Mooring deployment
A Seabird SeaFET V2 is among the instrumentation included in the benthic mooring array for the Beaufort Lagoon Ecosystems Long Term Ecological Research (BLE LTER) project. The SeaFET is buoyed from a benthic mooring so that the sensor is at 10 cm above the lagoon seafloor. Data were collected hourly. Approximately two weeks after instrument deployment and subsequent sensor conditioning, 500 mL of site bottom water was collected within the minute of instrument measurement for laboratory determination via spectrophotometry of pH (Clayton and Byrne 1993) to apply a single point calibration following the methods of Martz et al. (2010). During site occupation months later, another sample of site bottom water was collected to estimate uncertainty by calculating the absolute value of the difference between the laboratory-calculated in situ pH of the discrete water sample and the reported pH value from the calibrated SeaFET. Discrete water samples were stored in borosilicate amber bottles spiked with saturated mercuric chloride to halt microbial activity and kept at ~4 °C until analysis (Dickson et al. 2007).
Data calculation and validation
pH values are reported on the total hydrogen ion scale (pHT or pH_tot) Values are derived from the instrument’s raw voltage reading on the internal sensor using the following equation:
pHT = (Vint - CalOffset - CalSlope * T) / S
where:
Vint = voltage of internal sensor
CalOffset = the calibration internal offset coefficient set by manufacturer
CalSlope = the calibration internal slope coefficient set by manufacturer
S = Nersnt slope
The Nernst slope is defined as R * T * ln(10)) / F where
T = Temperature of sample water in Kelvin, determined by the internal sensor on the SeaFET
R = Universal Gas Constant, 8.31451 J mol-1 K-1
F = Faraday Constant, 96487 C mol-1
Note that CalOffset and CalSlope will differ every time the instrument is calibrated by the manufacturer. CalOffset was determined using the following equation:
CalOffset = -[pHemp * S - Vint + (CalSlope * T)]
where:
pHemp = empirical value for pH determined in laboratory with spectrophotometer
CalSlope is determined by Martz et al. (2010) as dCalOffset/dT and applies a temperature correction for all SeaFETs assuming a 100% Nernstian response (Miller et al. 2018).
Total alkalinity (AT) is measured in duplicate with an open-cell titration of hydrochloric acid using a Metrohm Titrino 848 (Dickson et al. 2007; SOP 3b). Spectrophotometric measurements of pH are made in triplicate using a Shimadzu 1800 fitted to maintain cuvette temperature at 25°C. The spectrophotometric method employs a colorimetric methodology with m-cresol purple, following SOP 6b from Dickson et al. (2007). An impurity correction factor of the m-cresol reagent was used to adjust the final measured pH value (Douglas and Byrne 2017). A YSI 3100 Conductivity meter is used to measure salinity of each discrete seawater sample. Certified Reference Material of seawater (CRM) is used to determine the AT uncertainty. In situ temperature of each discrete seawater sample is measured during time of collection. To estimate uncertainty, the calibrated SeaFET-measured value of pH is compared to the laboratory-measured value of pH of discrete water sample. However, since pH in the laboratory is measured at 25°C, it must be “back-corrected” to in situ temperature to make the comparison. The calculation used AT, empirical pH25°C, in situ temperature, and in situ salinity using CO2Calc (Robbins et al. 2010) with CO2 constants from Mehrbach et al. (1973) refit by Dickson and Millero (1987).
2018-2019 season: Uncertainty for this dataset was determined as 0.009 units. The manufacturer reports an expected stability of the sensor to be 0.005 units.
References
Clayton, T.D., Byrne, R.H., 1993. Spectrophotometric seawater pH measurements: total hydrogen ion concentration scale calibration of m-cresol purple and at-sea results. Deep Sea Res. Part I Oceanogr. Res. Pap. 40, 2115–2129. http://dx.doi.org/10.1016/0967-0637(93)90048-8.
Dickson, Andrew Gilmore, Christopher L. Sabine, and James Robert Christian. Guide to best practices for ocean CO2 measurements. North Pacific Marine Science Organization, 2007.
Dickson, A. G., & Millero, F. J. (1987). A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media. Deep Sea Research Part A. Oceanographic Research Papers, 34(10), 1733-1743.
Martz, T. R., Connery, J. G., & Johnson, K. S. (2010). Testing the Honeywell Durafet® for seawater pH applications. Limnology and Oceanography: Methods, 8(5), 172-184.
Mehrbach, C., Culberson, C. H., Hawley, J. E., & Pytkowicx, R. M. (1973). Measurement of the apparent dissociation constants of carbonic acid in seawater at atmospheric pressure 1. Limnology and Oceanography, 18(6), 897-907.
Miller, C. A., Pocock, K., Evans, W., & Kelley, A. L. (2018). An evaluation of the performance of Sea-Bird Scientific’s SeaFETTM autonomous pH sensor: considerations for the broader oceanographic community. Ocean Science, 14(4), 751–768. https://doi.org/10.5194/os-14-751-2018
Robbins, L.L., Hansen, M.E., Kleypas, J.A., and Meylan, S.C., 2010, CO2calc—A user-friendly seawater carbon calculator for Windows, Max OS X, and iOS (iPhone): U.S. Geological Survey Open-File Report 2010–1280, 17 p.