Monika Kasina

Archaeal community composition affects the function of anaerobic co-digesters in response to organic overload.

Microbial community diversity in two thermophilic laboratory-scale and three full-scale anaerobic co-digesters was analysed by genetic profiling based on PCR-amplified partial 16S rRNA genes. In parallel operated laboratory reactors a stepwise increase of the organic loading rate (OLR) resulted in a decrease of methane production and an accumulation of volatile fatty acids (VFAs). However, almost threefold different OLRs were necessary to inhibit the gas production in the reactors. During stable reactor performance, no significant differences in the bacterial community structures were detected, except for in the archaeal communities. Sequencing of archaeal PCR products revealed a dominance of the acetoclastic methanogen Methanosarcina thermophila, while hydrogenotrophic methanogens were of minor importance and differed additionally in their abundance between reactors. As a consequence of the perturbation, changes in bacterial and archaeal populations were observed. After organic overload, hydrogenotrophic methanogens (Methanospirillum hungatei and Methanoculleus receptaculi) became more dominant, especially in the reactor attributed by a higher OLR capacity. In addition, aggregates composed of mineral and organic layers formed during organic overload and indicated tight spatial relationships between minerals and microbial processes that may support de-acidification processes in over-acidified sludge. Comparative analyses of mesophilic stationary phase full-scale reactors additionally indicated a correlation between the diversity of methanogens and the VFA concentration combined with the methane yield. This study demonstrates that the coexistence of two types of methanogens, i.e. hydrogenotrophic and acetoclastic methanogens is necessary to respond successfully to perturbation and leads to stable process performance.

Comparison of different procedures to stabilize biogas formation after process failure in a thermophilic waste digestion system: influence of aggregate formation on process stability.

Following a process failure in a full-scale biogas reactor, different counter measures were undertaken to stabilize the process of biogas formation, including the reduction of the organic loading rate, the addition of sodium hydroxide (NaOH), and the introduction of calcium oxide (CaO). Corresponding to the results of the process recovery in the full-scale digester, laboratory experiments showed that CaO was more capable of stabilizing the process than NaOH. While both additives were able to raise the pH to a neutral milieu (pH>7.0), the formation of aggregates was observed particularly when CaO was used as the additive. Scanning electron microscopy investigations revealed calcium phosphate compounds in the core of the aggregates. Phosphate seemed to be released by phosphorus-accumulating organisms, when volatile fatty acids accumulated. The calcium, which was charged by the CaO addition, formed insoluble salts with long chain fatty acids, and caused the precipitation of calcium phosphate compounds. These aggregates were surrounded by a white layer of carbon rich organic matter, probably consisting of volatile fatty acids. Thus, during the process recovery with CaO, the decrease in the amount of accumulated acids in the liquid phase was likely enabled by (1) the formation of insoluble calcium salts with long chain fatty acids, (2) the adsorption of volatile fatty acids by the precipitates, (3) the acid uptake by phosphorus-accumulating organisms and (4) the degradation of volatile fatty acids in the aggregates. Furthermore, this mechanism enabled a stable process performance after re-activation of biogas production. In contrast, during the counter measure with NaOH aggregate formation was only minor resulting in a rapid process failure subsequent the increase of the organic loading rate.

Application of an early warning indicator and CaO to maximize the time-space-yield of an completely mixed waste digester using rape seed oil as co-substrate.

In order to increase the organic loading rate (OLR) and hereby the performance of biogas plants an early warning indicator (EWI-VFA/Ca) was applied in a laboratory-scale biogas digester to control process stability and to steer additive dosing. As soon as the EWI-VFA/Ca indicated the change from stable to instable process conditions, calcium oxide was charged as a countermeasure to raise the pH and to bind long-chain fatty acids (LCFAs) by formation of aggregates. An interval of eight days between two increases of the OLR, which corresponded to 38% of the hydraulic residence time (HRT), was sufficient for process adaptation. An OLR increase by a factor of three within six weeks was successfully used for biogas production. The OLR was increased to 9.5 kg volatile solids (VS) m(-3) d(-1) with up to 87% of fat. The high loading rates affected neither the microbial community negatively nor the biogas production process. Despite the increase of the organic load to high rates, methane production yielded almost its optimum, amounting to 0.9 m(3)(kg VS)(-1). Beneath several uncharacterized members of the phylum Firmicutes mostly belonging to the family Clostridiaceae, a Syntrophomonas-like organism was identified that is known to live in a syntrophic relationship to methanogenic archaea. Within the methanogenic group, microorganisms affiliated to Methanosarcina, Methanoculleus and Methanobacterium dominated the community.

Störungen des Betriebs geothermischer Anlagen durch mikrobielle Stoffwechselprozesse und Erfolg von Gegenmaßnahmen

ZusammenfassungIn geothermischen Anlagen können Biofilme die Mineralbildung und die Injektivität von Bohrungen sowie die Materialbeständigkeit beeinträchtigen. In drei bezüglich Temperatur und Salinität sehr unterschiedlichen Anlagen waren Organismen des Schwefelkreislaufs an Betriebsstörungen beteiligt: Die erhöhte Abundanz von Sulfat-reduzierenden Bakterien (SRB) auf der kalten Seite eines Wärmespeichers wies auf deren Beteiligung an der Korrosion und der Abnahme der Injektivität hin. In allen Anlagen führte der Zutritt von Sauerstoff bzw. der Eintrag von Nitrat zu einer temporären Zunahme Schwefel-oxidierender Bakterien (SOB) und hat vermutlich Korrosionsprozesse beschleunigt. Außerdem hatte in einem Kältespeicher die temporäre Zunahme der SOB ein Filterclogging zur Folge. Aufgrund ihrer entscheidenden Rolle bei mikrobiell induzierter Korrosion (MIC) weisen Änderungen in der Abundanz von SOB und SRB auf die Ursachen mikrobiell bedingter Störungen hin. Zur Beseitigung der Störungen wurden temporäre Erhöhungen der Temperatur, Säuerungen sowie die Zugabe von Wasserstoffperoxid (H2O2) oder Nitrat in den Anlagen getestet und aus mikrobiologischer Sicht bewertet.AbstractIn the context of geothermal systems, biofilms can influence mineral formation and material resistance against corrosion. In three geothermal plants with different salinity and temperature, organisms of the sulfur cycle have contributed to process failures. On the cold side of a heat store, the increased diversity and abundance of sulfate reducing bacteria (SRB) revealed their participation in corrosion processes and their contribution to a decline in injection efficiency. In all plants, a temporary ingress of oxygen or nitrate led to an increased abundance of sulfur oxidizing bacteria (SOB) that might have accelerated corrosion. In addition, the increase in SOB abundance led to filter clogging in a cold store. Based on their role in microbial-induced corrosion (MIC), changes in the abundance of SOB and SRB may indicate the cause of failure. Measures to control microbial growth, mineral deposits and corrosion, such as temporary increases in temperature, acidification, and addition of hydrogen peroxide (H2O2) and nitrate, were evaluated.

Mineral carbonation of metallurgical slags

Abstract Due to increasing emissions of greenhouse gases into the atmosphere number of methods are being proposed to mitigate the risk of climate change. One of them is mineral carbonation. Blast furnace and steel making slags are co-products of metallurgical processes composed of minerals which represent appropriate source of cations required for mineral carbonation. Experimental studies were performed to determine the potential use of slags in this process. Obtained results indicate that steel making slag can be a useful material in CO2 capture procedures. Slag components dissolved in water are bonded as stable carbonates in the reaction with CO2 from ambient air. In case of blast furnace slag, the reaction is very slow and minerals are resistant to chemical changes. More time is needed for minerals dissolution and release of cations essential for carbonate crystallisation and thus makes blast furnace slags less favourable in comparison with steel making slag.

Mineralogical and geochemical analysis of Fe-phases in drill-cores from the Triassic Stuttgart Formation at Ketzin CO2 storage site before CO2 arrival

Abstract Reactive iron (Fe) oxides and sheet silicate-bound Fe in reservoir rocks may affect the subsurface storage of CO2 through several processes by changing the capacity to buffer the acidification by CO2 and the permeability of the reservoir rock: (1) the reduction of three-valent Fe in anoxic environments can lead to an increase in pH, (2) under sulphidic conditions, Fe may drive sulphur cycling and lead to the formation of pyrite, and (3) the leaching of Fe from sheet silicates may affect silicate diagenesis. In order to evaluate the importance of Fe-reduction on the CO2 reservoir, we analysed the Fe geochemistry in drill-cores from the Triassic Stuttgart Formation (Schilfsandstein) recovered from the monitoring well at the CO2 test injection site near Ketzin, Germany. The reservoir rock is a porous, poorly to moderately cohesive fluvial sandstone containing up to 2–4 wt% reactive Fe. Based on a sequential extraction, most Fe falls into the dithionite-extractable Fe-fraction and Fe bound to sheet silicates, whereby some Fe in the dithionite-extractable Fe-fraction may have been leached from illite and smectite. Illite and smectite were detected in core samples by X-ray diffraction and confirmed as the main Fe-containing mineral phases by X-ray absorption spectroscopy. Chlorite is also present, but likely does not contribute much to the high amount of Fe in the silicate-bound fraction. The organic carbon content of the reservoir rock is extremely low (<0.3 wt%), thus likely limiting microbial Fe-reduction or sulphate reduction despite relatively high concentrations of reactive Fe-mineral phases in the reservoir rock and sulphate in the reservoir fluid. Both processes could, however, be fuelled by organic matter that is mobilized by the flow of supercritical CO2 or introduced with the drilling fluid. Over long time periods, a potential way of liberating additional reactive Fe could occur through weathering of silicates due to acidification by CO2.

Iron Metallurgy Slags as a Potential Source of Critical Elements - Nb, Ta and REE

Abstract The recovery of valuable metals from metallurgical slag disposals is a promising option to protect natural resources, limited due to technology development and increased consumption. The Ad-hoc Working Group on Defining Critical Raw Materials within the Raw Materials Supply Group has proposed a list of critical elements which have the greatest economic importance and meet the requirements of sustainable development in Europe. The goal of this study was to examine steelmaking- and blast-furnace slags from metallurgical processes to determine concentrations of elements of the greatest criticality for Poland, e.g. Nb, Ta and REE, and to discuss the viability of their recovery. Slag analyses indicate enrichment of REE relative to UCC, NASC and average chondrite compositions in blast-furnace slags and Nb and Ta in steelmaking slags. To make recovery of these critical elements reasonable and profitable, it is recommended that they be recovered together with other useful raw materials.

Process Recovery after CaO Addition Due to Granule Formation in a CSTR Co-Digester-A Tool to Influence the Composition of the Microbial Community and Stabilize the Process?

The composition, structure and function of granules formed during process recovery with calcium oxide in a laboratory-scale fermenter fed with sewage sludge and rapeseed oil were studied. In the course of over-acidification and successful process recovery, only minor changes were observed in the bacterial community of the digestate, while granules appeared during recovery. Fluorescence microscopic analysis of the granules showed a close spatial relationship between calcium and oil and/or long chain fatty acids. This finding further substantiated the hypothesis that calcium precipitated with carbon of organic origin and reduced the negative effects of overloading with oil. Furthermore, the enrichment of phosphate minerals in the granules was shown, and molecular biological analyses detected polyphosphate-accumulating organisms as well as methanogenic archaea in the core. Organisms related to Methanoculleus receptaculi were detected in the inner zones of a granule, whereas they were present in the digestate only after process recovery. This finding indicated more favorable microhabitats inside the granules that supported process recovery. Thus, the granule formation triggered by calcium oxide addition served as a tool to influence the composition of the microbial community and to stabilize the process after overloading with oil.