Characterisation and deployment of an immobilised pH sensor spot towards surface ocean pH measurements

• Published in: Analytica Chimica Acta
• Main Authors: Clarke, Jennifer S., Achterberg, Eric P., Rérolle, Victoire, Abi Kaed Bey, Samer, Floquet, Cedric F.A., Mowlem, Matthew C.
• Other Authors: National Oceanography Centre Southampton (NOC), University of Southampton, Helmholtz Centre for Ocean Research Kiel (GEOMAR), Austral, Boréal et Carbone (ABC), Laboratoire d'Océanographie et du Climat : Expérimentations et Approches Numériques (LOCEAN), Muséum national d'Histoire naturelle (MNHN)-Institut de Recherche pour le Développement (IRD)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut Pierre-Simon-Laplace (IPSL (FR_636)), École normale supérieure - Paris (ENS-PSL), Université Paris Sciences et Lettres (PSL)-Université Paris Sciences et Lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-École polytechnique (X)-Centre National d'Études Spatiales Toulouse (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris Sciences et Lettres (PSL)-Université Paris Sciences et Lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris Diderot - Paris 7 (UPD7)-École polytechnique (X)-Centre National d'Études Spatiales Toulouse (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Institut de Recherche pour le Développement (IRD)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut Pierre-Simon-Laplace (IPSL (FR_636)), Université Paris Sciences et Lettres (PSL)-Université Paris Sciences et Lettres (PSL)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris Diderot - Paris 7 (UPD7)-École polytechnique (X)-Centre National d'Études Spatiales Toulouse (CNES)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), American University of Science and Technology (AUST)
• Format: Article in Journal/Newspaper
• Language: English
• Published: HAL CCSD 2015
• Subjects: [SDU.STU.OC]Sciences of the Universe [physics]/Earth Sciences/Oceanography; [PHYS.PHYS.PHYS-GEO-PH]Physics [physics]/Physics [physics]/Geophysics [physics.geo-ph]; Southern Ocean
• Online Access: https://hal.sorbonne-universite.fr/hal-01225001; https://hal.sorbonne-universite.fr/hal-01225001/document; https://hal.sorbonne-universite.fr/hal-01225001/file/Clarke_2015_Characterisation.pdf; https://doi.org/10.1016/j.aca.2015.09.026

International audience The oceans are a major sink for anthropogenic atmospheric carbon dioxide, and the uptake causes changes to the marine carbonate system and has wide ranging effects on flora and fauna. It is crucial to develop analytical systems that allow us to follow the increase in oceanic pCO 2 and corresponding reduction in pH. Miniaturised sensor systems using immobilised fluorescence indicator spots are attractive for this purpose because of their simple design and low power requirements. The technology is increasingly used for oceanic dissolved oxygen measurements. We present a detailed method on the use of immobilised fluorescence indicator spots to determine pH in ocean waters across the pH range 7.6–8.2. We characterised temperature (−0.046 pH/°C from 5 to 25 °C) and salinity dependences (−0.01 pH/psu over 5–35), and performed a preliminary investigation into the influence of chlorophyll on the pH measurement. The apparent pKa of the sensor spots was 6.93 at 20 °C. A drift of 0.00014 R (ca. 0.0004 pH, at 25 °C, salinity 35) was observed over a 3 day period in a laboratory based drift experiment. We achieved a precision of 0.0074 pH units, and observed a drift of 0.06 pH units during a test deployment of 5 week duration in the Southern Ocean as an underway surface ocean sensor, which was corrected for using certified reference materials. The temperature and salinity dependences were accounted for with the algorithm, R=0.00034−0.17·pH+0.15·S2+0.0067·T−0.0084·S·1.075R=0.00034−0.17·pH+0.15·S2+0.0067·T−0.0084·S·1.075. This study provides a first step towards a pH optode system suitable for autonomous deployment. The use of a short duration low power illumination (LED current 0.2 mA, 5 μs illumination time) improved the lifetime and precision of the spot. Further improvements to the pH indicator spot operations include regular application of certified reference materials for drift correction and cross-calibration against a spectrophotometric pH system. Desirable future developments should involve ...