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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.

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

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.

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.

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.

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.

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.

International audience; Green rust (GR) as highly reactive iron mineral potentially plays a key role for the fate of (in)organic contaminants, such as chromium or arsenic, and nitroaromatic compounds functioning both as sorbent and reductant. GR forms as corrosion product of steel but is also naturally present in hydromorphic soils and sediments forming as metastable intermediate during microbial Fe(III) reduction. Although already suggested to form during microbial Fe(II) oxidation, clear evidence for GR formation during microbial Fe(II) oxidation was lacking. In the present study, powder XRD, synchrotronbased XAS, Mössbauer spectroscopy, and TEM demonstrated unambiguously the formation of GR as an intermediate product during Fe(II) oxidation by the nitratereducing Fe(II)-oxidizer Acidovorax sp. strain BoFeN1. The spatial distribution and Fe redox-state of the precipitates associated with the cells were visualized by STXM. It showed the presence of extracellular Fe(III), which can be explained by Fe(III) export from the cells or extracellular Fe(II) oxidation by an oxidant diffusing from the cells. Moreover, GR can be oxidized by nitrate/nitrite and is known as a catalyst for oxidation of dissolved Fe(II) by nitrite/nitrate and may thus contribute to the production of extracellular Fe(III). As a result, strain BoFeN1 may contribute to Fe(II) oxidation and nitrate reduction both by an direct enzymatic pathway and an indirect GR-mediated process.

We have investigated the nanotexture and crystallographic orientation of aragonite in a coral skeleton using synchrotron-based scanning transmission X-ray microscopy (STXM) and transmission electron microscopy (TEM). Polarization-dependent STXM imaging at 40-nm spatial resolution was used to obtain an orientation map of the c-axis of aragonite on a focused ion beam milled ultrathin section of a Porites coral. This imaging showed that one of the basic units of coral skeletons, referred to as the center of calcification (COC), consists of a cluster of 100-nm aragonite globules crystallographically aligned over several micrometers with a fan-like distribution and with the properties of single crystals at the mesoscale. The remainder of the skeleton consists of aragonite single-crystal fibers in crystallographic continuity with the nanoglobules comprising the COC. Our observation provides information on the nm-scale processes that led to biomineral formation in this sample. Importantly, the present study illustrates how the methodology described here, which combines HRTEM and polarization-dependent synchrotron-based STXM imaging, offers an interesting new approach for investigating biomineralizing systems at the nm-scale. (C) 2011 Elsevier B.V. All rights reserved.

article i nfo Soft X-ray scanning transmission X-ray microscopy (STXM) was used to measure the Fe L2, 3 X-ray magnetic circular dichroism (XMCD) signal from individual, 30 nm diameter magnetosomes in a magnetotactic bacterium, specifically the marine vibrio strain MV-1. The Fe L2, 3 spectra recorded with circularly polarized X-rays from an elliptically polarizing undulator were very similar in shape and magnitude to those of fully saturated magnetite (Fe3O4). As previously determined by other techniques, our results show that the magnetic moments of individual magnetosomes arranged in linear chains in intact cells of strain MV-1 are all oriented in the same direction. The magnitude of the XMCD signal averaged over a chain of 9 magnetosomes in one cell is similar to that of single crystal magnetite. The spectral shape is slightly different, and indicates that magnetosomes have excess Fe (II)

A method for the solvent-free photocatalytic conversion of solid and liquid substrates was developed, using a novel rod mill apparatus. In this setup, thin liquid films are realized which is crucial for an effective photocatalytic conversion due to the low penetration depth of light in heterogeneous systems. Several benzylic alcohols were oxidized with riboflavin tetraacetate as photocatalyst under blue light irradiation of the reaction mixture. The corresponding carbonyl compounds were obtained in moderate to good yields.

Fe(II)-oxidizing bacteria form biogenic cell-mineral aggregates (CMAs) composed of microbial cells, extracellular organic compounds, and ferric iron minerals. CMAs are capable of immobilizing large quantities of heavy metals, such as nickel, via sorption processes. CMAs play an important role for the fate of heavy metals in the environment, particularly in systems characterized by elevated concentrations of dissolved metals, such as mine drainage or contaminated sediments. We applied scanning transmission (soft) X-ray microscopy (STXM) spectrotomography for detailed 3D chemical mapping of nickel sorbed to CMAs on the submicron scale. We analyzed different CMAs produced by phototrophic or nitrate-reducing microbial Fe(II) oxidation and, in addition, a twisted stalk structure obtained from an environmental biofilm. Nickel showed a heterogeneous distribution and was found to be preferentially sorbed to biogenically precipitated iron minerals such as Fe(III)-(oxyhydr)oxides and, to a minor extent, associated with organic compounds. Some distinct nickel accumulations were identified on the surfaces of CMAs. Additional information obtained from scatter plots and angular distance maps, showing variations in the nickel-iron and nickel-organic carbon ratios, also revealed a general correlation between nickel and iron. Although a high correlation between nickel and iron was observed in 2D maps, 3D maps revealed this to be partly due to projection artifacts. In summary, by combining different approaches for data analysis, we unambiguously showed the heterogeneous sorption behavior of nickel to CMAs.