Ion‐sensitive field effect transistor‐based pH sensors have been shown to perform well in high frequency and long‐term ocean sampling regimes. The Honeywell Durafet is widely used due to its stability, fast response, and characterization over a large range of oceanic conditions. However, potentiometric pH monitoring is inherently complicated by the fact that the sensors require careful calibration. Offsets in calibration coefficients have been observed when comparing laboratory to field‐based calibrations and prior work has led to the recommendation that an in situ calibration be performed based on comparison to discrete samples. Here, we describe our work toward a self‐calibration apparatus integrated into a SeapHOx pH, dissolved oxygen, and CTD sensor package. This Self‐Calibrating SeapHOx is capable of autonomously recording calibration values from a high quality, traceable, primary reference standard: equimolar tris buffer. The Self‐Calibrating SeapHOx's functionality was demonstrated in a 6‐d test in a seawater tank at Scripps Institution of Oceanography (La Jolla, California, U.S.A.) and was successfully deployed for 2 weeks on a shallow, coral reef flat (Lizard Island, Australia). During the latter deployment, the tris‐based self‐calibration using 15 on‐board samples exhibited superior reproducibility to the standard spectrophotometric pH‐based calibration using > 100 discrete samples. Standard deviations of calibration pH using tris ranged from 0.002 to 0.005 whereas they ranged from 0.006 to 0.009 for the standard spectrophotometric pH‐based method; the two independent calibration methods resulted in a mean pH difference of 0.008. We anticipate that the Self‐Calibrating SeapHOx will be capable of autonomously providing climate quality pH data, directly linked to a primary seawater pH standard, and with improvements over standard calibration techniques.
Bioinspired design is an emerging field that takes inspiration from nature to develop high-performance materials and devices. The sea urchin mouthpiece, known as the Aristotle's lantern, is a compelling source of bioinspiration with an intricate network of musculature and calcareous teeth that can scrape, cut, chew food and bore holes into rocky substrates. We describe the bioinspiration process as including animal observation, specimen characterization, device fabrication and mechanism bioexploration. The last step of bioexploration allows for a deeper understanding of the initial biology. The design architecture of the Aristotle's lantern is analyzed with micro-computed tomography and individual teeth are examined with scanning electron microscopy to identify the microstructure. Bioinspired designs are fabricated with a 3D printer, assembled and tested to determine the most efficient lantern opening and closing mechanism. Teeth from the bioinspired lantern design are bioexplored via finite element analysis to explain from a mechanical perspective why keeled tooth structures evolved in the modern sea urchins we observed. This circular approach allows for new conclusions to be drawn from biology and nature.
A novel chemical sensor package named-WavepHOx‖ was developed in order to facilitate measurement of surface ocean pH, dissolved oxygen, and temperature from mobile platforms. The system comprises a Honeywell Durafet pH sensor, Aanderaa optode oxygen sensor, and chloride ion selective electrode, packaged into a hydrodynamic, lightweight housing. The WavepHOx has been deployed on a stand-up paddleboard and a Liquid Robotics Wave Glider in multiple near-shore settings in the Southern California Bight. Integration of the WavepHOx into these mobile platforms has enabled high spatiotemporal resolution pH and dissolved oxygen data collection. It is a particularly valuable tool for mapping shallow, fragile, or densely vegetated ecosystems which cannot be easily accessed by other platforms. Results from three surveys in San Diego, California, are reported. We show pH and dissolved oxygen variability > 0.3 and > 50% saturation, respectively, over tens to hundreds of meters to highlight the degree of natural spatial variability in these vegetated ecosystems. When deployed during an extensive discrete sampling program, the WavepHOx pH had a root mean squared error of 0.028 relative to pH calculated from fifty six measurements of total alkalinity and dissolved inorganic carbon, confirming its capacity for accurate, high spatiotemporal resolution data collection.
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