Andreas Reimer

Biofilm exopolymers control microbialite formation at thermal springs discharging into the alkaline Pyramid Lake, Nevada, USA

Calcium carbonate precipitation and microbialite formation at highly supersaturated mixing zones of thermal spring waters and alkaline lake water have been investigated at Pyramid Lake, Nevada. Without precipitation, pure mixing should lead to a nearly 100-fold supersaturation at 40oC. Physicochemical precipitation is modified or even inhibited by the properties of biofilms, dependent on the extent of biofilm development and the current precipitation rate. Mucus substances (extracellular polymeric substances, EPS, e.g., of cyanobacteria) serve as effective Ca 2C -buffers, thus preventing seed crystal nucleation even in a highly supersaturated macroenvironment. Carbonate is then preferentially precipitated in mucus-free areas such as empty diatom tests or voids. After the buffer capacity of the EPS is surpassed, precipitation is observed at the margins of mucus areas. Hydrocarbon biomarkers extracted from (1) a calcifying Phormidium-biofilm, (2) the stromatolitic carbonate below, and (3) a fossil ‘tufa’ of the Pleistocene pinnacles, indicate that the cyanobacterial primary producers have been subject to significant temporal changes in their species distribution. Accordingly, the species composition of cyanobacterial biofilms does not appear to be relevant for the formation of microbial carbonates in Pyramid Lake. The results demonstrate the crucial influence of mucus substances on carbonate precipitation in highly supersaturated natural environments.

Unusual distributions of long-chain alkenones and tetrahymanol from the highly alkaline Lake Van, Turkey

Long-chain C37 to C40 alkenones with di-, tri-, and tetra-unsaturation are very abundant in sediment trap material and Holocene to Late Pleistocene core samples from the Earths largest soda lake, Lake Van (Turkey). Thus, the known distribution range of these typical biomarkers for haptophyte microalgae is extended to highly alkaline environments. The observed unsaturation patterns differ strikingly from those found in open marine haptophytes and sediments by an enhanced relative abundance of the tetra-unsaturated compounds, especially the C37:4 methyl ketone. Their preponderance is suggested to be a facies marker pattern for lacustrine and marginal marine areas of sedimentation. Using published U37K calibrations, no reliable absolute temperatures were obtained for the Lake Van samples. Accordingly, marine sea surface temperature determinations based on long-chain alkenones should be applied with caution when a contribution of these compounds from coastal or nonmarine sources can not be excluded. The presence of tetrahymanol and gammacer-3-one in the Lake Van materials is attributed to organic matter contributions of ciliates. The relative abundance of long-chain alkenones and of tetrahymanol/gammacer-3-one is considered to reflect changes in the environmental conditions, in particular in the hydrological setting. We suggest that times of pronounced stagnation are recognised by very high tetrahymanol/gammacer-3-one concentrations together with drastically increased stanol/stenol ratios, and intervals of enhanced convection or of high freshwater input are characterised by high alkenone contributions.

Dating Late Glacial abrupt climate changes in the 14,570 yr long continuous varve record of Lake Van, Turkey

In summer 1990, during the third international expedition to Lake Van, eastern Anatolia, 10 sediment cores were retrieved from depths up to 446 m. As reported earlier, the sediments of the lake are finely laminated. The seven cores, recovered up to 30 km apart in the main lake basin, presented sediment sequences which correlate well with respect to ash layers and prominent colour changes, but also lamina for lamina. Here we report on the detailed evaluation of this record, which is varved continuously back to 14,570 yr B.P. (calendar years before 1950 AD). It is independent of 14C calibration, i.e. it is not a floating record, and it is the only detailed varve chronology known from the semi-arid Mediterranean region. Important Late Glacial events, such as the termination of the Oldest and Younger Dryas are clearly recorded in the sediments. Chronozones were defined on the basis of changes of the deposition rate and of chemical composition caused by environmental changes. Analysis of the annual deposition rates revealed abrupt changes within only a few years, declining for example by approximately 30% in the transition period between the Oldest Dryas and the Bolling. In most cases, alterations observed in the sedimentation rates are reflected in changes of the geochemical parameters, such as organic and inorganic carbon, opal, and the major elements Si, Ca, Mg, Al. Our results and palynological studies, performed on material recovered in an earlier expedition, are used to reconstruct palaeoenvironmental conditions. In this study, the termination of the Younger Dryas is dated to 10,920±132 yr B.P. This is younger than the recently published Greenland ice core dates but in accordance with, for example, the central European dendrochronology. We suspect, that higher sediment deposition rates during the cold periods are due to rapid melting and intense wash out of soil, which was fairly loose because of sparse vegetation. This would lead to higher river discharges. Based on the observed increase of the deposition rate in the record, melting of glaciers can only be detected after the termination of the Younger Dryas.

Calcification in cyanobacterial biofilms of alkaline salt lakes

Geomicrobiological analysis of calcifying biofilms of three alkaline salt lakes characterized by moderate to high carbonate alkalinity indicates that microbial carbonate rock formation is not directly linked to cyanobacterial carbon fixation. The present review summarizes results from two published case studies that have been carried out at Pyramid Lake, USA, and Lake Nuoertu, PR China. New observations and data are presented for a current project on Satonda Crater Lake, Indonesia, that revise previous conclusions concerning the relationship between cyanobacteria and biofilm calcification. Extracellular polymeric substances (EPS) in the investigated lakes are mostly produced by cyanobacteria; their properties are discussed as key factors in biofilm calcification. In particular, EPS are capable of binding divalent cations (e.g. Ca2+) from the liquid phase by their carboxylate and sulphate groups. Therefore, despite a high supersaturation of the lake water with respect to calcium carbonate minerals, precipi...

Climatically induced lake level changes at Lake Van, Turkey, during the Pleistocene/Holocene Transition

Sediment core K10 from Lake Van (eastern Turkey) provides a continuous varve record back to 14,570 calendar years B.P. (before present, 1950), the longest unbroken and non-floating lake varve sequence yet described. The underlying sediment is unvarved and hard. Changes in the aragonite/calcite ratio, the presence of protodolomite and magnesite in certain profile sections, the annual record of the sedimentation rate, the water content of the sediment, the concentrations of organic carbon and opal, and the texture of the sediments from this core provide a record of the lake level history. The new chronology enabled us to redate the old pollen profile [van Zeist and Woldring, 1978a, b] and to establish an accurate timescale for the reconstructed lake level change. Carbon 14 dates show that the highest lake terrace corresponds to high lake level at around 19,000 years B.P. during the Last Glacial, >70 m above its present level. Before 15,000 years B.P. the lake must have been completely dry, marking a reduction of lake level by 500 m in maximum 4000 years. Beginning at 14,600 years B.P. and ending at 12,040 years B.P., the lake level recovered by 250 m to fall again during the next 1400 years. By 10,600 years B.P. the lake began to rise and reached, following another regression between 9000 and 8100 years B.P., the Holocene highstand by about 7500 years B.P., dropping to todays level at about 3000 years B.P.

Phylogenetic Analysis of a Microbialite-Forming Microbial Mat from a Hypersaline Lake of the Kiritimati Atoll, Central Pacific

On the Kiritimati atoll, several lakes exhibit microbial mat-formation under different hydrochemical conditions. Some of these lakes trigger microbialite formation such as Lake 21, which is an evaporitic, hypersaline lake (salinity of approximately 170‰). Lake 21 is completely covered with a thick multilayered microbial mat. This mat is associated with the formation of decimeter-thick highly porous microbialites, which are composed of aragonite and gypsum crystals. We assessed the bacterial and archaeal community composition and its alteration along the vertical stratification by large-scale analysis of 16S rRNA gene sequences of the nine different mat layers. The surface layers are dominated by aerobic, phototrophic, and halotolerant microbes. The bacterial community of these layers harbored Cyanobacteria (Halothece cluster), which were accompanied with known phototrophic members of the Bacteroidetes and Alphaproteobacteria. In deeper anaerobic layers more diverse communities than in the upper layers were present. The deeper layers were dominated by Spirochaetes, sulfate-reducing bacteria (Deltaproteobacteria), Chloroflexi (Anaerolineae and Caldilineae), purple non-sulfur bacteria (Alphaproteobacteria), purple sulfur bacteria (Chromatiales), anaerobic Bacteroidetes (Marinilabiacae), Nitrospirae (OPB95), Planctomycetes and several candidate divisions. The archaeal community, including numerous uncultured taxonomic lineages, generally changed from Euryarchaeota (mainly Halobacteria and Thermoplasmata) to uncultured members of the Thaumarchaeota (mainly Marine Benthic Group B) with increasing depth.

Photosynthesis, Respiration and Exopolymer Calcium-Binding in Biofilm Calcification (Westerhöfer and Deinschwanger Creek, Germany)

The impact of microbial activity on biofilm calcification in aquatic environments is still a matter of debate, especially in settings where ambient water has high CaCO3 mineral supersaturation. In this study, biofilms of two CO2-degassing karst-water creeks in Germany, which attain high calcite supersaturation during their course downstream, were investigated with regard to water chemistry of the biofilm microenvironment. The biofilms mainly consisted of filamentous cyanobacteria (Phormidium morphotype) and heterotrophic bacteria (including sulfate-reducing bacteria), which affect the microenvironment and produce acidic exopolymers. In situ and ex situ microelectrode measurements showed that a strong pH increase, coupled with Ca2 + consumption, occurred in light conditions at the biofilm surface, while the opposite occurred in the dark. Calcite supersaturation at the biofilm surface, calculated from ex situ Ca2 + and CO3 2− microelectrode measurements, showed that photosynthesis resulted in high omega values during illumination, while respiration slightly lowered supersaturation values in the dark, compared to values in the water column. Dissociation calculation demonstrated that the potential amount of Ca2 + binding by exopolymers would be insufficient to explain the Ca2 + loss observed, although Ca2 + complexation to exopolymers might be crucial for calcite nucleation. No spontaneous precipitation occurred on biofilm-free limestone substrates under the same condition, regardless of high supersaturation. These facts indicate that photosynthesis is a crucial mechanism to overcome the kinetic barrier for CaCO3 precipitation, even in highly supersaturated settings.

Metabolic Microenvironmental Control by Photosynthetic Biofilms under Changing Macroenvironmental Temperature and pH Conditions

ABSTRACT Ex situ microelectrode experiments, using cyanobacterial biofilms from karst water creeks, were conducted under various pH, temperature, and constant-alkalinity conditions to investigate the effects of changing environmental parameters on cyanobacterial photosynthesis-induced calcification. Microenvironmental chemical conditions around calcifying sites were controlled by metabolic activity over a wide range of photosynthesis and respiration rates, with little influence from overlying water conditions. Regardless of overlying water pH levels (from 7.8 to 8.9), pH at the biofilm surface was approximately 9.4 in the light and 7.8 in the dark. The same trend was observed at various temperatures (4°C and 17°C). Biological processes control the calcium carbonate saturation state (Ω) in these and similar systems and are able to maintain Ω at approximately constant levels over relatively wide environmental fluctuations. Temperature did, however, have an effect on calcification rate. Calcium flux in this system is limited by its diffusion coefficient, resulting in a higher calcium flux (calcification and dissolution) at higher temperatures, despite the constant, biologically mediated pH. The ability of biological systems to mitigate the effects of environmental perturbation is an important factor that must be considered when attempting to predict the effects of increased atmospheric partial CO2 pressure on processes such as calcification and in interpreting microfossils in the fossil record.

Tufa-forming biofilms of German karstwater streams: microorganisms, exopolymers, hydrochemistry and calcification

Abstract To understand mechanisms of tufa biofilm calcification, selected karstwater stream stromatolites in Germany have been investigated with regard to their hydrochemistry, biofilm community, exopolymers, physicochemical microgradients, calcification pattern and lamination. In stream waters, CO2 degassing drives the increase in calcite saturation to maximum values of approximately 10-fold, independent from the initial Ca2+/alkalinity ratio. For the cyanobacteria of tufa biofilms, a culture-independent molecular approach showed that microscopy of resin-embedded biofilm thin sections underestimated the actual diversity of cyanobacteria, i.e. the six cyanobacteria morphotypes were opposed to nine different lineages of the 16S rDNA phylogeny. The same morphotype may even represent two genetically distant cyanobacteria and the closest relatives of tufa biofilm cyanobacteria may be from quite different habitats. Diatom diversity was even higher in the biofilm at the studied exemplar site than that of the cyanobacteria, i.e. 13 diatom species opposed to 9 cyanobacterial lineages. The non-phototrophic prokaryotic biofilm community is clearly different from the soil-derived community of the stream waters, and largely composed of flavobacteria, firmicutes, proteobacteria and actinobacteria. The exopolymeric biofilm matrix can be divided into three structural domains by fluorescence lectin-binding analysis. Seasonal and spatial variability of these structural EPS domains is low in the investigated streams. As indicated by microsensor data, biofilm photosynthesis is the driving mechanism in tufa stromatolite formation. However, photosynthesis-induced biofilm calcification accounts for only 10–20% of the total Ca2+ loss in the streams, and occurs in parallel to inorganic precipitation driven by CO2-degassing within the water column and on biofilm-free surfaces. Annual stromatolite laminae reflect seasonal changes in temperature and light supply. The stable carbon isotope composition of the laminae is not affected by photosynthesis-induced microgradients, but mirrors that of the bulk water body only reflecting climate fluctuations. Tufa stromatolites with their cyanobacterial–photosynthesis-related calcification fabrics form an analogue to porostromate cyanobacterial stromatolites in fossil settings high in CaCO3 mineral supersaturation but comparatively low in dissolved inorganic carbon. Here, the sum-effect of heterotrophic exopolymer-degradation and secondary Ca2+-release rather decreases calcite saturation, contrary to settings high in dissolved inorganic carbon such as soda lakes.

Soluble humic substances from in situ precipitated microcrystalline calcium carbonate, internal sediment, and spar cement in a Cretaceous carbonate mud-mound

Albian carbonate mud-mound limestones exposed near Iraneta, northern Spain, show a fabric- and particle-specific fluorescence. Intense fluorescence is restricted to in situ precipitated microcrystalline (automicritic) fabrics, calcified demosponges, and coralline sponges. Intermediate intensity derives from micritized bioclasts, pellets, and a rim of marine bladed cement. Most invertebrate skeletons, late-diagenetic equant cement, and crosscutting zones of dolomitization are weakly to nonfluorescent. Internal microcrystalline sediment (allomicrite) and red algae debris have variable fluorescence. Correlation between rock fluorescence and soluble humic substances was evaluated from 3 g of automicrite, allomicrite, and cement. Time-resolved laser-induced fluorescence spectroscopy (TRLFS) with ultra-short pulses on two extracrystalline fractions (NaOH-soluble) and two intracrystalline fractions (HCl-soluble and NaOH-soluble) showed that most of the soluble humic substances of automicrite are within the crystals; but conversely, are significantly enriched on outer surfaces of allomicrite. Spar cement is close to detection limits. Fluorescence lifetimes are in the range of 0.5–2 ns and 3.5–6 ns. We conclude that precipitation of automicrite took place during oxidative organic matter diagenesis, i.e., during condensation reactions of degradation products of marine biopolymers. By contrast, allomicrite formed by skeletal breakdown followed by ingestion, organic coating, and reingestion during deposit feeding. A humic-substance–based model of marine polymer gels represents a new approach for the understanding of ancient polygenetic carbonate muds, so typical of Phanerozoic mud-mounds in deeper water settings.