Ion selective electrode (ISE) sensors have been broadly applied for real-time in situ monitoring of ion concentrations in water environments. However, ISE sensors suffer from critical problems, such as ionophore leaching, water-penetration, poor electrochemical stability, and resulting short life spans. In this study, a template-guided membrane matrix immobilization strategy was pursued as a novel ISE sensor fabrication methodology to enhance its sensing characteristics and longevity. Specifically, nano-porous anodized aluminum oxide (AAO) was used as the template for an NH 4 + -specific ISE sensor. A nano-porous nickel mesh eventually replaced the template and formed a compact, high-surface juncture with the NH 4 + ion-selective membrane matrix. The resulting template-guided nano-mesh ISE (TN-ISE) sensor displayed enhanced electrochemical stability ( i.e. , capacitance increased by 50%, reading drift reduced by 75%) when compared to a regular single-wall carbon nanotube (SW-CNT) ISE sensor used as the standard. The interface between the nano-mesh electrode and the ion selective membrane matrix was compact enough to prevent water influx at the electrode interface. This minimized ionophore leaching and increased the mechanical integrity of the TN-ISE sensor. The practical advantages of the novel sensor were validated via long-term (360 hours) tests in real wastewater, returning a small average error of 1.28% over this time. The results demonstrate the feasibility of the template-guided nano-mesh design and fabrication strategy toward ISEs for long-term continuous monitoring of water or wastewater quality.
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A half-cell reaction approach for pH calculation using a solid-state chloride ion-selective electrode with a hydrogen ion-selective ion-sensitive field effect transistor
Here, we explicitly define a half-cell reaction approach for pH calculation using the electrode couple comprised of the solid-state chloride ion-selective electrode (Cl-ISE) as the reference electrode and the hydrogen ionselective ion-sensitive field effect transistor (ISFET) of the Honeywell Durafet as the hydrogen ion (H+)-sensitive measuring or working electrode. This new approach splits and isolates the independent responses of the Cl-ISE to the chloride ion (Cl−) (and salinity) and the ISFET to H+ (and pH), and calculates pH directly on the total scale (pHEXT total) in molinity (mol (kg-soln)−1) concentration units. We further apply and compare pHEXT total calculated using the half-cell and the existing complete cell reaction (defined by Martz et al. (2010)) approaches using measurements from two SeapHOx sensors deployed in a test tank. Salinity (on the Practical Salinity Scale) and pH oscillated between 1 and 31 and 6.9 and 8.1, respectively, over a six-day period. In contrast to established Sensor Best Practices, we employ a new calibration method where the calibration of raw pH sensor timeseries are split out as needed according to salinity. When doing this, pHEXT total had root-mean squared errors ranging between ±0.0026 and ±0.0168 pH calculated using both reaction approaches relative to pHtotal of the discrete bottle samples (pHdisc total). Our results further demonstrate the rapid response of the Cl-ISE reference to variable salinity with changes up to ±12 (30 min)−1. Final calculated pHEXT total were ≤±0.012 pH when compared to pHdisc total following salinity dilution or concentration. These results are notably in contrast to those of the few in situ field deployments over similar environmental conditions that demonstrated pHEXT total calculated using the Cl-ISE as the reference electrode had larger uncertainty in nearshore waters. Therefore, additional work beyond the correction of variable temperature and salinity conditions in pH calculation using the Cl-ISE is needed to examine the effects of other external stimuli on in situ electrode response. Furthermore, whereas past work has focused on in situ reference electrode response, greater scrutiny of the ISFET as the H+-sensitive measuring electrode for pH measurement in natural waters is also needed.
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- Award ID(s):
- 1757353
- PAR ID:
- 10513839
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Marine Chemistry
- Volume:
- 261
- Issue:
- C
- ISSN:
- 0304-4203
- Page Range / eLocation ID:
- 104373
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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