The chemistry and potential reactivity of the CO2-H2S charged injected waters at the basaltic CarbFix2 site, Iceland

Publisher's version (útgefin grein)The CarbFix2 project aims to capture and store the CO2 and H2S emissions from the Hellisheiði geothermal power plant in Iceland by underground mineral storage. The gas mixture is captured directly by its dissolution into water at elevated pressure. This fluid is then injected, along with effluent geothermal water, into subsurface basalts to mineralize the dissolved acid gases as carbonates and sulfides. Sampled effluent and gas-charged injection waters were analyzed and their mixing geochemically modeled using PHREEQC. Results suggest that carbonates, sulfides, and other secondary minerals would only precipitate after it has substantially reacted with the host basalt. Moreover, the fluid is undersaturated with respect to the most common primary and secondary minerals at the injection well outlet, suggesting that the risk of clogging fluid flow paths near the injection well is limited.This publication has been produced with support from Reykjavik Energy and the European Commission through the projects CarbFix (EC coordinated action 283148) and CO2-REACT (EC Project 317235).Peer Reviewe

The chemistry and saturation states of subsurface fluids during the in situ mineralisation of CO2 and H2S at the CarbFix site in SW-Iceland

In situ carbonation of basaltic rocks could provide a long-term carbon storage solution, which is essential for the success and public acceptance of carbon storage. To demonstrate the viability of this carbon storage solution, 175 tonnes (t) of pure CO2 and 73 tonnes (t) of a 75% CO2-24% H2S-1% H2-gas mixture were sequentially injected into basaltic rocks at the CarbFix site at Hellisheidi, SW-Iceland from January to August 2012. This paper reports the chemistry and saturation states with respect to potential secondary minerals of sub-surface fluids sampled prior to, during, and after the injections. All gases were dissolved in water during their injection into permeable basalts located at 500–800 m depth with temperatures ranging from 20 to 50 °C. A pH decrease and dissolved inorganic carbon (DIC) increase was observed in the first monitoring well, HN-04, about two weeks after each injection began. At storage reservoir target depth, this diverted monitoring well is located ∼125 m downstream from the injection well. A significant increase in H2S concentration, however, was not observed after the second injection. Sampled fluids from the HN-04 well show a rapid increase in Ca, Mg, and Fe concentration during the injections with a gradual decline in the following months. Calculations indicate that the sampled fluids are saturated with respect to siderite about four weeks after the injections began, and these fluids attained calcite saturation about three months after each injection. Pyrite is supersaturated prior to and during the mixed gas injection and in the following months. In July 2013, the HN-04 fluid sampling pump broke down due to calcite precipitation, verifying the carbonation of the injected CO2. Mass balance calculations, based on the recovery of non-reactive tracers co-injected into the subsurface together with the acid-gases, confirm that more than 95% of the CO2 injected into the subsurface was mineralised within a year, and essentially all of the injected H2S was mineralised within four months of its injection. These results demonstrate the viability of the in situ mineralisation of these gases in basaltic rocks as a long-term and safe storage solution for CO2 and H2S

CarbFix2: CO2 and H2S mineralization during 3.5 years of continuous injection into basaltic rocks at more than 250 °C

International audienceThe CarbFix method was upscaled at the Hellisheiði geothermal power plant to inject and mineralize the plant's CO 2 and H 2 S emissions in June 2014. This approach first captures the gases by their dissolution in water, and the resulting gas-charged water is injected into subsurface basalts. The dissolved CO 2 and H 2 S then react with the basaltic rocks liberating divalent cations, Ca 2+ , Mg 2+ , and Fe 2+ , increasing the fluid pH, and precipitating stable carbonate and sulfide minerals. By the end of 2017, 23,200 metric tons of CO 2 and 11,800 metric tons of H 2 S had been injected to a depth of 750 m into fractured, hydrothermally altered basalts at >250°C. The in situ fluid composition, as well as saturation indices and predominance diagrams of relevant secondary minerals at the injection and monitoring wells, indicate that sulfide precipitation is not limited by the availability of Fe or by the consumption of Fe by other secondary minerals; Ca release from the reservoir rocks to the fluid phase, however, is potentially the limiting factor for calcite precipitation, although dolomite and thus aqueous Mg may also play a role in the mineralization of the injected carbon. During the first phase of the CarbFix2 injection (June 2014 to July 2016) over 50% of injected carbon and 76% of sulfur mineralized within four to nine months, but these percentages increased four months after the amount of injected gas was doubled during the second phase of CarbFix2 (July 2016-December 2017) at over 60% of carbon and over 85% of sulfur. The doubling of the gas injection rate decreased the pH of the injection water liberating more cations for gas mineralization. Notably, the injectivity of the injection well has remained stable throughout the study period confirming that the host rock permeability has been essentially unaffected by 3.5 years of mineralization reactions. Lastly, although the mineralization reactions are accelerated by the high temperatures (>250°C), this is the upper temperature limit for carbon storage via the mineral carbonation of basalts as higher temperatures leads to potential decarbonation reactions

The chemistry and saturation states of subsurface fluids during the in situ mineralisation of CO2 and H2S at the CarbFix site in SW-Iceland

In situ carbonation of basaltic rocks could provide a long-term carbon storage solution, which is essential for the success and public acceptance of carbon storage. To demonstrate the viability of this carbon storage solution, 175 tonnes (t) of pure CO2 and 73 tonnes (t) of a 75% CO2-24% H2S-1% H2-gas mixture were sequentially injected into basaltic rocks at the CarbFix site at Hellisheidi, SW-Iceland from January to August 2012. This paper reports the chemistry and saturation states with respect to potential secondary minerals of sub-surface fluids sampled prior to, during, and after the injections. All gases were dissolved in water during their injection into permeable basalts located at 500–800 m depth with temperatures ranging from 20 to 50 °C. A pH decrease and dissolved inorganic carbon (DIC) increase was observed in the first monitoring well, HN-04, about two weeks after each injection began. At storage reservoir target depth, this diverted monitoring well is located ∼125 m downstream from the injection well. A significant increase in H2S concentration, however, was not observed after the second injection. Sampled fluids from the HN-04 well show a rapid increase in Ca, Mg, and Fe concentration during the injections with a gradual decline in the following months. Calculations indicate that the sampled fluids are saturated with respect to siderite about four weeks after the injections began, and these fluids attained calcite saturation about three months after each injection. Pyrite is supersaturated prior to and during the mixed gas injection and in the following months. In July 2013, the HN-04 fluid sampling pump broke down due to calcite precipitation, verifying the carbonation of the injected CO2. Mass balance calculations, based on the recovery of non-reactive tracers co-injected into the subsurface together with the acid-gases, confirm that more than 95% of the CO2 injected into the subsurface was mineralised within a year, and essentially all of the injected H2S was mineralised within four months of its injection. These results demonstrate the viability of the in situ mineralisation of these gases in basaltic rocks as a long-term and safe storage solution for CO2 and H2S

Rapid CO2 mineralisation into calcite at the CarbFix storage site quantified using calcium isotopes

The engineered removal of atmospheric CO2 is now considered a key component of mitigating climate warming below 1.5 °C. Mineral carbonation is a potential negative emissions technique that, in the case of Iceland’s CarbFix experiment, precipitates dissolved CO2 as carbonate minerals in basaltic groundwater settings. Here we use calcium (Ca) isotopes in both pre- and post-CO2 injection waters to quantify the amount of carbonate precipitated, and hence CO2 stored. Ca isotope ratios rapidly increase with the pH and calcite saturation state, indicating calcite precipitation. Calculations suggest that up to 93% of dissolved Ca is removed into calcite during certain phases of injection. In total, our results suggest that 165 ± 8.3 t CO2 were precipitated into calcite, an overall carbon storage efficiency of 72 ± 5%. The success of this approach opens the potential for quantification of similar mineral carbonation efforts where drawdown rates cannot be estimated by other means

The rapid and cost-effective capture and subsurface mineral storage of carbon and sulfur at the CarbFix2 site

One of the main challenges of worldwide carbon capture and storage (CCS) efforts is its cost. As much as 90% of this cost stems from the capture of pure or nearly pure CO2 from exhaust streams. This cost can be lowered by capturing gas mixtures rather than pure CO2. Here we present a novel integrated carbon capture and storage technology, installed at the CarbFix2 storage site at Hellisheiði, Iceland that lowers considerably the cost and energy required at this site. The CarbFix2 site, located in deeper and hotter rocks than the original CarbFix site, permits the continuous injection of larger quantities of CO2 and H2S than the original site. The integrated process consists of soluble gas mixture capture in water followed by the direct injection of the resulting CO2-H2S-charged water into basaltic rock, where much of the dissolved carbon and sulfur are mineralized within months. This integrated method provides the safe, long-term storage of carbon dioxide and other acid gases at a cost of US $25/ton of the gas mixture at the CarbFix2 site and might provide the technology for lower CCS cost at other sites

Using stable Mg isotope signatures to assess the fate of magnesium during the in situ mineralisation of CO₂ and H2_S at the CarbFix site in SW-Iceland

The in-situ carbonation of basaltic rocks could provide a long-term carbon storage solution. To investigate the viability of this carbon storage solution, 175 tonnes of pure CO2 and 73 tonnes of a 75% CO2-24% H2S-1% H2-gas mixture were sequentially injected into basaltic rocks as a dissolved aqueous fluid at the CarbFix site at Hellisheidi, SW-Iceland. This paper reports the Mg stable isotope compositions of sub-surface fluids sampled prior to, during, and after the CO2 injections. These Mg isotopic compositions are used to trace the fate of this element during the subsurface carbonation of basalts. The measured Mg isotopic compositions of the monitoring well fluids are isotopically lighter than the dissolving basalts and continue to become increasingly lighter for at least two years after the gas-charged water injection was stopped. The results indicate that the formation of isotopically heavy Mg-clays rather than Mg-carbonates are the predominant Mg secondary phases precipitating from the sampled fluids. Isotope mass balance calculations suggest that more than 70% of the Mg liberated from the basalt by the injected gas charged water was precipitated as Mg-clays, with this percentage increasing with time after the injection, consistent with the continued precipitation of Mg clays over the whole of the study period. The formation of Mg clays in response to the injection of CO2 into basalts, as indicated in this study, could be detrimental to carbon storage efforts because the formation of these minerals consume divalent Mg that could otherwise be used for the formation of carbonate minerals and because such clays could decrease host rock permeability

High reactivity of deep biota under anthropogenic CO2 injection into basalt

Basalts are recognized as one of the major habitats on Earth, harboring diverse and active microbial populations. Inconsistently, this living component is rarely considered in engineering operations carried out in these environments. This includes carbon capture and storage (CCS) technologies that seek to offset anthropogenic CO2 emissions into the atmosphere by burying this greenhouse gas in the subsurface. Here, we show that deep ecosystems respond quickly to field operations associated with CO2 injections based on a microbiological survey of a basaltic CCS site. Acidic CO2-charged groundwater results in a marked decrease (by ~ 2.5–4) in microbial richness despite observable blooms of lithoautotrophic iron-oxidizing Betaproteobacteria and degraders of aromatic compounds, which hence impact the aquifer redox state and the carbon fate. Host-basalt dissolution releases nutrients and energy sources, which sustain the growth of autotrophic and heterotrophic species whose activities may have consequences on mineral storage