The Development and Validation of a Profiling Glider Deep ISFET-Based pH Sensor for High Resolution Observations of Coastal and Ocean Acidification

Coastal and ocean acidification can alter ocean biogeochemistry, with ecological consequences that may result in economic and cultural losses. Yet few time series and high resolution spatial and temporal measurements exist to track the existence and movement of water low in pH and/or carbonate saturation. Past acidification monitoring efforts have either low spatial resolution (mooring) or high cost and low temporal and spatial resolution (research cruises). We developed the first integrated glider platform and sensor system for sampling pH throughout the water column of the coastal ocean. A deep ISFET (Ion Sensitive Field Effect Transistor)-based pH sensor system was modified and integrated into a Slocum glider, tank tested in natural seawater to determine sensor conditioning time under different scenarios, and validated in situ during deployments in the U.S. Northeast Shelf (NES). Comparative results between glider pH and pH measured spectrophotometrically from discrete seawater samples indicate that the glider pH sensor is capable of accuracy of 0.011 pH units or better for several weeks throughout the water column in the coastal ocean, with a precision of 0.005 pH units or better. Furthermore, simultaneous measurements from multiple sensors on the same glider enabled salinity-based estimates of total alkalinity (AT) and aragonite saturation state (ΩArag). During the Spring 2018 Mid-Atlantic deployment, glider pH and derived AT/ ΩArag data along the cross-shelf transect revealed higher pH and ΩArag associated with the depth of chlorophyll and oxygen maxima and a warmer, saltier water mass. Lowest pH and ΩArag occurred in bottom waters of the middle shelf and slope, and nearshore following a period of heavy precipitation. Biofouling was revealed to be the primary limitation of this sensor during a summer deployment, whereby offsets in pH and AT increased dramatically. Advances in anti-fouling coatings and the ability to routinely clean and swap out sensors can address this challenge. The data presented here demonstrate the ability for gliders to routinely provide high resolution water column data on regional scales that can be applied to acidification monitoring efforts in other coastal regions.

[1]  Andrew G. Dickson,et al.  Guide to best practices for ocean CO2 measurements , 2007 .

[2]  F. Millero CHAPTER 43 – Influence of Pressure on Chemical Processes in the Sea , 1983 .

[3]  W. Cai,et al.  Assessment of sample storage techniques for total alkalinity and dissolved inorganic carbon in seawater , 2012 .

[4]  B. Carter,et al.  An automated system for spectrophotometric seawater pH measurements , 2013 .

[5]  W. Cai,et al.  The Marine Inorganic Carbon System along the Gulf of Mexico and Atlantic Coast of the United States: Shelf-ocean exchange and Ocean Acidification Status , 2011 .

[6]  Scott C. Doney,et al.  The Growing Human Footprint on Coastal and Open-Ocean Biogeochemistry , 2010, Science.

[7]  Mark L. Green,et al.  Coastal Acidification by Rivers: A Threat to Shellfish? , 2008 .

[8]  W. Cai,et al.  Decadal fCO2 trends in global ocean margins and adjacent boundary current‐influenced areas , 2017 .

[9]  Adina Paytan,et al.  High-Frequency Dynamics of Ocean pH: A Multi-Ecosystem Comparison , 2011, PloS one.

[10]  Oscar Schofield,et al.  Slocum Gliders: Robust and ready , 2007, J. Field Robotics.

[11]  David M. Fratantoni,et al.  UNDERWATER GLIDERS FOR OCEAN RESEARCH , 2004 .

[12]  Richard A. Feely,et al.  Global relationships of total alkalinity with salinity and temperature in surface waters of the world's oceans , 2006 .

[13]  Oscar Schofield,et al.  Developing Coordinated Communities of Autonomous Gliders for Sampling Coastal Ecosystems , 2015 .

[14]  T. A. DelValls,et al.  The pH of buffers based on 2-amino-2-hydroxymethyl-1,3-propanediol (‘tris’) in synthetic sea water , 1998 .

[15]  A. Dickson Standard potential of the reaction: , and and the standard acidity constant of the ion HSO4− in synthetic sea water from 273.15 to 318.15 K , 1990 .

[16]  F. Millero The pH of estuarine waters , 1986 .

[17]  W. Cai,et al.  The marine carbonate system of the Arctic Ocean: Assessment of internal consistency and sampling considerations, summer 2010 , 2015 .

[18]  R. Feely,et al.  Direct observations of basin‐wide acidification of the North Pacific Ocean , 2010 .

[19]  Andrew G. Dickson,et al.  A sensor for in situ indicator-based measurements of seawater pH , 2008 .

[20]  A. Körtzinger,et al.  Calcifying invertebrates succeed in a naturally CO 2 -rich coastal habitat but are threatened by high levels of future acidification , 2010 .

[21]  W. Cai,et al.  Ocean acidification along the Gulf Coast and East Coast of the USA , 2015 .

[22]  Nicholas R. Bates,et al.  An International Observational Network for Ocean Acidification , 2010 .

[23]  Robert H. Byrne,et al.  Spectrophotometric seawater pH measurements: total hydrogen ion concentration scale calibration of m-cresol purple and at-sea results , 1993 .

[25]  R. Lukas,et al.  Physical and biogeochemical modulation of ocean acidification in the central North Pacific , 2009, Proceedings of the National Academy of Sciences.

[26]  F. Millero,et al.  A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media , 1987 .

[27]  S. Lentz Seasonal warming of the Middle Atlantic Bight Cold Pool , 2017 .

[28]  Philip J. Bresnahan,et al.  Best practices for autonomous measurement of seawater pH with the Honeywell Durafet , 2014 .

[29]  K. H. Khoo,et al.  Determination of hydrogen ion concentrations in seawater from 5 to 40.degree.C: standard potentials at salinities from 20 to 45% , 1977 .

[30]  Scott C. Doney,et al.  Ocean acidification’s potential to alter global marine ecosystem services , 2009 .

[31]  W. Cai,et al.  The marine inorganic carbon system along the Gulf of Mexico and Atlantic coasts of the United States: Insights from a transregional coastal carbon study , 2013 .

[32]  Taro Takahashi,et al.  Atmospheric CO2 uptake by a coastal upwelling system , 2005 .

[33]  R. Feely,et al.  Evidence for Upwelling of Corrosive "Acidified" Water onto the Continental Shelf , 2008, Science.

[34]  Bartolomé Garau,et al.  Thermal Lag Correction on Slocum CTD Glider Data , 2011 .

[35]  W. Cai,et al.  Air-sea CO2 fluxes on the U.S. South Atlantic Bight : Spatial and seasonal variability , 2008 .

[36]  W. Cai,et al.  Surface Ocean Alkalinity Distribution in the Western North Atlantic Ocean Margins , 2010 .

[37]  Todd R. Martz,et al.  Deep-Sea DuraFET: A Pressure Tolerant pH Sensor Designed for Global Sensor Networks. , 2016, Analytical chemistry.

[38]  D. Rudnick Ocean Research Enabled by Underwater Gliders. , 2016, Annual review of marine science.

[39]  Nicolas Gruber,et al.  Observing Biogeochemical Cycles at Global Scales With Profiling Floats and Gliders Prospects for a Global Array , 2009 .

[40]  K. Johnson Simultaneous measurements of nitrate, oxygen, and carbon dioxide on oceanographic moorings: Observing the Redfield Ratio in real time , 2010 .

[41]  Baoshan Chen,et al.  Short-term variability of aragonite saturation state in the central Mid-Atlantic Bight , 2017 .

[42]  James D. Irish,et al.  Temporal and spatial dynamics of CO2 air-sea flux in the Gulf of Maine , 2018 .

[43]  Robert H. Byrne,et al.  Purification and Characterization of meta-Cresol Purple for Spectrophotometric Seawater pH Measurements , 2011, Environmental science & technology.

[44]  W. Cai,et al.  Sea surface carbon dioxide at the Georgia time series site (2006–2007): Air–sea flux and controlling processes , 2016 .

[45]  W. Cai,et al.  Eutrophication induced CO₂-acidification of subsurface coastal waters: interactive effects of temperature, salinity, and atmospheric PCO₂. , 2012, Environmental science & technology.

[46]  C. Carlson,et al.  Dramatic Variability of the Carbonate System at a Temperate Coastal Ocean Site (Beaufort, North Carolina, USA) Is Regulated by Physical and Biogeochemical Processes on Multiple Timescales , 2013, PloS one.

[47]  C. Sabine,et al.  CO2 fluxes from a coastal transect: a time-series approach , 1998 .

[48]  C. Culberson,et al.  MEASUREMENT OF THE APPARENT DISSOCIATION CONSTANTS OF CARBONIC ACID IN SEAWATER AT ATMOSPHERIC PRESSURE1 , 1973 .

[49]  Todd R. Martz,et al.  The ocean acidification seascape and its relationship to the performance of calcifying marine invertebrates: Laboratory experiments on the development of urchin larvae framed by environmentally-relevant pCO2/pH , 2011 .

[50]  Richard A. Feely,et al.  The combined effects of ocean acidification, mixing, and respiration on pH and carbonate saturation in an urbanized estuary , 2010 .

[51]  Todd R. Martz,et al.  Testing the Honeywell Durafet® for seawater pH applications , 2010 .