Description: Accurate pH measurements in polar waters and sea ice brines require pH indicator dyes characterized at near-zero and below-zero temperatures and high salinities. We present experimentally determined physical and chemical characteristics of purified meta-Cresol Purple (mCP) pH indicator dye suitable for pH measurements in seawater and conservative seawater-derived brines at salinities (S) between 35 and 100 and temperatures (T) between their freezing point and 298.15 K (25 °C). Within this temperature and salinity range, using purified mCP and a novel thermostated spectrophotometric device, the pH on the total scale (pHT) can be calculated from direct measurements of the absorbance ratio R of the dye in natural samples as pHT=−log(kT2e2)+log(R−e11−Re3e2) Based on the mCP characterization in these extended conditions, the temperature and salinity dependence of the molar absorptivity ratios and − log(kT2e2) of purified mCP is described by the following functions: e1 = −0.004363 + 3.598 × 10−5T, e3/e2 = −0.016224 + 2.42851 × 10−4T + 5.05663 × 10−5(S − 35), and − log(kT2e2) = −319.8369 + 0.688159 S −0.00018374 S2 + (10508.724 − 32.9599 S + 0.059082S2) T−1 + (55.54253 − 0.101639 S) ln T −0.08112151T. This work takes the characterisation of mCP beyond the currently available ranges of 278.15 K ≤ T ≤ 308.15 K and 20 ≤ S ≤ 40 in natural seawater, thereby allowing high quality pHT measurements in polar systems.

Description: The stoichiometric dissociation constants of carbonic acid ( and ) were determined by measurement of all four measurable parameters of the carbonate system (total alkalinity, total dissolved inorganic carbon, pH on the total proton scale, and CO2 fugacity) in natural seawater and seawater-derived brines, with a major ion composition equivalent to that Reference Seawater, to practical salinity (SP) 100 and from 25 °C to the freezing point of these solutions and –6 °C temperature minimum. These values, reported in the total proton scale, provide the first such determinations at below-zero temperatures and for SP 〉 50. The temperature (T, in Kelvin) and SP dependence of the current and (as negative common logarithms) within the salinity and temperature ranges of this study (33 ≤ SP ≤ 100, –6 °C ≤ t ≤ 25 °C) is described by the following best-fit equations: = –176.48 + 6.14528 – 0.127714 SP + 7.396×10–5 + (9914.37 – 622.886 + 29.714 SP) T–1 + (26.05129 – 0.666812 ) lnT (σ = 0.011, n = 62), and = –323.52692 + 27.557655 + 0.154922 SP – 2.48396×10–4 + (14763.287 – 1014.819 – 14.35223 SP) T–1 + (50.385807 – 4.4630415 ) lnT (σ = 0.020, n = 62). These functions are suitable for application to investigations of the carbonate system of internal sea ice brines with a conservative major ion composition relative to that of Reference Seawater and within the temperature and salinity ranges of this study.

Description: Highlights • pH of Tris buffers determined in synthetic seawater and brines with the Harned cell. • pH determination of Tris buffers to the freezing point of synthetic solutions. • pH determination of the equimolal and non-equimolal Tris buffer variants. • pH measurement is facilitated at below-zero temperatures, such as in sea ice brines. The pH on the total proton scale of the Tris-HCl buffer system (pH(Tris)) was characterized rigorously with the electrochemical Flamed cell in salinity (S) 35 synthetic seawater and S = 45-100 synthetic seawater-derived brines at 25 and 0 degrees C, as well as at the freezing point of the synthetic solutions (-1.93 degrees C at S = 35 to -6 degrees C at S = 100). The electrochemical characterization of the common equimolal Tris buffer [R-Tris = m(Tris)/m(Tris-H+) = 1.0, with m(Tris) = m(Tris-H+) = 0.04 mol kg(H2O)(-1) = molality of the conjugate acid-base pair of 2-amino-2-hydroxymethyl-1,3-propanediol (Tris)] yielded pH(Tris) values which increased with increasing salinity and decreasing temperature. The electrochemical characterization of a non-equimolal Tris buffer variant (R-Tris = 0.5, with m(Tris) = 0.02 mol kg(H2O)(-1) and MTris-H+ = 0.04 mol kg(H2O)(-1)) yielded pH(Tris) values that were consistently less alkaline by 03 pH unit than those of the equimolal Tris buffer. This is in agreement with the values derived from the stoichiometric equilibrium of the Tris-H+ dissociation reaction, described by the Henderson - Hasselbalch equation, pH(Tris) = pK(Tris)* + logR(Tris), with pK(Tris)* = stoichiometric equilibrium dissociation constant of Tris-H+, equivalent to equimolal pH(Tris). This consistency allows reliable use of other R-Tris variants of the Tris-HCl buffer system within the experimental conditions reported here. The results of this study will facilitate the pH measurement in saline and hypersaline systems at below-zero temperatures, such as sea ice brines.

Description: High quality pH measurements are required in estuarine and coastal waters to assess the impacts of anthropogenic atmospheric CO 2 emissions on the marine carbonate system, including the resulting decrease in pH. In addition, pH measurements are needed to determine impacts on carbonate chemistry of phytoplankton blooms and their breakdown, following enhanced anthropogenic nutrient inputs. The spectrophotometric pH technique provides high quality pH data in seawater, and is advantageous for long-term deployments as it is not prone to drift and does not require in situ calibration. In this study, a field application of a fully automated submersible spectrophotometric analyzer for high-resolution in situ pH measurements in dynamic estuarine and coastal waters is presented. A Lab-on-Chip (LOC) pH sensor was deployed from a pontoon in the inner Kiel Fjord, southwestern Baltic Sea, for a total period of 6 weeks. We present a time-series of in situ pH T (total pH scale) and ancillary data, with sensor validation using discretely collected samples for pH T and laboratory analysis. The difference between the sensor and laboratory analyses of discrete samples was within ±0.015 pH T unit, with a mean difference of 0.001 (n=65), demonstrating that the LOC sensor can provide stable and accurate pH T measurements over several weeks.

Description: Carbon Capture and Storage (CCS) is a potential significant mitigation strategy to combat climate change and ocean acidification. The technology is well understood but its current implementation must be scaled up nearly by a hundredfold to become an effective tool that helps meet mitigation targets. Regulations require monitoring and verification at storage sites, and reliable monitoring strategies for detection and quantification of seepage of the stored carbon need to be developed. The Cseep method was developed for reliable determination of CO2 seepage signal in seawater by estimating and filtering out natural variations in dissolved inorganic carbon (C). In this work, we analysed data from the first-ever subsea CO2 release experiment performed in the north-western North Sea by the EU STEMM-CCS project. We successfully demonstrated the ability of the Cseep method to (i) predict natural C variations around the Goldeneye site over seasonal to interannual time scales; (ii) establish a process-based baseline C concentration with minimal variability; (iii) determine CO2 seepage detection threshold (DT) to reliably differentiate released- CO2 signal from natural variability and quantify released- CO2 dissolved in the sampled seawater. DT values were around 20 % of the natural C variations indicating high sensitivity of the method. Moreover, with the availability of DT value, the identification of released- CO2 required no preknowledge of seepage occurrence, but we used additional available information to assess the confidence of the results. Overall, the Cseep method features high sensitivity, automation suitability, and represents a powerful future monitoring tool both for large and confined marine areas.

Description: We present a novel approach to detecting and quantifying a subsea release of CO2 from within North Sea sediments, which mimicked a leak from a subsea CO2 reservoir. Autonomous lab-on-chip sensors performed in situ measurements of pH at two heights above the seafloor. During the 11 day experiment the rate of CO2 release was gradually increased. Whenever the currents carried the CO2-enriched water towards the sensors, the sensors measured a decrease in pH, with a strong vertical gradient within a metre of the seafloor. At the highest release rate, a decrease of over 0.6 pH units was observed 17 cm above the seafloor compared to background measurements. The sensor data was combined with hydrodynamic measurements to quantify the amount of CO2 escaping the sediments using an advective mass transport model. On average, we directly detected 43 ± 8% of the released CO2 in the water column. Accounting for the incomplete carbonate equilibration process increases this estimate to up to 61 ± 10%. This technique can provide long-term in situ monitoring of offshore CO2 reservoirs and hence provides a tool to support climate change mitigation activities. It could also be applied to characterising plumes and quantifying other natural or anthropogenic fluxes of dissolved solutes.

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.