves as a promising electrocatalyst for converting CO2 into valuable C2 products in CO2 reduction reactions (CO2RR). However, instability in CO* formation is crucial for CO2 adsorption‐ desorption still remains a challenge under reduction conditions. This study explores the impact of lanthanide oxide, particularly CeO2, on Cu‐based catalytic performances. By leveraging Ce's distinctive electronic structure, CO* species are stabilized during the reaction in CeO2─Cu2O, resulting in exceptional catalytic performance for CO2 electroreduction to C2 products. Hybridizing CeO2‐Cu2O with graphene aerogel enhances electrochemical active surface area and CO2RR efficiency. The resulting CeO2─Cu2O(10%)/GA electrocatalyst exhibits a remarkable faradaic efficiency for C2 products, exceeding 62%, alongside exceptional stability over 80 h with wide potential window (−0.8 to −1.2 V) using a H‐cell. Systematic investigations elucidate the intricate interplay between surface properties and catalytic activity. Furthermore, a solar cell‐ powered CO2 reduction system demonstrates consistent performance (−27.8 mA cm−2 at 3.46 V) under solar radiation of ≈100 mW cm−2, showcasing outstanding stability with nearly 100% retention over 4 h of continuous illumination. In short, by harnessing catalytic and electronic effects, this innovation advances the development of electrocatalysts with heightened CO2‐to‐C2 selectivity, bridging fundamental research with technological innovation to tackle critical global challenges.

Photodriven Sm(III)-to-Sm(II) Reduction for Catalytic Applications.

The selectivity of SmI2 as a one electron-reductant motivates the development of methods for reductive Sm-catalysis. Photochemical methods for SmI2 regeneration are desired for catalytic transformations. In particular, returning SmIII-alkoxides to SmII is a crucial step for Sm-turnover in many potential applications. To this end, photochemical conditions for reduction of both SmI3 and a model SmIII-alkoxide to SmI2(THF)n are described here. The Hantzsch ester can serve either as a direct photoreductant or as the reductive quencher for an Ir-based photoredox catalyst. In contrast to previous SmIII reduction methodologies, no Lewis acidic additives or byproducts are involved, facilitating selective ligand coordination to Sm. Accordingly, SmII species can be generated photochemically from SmI3 in the presence of protic, chiral, and/or Lewis basic additives. Both the photoreductant and photoredox methods for SmI2 generation translate to intermolecular ketone-acrylate coupling as a proof-of-concept demonstration of a photodriven, Sm-catalyzed reductive cross-coupling reaction.

Cathodic poised potential stimulated the electron-sensitive C-P lyase pathway in glyphosate biodegradation

Glyphosate, the most widely used herbicide globally, is accumulating in the environment and poses significant potential eco- and bio-toxicity risks. While natural attenuation of glyphosate has been reported, the efficacy varies considerably and the dominant metabolite, aminomethylphosphonic acid (AMPA), is potentially more persistent and toxic. This study investigated the bioelectrochemical system (BES) for glyphosate degradation under anaerobic, reductive conditions. Atomistic simulations using density functional theory (DFT) predicted increased thermodynamic favorability for the non-dominant C-P lyase degradation pathway under external charge, which suppressed AMPA production. Experimental results confirmed that cathodic poised potential (-0.4 V vs. Ag/AgCl) enhanced glyphosate degradation (75 % in BES vs. ∼40 % in the control conditions after 37 days), and lowered the AMPA yield (0.52 mol AMPA yield per mol glyphosate removed in BES vs. 0.77–0.86 mol mol-1 in the control conditions). Geobacter lovleyi was likely the active species driving the C-P lyase pathway, as evidenced by the increase of its relative abundance, the upregulation of its extracellular electron transfer genes (most notably mtr) and the up-regulation of its phnJ and hcp genes (encoding C-P layse and hydroxylamine reductase respectively).

Sorption retards remediation of clayey sulfuric soils with straw‐derived dissolved organic matter

AbstractWhen sulfidic soils become drained, oxidation of pyrite can cause acidification and formation of iron (Fe) oxyhydroxy sulfate phases such as jarosite. Remediation via re‐establishment of reducing conditions requires submergence and addition of biodegradable organic carbon (OC) to stimulate activity of reducing bacteria. Addition of straw‐derived dissolved organic carbon (DOC) has been shown to induce rapid microbial reduction in sandy sulfuric (pH <4) soils. In clayey sulfuric soil, DOC may be less efficient because of limited availability for microbes due to its sorption to reactive minerals. We tested the possible effect of sorption on the remediative potential of straw‐derived DOC using a set of incubation and sorption experiments, and used solid‐state 13C‐NMR spectroscopy for the chemical characterization of OC. The tested materials were a clayey, jarosite‐containing sulfuric soil (pH 3), and artificial model soils composed of synthesized jarosite either mixed with quartz powder or quartz powder + clay minerals. The results showed that addition of DOC from wheat straw induces reduction conditions varying with soil sorptivity. For the model soils, DOC sorption was little, and DOC additions of 0.8 mg OC g−1 were sufficient to achieve permanently reducing conditions and an increase in pH to >6.0. In the natural sulfuric soil, much higher DOC additions were needed (1.8 mg OC g−1) to facilitate continuous reducing conditions, but pH increased only to values no higher than 5.0–5.5. The natural soil revealed strong sorption of added DOC. Sorption preferentially reduced the proportion of proteins, while the proportion of lignin components, which can hardly be used by microorganisms under reducing conditions, remained relatively high in solution. Thus, high DOC additions were required to overcome the sorption‐induced limitations in OC availability. The results suggest that wheat straw‐derived DOC is a promising approach also for remediation of clayey sulfuric soils; however, OC additions need to be adjusted to compensate for possible sorption.

Hydrochemical processes and inorganic nitrogen sources of shallow groundwater in the Sanjiang Plain, northeast China.

This study investigates the chemical characteristics, formation, and sources of inorganic nitrogen (IN) of shallow groundwater across the Sanjiang Plain, aiming to enhance drinking water safety management and pollution control. A total of 167 groundwater and 27 surface water samples were collected for constituents and isotopes (H2 and O18). The hydrogeochemical characteristics showed that the major type is HCO3- Ca·Mg, with low total dissolved solids and a neutral to weak alkaline nature. Rock weathering processes govern the hydrochemical composition of groundwater. Hydrogen and oxygen stable isotopes analyses revealed that precipitation serves as the main water source. In alluvial areas, oxidative conditions lead to the enrichment of NO3-N concentrations, with sewage, manure, and fertilizers being the primary IN sources. In lacustrine areas, intensive rice cultivation results in reductive conditions and strong denitrification processes, causing the loss of NO3-N and leaving NH4-N as the dominant IN form. Organic matter mineralization is likely a more significant contributor to NH4-N concentrations than ammonium fertilizers. These findings provide valuable information for further research on natural sources and groundwater pollution in areas with similar hydrogeological conditions. PRACTITIONER POINTS: Rock weathering processes govern the hydrochemical composition of groundwater, and precipitation serves as the main water source. In alluvial areas, oxidative conditions lead to the enrichment of NO3-N. In lacustrine areas, intensive rice cultivation results in reductive conditions and strong denitrification processes. Organic matter mineralization is likely a more significant contributor to NH4-N concentrations than ammonium fertilizers. These findings provide references for water management and information for further research on natural sources and groundwater pollution in areas with similar hydrogeological conditions.

Study on the extraction of neodymium metal by calciothermic reduction process

The study on the technology of producing neodymium metal using the calciothermic reduction process is reported in this article. The process primarily involves the conversion of neodymium oxide (Nd2O3) into neodymium fluoride (NdF3) followed by the reduction of neodymium fluoride to neodymium metal using calcium as reductant. Fluorinating conditions were standardised to obtain the desired product (NdF3) free of any unwanted impurities. The calciothermic reduction of the resulting neodymium fluoride was studied in detail to establish the reduction conditions to achieve maximum yield and purity of the neodymium metal. This process obtained the neodymium metal with a purity of 99.6% before refining step.

In-situ prepared co exsolution nano catalyst for efficient hydrogen generation via ammonia decomposition

Active and durable catalytic material for ammonia (NH3) decomposition reaction is attracting attentions for utilization of NH3 as an innovative hydrogen carrier. In this study, diverse single metal and alloy nano catalysts are prepared via in-situ exsolution method and their NH3 decomposition properties are evaluated. Transition metal cations (Ni, Co, Fe ions) are doped into the La0.43Ca0.37MxNyTi1-(x+y)O3-δ (LCMNT) perovskite oxide structure and exsolved on its surface as supported nano particles under reduction condition. The maximum doping level and chemical composition of exsolution catalysts are investigated to optimize their NH3 decomposition activity. The exsolution catalyst demonstrates improved NH3 decomposition characteristics compared to conventionally prepared infiltration catalysts, indicating higher conversion efficiency and H2 production rate. The exsolved nano catalysts also exhibit great thermochemical stability against catalyst agglomeration or surface nitriding. The results obtained in this study suggest the potential utilization of exsolution catalysts for on-site production of H2 through NH3 decomposition catalysis.

Characterization and catalytic performance of rGO-enhanced MnFe2O4 nanocomposites in CO oxidation

In this work, different weight ratio of reduce graphene oxide (rGO) incorporated manganese ferrite (MnFe2O4) is successfully prepared using reduction photolysis method. To have good spacing of layer, expanded graphite was employed for synthesis of graphene oxide by Hummer modified method. The synthesized rGO/MnFe2O4 nanocomposite was characterized by FTIR, EDX, Raman, XRD, BET, XPS, TGA, TPR and FESEM, while the magnetic properties are investigated employing VSM technique. The catalytic results demonstrated that the MnO2 and Fe2O3 have low catalytic activity and it is not active at temperature lower than 130 °C. The highest efficiency was noted for the MnFe2O4 nanocomposite. The demonstrated results appeared that the doped of rGO inter MnFe2O4 considerably improved the efficiency for oxidation of CO. On the other hand, the highest conversion was obtained for the 1 wt% rGO doped MnFe2O4 and it displayed a CO conversion of 100 % at 80 °C. 1 wt% rGO/MnFe2O4 with conversion 98% CO demonstrated higher activity compared with Fe2O3 and MnFe2O4. On the other hand, the results exhibited that the 1 wt% rGO/MnFe2O4 pretreated under oxidizing conditions appeared higher activity compared with synthesized catalyst dealt under reductive conditions, which assign to the higher adsorption capacity of O2, as well as, the results also appeared that the catalyst showed high stability under wet and dry conditions.

Cation Enrichment Promotes High-rate CO Electroreduction to C2+ Liquid Products.

Electrochemical reduction of CO into valuable multicarbon (C2+) liquids is crucial for reducing CO2 emissions and advancing clean energy, yet mastering efficiency and selectivity in this process remains a tough challenge. Herein, we employ a surface-modification strategy using electrochemically active polymeric 1,4,5,8-naphthalenete-tracarboxylic dianhydride (PNTCDA)-modified copper nanosheets (PM-Cu) to rearrange reactive species in the electric double layer, where the PNTCDA triggers a distinctive enolization that anchor potassium ions (K+) onto the cathode surface under reduction condition. Electrochemical analysis and computational simulations revealed that this approach fine-tunes K+ distribution in the double layer, making the dehydration of hydrated K+ more efficient and reducing active water molecules at the interface, thus inhibiting the hydrogen evolution reaction while concurrently promoting CO reduction via enhanced C‒C coupling. For the first time, the PM-Cu catalyst demonstrates ampere-scale current densities with the exclusive selectivity of a C2+ liquid product yield exceeding 90%. Thus, by tailoring the local microenvironment with electrochemically active organics, it is possible to modulate CO reduction, improve sustainable energy storage, and increase industrial carbon utilization.

Examining the Importance of Hydrogen Bonding and Proton Transfer in Iron Porphyrin-Mediated Carbon Dioxide Upconversion.

ConspectusThe title should give a sense of the "big picture" of this Account, but what is it really about? An unexpected change in research direction? A series of courageous and creative students? A team taking on challenging problems in chemistry? The answer is a definite "yes" to all of the above. More specifically, the problem in which we are interested is the upconversion or valorization of carbon dioxide. This problem has captured the attention of a great many chemists in earnest following the gas crisis of the 1970s and more recently galvanized due to climate concerns arising from the ongoing release of anthropogenic carbon. Addressing the problem of atmospheric carbon accumulation requires effort in two very broad areas: capture and conversion. Storage is an alternative to conversion, but this eliminates the opportunity to use what might be otherwise a waste product. Our group has investigated a series of modified versions of iron(III)-5,10,15,20-tetraphenylporphyrin (FeTPP) that can convert CO2 to carbon monoxide, which is a versatile and useful precursor for other syntheses. Following pioneering work from Savéant and his colleagues in the 1990s and thereafter, we started with a simple question: how many pendent ancillary groups that can donate H-bonds or protons are needed to support efficient CO2-to-CO conversion? Using a molecule with only one 2-hydroxylphenyl group, we demonstrated that the single prepositioned -OH group gave rise to efficient turnover, but only when experiments were carried out in a weakly H-bond-accepting solvent system. In other words, the ability of a solvent to accept H-bonds can impede CO2 reduction. We followed up with a deeper investigation of the influence of H-bonding interactions with external acids in FeTPP-mediated CO2 reduction. Savéant's framework mechanism appears to be independent of solvent, and rate differences can be approximated by considering H-bonding equilibria. Following that work, we sought to better understand the minimum catalyst design requirements with respect to internal H-bond/proton donors. To that end, we produced all possible isomers of tetraarylpoprhyrins with 2,6-dihydroxyphenyl + phenyl groups. All else being equal, the complexes with a formally trans orientation of the 2,6-dihydroxyphenyl groups performed the best. Most recently, we surveyed the roles of internal and external Brønsted acids with different pKa values. Surprisingly, the best-performing catalysts have more weakly acidic internal groups. Overall, our work has demonstrated that CO2 reduction mediated by porphyrin catalysts can be improved by considering solvent H-bonding, the orientation of internal H-bonding groups, and the balance of the pKa values of internal and external acids. The future for molecular electrocatalysts is promising as more ideas emerge about how to design molecules and conditions for CO2 reduction.

Aggregation of Albumins under Reductive Radical Stress.

The reactions of radicals with human serum albumin (HSA) under reductive stress conditions were studied using pulse radiolysis and photochemical methods. It was proved that irradiation of HSA solutions under reductive stress conditions results in the formation of stable protein aggregates. HSA aggregates induced by ionizing radiation are characterized by unique emission, different from the UV emission of non-irradiated solutions. The comparison of transient absorption spectra and the reactivity of hydrated electrons (eaq-) with amino acids or HSA suggests that electron attachment to disulfide bonds is responsible for the transient spectrum recorded in the case of albumin solutions. The reactions of eaq- and CO2•- with HSA lead to the formation of the same products. Recombination of sulfur-centered radicals plays a crucial role in the generation of HSA nanoparticles, which are stabilized by intermolecular disulfide bonds. The process of creating disulfide bridges under the influence of ionizing radiation is a promising method for the synthesis of biocompatible protein nanostructures for medical applications. Our Raman spectroscopy studies indicate strong modification of disulfide bonds and confirm the aggregation of albumins as well. Low-temperature measurements indicate the possibility of electron tunneling through the HSA protein structure to specific CyS-SCy bridges. The current study showed that the efficiency of HSA aggregation depends on two main factors: dose rate (number of pulses per unit time in the case of pulse radiolysis) and the temperature of the irradiated solution.

Origin of copper dissolution under electrocatalytic reduction conditions involving amines.

Cu dissolution has been identified as the dominant process that causes cathode degradation and losses even under cathodic conditions involving methylamine. Despite extensive experimental research, our fundamental and theoretical understanding of the atomic-scale mechanism for Cu dissolution under electrochemical conditions, eventually coupled with surface restructuring processes, is limited. Here, driven by the observation that the working Cu electrode is corroded using mixtures of acetone and methylamine even under reductive potential conditions (-0.75 V vs. RHE), we employed Grand Canonical density functional theory to understand this dynamic process under potential from a microscopic perspective. We show that amine ligands in solution directly chemisorb on the electrode, coordinate with the metal center, and drive the rearrangement of the copper surface by extracting Cu as adatoms in low coordination positions, where other amine ligands can coordinate and stabilize a surface copper-ligand complex, finally forming a detached Cu-amine cationic complex in solution, even under negative potential conditions. Calculations predict that dissolution would occur for a potential of -1.1 V vs. RHE or above. Our work provides a fundamental understanding of Cu dissolution facilitated by surface restructuring in amine solutions under electroreduction conditions, which is required for the rational design of durable Cu-based cathodes for electrochemical amination or other amine involving reduction processes.

Reconstructive Approach to the Regiospecific Synthesis of N9‐Alkylated Purines

AbstractA regiospecific synthesis of N9‐alkylated purines as novel acyclic nucleosides was developed. This approach is based on reconstructive methodology involving the construction of a target heterocyclic scaffold on a readily available 5‐aminotetrazole moiety, which is subsequently cleaved under reductive conditions due to azido‐tetrazole tautomerism. It appeared that the rate of reduction for the azide fragment in 6‐nitro‐7‐alkylaminotetrazolo[1,5‐a]pyrimidines is much greater than the rate of nitro group reduction. Treatment of these heterocycles with hydrogen over a palladium catalyst resulted in the formation of triaminopyrimidines in excellent yields through the reduction of both the azide and nitro group. Triaminopyrimidines were transformed into the desired N9‐alkylated purines, and an analog of the marketed drug penciclovir was synthesized by the developed method.

Enhancing assimilatory sulfate reduction with ferrihydrite-humic acid coprecipitate in anaerobic sulfate-containing wastewater treatment

Sulfide produced from dissimilatory sulfate reduction can combine with hydrogen to form hydrogen sulfide, causing odor issues and environmental pollution. To address this problem, ferrihydrite-humic acid coprecipitate was added to improve assimilatory sulfate reduction (ASR), resulting in a decrease in sulfide production (190.2 ± 14.6 mg/L in the Fh-HA group vs. 246.3 ± 8.1 mg/L in the Fh group) with high sulfate removal. Humic acid, adsorbed on the surface of ferrihydrite, delayed secondary mineralization of ferrihydrite under sulfate reduction condition. Therefore, more iron-reducing species (e.g. Trichococcus, Geobacter) were enriched with ferrihydrite-humic acid coprecipitate to transfer more electrons to other species, which led to more COD reduction, an increase in electron transfer capacity, and a decrease in the NADH/NAD+ ratio. Metagenomic analysis also indicated that functional genes related to ASR was enhanced with ferrihydrite-humic acid coprecipitate. Thus, the addition of ferrihydrite-humic acid coprecipitate can be considered as a promising candidate for anaerobic sulfate wastewater treatment.

The rise of electrochemical surface science: From in situ interface structure to operando dynamics

Surface science studies of electrochemical interfaces and processes have gained increasing popularity in the last decades, owning to the increasing importance of electrochemistry for key technologies of the 21th century, especially in electric energy storage and conversion. In situ and operando surface-sensitive methods, such as scanning probe microscopy and surface X-ray diffraction, as well as complementary ab initio theory can provide atomic-scale information on solid electrode surface in contact with liquid electrolytes, including structural changes under reaction conditions. The level of detail obtainable by these approaches is illustrated in this short review for selected examples. These include the adsorption of sulfate and other oxyanions, where a crucial role of coadsorbed water is found, the restructuring of Cu electrode surfaces under hydrogen evolution and CO2 reduction conditions, and the mechanisms of electrochemical Pt oxidation and its correlation with Pt dissolution.

Use of isotopic (C, Cl) and molecular biology tools to assess biodegradation in a source area of chlorinated ethenes after biostimulation with Emulsified Vegetable Oil (EVO)

Enhanced In Situ Bioremediation (EISB) using Emulsified Vegetable Oil (EVO) as a long-term electron donor has gained prominence for the treatment of groundwater contaminated with chlorinated ethenes (CEs). This study explores the potential of isotopic and molecular biology tools (MBT) to investigate the CEs (PCE, TCE and cis-DCE) bioremediation using EVO in a contaminated site. A multiple approach using C and Cl-CSIA, quantification of Dehalococcoides (Dhc) and specific reductive dechlorination (RD) gene population, and hydrochemical data in microcosm experiments and field samples was applied. Despite the high partitioning of CEs into the EVO phase, the carbon isotopic values of the remaining CEs fraction in the aqueous phase did not exhibit significant changes caused by phase partitioning in laboratory experiments. Both microcosm experiments and field data revealed a rapid RD of PCE and TCE, resulting in the transient accumulation of cis-DCE, which was slowly degraded to vinyl chloride (VC). These results agreed with the presence of Dhc populations and a shift to stronger reducing conditions in the field: i) RD functional genes (tceA, vcrA and bvcA) exhibited a trend to higher values and ii) a substantial increase in Dhc populations (up to 30% of the total bacterial populations) was observed over time. The dual-element isotope slope ΛC-Cl for RD of cis-DCE obtained from field data (ΛC – Cl = 5 ± 3) was similar to the one determined from the microcosm experiments under controlled anoxic conditions (ΛC – Cl = 4.9 ± 0.8). However, ΛC-Cl values differ from those reported so far for laboratory studies with Dhc strains and mixed cultures containing Dhc, i.e., between 8.3 and 17.8. This observation underscores the potential variety of reductive dehalogenases involved during cis-DCE RD and the importance of determining site-specific Λ and ɛ values in order to improve the identification and quantification of transformation processes in the field.

Ultrasonic-driven chemical reduction synthesis of alizarin complexone-modified gold nanoparticles for dual-signal colorimetric and fluorometric sensing of histamine in seafood products

Alizarin complexone-modified gold nanoparticles (Au0-NPsALz) were synthesized using a proposed ultrasonic irradiation-assisted chemical reduction method. Ultrasonic irradiation powers, reaction time and alizarin complexone concentration had been proven to be the main parameters for controlling the nucleation and growth of Au0-NPsALz. In the synthesized ultrasonic irradiation-assisted chemical reduction conditions, Au0-NPsALz had a spherical oriented morphology with a uniform size of 17.84 ± 1.37 nm and are shiny red with a surface plasmon resonance (SPR) of 535 nm. A rapid colorimetric and fluorometric dual-mode detection strategy for selective detection of histamine in seafood was developed based on the self-assembly of Au0-NPsALz-Ni (II) complexes. Ni (II) can capture the histamine molecules close to Au0-NPsALz surfaces, making changes in the colorimetric and fluorometric responses of the solution. The quantitative analysis of histamine was realized through the variation of dual-signal colorimetric and fluorometric responses. Such Au0-NPsALz sensor offered good detection sensitivity for histamine with a detection limit (LOD) of 59.32 μmol L−1 and 116.20 μmol L−1 and wide linear response within the range of 10–10000 μmol L−1 (R2 = 0.9952) and 100–5000 μmol L−1 (R2 = 0.9947) for colorimetric and fluorometric measurement, respectively. Recoveries ranging from 94.99 to 103.29 % and 97.67–106.88 % for colorimetric and fluorometric assay were obtained, showing low levels of matrix effects. Particularly, the results of the dual-mode sensor were also validated by comparing with the HPLC method for improving the assay accuracy and dependability. Ultimately, the developed Au0-NPsALz colorimetric and fluorometric probe performs excellently in practical applications, with promising results for detecting histamine in seafood products.