4 Material und Umwelt
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Biocide mitigation strategies of microbiologically influenced corrosion (MIC) in the oil and gas industry have been primarily used to eliminate the growths of sulfate-reducing microorganisms (SRM). However, methanogenic Archaea (MA) can also be highly corrosive by using iron as an electron source for methanogenesis. Because of the fundamental physiological differences between archaea and bacteria, responses of MA towards SRM-specific biocides cannot be deduced using SRM. Due to the lack of information available on the effect of biocides on corrosive MA, we selected THPS, glutaraldehyde, nitrate and perchlorate to compare against corrosive SRM.
Preliminary results showed that at low concentrations of THPS (0-10 ppm), growth of MA was not affected, methane production and corrosion rates (0.1 mm/yr) were comparable between the different THPS concentrations. On the contrary, the SRM strain showed decreased corrosion rates (0.18 mm/yr to 0.03 mm/yr) with increasing THPS concentrations. Further corrosion tests including electrochemical measurements of different biocides on the growth of MA and SRM will be conducted. Such knowledge not only provide important insights on the physiological response of MA to biocides but also contribute to more effective mitigation strategies that can be both economic and environmentally beneficial.
Microbiologically induced corrosion due to bacterial biofilms causes several problems in industrial systems, technical applications and in medicine. Prior to the formation of a biofilm on a substrate, planktonic cells attach on the surface. Hence, the properties of the surface play a key role in biofilm formation and are of great importance for the development of strategies to prevent bacterial attachment and biofilm formation.
This project aims at clarifying to which extent surface micro-/nanostructuring and chemical functionalization affects bacterial attachment and whether a synergistic combination of the two can be used to control bacterial adhesion. To answer these questions, model surfaces with regular patterns of 5-10 micrometers in size have been prepared, which provide distinct zones differing in terms of their chemistry or nano-roughness. This was achieved by micro contact printing of self-assembled monolayers with different functional groups and deposition of patterned ZnO nanorod arrays for studying the effect of surface chemistry and morphology, respectively. Typical contrasts studied were combinations of positively/negatively charged, hydrophobic/hydrophilic or flat/rough.
The attachment behavior of bacteria on tailored surfaces were studied in a flow chamber as a function of time. The strain Pseudomonas fluorescens SBW25 was chosen as a model organism. DNA-intercalating dyes such as Syto9 have a high affinity to adsorb on ZnO nanorods. To overcome this limitation a genetic modification was performed by introducing a gene which expresses a green fluorescent protein in P. fluorescens SBW25 enabling the quantitative evaluation of the flow chamber studies by means of fluorescence microscopy. Further analysis of the attachment behavior was performed by means of scanning electron microscopy.
The presentation will summarize the results of our systematic study on the role of individual parameters on bacterial attachment and highlight synergistic combinations, showing an inhibition or enhancing effect. As the investigations with model substrates enable a precise control of the surface parameters, this approach can be applied to different microorganisms and material systems to achieve a correlative description of bacterial adhesion on solid surfaces.
Flow-back and produced waters from shale gas and shale oil fields contain high ammonium, which can be formed by methanogenic degradation of methylamines into methane and ammonium. Methylamines are added to fracturing fluid to prevent clay swelling or can originate from metabolism of the osmolyte triglycinebetaine (GB).
We analyzed field samples from a shale gas reservoir in the Duvernay Formation and from a shale oil reservoir in the Bakken formation in Canada to determine the origin of high ammonium. Fresh waters used to make fracturing fluid, early flow-back waters, and late flow back waters from the shale gas reservoir had increasing salinity of 0.01, 0.58, and 2.66 Meq of NaCl, respectively. Microbial community analyses reflected this fresh water to saline transition with halophilic taxa including Halomonas, Halanaerobium, and Methanohalophilus being increasingly present. Early and late flow-back waters had high ammonium concentrations of 32 and 15 mM, respectively.
Such high concentrations had also been found in the Bakken produced waters.
Enrichment cultures of Bakken produced waters in medium containing mono, di-, or trimethylamine, or triglycinebetaine (GB) converted these substrates into ammonium (up to 20 mM) and methane. The methylotrophic methanogen Methanohalophilus, which uses methylamines for its energy metabolism and uses GB as an osmolyte, was a dominant community member in these enrichments. Halanaerobium was also a dominant community member that metabolizes GB into trimethylamine, which is then metabolized further by Methanohalophilus. However, the micromolar concentrations of GB measured in shale reservoirs make them an unlikely source for the 1,000-fold higher ammonium concentrations in flow-back waters. This ammonium either originates directly from the reservoir or is formed from methylamines, which originate from the reservoir, or are added during the hydraulic fracturing process. These methylamines are then converted into ammonium and methane by halophilic methylotrophic methanogens, such as Methanohalophilus, present in flow-back waters.
Microbiologically influenced corrosion is a multidisciplinary research area. To develop successful mitigation strategies, expertise from the industry and research institutes are essential. In Department 4.1, we developed an innovative laboratory flow model (Hi-Tension) that allows effective monitoring of MIC under both standard and non-standard conditions. The flow model allows flexibility with material selection, flow rates, temperature and other environmental parameters changes. Furthermore, the flow model allows integration of electrochemical measurements using microsensors, providing a comprehensive view of corrosion at the biofilm level. Currently, initial results indicate corrosion in the flow model is significantly higher than that of standard laboratory set ups, i.e. static incubations, particularly for methane-producing microorganisms.
Microbiologically influenced corrosion (MIC) is the deterioration of metals due to the metabolic activities of microorganisms. Microorganisms can take electrons directly from the metal surface (EMIC) thereby causing corrosion. Well known culprits of EMIC are: sulfate-reducing bacteria (SRB), acetogens and methanogens.
Microbiologically influenced corrosion (MIC) is the deterioration of metals due to the metabolic activities of microorganisms. Microorganisms can take electrons directly from the metal surface (EMIC) thereby causing corrosion. Well known culprits of EMIC are: sulfate-reducing bacteria (SRB), acetogens and methanogens.
Our aims
- Develop a novel flow system to study MIC by methanogens to mimic industrial Environments
- Investigate the inhibitory concentrations of biocides targeting SRB on corrosive methanogenic strains
- Investigate the inhibitory effects of corrosion inhibitors on methanogens
- Compare the inhibitory concentrations to SRB
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons in electrical contact with the metal. Methanogenic archaea can also cause MIC by directly withdrawing electrons from the iron surface for methanogenesis. However, the mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite, a by-product of methanogenesis, (4Fe + 5HCO3 + 5H+ 4FeCO3 + CH4 + 3H2O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO3 precipitation may be significantly influenced by environmental conditions such as pH and advective processes.
Microbiologically influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) in offshore industries, such as the oil and gas pipelines, due to the high concentrations of sulfate in the seawater. SRM act upon the metal by the reactiveness of hydrogen sulfide (HS-), and by withdrawal of the available electrons (Fe --> Fe2+ + 2e-; E° = -0.47 V) in electrical contact with the metal (EMIC). However, methanogenic archaea can also cause MIC. Because they do not produce HS-, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood.
To investigate the corrosion potential of methanogens, we studied the EMIC methanogenic strains isolated from marine sediments (Methanobacterium-affiliated strain IM1) and crude oil tanks (Methanococcus maripaludis Mic1c10), in an in-house developed flow-through cell to simulate a fluctuating environment. A co-culture of M. maripaludis and D. alaskensis was also established to study the effect of syntrophic growth on metal corrosion that may occur in industrial pipelines. Results indicate that the rates of iron corrosion due to coupled methanogenesis (up to 0.4 mm/yr) are higher to that caused by the marine SRM Desulfovibrio alaskensis (0.15 mm/yr). Surface analyses of the metal showed severe pitting with high methane production. Genomic analysis of the EMIC methanogen M. maripaludis Mic1c10 will provide an insight on the mechanisms of MIC. Such knowledge and deeper understanding also from an electrokinetic point of view may not only provide further models in microbial electrophysiology, but also contribute to mitigation strategies in MIC
Microbiologically influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) in offshore industries, such as the oil and gas pipelines, due to the high concentrations of sulfate in the seawater. SRM act upon the metal by the reactiveness of hydrogen sulfide (HS-), and by withdrawal of the available electrons (Fe --> Fe2+ + 2e-; E° = -0.47 V) in electrical contact with the metal (EMIC). However, methanogenic archaea can also cause MIC. Because they do not produce HS-, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood.
To investigate the corrosion potential of methanogens, we studied the EMIC methanogenic strains isolated from marine sediments (Methanobacterium-affiliated strain IM1) and crude oil tanks (Methanococcus maripaludis Mic1c10), in an in-house developed flow-through cell to simulate a fluctuating environment. A co-culture of M. maripaludis and D. alaskensis was also established to study the effect of syntrophic growth on metal corrosion that may occur in industrial pipelines. Results indicate that the rates of iron corrosion due to coupled methanogenesis (up to 0.4 mm/yr) are higher to that caused by the marine SRM Desulfovibrio alaskensis (0.15 mm/yr). Surface analyses of the metal showed severe pitting with high methane production. Genomic analysis of the EMIC methanogen M. maripaludis Mic1c10 will provide an insight on the mechanisms of MIC. Such knowledge and deeper understanding also from an electrokinetic point of view may not only provide further models in microbial electrophysiology, but also contribute to mitigation strategies in MIC