Evidence for heterothermic endothermy and reptile-like eggshell mineralization in Troodon, a non-avian maniraptoran theropod.

The dinosaur-bird transition involved several anatomical, biomechanical, and physiological modifications of the theropod bauplan. Non-avian maniraptoran theropods, such as Troodon, are key to better understand changes in thermophysiology and reproduction occurring during this transition. Here, we applied dual clumped isotope (Δ47 and Δ48) thermometry, a technique that resolves mineralization temperature and other nonthermal information recorded in carbonates, to eggshells from Troodon, modern reptiles, and modern birds. Troodon eggshells show variable temperatures, namely 42 and 29 ± 2 °C, supporting the hypothesis of an endothermic thermophysiology with a heterothermic strategy for this extinct taxon. Dual clumped isotope data also reveal physiological differences in the reproductive systems between Troodon, reptiles, and birds. Troodon and modern reptiles mineralize their eggshells indistinguishable from dual clumped isotope equilibrium, while birds precipitate eggshells characterized by a positive disequilibrium offset in Δ48. Analyses of inorganic calcites suggest that the observed disequilibrium pattern in birds is linked to an amorphous calcium carbonate (ACC) precursor, a carbonate phase known to accelerate eggshell formation in birds. Lack of disequilibrium patterns in reptile and Troodon eggshells implies these vertebrates had not acquired the fast, ACC-based eggshell calcification process characteristic of birds. Observation that Troodon retained a slow reptile-like calcification suggests that it possessed two functional ovaries and was limited in the number of eggs it could produce; thus its large clutches would have been laid by several females. Dual clumped isotope analysis of eggshells of extinct vertebrates sheds light on physiological information otherwise inaccessible in the fossil record.

Glass transition temperatures and crystallization kinetics of a synthetic, anhydrous, amorphous calcium-magnesium carbonate.

We report the first calorimetric observations of glass transition temperatures and crystallization rates of anhydrous, amorphous calcium-magnesium carbonate using fast scanning differential scanning calorimetry. Hydrous amorphous Ca0.95Mg0.05CO3 · 0.5H2O (ACMC) solid was precipitated from a MgCl2-NaHCO3 buffered solution, separated from the supernatant, and freeze-dried. An aliquot of the freeze-dried samples was additionally dried at 250°C for up to 6 h in a furnace and in a high-purity N2 atmosphere to produce anhydrous ACMC. The glass transition temperature of the anhydrous Ca0.95Mg0.05CO3 was determined by applying different heating rates (1000-6000 K s-1) and correcting for thermal lag to be 376°C and the relaxational heat capacity was determined to be Cp = 0.16 J/(g K). Additionally, the heating rate dependence of the temperature that is associated with the corrected crystallization peaks is used to determine the activation energy of crystallization to be 275 kJ mol-1. A high-resolution transmission electron microscopy study on the hydrous and anhydrous samples provided further constraints on their compositional and structural states. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Solubility investigations in the amorphous calcium magnesium carbonate system.

Amorphous precursors are known to occur in the early stages of carbonate mineral formation in both biotic and abiotic environments. Although the Mg content of amorphous calcium magnesium carbonate (ACMC) is a crucial factor for its temporal stabilization, to date little is known about its control on ACMC solubility. Therefore, amorphous Ca x Mg1-x CO3·nH2O solids with 0 ≤ x ≤ 1 and 0.4 ≤ n ≤ 0.8 were synthesized and dispersed in MgCl2-NaHCO3 buffered solutions at 24.5 ± 0.5 °C. The chemical evolution of the solution and the precipitate clearly shows an instantaneous exchange of ions between ACMC and aqueous solution. The obtained ion activity product for ACMC (IAPACMC = "solubility product") increases as a function of its Mg content ([Mg]ACMC = (1 - x) × 100 in mol%) according to the expression: log(IAPACMC) = 0.0174 (±0.0013) × [Mg]ACMC - 6.278 (±0.046) (R 2 = 0.98), where the log(IAPACMC) shift from Ca (-6.28 ± 0.05) to Mg (-4.54 ± 0.16) ACMC endmember, can be explained by the increasing water content and changes in short-range order, as Ca is substituted by Mg in the ACMC structure. The results of this study shed light on the factors controlling ACMC solubility and its temporal stability in aqueous solutions.

Substantial Copper (Cu2+) Uptake by Metakaolin-Based Geopolymer and Its Resistance to Acid Leaching and Ion Exchange.

Geopolymers are inorganic, chemically resistant aluminosilicate-based binding agents, which remove hazardous metal ions from exposed aqueous media. However, the removal efficiency of a given metal ion and the potential ion remobilization have to be assessed for individual geopolymers. Therefore, copper ions (Cu2+) were removed by a granulated, metakaolin-based geopolymer (GP) in water matrices. Subsequent ion exchange and leaching tests were used to determine the mineralogical and chemical properties as well as the resistance of the Cu2+-bearing GPs to corrosive aquatic environments. Experimental results indicate the pH of the reacted solutions to have a significant impact on the Cu2+ uptake systematics: the removal efficiency ranged from 34-91% at pH 4.1-5.7 up to ~100% at pH 11.1-12.4. This is equivalent to Cu2+ uptake capacities of up to 193 mg/g and 560 mg/g in acidic versus alkaline media. The uptake mechanism was governed by Cu2+-substitution for alkalis in exchangeable GP sites and by co-precipitation of gerhardtite (Cu2(NO3)(OH)3) or tenorite (CuO) and spertiniite (Cu(OH)2). All Cu-GPs showed excellent resistance to ion exchange (Cu2+ release: 0-2.4%) and acid leaching (Cu2+ release: 0.2-0.7%), suggesting that tailored GPs have a high potential to immobilize Cu2+ ions from aquatic media.

Neotropical ostracode oxygen and carbon isotope signatures: implications for calcification conditions.

Calcitic valves of non-marine ostracodes are important geochemical archives. Investigations of the relationship between the ranges of oxygen and carbon isotope values of modern ostracode populations and their host water provide important information on local or regional conditions and influences. Here we present the first δ18Oostracode and δ13C of the freshwater ostracode species Cytheridella ilosvayi along with the isotopic composition of the waters in which the ostracodes calcified, δDwater, δ18Owater, δ13CDIC values-covering a large geographical range (Florida to Brazil). With this data we extended a newly developed approach based on the estimation of δ18O values of monthly equilibrium calcites as references for the interpretation of δ18Oostracode values. The expected apparent oxygen isotope fractionation between CaCO3 and H2O is correlated with temperature with smaller values occurring at higher temperatures as valid at isotope equilibrium (δ18Ocalcite_eq). Uncertainties about the expected equilibrium calcites derive from incomplete knowledge of high-frequency variations of the water bodies caused by interplay of mixing, evaporation, and temperature. Coincidence between δ18Oostracode and δ18Ocalcite_eq is restricted to few months indicating a seasonal calcification of Cytheridella. There is a characteristic pattern in its difference between mean δ18Oostracode and δ18Ocalcite_eq which implies that Cytheridella provides a synchronous life cycle in its geographical range with two calcification periods in spring (May, June) and autumn (October). This ubiquitous life cycle of Cytheridella in the entire study area is considered to be phylogenetically inherited. It might have originally been adapted to environmental conditions but has been conserved during the migration and radiation of the group over the Neotropical realm. Supplementary Information: The online version contains supplementary material available at 10.1007/s10533-022-00917-9.

Synthesis of Zeolites from Fine-Grained Perlite and Their Application as Sorbents.

The hydrothermal alteration of perlite into zeolites was studied using a two-step approach. Firstly, perlite powder was transformed into Na-P1 (GIS) or hydro(xy)sodalite (SOD) zeolites at 100 °C and 24 h using 2 or 5 M NaOH solutions. Secondly, the Si:Al molar ratio of the reacted Si-rich solution was adjusted to 1 by Na-aluminate addition to produce zeolite A (LTA) at 65 or 95 °C and 6 or 24 h at an efficiency of 90 ± 9% for Al and 93 ± 6% for Si conversion. The performance of these zeolites for metal ion removal and water softening applications was assessed by sorption experiments using an artificial waste solution containing 4 mmol/L of metal ions (Me2+: Ca2+, Mg2+, Ba2+ and Zn2+) and local tap water (2.1 mmol/L Ca2+ and 0.6 mmol/L Mg2+) at 25 °C. The removal capacity of the LTA-zeolite ranged from 2.69 to 2.86 mmol/g for Me2+ (=240-275 mg/g), which is similar to commercial zeolite A (2.73 mmol/g) and GIS-zeolite (2.69 mmol/g), and significantly higher compared to the perlite powder (0.56 mmol/g) and SOD-zeolite (0.88 mmol/g). The best-performing LTA-zeolite removed 99.8% Ca2+ and 93.4% Mg2+ from tap water. Our results demonstrate the applicability of the LTA-zeolites from perlite for water treatment and softening applications.

Green inhibitors reduce unwanted calcium carbonate precipitation: Implications for technical settings.

Mineral scale deposits in water drainage and supply systems are a common and challenging issue, especially by clogging the water flow. The removal of such unwanted deposits is cost intensive arguing for case-specific and sustainable prevention strategies. In the present study, a novel on-site approach to prevent calcium carbonate (CaCO3) scale formation was assessed in two road tunnel drainages: Application of the eco-friendly green inhibitor polyaspartate (PASP) caused (i) a significant inhibition of CaCO3 precipitation, (ii) a more porous or even unconsolidated consistence of the deposits, and (iii) a shift from calcite to the metastable aragonite and vaterite polymorphs. Even relatively low PASP concentrations (1-33 mg/l) can significantly decrease CaCO3 scale deposition, removing up to ∼7 t CaCO3/year at an efficiency up to 84%. Application of PASP for water conditioning should also consider case-specific microbial activity effects, where consumption of PASP, e.g. by Leptothrix ochracea, can limit inhibition effects.

Impact of green clay authigenesis on element sequestration in marine settings.

Retrograde clay mineral reactions (reverse weathering), including glauconite formation, are first-order controls on element sequestration in marine sediments. Here, we report substantial element sequestration by glauconite formation in shallow marine settings from the Triassic to the Holocene, averaging 3 ± 2 mmol·cm-²·kyr-1 for K, Mg and Al, 16 ± 9 mmol·cm-²·kyr-1 for Si and 6 ± 3 mmol·cm-²·kyr-1 for Fe, which is ~2 orders of magnitude higher than estimates for deep-sea settings. Upscaling of glauconite abundances in shallow-water (0-200 m) environments predicts a present-day global uptake of ~≤ 0.1 Tmol·yr-1 of K, Mg and Al, and ~0.1-0.4 Tmol·yr-1 of Fe and Si, which is ~half of the estimated Mesozoic elemental flux. Clay mineral authigenesis had a large impact on the global marine element cycles throughout Earth's history, in particular during 'greenhouse' periods with sea level highstand, and is key for better understanding past and present geochemical cycling in marine sediments.

Chemical weathering and progressing alteration as possible controlling factors for creeping landslides.

Landslides can behave as dynamic processes, which emerge from the complex interplay of tectonics, erosion, weathering and gravitational influences, triggered by various hydrological, mineralogical, biological and geotechnical factors. Integral studies to assess the mechanisms underlying landslide initiation and progression are mainly focussed on specific cases with high geohazard potential. The landslide near Stadtschlaining (Austria) represents a key study site to elucidate the impacts of pelitic sediment composition, weathering regime, alteration patterns and hydrochemistry on recurrent damage progression in the local infrastructure. Based on field work, soil-mechanical logging (Atterberg limits, undrained strength, friction angles), water chemistry (ICP-OES, IC, hydrochemical modeling), solid-phase characterization (XRD, XRF, SEM) and sorption experiments we establish a conceptual model for initiating and progressing of landslides: Infiltration of low mineralized meteoric water (EC: <200 µS/cm) in permeable limonitic gravels triggers chemical weathering of greenschist-derived detritus and promotes its transformation into kaolinite and smectite. The clayey strata (>50 wt% of clay minerals) create zones of mechanical and chemical weakness in the underground (~4-6 m below ground level), which are characterized by particle disintegration/delamination, slip bedding and deformations, and development of porous layers depicting water flow paths. Subsequent Na+ exchange for bivalent ions in the smectite interlayer delivered by percolating, highly mineralized water (EC: 1600-5100 µS/cm) is caused by de-icing salt and fertilizer applications during winter and late summer, and yield in i) decohesion and physical breakdown of the particle aggregates and ii) swelling of the clay matrix in early spring and autumn. These processes reduce the shear strength of the pelitic sediments, resulting in failure and initiation of landslides (deformation: ~500 mm within a month) and subsequent steady creeping motion (deformation: ~100 mm in 6 months). Customized engineered solutions to prevent landslides in this area are presented, which can be conveyed to analogous landslide-affected areas worldwide.

A novel nZVI-bentonite nanocomposite to remove trichloroethene (TCE) from solution.

Nanoscale zero-valent iron (nZVI) based (nano)composites supported by clay mineral substrates are a promising technology for the in-situ remediation of groundwater and (sub)soils contaminated with chlorinated hydrocarbons, such as trichloroethene (TCE). However, the physicochemical processes and interaction mechanisms between nZVI particles, clay minerals and TCE are poorly understood, yet. We immobilized nZVI particles on a commercial bentonite substrate to prepare a novel nZVI-B nanocomposite and tested its performance for TCE removal from solution against pure nZVI in batch reactors. The nZVI-B exhibited a higher reactivity (2.2·10-3 L h-1·m-2) and efficiency (94%) for TCE removal than nZVI (2.2·10-4 L h-1·m-2; 45%). Sorption of TCE onto the clay surfaces and reductive de-chlorination in "micro-reactors" developing within the nZVI-B controlled the kinetics and the magnitude of TCE loss from solution. Contrary to pure nZVI, no signs of nZVI particle agglomeration or inactivation due to oxide shell formation were found in nZVI-B. We attribute this to the uptake of dissolved Fe species that are liberated via progressing nZVI particle corrosion by the bentonite substrate to form Fe-smectite (nontronite domains), which prevented from a deterioration of the properties and reactivity of the nZVI-B. The use of nZVI-B in permeable reactive barriers at contaminated field sites could be feasible, where a system-inherent reduction of the soil-bearing capacity has to be minimized.

A coherent method for combined stable magnesium and radiogenic strontium isotope analyses in carbonates (with application to geological reference materials SARM 40, SARM 43, SRM 88A, SRM 1B).

We undertook 87Sr/86Sr analyses for a range of carbonate bearing geological reference materials, and combined these with δ26Mg for a subset of samples. Following chemical purification in a series of chromatographic extractions, isotope ratios were measured by Multi-Collector-ICP-MS using a Plasma II (Nu instruments, Wrexham, UK). To validate efficient sample digestion procedures of carbonate fractions, total samples were treated with either 3 mol l-1 HNO3 and 0.5 mol l-1 HCl, respectively. Results of both leaching procedures are identical within reproducibility. Reference values for SRM 88A (formerly NBS 88A), SRM 1B (formerly NBS 1B), SARM 40, SARM 43, JDo-1, JLs-1, and San Carlos olivine range from 0.70292 to 0.73724 in 87Sr/86Sr and from -2.80 to -0.41 ‰ for δ26Mg, respectively. This set of geological reference materials can be used for sedimentary rock material with different carbonate mineral and matrix composition as quality control measurements of combined stable Mg and radiogenic Sr isotope analyses.•We present a protocol that facilitates the chemical separation of Mg and Sr in carbonate bearing geological reference materials including 87Sr/86Sr and δ26Mg of certified reference materials.

Scale deposits in tunnel drainage systems - A study on fabrics and formation mechanisms.

Rapid deposition of chemical sediments, particularly calcium carbonate, is a widespread phenomenon in tunnel constructions, which can significantly disturb water draining. The removal of the scale deposits in the drainage setting is labor and cost intensive. Prediction or prevention of these unwanted scale deposits are challenging and require detailed knowledge on their site-specific source, formation mechanisms and environmental dependencies. This case study combines a mineralogical, (micro)structural, isotopic, microbiological, and hydrochemical approach to understand the formation of scale deposits in an Austrian motorway tunnel. Chemical and isotopic results revealed that all investigated solutions originate from a distinct local aquifer. High pH (11), indicative high alkaline element concentrations (Na 26 mg/l; K 67 mg/l), originated from concrete leaching, and a strong supersaturation in respect to calcite (SI > 1) are representative for the environmental setting of scaling type 1. This type is characterized by the formation of calcite, aragonite, and rarely documented dypingite (Mg5(CO3)4(OH)2*5H2O), and yields in a highly porous material showing minor indications of microbial presence. In contrast, scale deposits of type 2 are strongly microbially influenced, yielding dense and layered mineral deposits, typically consisting of calcite. The corresponding aqueous solution revealed elevated Mg concentration (38 mg/l) and a high molar Mg/Ca ratio (0.8). Scale deposits containing distinct aragonite precipitates next to calcite, mostly growing in pore spaces of the scale fabric, are accounted as type 3. Therein, dypingite is always growing on top of aragonite needles, indicative for prior CaCO3 precipitation. The composition of corresponding solutions shows the highest Mg/Ca ratio (1.1). Scale type 4 is characterized as a compact deposit consisting entirely of calcite. Its corresponding solution exhibits a molar Mg/Ca ratio of 0.6. From the obtained data sets a conceptual model was developed describing the distinct operative and (micro)environmental conditions responsible for the distinct diversity of scale deposits.

In-situ Raman spectroscopy of amorphous calcium phosphate to crystalline hydroxyapatite transformation.

Amorphous calcium phosphate (Ca3(PO4)2xnH2O; n = 3-4.5; ACP) is a precursor phase of the mineral hydroxyapatite (Ca5(PO4)3(OH); HAP) that in natural settings occurs during both authigenic and biogenic mineral formation. In aqueous solutions ACP transforms rapidly to the crystalline phase. The transformation rate is highly dependent on the prevailing physico-chemical conditions, most likely on: Ca & PO4 concentration, pH and temperature. In this study, we conducted a calcium phosphate precipitation experiment at 20 °C and pH 9.2, in order to study the temporal evolution of the phosphate mineralogy. We monitored and assessed the transformation process of ACP to crystalline HAP using highly time-resolved in-situ Raman spectroscopy at 100 spectra per hour, in combination with solution chemistry and XRD data. Transformation of ACP to crystalline HAP occurred within 18 h, as it is illustrated in a clear peak shift in Raman spectra from 950 cm-1 to 960 cm-1 as well as in a sharpening of the 960 cm-1 peak. The advantages of this method are: •In-situ Raman spectroscopy facilitates quasi - continuous monitoring of phase transitions.•It is an easy to handle and non-invasive method.

Advances in concrete materials for sewer systems affected by microbial induced concrete corrosion: A review.

Microbial induced concrete corrosion (MICC) is recognized as one of the main degradation mechanisms of subsurface infrastructure worldwide, raising the demand for sustainable construction materials in corrosive environments. This review aims to summarize the key research progress acquired during the last decade regarding the understanding of MICC reaction mechanisms and the development of durable materials from an interdisciplinary perspective. Special focus was laid on aspects governing concrete - micoorganisms interaction since being the central process steering biogenic acid corrosion. The insufficient knowledge regarding the latter is proposed as a central reason for insufficient progress in tailored material development for aggressive wastewater systems. To date no cement-based material exists, suitable to withstand the aggressive conditions related to MICC over its entire service life. Research is in particular needed on the impact of physiochemical material parameters on microbial community structure, growth characteristics and limitations within individual concrete speciation. Herein an interdisciplinary approach is presented by combining results from material sciences, microbiology, mineralogy and hydrochemistry to stimulate the development of novel and sustainable materials and mitigation strategies for MICC. For instance, the application of antibacteriostatic agents is introduced as an effective instrument to limit microbial growth on concrete surfaces in aggressive sewer environments. Additionally, geopolymer concretes are introduced as highly resistent in acid environments, thus representing a possible green alternative to conventional cement-based construction materials.

Tracing formation and durability of calcite in a Punic-Roman cistern mortar (Pantelleria Island, Italy).

Ancient hydraulic lime mortar preserves chemical and isotopic signatures that provide important information about historical processing and its durability. The distribution and isotopic composition of calcite in a mortar of a well-preserved Punic-Roman cistern at Pantelleria Island (Italy) was used to trace the formation conditions, durability, and individual processing periods of the cistern mortar. The analyses of stable carbon and oxygen isotopes of calcite revealed four individual horizons, D, E, B-1 and B-2, of mortar from the top to the bottom of the cistern floor. Volcanic and ceramic aggregates were used for the production of the mortar of horizons E/D and B-1/B-2, respectively. All horizons comprise hydraulic lime mortar characterized by a mean cementation index of 1.5 ± 1, and a constant binder to aggregate ratio of 0.31 ± 0.01. This suggests standardized and highly effective processing of the cistern. The high durability of calcite formed during carbonation of slaked lime within the matrix of the ancient mortar, and thus the excellent resistance of the hydraulic lime mortar against water, was documented by (i) a distinct positive correlation of δ(18)Ocalcite and δ(13)Ccalcite; typical for carbonation through a mortar horizon, (ii) a characteristic evolution of δ(18)Ocalcite and δ(13)Ccalcite through each of the four mortar horizons; lighter follow heavier isotopic values from upper to lower part of the cistern floor, and (iii) δ(18)Ocalcite varying from -10 to -5 ‰ Vienna Pee Dee belemnite (VPDB). The range of δ(18)Ocalcite values rule out recrystallization and/or neoformation of calcite through chemical attack of water stored in cistern. The combined studies of the chemical composition of the binder and the isotopic composition of the calcite in an ancient mortar provide powerful tools for elucidating the ancient techniques and processing periods. This approach helps to evaluate the durability of primary calcite and demonstrates the importance of calcite as a proxy for chemical attack and quality of the ancient inorganic binder.

Temporal and spatial variability of chemical and isotopic composition of soil solutions from cambisols - field study and experiments.

The chemical and isotopic composition of soil solutions is highly relevant for environmental and forensic tasks. We investigated interstitial solutions from soil horizons of three cambisols in Styria (Austria). The soils consisted mainly of quartz, feldspar and clay minerals with a vertical variability. Two soil solution fractions from meso-, macro- and micropores (m) and micropores only (µ) were extracted at two subsequent hydraulic pressure steps corresponding to matrix potentials of up to pF 5.43 and from 5.43 to 5.73, respectively. While solute concentrations indicated diverse distribution in soil solution fractions m and µ, heavy stable hydrogen and oxygen isotopes of H2O (-92.5‰<δ2H<-34.4‰; -11.9‰<δ18O<-4.0‰, VSMOW) are clearly enriched in the µ versus m fractions. Principal component analysis on the hydrochemical data set indicates that the intensity of the overall silicate weathering is higher in autumn versus spring, whereas the anthropogenic impact on weathering behaves inversely. The anthropogenic impact is related to seasonal variability of nitrification of N-fertilizers. In consequence of evaluated signals for overall silicate weathering about three-fourths of the soil solutions sampled in autumn indicated elevated total dissolved solid concentration vs. those in spring accompanied with washing out solutes from the soil cover following precipitation events in autumn before sampling. Isotopic shift of soil solutions from the local meteoric water line in spring obviously followed an evaporation trend because of less precipitation and high evaporation before sampling. Experimentally simulated evaporation of soil samples confirmed the observed isotopic evaporation trend. Wetting experiments indicated the infiltration of water within minutes into the micropores of the soils. Exchange of water molecules between micro-, meso- and macropores is an almost instantaneous process and soil solutions in micropores are not as isolated from the soil water system as it was formerly suggested, e.g. for plant uptake. Highly dynamic and complex mechanisms in the gas-water-solid system of soils have to be considered for the application of elemental and isotope proxies related to environmental, forensic and agricultural tasks.

High-aluminum-affinity silica is a nanoparticle that seeds secondary aluminosilicate formation.

Despite the importance and abundance of aluminosilicates throughout our natural surroundings, their formation at neutral pH is, surprisingly, a matter of considerable debate. From our experiments in dilute aluminum and silica containing solutions (pH ~ 7) we previously identified a silica polymer with an extraordinarily high affinity for aluminium ions (high-aluminum-affinity silica polymer, HSP). Here, further characterization shows that HSP is a colloid of approximately 2.4 nm in diameter with a mean specific surface area of about 1,000 m(2) g(-1) and it competes effectively with transferrin for Al(III) binding. Aluminum binding to HSP strongly inhibited its decomposition whilst the reaction rate constant for the formation of the ß-silicomolybdic acid complex indicated a diameter between 3.6 and 4.1 nm for these aluminum-containing nanoparticles. Similarly, high resolution microscopic analysis of the air dried aluminum-containing silica colloid solution revealed 3.9 ± 1.3 nm sized crystalline Al-rich silica nanoparticles (ASP) with an estimated Al:Si ratio of between 2 and 3 which is close to the range of secondary aluminosilicates such as imogolite. Thus the high-aluminum-affinity silica polymer is a nanoparticle that seeds early aluminosilicate formation through highly competitive binding of Al(III) ions. In niche environments, especially in vivo, this may serve as an alternative mechanism to polyhydroxy Al(III) species binding monomeric silica to form early phase, non-toxic aluminosilicates.

Concrete under sulphate attack: an isotope study on sulphur sources.

The formation of secondary sulphate minerals such as thaumasite, ettringite and gypsum is a process causing severe damage to concrete constructions. A major key to understand the complex reactions, involving concrete deterioration is to decipher the cause of its appearance, including the sources of the involved elements. In the present study, sulphate attack on the concrete of two Austrian tunnels is investigated. The distribution of stable sulphur isotopes is successfully applied to decipher the source(s) of sulphur in the deteriorating sulphate-bearing minerals. Interestingly, δ(34)S values of sulphate in local groundwater and in the deteriorating minerals are mostly in the range from+14 to+27 ‰. These δ(34)S values match the isotope patterns of regional Permian and Triassic marine evaporites. Soot relicts from steam- and diesel-driven trains found in one of the tunnels show δ(34)S values from-3 to+5 ‰, and are therefore assumed to be of minor importance for sulphate attack on the concretes. In areas of pyrite-containing sedimentary rocks, the δ(34)S values of sulphate from damaged concrete range between-1 and+11 ‰. The latter range reflects the impact of sulphide oxidation on local groundwater sulphate.

Heterotrophic prokaryotic production in ultraoligotrophic alpine karst aquifers and ecological implications.

Spring waters from alpine karst aquifers are important drinking water resources. To investigate in situ heterotrophic prokaryotic production and its controlling factors, two different alpine karst springs were studied over two annual cycles. Heterotrophic production in spring water, as determined by [(3)H]leucine incorporation, was extremely low ranging from 0.06 to 6.83 pmol C L(-1) h(-1) (DKAS1, dolomitic-karst-spring) and from 0.50 to 75.6 pmol C L(-1) h(-1) (LKAS2, limestone-karst-spring). Microautoradiography combined with catalyzed reporter deposition-FISH showed that only about 7% of the picoplankton community took up [(3)H]leucine, resulting in generation times of 3-684 days. Principal component analysis, applying hydrological, chemical and biological parameters demonstrated that planktonic heterotrophic production in LKAS2 was governed by the respective hydrological conditions, whereas variations in DKAS1 changed seemingly independent from discharge. Measurements in sediments recovered from LKAS2, DKAS1 and similar alpine karst aquifers (n=12) revealed a 10(6)-fold higher heterotrophic production (average 19 micromol C dm(-3) h(-1)) with significantly lower generation times as compared with the planktonic fraction, highlighting the potential of surface-associated communities to add to self-purification processes. Estimates of the microbially mediated CO(2) in this compartment indicated a possible contribution to karstification.