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Composites formed by a metal–organic framework (MOF) and an ionic liquid (IL) are potentially interesting materials for applications ranging from gas separation to electrochemical devices. Consequently, there is a need for robust and low-cost preparation procedures that are compatible with the desired applications. We herein report a solvent-free, one-step, and vapor-based ship-in-bottle synthesis of the IL@MOF composite 1-butyl-3-methylimidazolium bromide@ZIF-8 in powder and thin film forms. In this approach, volatile IL precursors evaporate and subsequently adsorb and react within the MOF cages to form the IL.

Redox-driven biogeochemical element cycles play a central role in converting organic matter in aquatic ecosystems. They also perform key functions such as removing nitrate, mitigating the formation of greenhouse gases and weakening the effects of contaminants. Recent research has revealed the presence of redox-active compounds in these ecosystems with hitherto unknown redox properties. These substances are metastable (that is, non-equilibrium solid phases), which can both donate and accept electrons. They are highly redox reactive and recyclable and may act as biogeobatteries by temporarily storing electrons. Their lifetime, however, is limited, and with time they become more crystalline and less reactive. In this Review, we argue that these redox-active metastable phases require activation by fluctuating redox conditions to maintain their high reactivity. In aquatic ecosystems, switching between oxidizing and reducing conditions can be achieved only through hydrological perturbations at hydrological interfaces (for example, water level fluctuations). We present a novel framework that links microscale biogeochemical processes to large-scale hydrological processes, and discuss implications and future research directions for biogeochemical element cycles in aquatic systems exposed to frequent hydrological disturbances. Highly redox-active compounds play an important role in biogeochemical element cycles in aquatic systems that are exposed to frequent hydrological disturbances.

Rice cultivation requires high amounts of phosphorus (P). However, significant amounts of P fertilizer additions may be retained by Fe oxides and are thus unavailable for plants. At the same time, rice cultivation has a high demand for Si, reducing Si availability after short duration of rice cultivation. By studying a paddy chronosequence with rice cultivation up to 2000 years, we show that silicic acid (Si) limitation, observed as early as a few decades of rice cultivation, is limiting P availability along the paddy soils chronosequence. Using Near edge X-ray absorption Fine Structure spectroscopy (NEXAFS) in a scanning transmission (soft) X-ray microscope (STXM) we show respective release of available P was linked to a Si-induced change in speciation of Fe-phases in soil particles and competition of Si with P for binding sites. Hence, low Si availability is limiting P availability in paddy soils. We propose that proper management of Si availability is a promising tool to reduce the requirements of paddy soils for P fertilization, making rice production more sustainable in future.

ispartof: ACS APPLIED NANO MATERIALS vol:5 issue:4 pages:5006-5016 status: published

Microplastic (MP) residence times are currently poorly constrained in lakes, especially at a quantitative level. In this work settling experiments with pristine and biofilm-colonized MPs were combined with model calculations to evaluate settling velocities, particle distributions and residence times in the epi- meta and hypolimnion of a hypothetical stratified lake broadly based on Upper Lake Constance. Settling velocities of various biodegradable and non-biodegradable polymers of various shapes, sizes and biofilm colonization were measured in a settling column. The settling velocities ranged between ~ 0.30 and ~50 mm s-1. Particle sizes and polymer densities were identified as primary controls on settling rates. MPs that had been exposed to a lake environment for up to 30 weeks were colonized by a range of biofilms and associated extracellular polymeric substances; surprisingly, however, the settling velocity did not vary significantly between pristine and colonized MP particles. Simulated MP residence times in the model lake varied over a wide range of time scales (10-1 - 105 days) and depended mainly on the size of the particles and depth of the lake layer. Long residence times on the order of 105 days (for 1 µm MPs) imply that for small MP particles there is a high probability that they will be taken up at some stage by lake organisms. It also suggests that insignificant amounts of small MPs will be found in the lake sediment unless some process increases their settling velocity as their residence time is considerably longer than the theoretical retention time of Lake Constance (~4.5 years).

Aquatic environmental microbial biofilms grow in a broad range of redox environments from oxic to methanogenic, and they often also establish internal redox gradients. In technical applications, biofilms are also subjected to controlled redox conditions. Studies on biofilms often make use of fluorescence microscopic imaging techniques together with lectin binding analysis to gain insights into structure, composition, and functions of the biofilms. Here we studied the direct influence of redox potentials on fluorescence lectin binding analyses (FLBA) for two commonly used lectin-fluorophore conjugates. An effect of the electrical potential on signal intensity was observed and found to be statistically significant. The signal intensity changes however, remained within the range of a few percent total. A significant drop in intensity was only observed for extremely oxidizing potentials, typically not found under environmental conditions. Our results showed that the fluorophore itself and not the lectin binding to the respective glycoconjugate causes fluorescence changes. The two tested lectin-fluorophores are shown to be suitable for studying the distribution and composition of EPS in environmental biofilms or technical applications and under varying redox conditions.

Rice cultivation requires high amounts of phosphorus (P). However, significant amounts of P fertilizer additions may be retained by iron (Fe) oxides and are thus unavailable for plants. At the same time, rice cultivation has a high demand for silicic acid (Si), reducing Si availability after short duration of rice cultivation. By studying a paddy chronosequence with rice cultivation up to 2000 years, we show that Si limitation, observed as early as a few decades of rice cultivation, is limiting P availability along the paddy soils chronosequence. Using near edge X-ray absorption fine structure spectroscopy (NEXAFS) in a scanning transmission (soft) X-ray microscope (STXM) we show release of available P was linked to a Si-induced change in speciation of Fe-phases in soil particles and competition of Si with P for binding sites. Hence, low Si availability is limiting P availability in paddy soils. We propose that proper management of Si availability is a promising tool to improve the P supply of paddy plants.

Environmental microplastic (MP) is ubiquitous in aquatic and terrestrial ecosystems providing artificial habitats for microbes. Mechanisms of MP colonization, MP polymer impacts, and effects on soil microbiomes are largely unknown in terrestrial systems. Therefore, we experimentally tested the hypothesis that MP polymer type is an important deterministic factor affecting MP community assembly by incubating common MP polymer types in situ in landfill soil for 14 months. 16S rRNA gene amplicon sequencing indicated that MP polymers have specific impacts on plastisphere microbiomes, which are subsets of the soil microbiome. Chloroflexota, Gammaproteobacteria, certain Nitrososphaerota, and Nanoarchaeota explained differences among MP polymers and time points. Plastisphere microbial community composition derived from different MP diverged over time and was enriched in potential pathogens. PICRUSt predictions of pathway abundances and quantitative PCR of functional marker genes indicated that MP polymers exerted an ambivalent effect on genetic potentials of biogeochemical cycles. Overall, the data indicate that (i) polymer type as deterministic factor rather than stochastic factors drives plastisphere community assembly, (ii) MP impacts greenhouse gas metabolism, xenobiotic degradation and pathogen distribution, and (iii) MP serves as an ideal model system for studying fundamental questions in microbial ecology such as community assembly mechanisms in terrestrial environments.

Film deposition and high-resolution patterning of ionic liquids (ILs) remain a challenge, despite a broad range of applications that would benefit from this type of processing. Here, we demonstrate for the first time the chemical vapor deposition (CVD) of ILs. The IL-CVD method is based on the formation of a non-volatile IL through the reaction of two vaporized precursors. Ionogel micropatterns can be easily obtained via the combination of IL-CVD and standard photolithography, and the resulting microdrop arrays can be used as microreactors. The IL-CVD approach will facilitate leveraging the properties of ILs in a range of applications and microfabricated devices. ispartof: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol:60 issue:49 pages:25668-25673 ispartof: location:Germany status: published

Cadmium (Cd) adversely affects human health by entering the food chain via anthropogenic activity. In order to mitigate risk, a better understanding of the biogeochemical mechanisms limiting Cd mobility in the environment is needed. While Cd is not redox-active, Cd speciation varies (i.e., aqueous, complexed, adsorbed), and influences mobility. Here, the cycling of Cd in relation to initial speciation during the growth of Geobacter sulfurreducens was studied. Either fumarate or ferrihydrite (Fh) was provided as an electron acceptor and Cd was present as: (1) an aqueous cation, (2) an aqueous complex with cysteine, which is often present in metal stressed soil environments, or (3) adsorbed to Fh. During microbial Fe(III) reduction, the removal of Cd was substantial (∼80% removal), despite extensive Fe(II) production (ratio Fe(II)total : Fetotal = 0.8). When fumarate was the electron acceptor, there was higher removal from solution when Cd was complexed with cysteine (97–100% removal) compared to aqueous Cd (34–50%) removal. Confocal laser scanning microscopy (CLSM) demonstrated the formation of exopolymeric substances (EPS) in all conditions and that Cd was correlated with EPS in the absence of Fe minerals (r = 0.51–0.56). Most notable is that aqueous Cd was more strongly correlated with Geobacter cells (r = 0.72) compared to Cd–cysteine complexes (r = 0.51). This work demonstrates that Cd interactions with cell surfaces and EPS, and Cd solubility during metabolic activity are dependent upon initial speciation. These processes may be especially important in soil environments where sulfur is limited and Fe and organic carbon are abundant.

Chemical vapor deposition of metal-organic frameworks (MOF-CVD) will facilitate the integration of porous and crystalline coatings in electronic devices. In the two-step MOF-CVD process, a precursor layer is first deposited and subsequently converted to a MOF through exposure to linker vapor. We herein report the impact of different metal oxide and metalcone layers as precursors for zeolitic imidazolate framework ZIF-8 films. ispartof: DALTON TRANSACTIONS vol:50 issue:20 pages:6784-6788 ispartof: location:England status: published

Plastics are among the most widespread contaminants on Earth. They build up in fresh water bodies with high concentrations and migrate between different environmental compartments. In thermally stratified lakes, in summer, MPs pollutants can migrate between epilimnion, metalimnion and hypolimnion. This increases the probability of that microplastic will be filtered by filter feeders allowing MPs to migrate through different trophic levels. In this study, the transport of MPs in lake systems is presented through laboratory experiments as well as numerical modelling. The settling velocities of various biodegradable and non-biodegradable particles with various shapes and sizes were measured in the settling column under laminar conditions using particle image velocimetry (PIV). The particles used ranged between 150 to 2400 µm in diameter. The experimental results presented that shape, size and density of a particle are the key parameters controlling the sedimentation behavior of the particles. The measured settling velocities ranged between 0.4 to 50 mms-1. In parallel, the transport of the particles used in the laboratory experiments was simulated using CFD. The laboratory experiments and CFD have shown consistent results. Subsequently, the same MPs used in the first lab experiments were incubated in a pond at the University of Bayreuth for 6, 8 and 10 weeks. The formation of biofilm on the incubated particles was investigated using confocal laser scanning microscopy. Also, the effect of biofouling of microplastics on the physical properties and thus settling velocity was investigated experimentally. It was observed that biofilm-building organisms has only colonized few regions on the surface of MPs and the whole surface was not coated with biofilm as it was anticipated. In addition, no changes in shape, size and density of the incubated were detected. After 6, 8 and 10 weeks of incubation, no significant change in the settling velocity of the incubated particles was observed. The detected changes in the settling velocity ranged between ± 5 % which was considered as a measurement error. Finally, the residence time in suspension and the distribution of MPs throughout a virtual lake water column was simulated using a simplified model. The effect of turbulences and the temperature gradient on the settling velocity were considered during the simulations. The model presented that turbulences, water temperature and layer depth control the settling velocity and thus the residence time of the MPs.

Microplastic (MP) is a pervasive pollutant in nature that is colonised by diverse groups of microbes, including potentially pathogenic species. Fungi have been largely neglected in this context, despite their affinity for plastics and their impact as pathogens. To unravel the role of MP as a carrier of fungal pathogens in terrestrial ecosystems and the immediate human environment, epiplastic mycobiomes from municipal plastic waste from Kenya were deciphered using ITS metabarcoding as well as a comprehensive meta-analysis, and visualised via scanning electron as well as confocal laser scanning microscopy. Metagenomic and microscopic findings provided complementary evidence that the terrestrial plastisphere is a suitable ecological niche for a variety of fungal organisms, including important animal and plant pathogens, which formed the plastisphere core mycobiome. We show that MPs serve as selective artificial microhabitats that not only attract distinct fungal communities, but also accumulate certain opportunistic human pathogens, such as cryptococcal and Phoma-like species. Therefore, MP must be regarded a persistent reservoir and potential vector for fungal pathogens in soil environments. Given the increasing amount of plastic waste in terrestrial ecosystems worldwide, this interrelation may have severe consequences for the trans-kingdom and multi-organismal epidemiology of fungal infections on a global scale.

Organic synthesis without an organic solvent is still the exception. In this microreview we discuss and compare different synthetic methods that proceed in the absence of conventional organic solvents. This includes solvent-free methods in solids (mechanochemistry and solid-state photochemistry), and in neat liquids (thermal and photocatalytic), as well as the application of unconventional solvents, such as ionic liquids and deep-eutectic solvents. The different approaches are briefly introduced and examples illustrate their specific advantages, followed by a critical discussion of their limitations. Some methods have the intrinsic benefits of solvent-free operation, such as avoiding solubility problems and side-reactions with the solvent. However, every method has specific advantages and the demand of the synthetic application is crucial for selecting the best technique.

Measuring angles in the Euclidean plane is a well-known topic, but for general normed planes there exists a variety of different concepts. These can be of a special kind, e.g. also preserving special orthogonality types. But these concepts are no angle measures in the sense of measure theory since they are not additive. This motivates us to define a new angle measure for normed planes that is in fact a measure in the sense of measure theory. Furthermore, we look at related types of rotation and reflection.

The coupling of an aldehyde, an amine, and an alkyne to yield propargyl amines was performed in a deep-eutectic solvent composed of zinc chloride and dimethylurea. The deep-eutectic solvent acts simultaneously as catalyst and solvent giving access to a variety of propargyl amines, which were isolated in moderate to very good yields.

A novel reactor for solvent-free, visible-light-driven photocatalytic transformations was developed. By rotation of the reaction vessel, the reaction mixture forms a thin film, which allows efficient excitation of the photocatalyst. The reactor was used for the coupling of aryl halides with pyrrole derivatives and phosphites, applying rhodamine 6G as the photocatalyst and DIPEA as the sacrificial electron donor. The necessary amounts of photocatalyst, trapping reagent, and sacrificial electron donor were reduced significantly compared to those for literature known reactions in solution, while isolating the products in moderate to good yields. In general terms, this solvent-free methodology is an interesting alternative to solution photocatalysis due to the presence of high mole fractions of trapping reagent, the exclusion of by-products formed with the solvent, and the reduction of toxic solvent waste.

A broad-spectrum fluorescent probe, which can be applied to monitoring H2S in various biological systems, has been rationally designed and synthesized. This specific probe was applied to localize the endogenous H2S in living Raw264.7 macrophage cells, HepG2 cells, and H9C2 cells. At the same time, the probe has successfully visualized CBS- and CSE-induced endogenous H2S production and monitored CBS and CSE activity in H9C2 cells. This probe could serve as a powerful molecular imaging tool to further explore the physiological function and the molecular mechanisms of endogenous H2S in living animal systems.

Innovative microanalytical methods are valuable tools in geomicrobiology. They often require the use of dried samples, demanding a challenging sample preparation. Since geomicrobiological samples typically have a strongly heterogeneous composition, choosing a preparation method is not straightforward. We therefore compared how different drying methods (critical point drying, hexamethyldisilazane drying, air drying and freeze drying) influence the structure of bacterial cell-mineral aggregates. Each method proved suitable for a specific purpose, but none was able to completely preserve the sample structure. Additional information was obtained on surface alterations by sputter coating and on preservation of extracellular polymeric substances during resin embedding.

Most studies on microbial phototrophic Fe(II) oxidation (photoferrotrophy) have focused on purple bacteria, but recent evidence points to the importance of green-sulfur bacteria (GSB). Their recovery from modern ferruginous environments suggests that these photoferrotrophs can offer insights into how their ancient counterparts grew in Archean oceans at the time of banded iron formation (BIF) deposition. It is unknown, however, how Fe(II) oxidation rates, cell–mineral aggregate formation, and Fe-mineralogy vary under environmental conditions reminiscent of the geological past. To address this, we studied the Fe(II)-oxidizer Chlorobium ferrooxidans KoFox, a GSB living in co-culture with the heterotrophic Geospirillum strain KoFum. We investigated the mineralogy of Fe(III) metabolic products at low/high light intensity, and in the presence of dissolved silica and/or fumarate. Silica and fumarate influenced the crystallinity and particle size of the produced Fe(III) minerals. The presence of silica also enhanced Fe(II) oxidation rates, especially at high light intensities, potentially by lowering Fe(II)-toxicity to the cells. Electron microscopic imaging showed no encrustation of either KoFox or KoFum cells with Fe(III)-minerals, though weak associations were observed suggesting co-sedimentation of Fe(III) with at least some biomass via these aggregates, which could support diagenetic Fe(III)-reduction. Given that GSB are presumably one of the most ancient photosynthetic organisms, and pre-date cyanobacteria, our findings, on the one hand, strengthen arguments for photoferrotrophic activity as a likely mechanism for BIF deposition on a predominantly anoxic early Earth, but, on the other hand, also suggest that preservation of remnants of Fe(II)-oxidizing GSB as microfossils in the rock record is unlikely.

Aggregates consisting of bacterial cells, extracellular polymeric substances (EPS) and Fe(III) minerals formed by Fe(II)-oxidizing bacteria are common at bulk or microscale chemical interfaces where Fe cycling occurs. The high sorption capacity and binding capacity of cells, EPS, and minerals controls the mobility and fate of heavy metals. However, it remains unclear to which of these component(s) the metals will bind in complex aggregates. To clarify this question, the present study focuses on 3D mapping of heavy metals sorbed to cells, glycoconjugates that comprise the majority of EPS constituents, and Fe(III) mineral aggregates formed by the phototrophic Fe(II)-oxidizing bacteria Rhodobacter ferrooxidans SW2 using confocal laser scanning microscopy (CLSM) in combination with metal- and glycoconjugates-specific fluorophores. The present study evaluated the influence of glycoconjugates, microbial cell surfaces, and (biogenic) Fe(III) minerals, and the availability of ferrous and ferric iron on heavy metal sorption. Analyses in this study provide detailed knowledge on the spatial distribution of metal ions in the aggregates at the sub-μm scale, which is essential to understand the underlying mechanisms of microbe–mineral–metal interactions. The heavy metals (Au3+, Cd2+, Cr3+, CrO42−, Cu2+, Hg2+, Ni2+, Pd2+, tributyltin (TBT) and Zn2+) were found mainly sorbed to cell surfaces, present within the glycoconjugates matrix, and bound to the mineral surfaces, but not incorporated into the biogenic Fe(III) minerals. Statistical analysis revealed that all ten heavy metals tested showed relatively similar sorption behavior that was affected by the presence of sorbed ferrous and ferric iron. Results in this study showed that in addition to the mineral surfaces, both bacterial cell surfaces and the glycoconjugates provided most of sorption sites for heavy metals. Simultaneously, ferrous and ferric iron ions competed with the heavy metals for sorption sites on the organic compounds. In summary, the information obtained by the present approach using a microbial model system provides important information to better understand the interactions between heavy metals and biofilms, and microbially formed Fe(III) minerals and heavy metals in complex natural environments.

Soft X-ray Scanning Transmission X-ray microscopy (STXM) is a synchrotron-based technique which can provide both spectroscopic characterization (near edge X-ray absorption fine structure, NEXAFS) and chemically selective imaging with high spatial resolution (~30 nm). Recently, we have developed in situ flow electrochemical devices [1,2] which allow control of the electrochemical environment while conducting STXM measurements, thus providing a platform for in-situ studies of electrochemical oxidation and reduction processes. This presentation reports results of in situ flow electrochemical STXM studies on three different systems to demonstrate the present capabilities. First, the ability to rapidly exchange the electrolyte is demonstrated by a STXM Fe 2p and in situ electrochemical study of the ferro/ferricyanide solution redox system. Second Cu and Ag-doped Cu catalysts for CO2 electrochemical reduction (CO2R) were successfully prepared using in situ electrodeposition. Third, the electrolyte was changed from CuSO4 to NaHCO3 (as substrate for CO2R) and the cell was operated under electrochemical CO2 reduction conditions, while monitoring the changes to the Cu deposited layer at various potentials, including –0.5 V where CO2 reduction is expected [3]. The figure shows a cyclic voltammogram (CV) and color-coded Cu oxidation state maps which were derived from Cu 2p stacks measured under chronoamperometric conditions at the indicated potentials. These results demonstrate that in situ flow electrochemical STXM measurements can be performed in our device under varying electrochemical reaction conditions, enabling visualization of the morphology changes from selective energy imaging, and quantitative tracking of electrochemical transformations from spectromicroscopy. This system will be used for in situ studies of CO2 electrochemical reduction catalysis with the goal of obtaining mechanistic insights to guide the development of catalysts with improved efficiency and selectivity. In addition, the system will be used to study a variety of material science, chemistry and environmental science related questions associated with oxidation or reduction processes, such as mechanisms of extra-cellular electron transport in marine sediment microbial biofilms [4]. This research is supported by NSERC (Canada). STXM measurements were performed at the ambient STXM facility at the Canadian Light Source, which is funded by the Canadian Foundation for Innovation. [1] V. Prabu et al., Rev. Sci. Inst. 89 (2018) 063702. [2] P. Ingino, et al., in preparation [3] L. Wang, D.C. Higgins, et al., Proc. Nat. Acad. Sci. (2020) 01821683. DOI: 10.1073/pnas.1821683117 [4] M. Obst, et al., Microsc. Microanal. 24 (S-2) (2018) 502-504. Figure 1

Prior studies have shown that silicon (Si) increases the dissolution of iron (Fe) phosphates, releasing phosphorus (P) into the soil solution of fen peat and thereby changing the composition of organic matter (OM). We formulated three questions on the occurring processes: [i] Does high Si concentration cause a mobilization of Fe phosphates? [ii] Does this mobilization result in a higher concentration of P, Fe, and dissolved organic carbon? [iii] Are there changes in the composition of organic matter? To this end, we conducted a laboratory experiment adding amorphous silica to fen peat and analyzed Fe mineralogy and carbon quality of the peat material by X-ray absorption spectroscopy (XAS). Under high Si concentration, significantly higher concentrations of P and Fe were found in soil solution. Moreover, XAS data indicated a dissolution of Fe (II) phosphates and a change in the composition of OM available to microbes with decreasing contributions of carboxylic groups and quinones. We propose to explain the effects as follows: under high Si concentration Fe (II) phosphates dissolve and OM rich in carboxylic groups are mobilized. As the nutrient concentration in the soil solution increased, the degradation of oxidized components of the OM, such as quinones and carboxylic groups is enhanced.

Microbial Fe(III) reduction plays an important role for biogeochemical carbon and iron cycling in sediments and soils. Biochar is used as a soil amendment to increase fertility and lower N2O/CO2 emissions. It is redox-active and can stimulate microbial Fe(III) mineral reduction. It is currently unknown, however, how the aggregation of cells and Fe(III) minerals with biochar particles influence microbial Fe(III) reduction. Therefore, we determined rates and extent of ferrihydrite (Fh) reduction in S. oneidensis MR-1 cell suspensions with different particles sizes of wood-derived Swiss biochar and KonTiki biochar at different biochar/Fh ratios. We found that at small biochar particle size and high biochar/Fh ratios, the biochar, MR-1 cells and Fh closely aggregated, therefore addition of biochar stimulated electron transfer and microbial Fh reduction. In contrast, large biochar particles and low biochar/Fh ratios inhibited the electron transfer and Fe(III) reduction due to the lack of effective aggregation. These results suggest that for stimulating Fh reduction, a certain biochar particle size and biochar/Fh ratio is necessary leading to a close aggregation of all phases. This aggregation favors electron transfer from cells to Fh via redox cycling of the electron donating and accepting functional groups of biochar and via direct electron transfer through conductive biochar carbon matrices. These findings improve our understanding of electron transfer between microorganisms and Fe(III) minerals via redox-active biochar and help to evaluate the impact of biochar on electron transfer processes in the environment.

We report the design and performance of a 3-electrode device for real time in situ scanning transmission X-ray microscopy studies of electrochemical processes under both static (sealed, non-flow) conditions and with a continuous flow of electrolytes. The device was made using a combination of silicon microfabrication and 3D printing technologies. The performance is illustrated by results of a study of copper deposition and stripping at a gold working electrode. X-ray absorption spectromicroscopy at the Cu 2p edge was used to follow the evolution as a function of potential and time of the spatial distributions of Cu(0) and Cu(i) species electro-deposited from an aqueous solution of copper sulphate. The results are interpreted in terms of competing mechanisms for the reduction of Cu(ii).

The reconstruction of the history of microbial life since its emergence on early Earth is impaired by the difficulty to prove the biogenicity of putative microfossils in the rock record. While most of the oldest rocks on Earth have been exposed to different grades of diagenetic alterations, little is known about how the remains of micro-organisms evolve when exposed to pressure (P) and temperature (T) conditions typical of diagenesis. Using spectroscopy and microscopy, we compared morphological, mineralogical, and chemical biosignatures exhibited by Fe mineral-encrusted cells of the bacterium Acidovorax sp. BoFeN1 after long-term incubation under ambient conditions and after experimental diagenesis. We also evaluated the effects of Si on the preservation of microbial cells during the whole process. At ambient conditions, Si affected the morphology but not the identity (goethite) of Fe minerals that formed around cells. Fe-encrusted cells were morphologically well preserved after 1 week at 250 °C-140 MPa and after 16 weeks at 170 °C-120 MPa in the presence or in the absence of Si. Some goethite transformed to hematite and magnetite at 250 °C-140 MPa, but in the presence of Si more goethite was preserved. Proteins-the most abundant cellular components-were preserved over several months at ambient conditions but disappeared after incubations at high temperature and pressure conditions, both in the presence and in the absence of Si. Other organic compounds, such as lipids and extracellular polysaccharides seemed well preserved after exposure to diagenetic conditions. This study provides insights about the composition and potential preservation of microfossils that could have formed in Fe- and Si-rich Precambrian oceans.

Organo-soluble amino cellulose derivatives were synthesized in a one-pot synthesis by simultaneous reaction of tosyl celluloses with ethylenediamine and 4-chlorobenzylamine. The soluble products obtained form nanoparticles in water by nanoprecipitation. As shown by dynamic light scattering (DLS) and scanning electron microscopy (SEM), their hydrodynamic diameter, zeta-potential, and PDI decrease with increasing hydrophobicity. Moreover, the derivative could be labeled with Fluorescein isothiocyanate (FITC) and forms fluorescent nanoparticles with an unexpected low ydrodynamic diameter, useful for the labeling of biomolecules in bioassays.

This paper discusses the sorbent properties of magnetic activated carbons and biochars produced by wet impregnation with iron oxides. The sorbents had magnetic susceptibilities consistent with theoretical predictions for carbon-magnetite composites. The high BET surface areas of the activated carbons were preserved in the synthesis, and enhanced for one low surface area biochar by dissolving carbonates. Magnetization decreased the point of zero charge. Organic compound sorption correlated strongly with BET surface areas for the pristine and magnetized materials, while metal cation sorption did not show such a correlation. Strong sorption of the hydrophobic organic contaminant phenanthrene to the activated carbon or biochar surfaces was maintained following magnetite impregnation, while phenol sorption was diminished, probably due to enhanced carbon oxidation. Copper, zinc and lead sorption to the activated carbons and biochars was unchanged or slightly enhanced by the magnetization, and iron oxides also contributed to the composite metal sorption capacity. While a magnetic biochar with 219 ± 3.7 m(2)/g surface area nearly reached the very strong organic pollutant binding capacity of the two magnetic activated carbons, a magnetic biochar with 68 ± 2.8 m(2)/g surface area was the best metal sorbent. Magnetic biochars thus hold promise as more sustainable alternatives to coal-derived magnetic activated carbons.

Microscopy in the mid-infrared spectral range provides detailed chemical information on a sample at moderate spatial resolution and is being used increasingly in the characterization of biological entities as challenging as single cells. However, a conventional cellular 2D imaging measurement is limited in its ability to associate specific compositional information to subcellular structures because of the interference from the complex topography of the sample. Herein we provide a method and protocols that overcome this challenge in which tilt-series infrared tomography is used with a standard benchtop infrared microscope. This approach gives access to the quantitative 3D distribution of molecular components based on the intrinsic contrast provided by the sample. We demonstrate the method by quantifying the distribution of an exogenous metal carbonyl complex throughout the cell and by reporting changes in its coordination sphere in different locations in the cell.

Here we present the first examples of fluorescent and colorimetric probes for microscopic TBT imaging. The fluorescent probes are highly selective and sensitive to TBT and have successfully been applied for imaging of TBT in bacterial Rhodobacter ferrooxidans sp. strain SW2 cell-EPS-mineral aggregates and in cell suspensions of the marine cyanobacterium Synechococcus PCC 7002 by using confocal laser scanning microscopy.

Amending soil with biochar (pyrolized biomass) is suggested as a globally applicable approach to address climate change and soil degradation by carbon sequestration, reducing soil-borne greenhouse-gas emissions and increasing soil nutrient retention. Biochar was shown to promote plant growth, especially when combined with nutrient-rich organic matter, e.g., co-composted biochar. Plant growth promotion was explained by slow release of nutrients, although a mechanistic understanding of nutrient storage in biochar is missing. Here we identify a complex, nutrient-rich organic coating on co-composted biochar that covers the outer and inner (pore) surfaces of biochar particles using high-resolution spectro(micro)scopy and mass spectrometry. Fast field cycling nuclear magnetic resonance, electrochemical analysis and gas adsorption demonstrated that this coating adds hydrophilicity, redox-active moieties, and additional mesoporosity, which strengthens biochar-water interactions and thus enhances nutrient retention. This implies that the functioning of biochar in soil is determined by the formation of an organic coating, rather than biochar surface oxidation, as previously suggested., Biochar promotes plant growth via a slow release of nutrients; however, a mechanistic understanding of nutrient storage in biochar is lacking. Here, using high-resolution spectromicroscopy and mass spectrometry, the authors identify an organic coating on co-composted particles that enhances nutrient retention.

Most described nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOB) are mixotrophic and depend on organic cosubstrates for growth. Encrustation of cells in Fe(III) minerals has been observed for mixotrophic NRFeOB but not for autotrophic phototrophic and microaerophilic Fe(II) oxidizers. So far, little is known about cell-mineral associations in the few existing autotrophic NRFeOB. Here, we investigate whether the designated autotrophic Fe(II)-oxidizing strain (closely related to Gallionella and Sideroxydans ) or the heterotrophic nitrate reducers that are present in the autotrophic nitrate-reducing Fe(II)-oxidizing enrichment culture KS form mineral crusts during Fe(II) oxidation under autotrophic and mixotrophic conditions. In the mixed culture, we found no significant encrustation of any of the cells both during autotrophic oxidation of 8 to 10 mM Fe(II) coupled to nitrate reduction and during cultivation under mixotrophic conditions with 8 to 10 mM Fe(II), 5 mM acetate, and 4 mM nitrate, where higher numbers of heterotrophic nitrate reducers were present. Two pure cultures of heterotrophic nitrate reducers ( Nocardioides and Rhodanobacter ) isolated from culture KS were analyzed under mixotrophic growth conditions. We found green rust formation, no cell encrustation, and only a few mineral particles on some cell surfaces with 5 mM Fe(II) and some encrustation with 10 mM Fe(II). Our findings suggest that enzymatic, autotrophic Fe(II) oxidation coupled to nitrate reduction forms poorly crystalline Fe(III) oxyhydroxides and proceeds without cellular encrustation while indirect Fe(II) oxidation via heterotrophic nitrate-reduction-derived nitrite can lead to green rust as an intermediate mineral and significant cell encrustation. The extent of encrustation caused by indirect Fe(II) oxidation by reactive nitrogen species depends on Fe(II) concentrations and is probably negligible under environmental conditions in most habitats. IMPORTANCE Most described nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOB) are mixotrophic (their growth depends on organic cosubstrates) and can become encrusted in Fe(III) minerals. Encrustation is expected to be harmful and poses a threat to cells if it also occurs under environmentally relevant conditions. Nitrite produced during heterotrophic denitrification reacts with Fe(II) abiotically and is probably the reason for encrustation in mixotrophic NRFeOB. Little is known about cell-mineral associations in autotrophic NRFeOB such as the enrichment culture KS. Here, we show that no encrustation occurs in culture KS under autotrophic and mixotrophic conditions while heterotrophic nitrate-reducing isolates from culture KS become encrusted. These findings support the hypothesis that encrustation in mixotrophic cultures is caused by the abiotic reaction of Fe(II) with nitrite and provide evidence that Fe(II) oxidation in culture KS is enzymatic. Furthermore, we show that the extent of encrustation caused by indirect Fe(II) oxidation by reactive nitrogen species depends on Fe(II) concentrations and is probably negligible in most environmental habitats.

We present ScatterJ, an ImageJ plugin that allows for extracting qualitative as well as quantitative information from analytical microscopy datasets. A large variety of analytical microscopy methods are used to obtain spatially resolved chemical information. The resulting datasets are often large and complex, and can contain information that is not obvious or directly accessible. ScatterJ extends and complements existing methods to extract information on correlation and colocalization from pairs of species-specific or element-specific maps. We demonstrate the possibilities to extract information using example datasets from biogeochemical studies, although the plugin is not restricted to this type of research. The information that we could extract from our existing data helped to further our understanding of biogeochemical processes such as mineral formation or heavy metal sorption. ScatterJ can be used for a variety of different two-dimensional (2D) and three-dimensional (3D) datasets such as energy-dispersive X-ray spectroscopy maps, 3D confocal laser scanning microscopy maps, and 2D scanning transmission X-ray microscopy maps.

Mikroskopie im mittleren infraroten Spektralbereich liefert detaillierte chemische Informationen uber eine Probe bei moderater Ortsauflosung und wird daher immer haufiger fur die Charakterisierung von biologischen Proben wie etwa einzelnen Zellen verwendet. Aufgrund der Komplexitat der Probentopographie sind konventionelle 2D-Bildgebungen jedoch in ihren Moglichkeiten limitiert, spezifische Informationen zur Probenzusammensetzung mit subzellularen Strukturen in Verbindung zu bringen. Wir stellen hier eine Methode und detaillierte Versuchsbeschreibungen vor, welche es ermoglichen, diese Einschrankungen durch Kippserientomographie mit einem konventionellen Infrarot-Labormikroskop zu umgehen. Basierend auf dem intrinsischen IR-Absorptionskontrast ermoglicht dieser Ansatz, quantitative 3D-Verteilungen von molekularen Komponenten zu erstellen. Wir demonstrieren die Methode anhand der Quantifizierung der Verteilung eines exogenen Metallcarbonyl-Komplexes innerhalb einer Zelle sowie durch die Darstellung der Veranderungen der Koordinationsumgebung des Komplexes in verschiedenen Zellkompartimenten.

Fe(III) (oxyhydr)oxides are ubiquitous in modern soils and sediments, and their large surface area leads to scavenging of trace elements. Experimental trace element partitioning between Fe(III) (oxyhydr)oxides and aqueous solutions have been used to elucidate the geochemical composition of the Precambrian oceans based on the trace element concentrations in Precambrian banded iron formations (BIFs). However, previous partitioning experiments did not consider the potential influence of microbially-derived organic material, even though it is widely believed that bacterial phytoplankton was involved in Fe(II) oxidation and the deposition of BIF primary minerals. Therefore, the present study focuses on sorption of Ni to, and co-precipitation of Ni with, both biogenic ferrihydrite precipitated by the freshwater photoferrotroph Rhodobacter ferrooxidans SW2 and the marine photoferrotroph Rhodovulum iodosum, as well as chemically synthesized ferrihydrite. We considered the influence of cellular organic material, medium composition and the availability of dissolved silica. Our results show a preferential association of Ni with ferrihydrite, and not with the microbial cells or extracellular organic substances. We found that the addition of silica (2 mM) did not influence Ni partitioning but led to the encrustation of some cells with ferrihydrite and amorphous silica. The two- to threefold lower Ni/Fe ratio in biogenic as compared to abiogenic ferrihydrite is probably due to a competition between Ni and organic matter for sorption sites on the mineral surface. Additionally, the competition of ions present at high concentrations in marine medium for sorption sites led to decreased Ni sorption or co-precipitation. Based on our data we conclude that, if the Fe(III) minerals deposited in BIFs were – at least to some extent – biological, then the Ni concentrations in the early ocean would have been higher than previously suggested. This study shows the importance of considering the presence of microbial biomass and seawater ions in paleomarine reconstructions.

Microorganisms have been observed to oxidize Fe(II) at neutral pH under anoxic and microoxic conditions. While most of the mixotrophic nitrate-reducing Fe(II)-oxidizing bacteria become encrusted with Fe(III)-rich minerals, photoautotrophic and microaerophilic Fe(II) oxidizers avoid cell encrustation. The Fe(II) oxidation mechanisms and the reasons for encrustation remain largely unresolved. Here we used cultivation-based methods and electron microscopy to compare two previously described nitrate-reducing Fe(II) oxidizers ( Acidovorax sp. strain BoFeN1 and Pseudogulbenkiania sp. strain 2002) and two heterotrophic nitrate reducers ( Paracoccus denitrificans ATCC 19367 and P. denitrificans Pd 1222). All four strains oxidized ∼8 mM Fe(II) within 5 days in the presence of 5 mM acetate and accumulated nitrite (maximum concentrations of 0.8 to 1.0 mM) in the culture media. Iron(III) minerals, mainly goethite, formed and precipitated extracellularly in close proximity to the cell surface. Interestingly, mineral formation was also observed within the periplasm and cytoplasm; intracellular mineralization is expected to be physiologically disadvantageous, yet acetate consumption continued to be observed even at an advanced stage of Fe(II) oxidation. Extracellular polymeric substances (EPS) were detected by lectin staining with fluorescence microscopy, particularly in the presence of Fe(II), suggesting that EPS production is a response to Fe(II) toxicity or a strategy to decrease encrustation. Based on the data presented here, we propose a nitrite-driven, indirect mechanism of cell encrustation whereby nitrite forms during heterotrophic denitrification and abiotically oxidizes Fe(II). This work adds to the known assemblage of Fe(II)-oxidizing bacteria in nature and complicates our ability to delineate microbial Fe(II) oxidation in ancient microbes preserved as fossils in the geological record.

Fe(III) (oxyhydr)oxides affect the mobility of contaminants in the environment by providing reactive surfaces for sorption. This includes the toxic metal cadmium (Cd), which prevails in agricultural soils and is taken up by crops. Fe(III)-reducing bacteria can mobilize such contaminants by Fe(III) mineral dissolution or immobilize them by sorption to or coprecipitation with secondary Fe minerals. To date, not much is known about the fate of Fe(III) mineral-associated Cd during microbial Fe(III) reduction. Here, we describe the isolation of a new Geobacter sp. strain Cd1 from a Cd-contaminated field site, where the strain accounts for 10(4) cells g(-1) dry soil. Strain Cd1 reduces the poorly crystalline Fe(III) oxyhydroxide ferrihydrite in the presence of at least up to 112 mg Cd L(-1). During initial microbial reduction of Cd-loaded ferrihydrite, sorbed Cd was mobilized. However, during continuous microbial Fe(III) reduction, Cd was immobilized by sorption to and/or coprecipitation within newly formed secondary minerals that contained Ca, Fe, and carbonate, implying the formation of an otavite-siderite-calcite (CdCO3-FeCO3-CaCO3) mixed mineral phase. Our data shows that microbially mediated turnover of Fe minerals affects the mobility of Cd in soils, potentially altering the dynamics of Cd uptake into food or phyto-remediating plants.

Surface sediments at the former military base Hradcany, Czech Republic, heavily contaminated with hydrocarbons, were remediated over years by air-sparging. The sediments show a strong magnetic enhancement at the groundwater fluctuation zone. Here we describe the isolation of a new Fe(III)-reducing and magnetite-producing bacterial strain Geothrix fermentans HradG1from this magnetic and redox-dynamic layer. This isolation underlines that the genus Geothrix is a relevant group of bacteria in hydrocarbon-contaminated environments that undergo dynamic oxic-anoxic redox fluctuations. The Fe(III)-reducing metabolic activity of these organisms potentially leads to changing magnetic soil properties that can potentially be used to identify biogeochemical hotspots.

Organic matter (OM) is present in most terrestrial environments and is often found coprecipitated with ferrihydrite (Fh). Sorption or coprecipitation of OM with Fe oxides has been proposed to be an important mechanism for long-term C preservation. However, little is known about the impact of coprecipitated OM on reductive dissolution and transformation of Fe(III) (oxyhydr)oxides. Thus, we study the effect of humic acid (HA) coprecipitation on Fh reduction and secondary mineral formation by the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens strain CN32. Despite similar crystal structure for all coprecipitates investigated, resembling 2-line Fh, the presence of coprecipitated HA resulted in lower specific surface areas. In terms of reactivity, coprecipitated HA resulted in slower Fh bioreduction rates at low C/Fe ratios (i.e., C/Fe ≤ 0.8), while high C/Fe ratios (i.e., C/Fe ≥ 1.8) enhanced the extent of bioreduction compared to pure Fh. The coprecipitated HA also altered the secondary Fe mineralization pathway by inhibiting goethite formation, reducing the amount of magnetite formation, and increasing the formation of a green rust-like phase. This study indicates that coprecipitated OM may influence the rates, pathway, and mineralogy of biogeochemical Fe cycling and anaerobic Fe respiration within soils.

Two novel fluorescein-based OCl − chemosensors were designed, synthesized and characterized. Both fluorescence probes utilize an irreversible OCl − -promoted oxidation reaction to trigger the activation of fluorescence. These probes were shown to be highly selective for OCl − , and showed real time responses as well as a positive linear relationship to OCl − concentrations. The probes were successfully applied for the detection of OCl − in tap water and for fluorescence imaging of OCl − in bacterial Rhodobacter ferrooxidans sp. strain SW2 cell–EPS–mineral aggregates.

A novel rhodamine based probe with a unique six-membered spirocycle was rationally designed for detection of Hg(2+) with greatly improved selectivity, sensitivity, and photostability. The probe has been shown to be suitable for Hg(2+) imaging in living cells and mapping Hg(2+) distribution in living cell-EPS-mineral aggregates under anoxic conditions.

Carbon nanotube (CNT) membranes were produced from multi-walled CNTs by a filtration technique and used for the removal of the betablocker metoprolol by adsorptive and reactive processes. The reactivity of CNT membranes was enhanced by nanoparticulate zero-valent iron (NZVI) which was deposited on the CNT membranes by pulsed voltammetry applying defined number of pulses (Fe-CNT (100) and Fe-CNT (400) membranes). Surface analysis with SEM showed iron nanoparticle sizes between 19 and 425 nm. Pore size distribution for the different membranes was determined by capillary flow porometry (Galwick fluid). Pore size distribution for all membranes was similar (40 nm), which resulted in a water permeability typical for microfiltration membranes. Metoprolol was removed by the CNT membrane only by sorption, whereas the Fe-CNT membrane revealed also metoprolol degradation due to Fenton type reactions. Further application of electrochemical potentials on both the CNT and the Fe-CNT membranes improved the removal efficiencies to 74% for CNT membranes at 1 V and to 97% for Fe-CNT (400) membranes at 1 V. Seven transformation products have been identified for metoprolol by high-resolution mass spectrometry when electrochemical degradation was performed with CNT and Fe-CNT membranes. Additionally, two of the identified transformation products (TPs) were also observed for Fe-CNT membranes without the application of electrochemical potential. However, only 10% of the degraded metoprolol could be explained by the formation of TPs.

A series of Cu2+ probe which contains 9 probes have been synthesized and established. All the probes were synthesized using Rhodamine B as the fluorophore, conjugated to various differently substituted cinnamyl aldehyde with C=N Schiff base structural motif as their core moiety. The structure-property relationships of these probes have been investigated. The change of optical properties, caused by different electronic effect and steric effect of the recognition group, has been analyzed systematically. DFT calculation simulation of the Ring-Close and Ring-Open form of all the probes have been employed to illuminate, summarize and confirm these correlations between optical properties and molecular structures. In addition, biological experiment demonstrated that all the probes have a high potential for both sensitive and selective detection, mapping of adsorbed Cu2+ both in vivo and environmental microbial systems. This approach provides a significant strategy for studying structure-property relationships and guiding the synthesis of probes with various optical properties.