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  • 1
    Publication Date: 2021-12-15
    Description: Carbon capture and storage (CCS) is a key technology to reduce carbon dioxide (CO2) emissions from industrial processes in a feasible, substantial, and timely manner. For geological CO2 storage to be safe, reliable, and accepted by society, robust strategies for CO2 leakage detection, quantification and management are crucial. The STEMM-CCS (Strategies for Environmental Monitoring of Marine Carbon Capture and Storage) project aimed to provide techniques and understanding to enable and inform cost-effective monitoring of CCS sites in the marine environment. A controlled CO2 release experiment was carried out in the central North Sea, designed to mimic an unintended emission of CO2 from a subsurface CO2 storage site to the seafloor. A total of 675 kg of CO2 were released into the shallow sediments (~3 m below seafloor), at flow rates between 6 and 143 kg/d. A combination of novel techniques, adapted versions of existing techniques, and well-proven standard techniques were used to detect, characterise and quantify gaseous and dissolved CO2 in the sediments and the overlying seawater. This paper provides an overview of this ambitious field experiment. We describe the preparatory work prior to the release experiment, the experimental layout and procedures, the methods tested, and summarise the main results and the lessons learnt.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev , info:eu-repo/semantics/article
    Format: application/pdf
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  • 2
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    American Chemical Society
    In:  Analytical Chemistry, 85 (6). pp. 3271-3279.
    Publication Date: 2014-06-17
    Description: New indicators for optical CO2 sensors are synthesized in two steps from the commercially available diketo-pyrrolo-pyrrole (DPP) pigments Irgazin Ruby and Irgazin Scarlet. After introduction of bis(2-ethylhexyl) sulfonamide groups via a simple two-step synthesis, the pigments are rendered highly soluble in organic solvents and in polymers and show pH-dependent absorption and emission spectra. The new indicators have molar absorption coefficients in a 20 000–50 000 M–1 cm–1 range, possess quantum yields close to unity, and feature good photostability. The indicators along with a quaternary ammonium base are embedded into ethyl cellulose to give optical carbon dioxide sensors. The absorption and emission spectra of the deprotonated form are bathochromically shifted by more than 100 nm compared to the neutral form (λmax absorption 496–550 nm; λmax emission 564–587 nm). This enables colorimetric read-out and self-referenced ratiometric fluorescence intensity measurements. Importantly, the dynamic range of the sensors based on the new indicators is significantly different (0–10 kPa and 1–100 kPa CO2) that enables a broad variety of applications. New DPP dyes are conveniently prepared from commercially available pigments and represent a new class of colorimetric and fluorescent pH indicators for optical carbon dioxide sensors.
    Type: Article , PeerReviewed
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  • 3
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    IOP Publishing
    In:  Methods and Applications in Fluorescence, 2 (2). 024001.
    Publication Date: 2016-04-29
    Description: A new diketo-pyrrolo-pyrrole (DPP) indicator dye for optical sensing of carbon dioxide is prepared via a simple one step synthesis from commercially available low cost 'Pigment Orange 73'. The pigment is modified via alkylation of one of the lactam nitrogens with a tert-butylbenzyl group. The indicator dye is highly soluble in organic solvents and in polymers and shows pH-dependent absorption (λmax 501 and 572 nm for the protonated and deprotonated forms, respectively) and emission spectra (λmax 524 and 605 nm for the protonated and deprotonated forms, respectively). Both the protonated and the deprotonated forms show high fluorescence quantum yields (Φprot 0.86; Φdeprot 0.66). Hence, colorimetric read-out and ratiometric fluorescence intensity measurements are possible. The emission of the two forms of the indicator excellently matches the response of the green and the red channels of an RGB camera. This enables imaging of carbon dioxide distribution with a simple and low cost optical set-up. The sensor based on the new DPP dye shows very high sensitivity and is particularly promising for monitoring atmospheric levels of carbon dioxide.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2016-04-29
    Description: A new class of pH-sensitive indicator dyes for optical carbon dioxide sensors based on di-OH-aza-BODIPYs is presented. These colorimetric indicators show absorption maxima in the near infrared range (λmax 670–700 nm for the neutral form, λmax 725–760 nm for the mono-anionic form, λmax 785–830 nm for the di-anionic form), high molar absorption coefficients of up to 77 000 M−1 cm−1 and unmatched photostability. Depending on the electron-withdrawing or electron-donating effect of the substituents the pKa values are tunable (8.7–10.7). Therefore, optical carbon dioxide sensors based on the presented dyes cover diverse dynamic ranges (0.007–2 kPa; 0.18–20 kPa and 0.2–100 kPa), which enables different applications varying from marine science and environmental monitoring to food packaging. The sensors are outstandingly photostable in the absence and presence of carbon dioxide and can be read out via absorption or via the luminescence-based ratiometric scheme using the absorption-modulated inner-filter effect. Monitoring of the carbon dioxide production/consumption of a Hebe plant is demonstrated.
    Type: Article , PeerReviewed
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  • 5
    Publication Date: 2020-07-23
    Description: A new class of pH-sensitive indicator dyes for optical carbon dioxide sensors based on di-OH-aza-BODIPYs is presented. These colorimetric indicators show absorption maxima in the near infrared range (λmax 670–700 nm for the neutral form, λmax 725–760 nm for the mono-anionic form, λmax 785–830 nm for the di-anionic form), high molar absorption coefficients of up to 77 000 M−1 cm−1 and unmatched photostability. Depending on the electron-withdrawing or electron-donating effect of the substituents the pKa values are tunable (8.7–10.7). Therefore, optical carbon dioxide sensors based on the presented dyes cover diverse dynamic ranges (0.007–2 kPa; 0.18–20 kPa and 0.2–100 kPa), which enables different applications varying from marine science and environmental monitoring to food packaging. The sensors are outstandingly photostable in the absence and presence of carbon dioxide and can be read out via absorption or via the luminescence-based ratiometric scheme using the absorption-modulated inner-filter effect. Monitoring of the carbon dioxide production/consumption of a Hebe plant is demonstrated.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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  • 6
    Publication Date: 2022-03-09
    Description: Herein, we present a small and versatile optode system with integrated battery and logger for monitoring of O-2, pH, and pCO(2) in seawater. Three sensing materials designed for seawater measurements are optimized with respect to dynamic measurement range and long-term stability. The spectral properties of the sensing materials were tailored to be compatible with a commercially available laboratory oxygen logger that was fitted into a pressure housing. Interchangeable sensor caps with appropriate "sensing chemistry" are conveniently attached to the end of the optical fiber. This approach allows using the same instrument for multiple analytes, which offers great flexibility and minimizes hardware costs. Applications of the new optode system were demonstrated by recording depth profiles for the three parameters during a research cruise in the Baltic Sea and by measuring surface water transects of pH. The optode was furthermore used to monitor the concentration of dissolved oxygen in a seagrass meadow in the Limfjord, Denmark, and sensor packages consisting of pO(2), pH, and pCO(2) were deployed in the harbors of Kiel, Germany, and Southampton, England, for 6 d. The measurements revealed that the system can resolve typical patterns in seawater chemistry related to spatial heterogeneities as well as temporal changes caused by biological and tidal activity.
    Type: Article , PeerReviewed
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  • 7
    Publication Date: 2024-02-07
    Description: Highlights • Approaches for CO2 leakage detection, attribution and quantification monitoring exist. • Many approaches cover multiple monitoring tasks simultaneously. • Sonars and chemical sensors on ships or AUVs can cover large areas. • Newer, more specific technologies can detect, verify and quantify smaller, localised leaks. Environmental monitoring of offshore Carbon Capture and Storage (CCS) complexes requires robust methodologies and cost-effective tools to detect, attribute and quantify CO2 leakage in the unlikely event it occurs from a sub-seafloor reservoir. Various approaches can be utilised for environmental CCS monitoring, but their capabilities are often undemonstrated and more detailed monitoring strategies need to be developed. We tested and compared different approaches in an offshore setting using a CO2 release experiment conducted at 120 m water depth in the Central North Sea. Tests were carried out over a range of CO2 injection rates (6 - 143 kg d−1) comparable to emission rates observed from abandoned wells. Here, we discuss the benefits and challenges of the tested approaches and compare their relative cost, temporal and spatial resolution, technology readiness level and sensitivity to leakage. The individual approaches demonstrate a high level of sensitivity and certainty and cover a wide range of operational requirements. Additionally, we refer to a set of generic requirements for site-specific baseline surveys that will aid in the interpretation of the results. Critically, we show that the capability of most techniques to detect and quantify leakage exceeds the currently existing legal requirements.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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