CO2SINK—From site characterisation and risk assessment to monitoring and verification: One year of operational experience with the field laboratory for CO2 storage at Ketzin, Germany

The CO₂SINK pilot project at Ketzin is aimed at a better understanding of geological CO₂ storage operation in a saline aquifer. The reservoir consists of fluvial deposits with average permeability ranging between 50 and 100 mDarcy. The main focus of CO₂SINK is developing and testing of monitoring and verification technologies. All wells, one for injection and two for observation, are equipped with smart casings (sensors behind casing, facing the rocks) containing a Distributed Temperature Sensing (DTS) and electrodes for Electrical Resistivity Tomography (ERT). The in-hole Gas Membrane Sensors (GMS) observed the arrival of tracers and CO₂ with high temporal resolution. Geophysical monitoring includes Moving Source Profiling (MSP), Vertical Seismic Profiling (VSP), crosshole, star and 4-D seismic experiments. Numerical models are benchmarked via the monitoring results indicating a sufficient match between observation and prediction, at least for the arrival of CO₂ at the first observation well. Downhole samples of brine showed changes in the fluid composition and biocenosis. First monitoring results indicate anisotropic flow of CO₂ coinciding with the “on-time” arrival of CO₂ at observation well one (Ktzi 200) and the later arrival at observation well two (Ktzi 202). A risk assessment was performed prior to the start of injection. After one year of operations about 18,000 t of CO₂ were injected safely.     

Monitoring of the microbial community composition in saline aquifers during CO2 storage by fluorescence in situ hybridisation

This study reveals the first analyses of the composition and activity of the microbial community of a saline CO₂ storage aquifer. Microbial monitoring during CO₂ injection has been reported. By using fluorescence in situ hybridisation (FISH), we have shown that the microbial community was strongly influenced by the CO₂ injection. Before CO₂ arrival, up to 6 × 10⁶ cells ml⁻¹ were detected by DAPI staining at a depth of 647 m below the surface. The microbial community was dominated by the domain Bacteria that represented approximately 60% to 90% of the total cell number, with Proteobacteria and Firmicutes as the most abundant phyla comprising up to 47% and 45% of the entire population, respectively. Both the total cell counts as well as the counts of the specific physiological groups revealed quantitative and qualitative changes after CO₂ arrival. Our study revealed temporal outcompetition of sulphate-reducing bacteria by methanogenic archaea. In addition, an enhanced activity of the microbial population after five months CO₂ storage indicated that the bacterial community was able to adapt to the extreme conditions of the deep biosphere and to the extreme changes of these atypical conditions.     

Effects of mussel (Perna canaliculus) biodeposit decomposition on benthic respiration and nutrient fluxes

Suspension-feeding bivalves increase the quantity and quality of sedimenting organic matter through the production of faeces and pseudofaeces that are remineralised in coastal sediments and thus increase sediment oxygen demand and nutrient regeneration. Bivalves are intensively cultivated worldwide; however, no bivalve biodeposit decay rates are available to parameterise models describing the environmental effects of bivalve culture. We examined sediment biogeochemical changes as bivalve biodeposits age by incubating coastal sediments to which we added fresh mussel (Perna canaliculus) biodeposits and measured O₂ and nutrient fluxes as well as sediment characteristics over an 11-day period. Biodeposits elevated organic matter, chlorophyll a, phaeophytin a, organic carbon and nitrogen concentrations in the surface sediments. Sediment oxygen consumption (SOC) increased significantly (P=0.016) by ∼1.5 times to 1,010 μmol m⁻² h⁻¹ immediately after biodeposit addition and remained elevated compared to control cores without additions for the incubation period. This increase is in the range of observed in situ oxygen demand enhancements under mussel farms. To calculate a decay rate for biodeposits in sediments we fitted a first-order G model to the observed increase in SOC. The significant model fit (P=0.001, r ²=0.72) generated a decay rate of 0.16 day⁻¹ (P=0.033, SE=0.05) that corresponds to a half-life time of 4.3 day. This decay rate is 1–2 orders of magnitude higher than published decay rates of coastal sediments without organic enrichment but similar to rates of decaying zooplankton faecal pellets. NH₄⁺ release increased rapidly on the day of biodeposit addition (P=0.013) and reached a maximum of 144 μmol m⁻² h⁻¹ after 5 days which was 3.6 times higher compared to control cores. During this period NH₄⁺ release was significantly (P<0.001 to P=0.043) higher in the cores with biodeposit additions than in control cores.     

Modelling the spatial population dynamics of the green oak leaf roller (Tortrix viridana) using density dependent competitive interactions: Effects of herbivore mortality and varying host-plant quality

Cyclic population dynamics of forest insects with periods of more than two generations have been discussed in relation to a variety of extrinsic and intrinsic forces. In the present study, we employed the selection pressure of density dependent competitive interactions according to Witting's equations (Witting, 2000) as driver for a discrete spatiotemporal model of the green oak leaf roller (Tortrix viridana). The model was successfully parameterised to rebuild the cyclic population dynamics of an empirical data set of a 30-year leaf roller monitoring in Russia. Our analysis focussed on the role of herbivore mortality and host plant food quality, which have a significant effect on T. viridana population dynamics. An additional egg or larvae mortality lowers population density and can lead to selection pressures that favour individuals with higher growth rate. This increased population growth rate can not only compensate the additional mortality, but also can lead to higher average moth abundances in subsequent generations. Furthermore, we analysed the effect of inter- and intraspecific variation in host plant quality on herbivore population dynamics and the spatial distribution of abundance and defoliation patterns. We found significant effects of the qualitative composition of a trees neighbourhood on the herbivore population of the respective tree. Also, the patchy damage patterns observable in reality have been reproduced by the present model. The applicability of the model approach and the putative genetic processes underlying Witting's model are discussed.     

High bromine oxide concentrations in the semi-polluted boundary layer

Bromine chemistry in the marine boundary layer is recognized to play an important role through catalytic ozone destruction, changes to the atmospheric oxidising capacity (by changing the OH/HO₂ and NO/NO₂ ratio) and oxidation of compounds such as dimethyl sulphide (DMS). However, the chemistry of bromine in polluted environments is not well understood and its effects are thought to be inhibited by reactions involving NO_x (NO₂ & NO). This paper describes long-path Differential Optical Absorption Spectroscopy (DOAS) observations of bromine oxide (BrO) at a semi-polluted coastal site in Roscoff, France. Significant concentrations of BrO (up to 7.5 ± 1.0 pptv) were measured during daytime, indicating the presence of unknown sources or efficient recycling of reactive bromine from bromine nitrate (BrONO₂), which should be the major reservoir for bromine in a high NO_x environment. These measurements indicate that bromine chemistry can play an important role in polluted environments.     

Assessing drilling mud and technical fluid contamination in rock core and brine samples intended for microbiological monitoring at the CO2 storage site in Ketzin using fluorescent dye tracers

The CO₂SINK project in Ketzin represents a field laboratory for the storage of CO₂ in a 650-m deep saline aquifer. The project is accompanied by a microbiological monitoring programme to characterise the composition and activity of the autochthonous microbial community in rock and brine samples and their changes in response to CO₂ storage. A prerequisite of these studies is the acquisition of samples free of contamination from microorganisms and organic and inorganic components. Drilling mud and technical fluids are the main sources of contamination. This study describes the application of the fluorescent dye tracers fluorescein and rhodamine B as contamination controls for rock core and brine samples. Fluorescein was added to drilling mud that was used during the coring phase of the Ketzin wells Ktzi 200, 201 and 202. In addition, total organic carbon (TOC) concentrations, reflecting the carboxymethyl cellulose (CMC) component of the drilling mud, were determined to verify the tracer results. The fluorescence and TOC analyses revealed that drilling mud filtrate penetrated the outer 20 mm of mildly permeable sandstone cores. Rhodamine B was added to brines that were used to displace the drilling mud and to flush the wells after completion. The tracer monitoring during the discharge of drilling mud and displacement brines from the wells during hydraulic tests and nitrogen lifts enabled the quantification of reservoir fluid quality. After the production of 140–190 m³ (16–21 borehole volumes) of fluid, the drilling mud concentration was reduced to about 0.05%. The use of fluorescein emerged as a field-capable, sensitive and reliable method during the sampling of rock core and formation brine samples.     

Re-establishment of the proper injectivity of the CO2-injection well Ktzi 201 in Ketzin, Germany

The onshore CO₂-storage site Ketzin consists of one CO₂-injection well and two observation wells. Hydraulic tests revealed permeabilities between 50 and 100 mD for the sandstone rock units. The designated injection well Ktzi 201 showed similar production permeability. After installation of the CO₂-injection string, an injection test with water yielded a significantly lower injectivity of 0.002 m³/d kPa, while the observation wells showed an injection permeability in the same range as the productivity. Several possible reasons for the severe decline in injectivity are discussed. Acidification of the reservoir interval, injection at high wellhead pressure, controlled mini-fractures and back-production of the well are discussed to remove the plugging material to re-establish the required injectivity of the well. It has been decided to perform a nitrogen lift and analyse the back-produced fluids. Initially during the lift, the back-produced fluids were dark-black. Chemical and XRD analyses proved that the black solids consisted mainly of iron sulphide. Sulphate-reducing bacteria (SRB) were detected in fluid samples with up to 10⁶ cells/ml by fluorescent in situ hybridisation (FISH) indicating that the formation of iron sulphide was caused by bacterial activity. Organic compounds within the drilling mud and other technical fluids were likely left during the well completion process, thus providing the energy source for strong proliferation of bacteria. During the lift, the fraction of SRB in the whole bacterial community decreased from approximately 32% in downhole samples to less than 5%. The lift of Ktzi 201 succeeded in the full restoration of the well productivity and injectivity. Additionally, the likely energy source of the SRB was largely removed by the lifting, thus ensuring the long-term preservation of the injectivity.     

Hydraulic characterisation of the Stuttgart formation at the pilot test site for CO2 storage, Ketzin, Germany

The paper presents an approach for the interpretation of hydraulic tests of a CO₂ storage reservoir. The sandstone reservoir is characterised by a fluviatile channel structure embedded in a low-permeability matrix. Pumping tests were carried out in three wells, with simultaneous pressure monitoring in each well.The hydraulic parameters (permeability and storativity) and the boundary configurations were calibrated using three different approaches: (i) parameter calibration and type curve interpretation for single-hole tests, (ii) calibration of the entire build-up phase for cross-hole tests, and (iii) calibration of the initial pressure response for cross-hole pumping tests. In addition, the arrival time of the pressure response was determined and provides additional information about the pathways of hydraulic connection.The measured pumping test permeabilities of the formation were much lower than those measured on the cores, which is very unusual. The pumping test permeabilities are mainly between 50 mD and 100 mD (millidarcy), while core samples show a mean aquifer permeability of 500–1100 mD. Based on this it was concluded that some kind of continuous low-permeability structure exists, which was supported by core material. Three possible aquifer configurations were considered. The first and second were derived from traditional pumping test analysis and were conceptualised using flow boundaries. Each of the analyses provides a different result. A method was developed in which these differences were resolved by interpreting the pressure response with respect to its spatial and temporal sensitivity. This solution lead to a third configuration which was mainly based on spatially-variable permeabilities. Taking into account the pumping test results, the geological background and the behaviour of injected CO₂, we consider only the third configuration to be realistic. The results are in good agreement with modelled CO₂ arrival times and pressure history.