An obituary: Dr. Helmut Cölfen 1965-2023.

Dr. Helmut Cölfen, an exceptional interdisciplinary scientist, mentor, colleague, and dear friend, passed away in November 2023 at the age of 58. His untimely departure is a profound loss for the fields of analytical ultracentrifugation, colloid, crystallization, and polymer research. This obituary pays tribute to Helmut, honoring his remarkable academic career and contributions to the study of nanochemistry, biophysics, and life sciences. Helmut was renowned for his pioneering research contributions in several key research areas: (1) Development of advanced analytical techniques: Helmut made major contributions to techniques such as analytical ultracentrifugation and field flow fractionation, which are widely utilized to characterize the structure of biomolecules and the growth of nanostructured crystalline materials; (2) Study of nucleation and crystallization processes: Helmut explored the early stages of crystallization which led to the discovery of pre-nucleation clusters and mesocrystal intermediates, in the presence of additives and templates; and (3) Investigation of structure and morphogenesis of mesocrystals, examining their molecular properties.

Computational assessment of the potential of cross-catalytic coprecipitating systems for the bottom-up design of nanocomposites.

The production of nanocomposites is often economically and environmentally costly. Silica-witherite biomorphs, known for producing a wealth of life-like shapes, are nanocomposites entirely formed through self-organization processes. Behind these precipitates are two precipitation reactions that catalyze each other. Using a simple computational approach, we show here that this type of chemical system - defined here as Cross-Catalytic Coprecipitating Systems (CCCSs) - is of great interest to material design. Provided that cross-catalytic effects are sufficient to overcome the precipitation thresholds for each phase, all CCCSs can be expected to self-organize into nanocomposite materials through a one-pot, one-step synthesis protocol. Symmetry-breaking events generating various complex, ordered textures are predicted in CCCSs involving crystalline phases. While high levels of stochasticity lead to a loss of ordering, coprecipitation is found to be robust to diffusion or advection in the solution. This model shows that a couple of chemical reactions can generate a range of complex textures - with possibly distinct physical/chemical properties. Cross-catalytic coprecipitating systems consequently represent a promising avenue for producing nanocomposites with complex textures at reduced economic and environmental costs.

A fluctuating solution to the dolomite problem.

Episodes of dissolution and crystal growth stoke the formation of a common carbonate mineral.

Localized Crystallization of Calcium Phosphates by Light-Induced Processes.

Medical treatment options for bones and teeth can be significantly enhanced by taking control over the crystallization of biomaterials like hydroxyapatite in the healing process. Light-induced techniques are particularly interesting for this approach as they offer tremendous accuracy in spatial resolution. However, in the field of calcium phosphates, light-induced crystallization has not been investigated so far. Here, proof of principle is established to successfully induce carbonate-hydroxyapatite precipitation by light irradiation. Phosphoric acid is released by a photolabile molecule exclusively after irradiation, combining with calcium ions to form a calcium phosphate in the crystallization medium. 4-Nitrophenylphosphate (4NPP) is established as the photolabile molecule and the system is optimized and fully characterized. A calcium phosphate is crystallized exclusively by irradiation in aqueous solution and identified as carbonate apatite. Control over the localization and stabilization of the carbonate apatite is achieved by a pulsed laser, triggering precipitation in calcium and 4NPP-containing gel matrices. The results of this communication open up a wide range of new opportunities, both in the field of chemistry for more sophisticated reaction control in localized crystallization processes and in the field of medicine for enhanced treatment of calcium phosphate containing biomaterials.

101 contact twins in gypsum experimentally obtained from calcium carbonate enriched solutions: mineralogical implications for natural gypsum deposits.

Gypsum twins are frequently observed in nature, triggered by a wide array of impurities that are present in their depositional environments and that may exert a critical role in the selection of different twin laws. Identifying the impurities able to promote the selection of specific twin laws has relevance for geological studies aimed at interpreting the gypsum depositional environments in ancient and modern deposits. Here, the effect of calcium carbonate (CaCO3) on gypsum (CaSO4·2H2O) growth morphology has been investigated by performing temperature-controlled laboratory experiments with and without the addition of carbonate ions. The precipitation of twinned gypsum crystals has been achieved experimentally (101 contact twin law) by adding carbonate to the solution, and the involvement of rapidcreekite (Ca2SO4CO3·4H2O) in selecting the 101 gypsum contact twin law was supported, suggesting an epitaxial mechanism. Moreover, the occurrence of 101 gypsum contact twins in nature has been suggested by comparing the natural gypsum twin morphologies observed in evaporitic environments with those obtained in experiments. Finally, both orientations of the primary fluid inclusions (of the negative crystal shape) with respect to the twin plane and the main elongation of sub-crystals that form the twin are proposed as a fast and useful method (especially in geological samples) to distinguish between the 100 and 101 twin laws. The results of this study provide new insights into the mineralogical implications of twinned gypsum crystals and their potential as a tool to better understand natural gypsum deposits.

Mechanisms shaping the gypsum stromatolite-like structures in the Salar de Llamara (Atacama Desert, Chile).

The explanation of the origin of microbialites and specifically stromatolitic structures is a problem of high relevance for decoding past sedimentary environments and deciphering the biogenicity of the oldest plausible remnants of life. We have investigated the morphogenesis of gypsum stromatolite-like structures currently growing in shallow ponds (puquíos) in the Salar de Llamara (Atacama Desert, Northern Chile). The crystal size, aspect ratio, and orientation distributions of gypsum crystals within the structures have been quantified and show indications for episodic nucleation and competitive growth of millimetric to centimetric selenite crystals into a radial, branched, and loosely cemented aggregate. The morphogenetical process is explained by the existence of a stable vertical salinity gradient in the ponds. Due to the non-linear dependency of gypsum solubility as a function of sodium chloride concentration, the salinity gradient produces undersaturated solutions, which dissolve gypsum crystals. This dissolution happens at a certain depth, narrowing the lower part of the structures, and producing their stromatolite-like morphology. We have tested this novel mechanism experimentally, simulating the effective dissolution of gypsum crystals in stratified ponds, thus providing a purely abiotic mechanism for these stromatolite-like structures.

Mineralochemical Mechanism for the Formation of Salt Volcanoes: The Case of Mount Dallol (Afar Triangle, Ethiopia).

A genetic model is proposed for the formation and evolution of volcano-like structures from materials other than molten silicate rocks. The model is based on Mount Dallol (Afar Triangle, Ethiopia), currently hosting a conspicuous hydrothermal system with hot, hyper-acidic springs, forming a colorful landscape of unique mineral patterns. We reason that Mount Dallol is the last stage of the formation of a salt volcano driven by the destabilization of a thick sequence of hydrated minerals (the Houston Formation) after the emplacement of an igneous intrusion beneath the thick Danakil evaporitic sequence. Our claim is supported by field studies, calculations of the mineral/water volume balance upon mineral dehydration, and by a geothermal model of the Danakil basin predicting a temperature up to 220 °C at the Houston Formation after the intrusion of a basaltic magma without direct contact with the evaporitic sequence. Although insufficient for salt melting, this heating triggers mineral dehydration and hydrolysis, leading to a total volume increase of at least 25%. The released brine is segregated upward into a pressurized chamber, where the excess volume produced the doming of Mount Dallol. Later, the collapse of the dome formed a caldera and the emission of clastic flows. The resulting structures and materials resemble volcanic lava flows in distribution, structure, and texture but are entirely made of salty materials. This novel mechanism of the generation of pressurized brines and their later eruption extends the relevance of volcanologic studies to lower temperature ranges and unanticipated geologic contexts on Earth and possibly also on other planets.

A Comprehensive Methodology for Monitoring Evaporitic Mineral Precipitation and Hydrochemical Evolution of Saline Lakes: The Case of Lake Magadi Soda Brine (East African Rift Valley, Kenya).

Lake Magadi, East African Rift Valley, is a hyperalkaline and saline soda lake highly enriched in Na+, K+, CO3 2-, Cl-, HCO3 -, and SiO2 and depleted in Ca2+ and Mg2+, where thick evaporite deposits and siliceous sediments have been forming for 100 000 years. The hydrogeochemistry and the evaporite deposits of soda lakes are subjects of growing interest in paleoclimatology, astrobiology, and planetary sciences. In Lake Magadi, different hydrates of sodium carbonate/bicarbonate and other saline minerals precipitate. The precipitation sequence of these minerals is a key for understanding the hydrochemical evolution, the paleoenvironmental conditions of ancient evaporite deposits, and industrial crystallization. However, accurate determination of the precipitation sequence of these minerals was challenging due to the dependency of the different hydrates on temperature, water activity, pH and pCO2, which could induce phase transformation and secondary mineral precipitation during sample handling. Here, we report a comprehensive methodology applied for monitoring the evaporitic mineral precipitation and hydrochemical evolution of Lake Magadi. Evaporation and mineral precipitations were monitored by using in situ video microscopy and synchrotron X-ray diffraction of acoustically levitated droplets. The mineral patterns were characterized by ex situ Raman spectroscopy, X-ray diffraction, and scanning electron microscopy. Experiments were coupled with thermodynamic models to understand the evaporation and precipitation-driven hydrochemical evolution of brines. Our results closely reproduced the mineral assemblages, patterns, and textural relations observed in the natural setting. Alkaline earth carbonates and fluorite were predicted to precipitate first followed by siliceous sediments. Among the salts, dendritic and acicular trona precipitate first via fractional crystallization-reminiscent of grasslike trona layers of Lake Magadi. Halite/villiaumite, thermonatrite, and sylvite precipitate sequentially after trona from residual brines depleted in HCO3 -. The precipitation of these minerals between trona crystals resembles the precipitation process observed in the interstitial brines of the trona layers. Thermonatrite precipitation began after trona equilibrated with the residual brines due to the absence of excess CO2 input. We have shown that evaporation and mineral precipitation are the major drivers for the formation of hyperalkaline, saline, and SiO2-rich brines. The discrepancy between predicted and actual sulfate and phosphate ion concentrations implies the biological cycling of these ions. The combination of different in situ and ex situ methods and modeling is key to understanding the mineral phases, precipitation sequences, and textural relations of modern and ancient evaporite deposits. The synergy of these methods could be applicable in industrial crystallization and natural brines to reconstruct the hydrogeochemical and hydroclimatic conditions of soda lakes, evaporite settings, and potentially soda oceans of early Earth and extraterrestrial planets.

The role of borosilicate glass in Miller-Urey experiment.

We have designed a set of experiments to test the role of borosilicate reactor on the yielding of the Miller-Urey type of experiment. Two experiments were performed in borosilicate flasks, two in a Teflon flask and the third couple in a Teflon flask with pieces of borosilicate submerged in the water. The experiments were performed in CH4, N2, and NH3 atmosphere either buffered at pH 8.7 with NH4Cl or unbuffered solutions at pH ca. 11, at room temperature. The Gas Chromatography-Mass Spectroscopy results show important differences in the yields, the number of products, and molecular weight. In particular, a dipeptide, multi-carbon dicarboxylic acids, PAHs, and a complete panel of biological nucleobases form more efficiently or exclusively in the borosilicate vessel. Our results offer a better explanation of the famous Miller's experiment showing the efficiency of borosilicate in a triphasic system including water and the reduced Miller-Urey atmosphere.

Local Light-Controlled Generation of Calcium Carbonate and Barium Carbonate Biomorphs via Photochemical Stimulation.

Photochemical activation is proposed as a general method for controlling the crystallization of sparingly soluble carbonates in space and time. The photogeneration of carbonate in an alkaline environment is achieved upon photo-decarboxylation of an organic precursor by using a conventional 365 nm UV LED. Local irradiation was conducted focusing the LED light on a 300 µm radius spot on a closed glass crystallization cell. The precursor solution was optimized to avoid the precipitation of the photoreaction organic byproducts and prevent photo-induced pH changes to achieve the formation of calcium carbonate only in the corresponding irradiated area. The crystallization was monitored in real-time by time-lapse imaging. The method is also shown to work in gels. Similarly, it was also shown to photo-activate locally the formation of barium carbonate biomorphs. In the last case, the morphology of these biomimetic structures was tuned by changing the irradiation intensity.

An Alternative Approach for Assessing Biogenicity.

The search for signs of life in the ancient rock record, extreme terrestrial environments, and other planetary bodies requires a well-established, universal, and unambiguous test of biogenicity. This is notably true for cellular remnants of microbial life, since their relatively simple morphologies resemble various abiogenic microstructures that occur in nature. Although lists of qualitative biogenicity criteria have been devised, debates regarding the biogenicity of many ancient microfossils persist to this day. We propose here an alternative quantitative approach for assessing the biogenicity of putative microfossils. In this theoretical approach, different hypotheses-involving biology or not and depending on the geologic setting-are put forward to explain the observed objects. These hypotheses correspond to specific types of microstructures/systems. Using test samples, the morphology and/or chemistry of these systems are then characterized at the scale of populations. Morphologic parameters include, for example, circularity, aspect ratio, and solidity, while chemical parameters could include elementary ratios (e.g., N/C ratio), isotopic enrichments (e.g., δ13C), or chirality (e.g., molar proportion of stereoisomers), among others. Statistic trends distinguishing the different systems are then searched for empirically. The trends found are translated into "decision spaces" where the different systems are quantitatively discriminated and where the potential microfossil population can be located as a single point. This approach, which is formulated here on a theoretical level, will solve several problems associated with the classical qualitative criteria of biogenicity. Most importantly, it could be applied to reveal the existence of cellular life on other planets, for which characteristics of morphology and chemical composition are difficult to predict.

Prebiotic Organic Chemistry of Formamide and the Origin of Life in Planetary Conditions: What We Know and What Is the Future.

The goal of prebiotic chemistry is the depiction of molecular evolution events preceding the emergence of life on Earth or elsewhere in the cosmos. Plausible experimental models require geochemical scenarios and robust chemistry. Today we know that the chemical and physical conditions for life to flourish on Earth were at work much earlier than thought, i.e., earlier than 4.4 billion years ago. In recent years, a geochemical model for the first five hundred million years of the history of our planet has been devised that would work as a cradle for life. Serpentinization processes in the Hadean eon affording self-assembled structures and vesicles provides the link between the catalytic properties of the inorganic environment and the impressive chemical potential of formamide to produce complete panels of organic molecules relevant in pre-genetic and pre-metabolic processes. Based on an interdisciplinary approach, we propose basic transformations connecting geochemistry to the chemistry of formamide, and we hint at the possible extension of this perspective to other worlds.

Nanoscale Anatomy of Iron-Silica Self-Organized Membranes: Implications for Prebiotic Chemistry.

Iron-silica self-organized membranes, so-called chemical gardens, behave as fuel cells and catalyze the formation of amino/carboxylic acids and RNA nucleobases from organics that were available on early Earth. Despite their relevance for prebiotic chemistry, little is known about their structure and mineralogy at the nanoscale. Studied here are focused ion beam milled sections of iron-silica membranes, grown from synthetic and natural, alkaline, serpentinization-derived fluids thought to be widespread on early Earth. Electron microscopy shows they comprise amorphous silica and iron nanoparticles of large surface areas and inter/intraparticle porosities. Their construction resembles that of a heterogeneous catalyst, but they can also exhibit a bilayer structure. Surface-area measurements suggest that membranes grown from natural waters have even higher catalytic potential. Considering their geochemically plausible precipitation in the early hydrothermal systems where abiotic organics were produced, iron-silica membranes might have assisted the generation and organization of the first biologically relevant organics.

Light-switchable anchors on magnetized biomorphic microcarriers.

Microcarriers with the ability to release and catch substances are highly desired metamaterials and difficult to obtain. Herein, we report a straightforward strategy to synthesize these materials by combining silica-biomorphs with mesocrystals. An easy access to microcarrier hulls with covalently bound spiropyrans as light-switchable anchor points is presented.

Mineral self-organization on a lifeless planet.

It has been experimentally demonstrated that, under alkaline conditions, silica is able to induce the formation of mineral self-assembled inorganic-inorganic composite materials similar in morphology, texture and nanostructure to the hybrid biomineral structures that, millions of years later, life was able to self-organize. These mineral self-organized structures (MISOS) have been also shown to work as effective catalysts for prebiotic chemical reactions and to easily create compartmentalization within the solutions where they form. We reason that, during the very earliest history of this planet, there was a geochemical scenario that inevitably led to the existence of a large-scale factory of simple and complex organic compounds, many of which were relevant to prebiotic chemistry. The factory was built on a silica-rich high-pH ocean and powered by two main factors: a) a quasi-infinite source of simple carbon molecules synthesized abiotically from reactions associated with serpentinization, or transported from meteorites and produced from their impact on that alkaline ocean, and b) the formation of self-organized silica-metal mineral composites that catalyze the condensation of simple molecules in a methane-rich reduced atmosphere. We discuss the plausibility of this geochemical scenario, review the details of the formation of MISOS and its catalytic properties and the transition towards a slightly alkaline to neutral ocean.

Identifying microbial life in rocks: Insights from population morphometry.

The identification of cellular life in the rock record is problematic, since microbial life forms, and particularly bacteria, lack sufficient morphologic complexity to be effectively distinguished from certain abiogenic features in rocks. Examples include organic pore-fillings, hydrocarbon-containing fluid inclusions, organic coatings on exfoliated crystals and biomimetic mineral aggregates (biomorphs). This has led to the interpretation and re-interpretation of individual microstructures in the rock record. The morphologic description of entire populations of microstructures, however, may provide support for distinguishing between preserved micro-organisms and abiogenic objects. Here, we present a statistical approach based on quantitative morphological description of populations of microstructures. Images of modern microbial populations were compared to images of two relevant types of abiogenic microstructures: interstitial spaces and silica-carbonate biomorphs. For the populations of these three systems, the size, circularity, and solidity of individual particles were calculated. Subsequently, the mean/SD, skewness, and kurtosis of the statistical distributions of these parameters were established. This allowed the qualitative and quantitative comparison of distributions in these three systems. In addition, the fractal dimension and lacunarity of the populations were determined. In total, 11 parameters, independent of absolute size or shape, were used to characterize each population of microstructures. Using discriminant analysis with parameter subsets, it was found that size and shape distributions are typically sufficient to discriminate populations of biologic and abiogenic microstructures. Analysis of ancient, yet unambiguously biologic, samples (1.0 Ga Angmaat Formation, Baffin Island, Canada) suggests that taphonomic effects can alter morphometric characteristics and complicate image analysis; therefore, a wider range of microfossil assemblages should be studied in the future before automated analyses can be developed. In general, however, it is clear from our results that there is great potential for morphometric descriptions of populations in the context of life recognition in rocks, either on Earth or on extraterrestrial bodies.

A Polyextreme Hydrothermal System Controlled by Iron: The Case of Dallol at the Afar Triangle.

One of the latest volcanic features of the Erta Ale range at the Afar Triangle (NE Ethiopia) has created a polyextreme hydrothermal system located at the Danakil depression on top of a protovolcano known as the dome of Dallol. The interaction of the underlying basaltic magma with the evaporitic salts of the Danakil depression has generated a unique, high-temperature (108 °C), hypersaline (NaCl supersaturated), hyperacidic (pH values from 0.1 to -1.7), oxygen-free hydrothermal site containing up to 150 g/L of iron. We find that the colorful brine pools and mineral patterns of Dallol derive from the slow oxygen diffusion and progressive oxidation of the dissolved ferrous iron, the iron-chlorine/-sulfate complexation, and the evaporation. These inorganic processes induce the precipitation of nanoscale jarosite-group minerals and iron(III)-oxyhydroxides over a vast deposition of halite displaying complex architectures. Our results suggest that life, if present under such conditions, does not play a dominant role in the geochemical cycling and mineral precipitation at Dallol as opposed to other hydrothermal sites. Dallol, a hydrothermal system controlled by iron, is a present-day laboratory for studying the precipitation and progressive oxidation of iron minerals, relevant for geochemical processes occurring at early Earth and Martian environments.

A Universal Geochemical Scenario for Formamide Condensation and Prebiotic Chemistry.

The condensation of formamide has been shown to be a robust chemical pathway affording molecules necessary for the origin of life. It has been experimentally demonstrated that condensation reactions of formamide are catalyzed by a number of minerals, including silicates, phosphates, sulfides, zirconia, and borates, and by cosmic dusts and meteorites. However, a critical discussion of the catalytic power of the tested minerals, and the geochemical conditions under which the condensation would occur, is still missing. We show here that mineral self-assembled structures forming under alkaline silica-rich solutions are excellent catalysts for the condensation of formamide with respect to other minerals. We also propose that these structures were likely forming as early as 4.4 billion years ago when the whole earth surface was a reactor, a global scale factory, releasing large amounts of organic compounds. Our experimental results suggest that the conditions required for the synthesis of the molecular bricks from which life self-assembles, rather than being local and bizarre, appears to be universal and geologically rather conventional.

Thermal assisted self-organization of calcium carbonate.

Fabrication of mineral multi-textured architectures by self-organization is a formidable challenge for engineering. Current approaches follow a biomimetic route for hybrid materials based on the coupling of carbonate and organic compounds. We explore here the chemical coupling of silica and carbonate, leading to fabrication of inorganic-inorganic biomimetic structures known as silica-carbonate biomorphs. So far, biomorphic structures were restricted to orthorhombic barium, strontium, and calcium carbonate. We demonstrate that, monohydrocalcite a hydrous form of calcium carbonate with trigonal structure can also form biomorphic structures, thus showing biomorphic growth is not dictated by the carbonate crystal structure. We show that it is possible to control the growth regime, and therefore the texture and overall shape, by tuning the growth temperature, thereby shifting the textural pattern within the production of a given architecture. This finding opens a promising route to the fabrication of complex multi-textured self-organized material made of silica and chalk.