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While the pH cross-sensitivity of chromoionophore-based ion-selective optodes (ISOs) has often been regarded as a significant limitation, this paper demonstrates how this apparent drawback can be transformed into a beneficial feature. The response range of chromoionophore-based ISOs shifts proportionally with changes in the sample pH. Thus, integrating them with a stable pH gradient across the optode surface, such as those provided by immobilized pH gradient (IPG) gels, allows for significant enhancement of the effective measuring range of chromoionophore-based ISOs while preserving their maximum sensitivity. We show that the measuring range of sodium-selective chromoionophore-based optodes can be increased up to 2.5 log units when used with commercially available IPG gels. This improvement in measuring range is directly correlated with the pH difference in the pH gradient across the optode, suggesting that even greater enhancements are possible with more substantial pH gradients. Furthermore, this approach is not confined to sodium-selective optodes but can be readily adapted to other ion-selective chromoionophore-based optodes, broadening their potential applications and impact in the field of chemical sensing. This work paves the way for the development of more versatile and highly sensitive optodes across a broad range of analytes, leveraging the pH cross-sensitivity as a tool for enhanced performance.

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Accurate measurement of pH-dependent analytes is crucial for a wide range of applications, including environmental monitoring, industrial processes, and healthcare diagnostics. In multi-sensor systems, combining data from multiple sensors offers the potential for more comprehensive analysis, yet it is important to be aware of the limitations of this approach. In this paper, we investigate the often-overlooked issue of response time mismatch among sensors, which can introduce significant errors in calculated sum parameters. We present a model and software application (SensinSilico) that allows predicting the error arising from a mismatch of sensor response times. The model was compared and validated using experimental results from calculations of total dissolved sulphide (TDS). These calculations were based on data from concurrent sensor measurements of hydrogen sulfide (H2S) and pH, which had different response times. We believe that SensinSilico has the potential to be a powerful tool for researchers, professionals, and end-users, enabling them to estimate and minimize errors arising from response time mismatches, enhancing the accuracy and reliability of their results.

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Dissolved inorganic carbon (DIC) is a key component of the global carbon cycle and plays a critical role in ocean acidification and proliferation of phototrophs. Its quantification at a high spatial resolution is essential for understanding various biogeochemical processes. We present an analytical method for 2D chemical imaging of DIC by combining a conventional CO2 optode with localized electrochemical acidification from a polyaniline (PANI)-coated stainless-steel mesh electrode. Initially, the optode response is governed by local concentrations of free CO2 in the sample, corresponding to the established carbonate equilibrium at the (unmodified) sample pH. Upon applying a mild potential-based polarization to the PANI mesh, protons are released into the sample, shifting the carbonate equilibrium toward CO2 conversion (>99%), which corresponds to the sample DIC. It is herein demonstrated that the CO2 optode-PANI tandem enables the mapping of free CO2 (before PANI activation) and DIC (after PANI activation) in complex samples, providing high 2D spatial resolution (approx. 400 µm). The significance of this method was proven by inspecting the carbonate chemistry of complex environmental systems, including the freshwater plant Vallisneria spiralis and lime-amended waterlogged soil. This work is expected to pave the way for new analytical strategies that combine chemical imaging with electrochemical actuators, aiming to enhance classical sensing approaches via in situ (and reagentless) sample treatment. Such tools may provide a better understanding of environmentally relevant pH-dependent analytes related to the carbon, nitrogen, and sulfur cycles.

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Biofouling is a major challenge in environmental sensing. Current mitigation strategies are often expensive, energy consuming or require toxic chemicals. In this contribution electrochemical biofouling control is evaluated as an alternative approach to reduce biofouling on an optical O2 sensor (optode). By using the outer stainless-steel sleeve of the optode as an electrode, water splitting increases the local pH and forms H2 bubbles close to the optode surface. As seen in a biofouling assay, the combination of those processes leads to biofilm removal when compared to a non-modified optode. The findings suggest that electrochemical biofouling control can be an attractive, low-cost alternative to current biofouling mitigation strategies and that this approach may not be limited to O2 optodes.

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Total Dissolved Sulfide (TDS) concentrations can either be derived from simultaneous measurement of pH and one of the sulfide species or determined indirectly in samples following an acidification step. Here we report a microsensor that allows for direct measurement of TDS in aquatic media without the need for pH monitoring. An acidic chamber placed in front of a commercial, amperometric H2S microsensor allows for the in-situ conversion of dissolved ionic sulfide species to H2S, which in turn is oxidized at the transducer anode. A typical sensor had a tip opening of 30 µm, a response time of <50 s and linear range between 0.5 and 650 µM. The sensor performance can be largely tuned by altering the geometry of the chamber. Sensors of different sensitivity (0.04-2.93 pA/µM) showed no noticeable change in zero current and sensitivity during continuous polarization over 7 weeks. The sensor was successfully applied to resolve microscale TDS gradients in freshwater and marine sediments. Other avenues of application include the online monitoring of industrial and urban sewers.

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In this letter, we demonstrate 2D acidification of samples at environmental and physiological pH with an electrochemically activated polyaniline (PANI) mesh. A novel sensor-actuator concept is conceived for such a purpose. The sample is sandwiched between the PANI (actuator) and a planar pH optode (sensor) placed at a very close distance (∼0.50 mm). Upon application of a mild potential to the mesh, in contrast to previously reported acidification approaches, PANI releases a significant number of protons, causing an acid-base titration in the sample. This process is monitored in time and space by the pH optode, providing chemical imaging of the pH decrease along the dynamic titration via photographic acquisition. Acidification of samples at varying buffer capacity has been investigated: the higher the buffer capacity, the more time (and therefore proton charge) was needed to reach a pH of 4.5 or even lower. Also, the ability to map spatial differences in buffer capacity within a sample during the acid-base titration was unprecedentedly proven. The sensor-actuator concept could be used for monitoring certain analytes in samples that specifically require acidification pretreatment. Particularly, in combination with different optodes, dynamic mapping of concentration gradients will be accessible in complex environmental samples ranging from roots and sediments to bacterial aggregates.

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We present a dipping probe total dissolved inorganic carbon (DIC) microsensor based on a localized acidic microenvironment in front of an amperometric CO2 microsensor. The acidic milieu facilitates conversion of bicarbonate and carbonate to CO2, which in turn is reduced at a silver cathode. Interfering oxygen is removed by an acidic CrCl2 oxygen trap. Theoretical simulations of microsensor functioning were performed to find a suitable compromise between response time and near-complete conversion of bicarbonate to CO2. The sensor exhibited a linear response over a wide range of 0-8 mM DIC, with a calculated LOD of 5 µM and a 90% response time of 150 s. The sensor was successfully tested in measuring DIC in bottled mineral water and seawater. This DIC microsensor holds the potential to become an important tool in environmental sensing and beyond for measurements of DIC at high spatial and temporal resolution.

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State-of-the-art electrochemical and optical sensors present distinct advantages and disadvantages when used individually. Combining both methodologies offers interesting synergies and makes it possible to exploit strengths and circumvent possible problems of the individual methods. We report a dynamic sensing concept for buffer capacity by applying water electrolysis to modulate the pH microenvironment in front of an optical pH sensor placed in a flow cell. Using this combinatory approach in a nonequilibrium readout mode allowed us to assess the concentration of different buffer species in relatively short time (1 min per measurement). Theoretical simulations of the system were performed to validate the presented method. Additionally, the dynamic measurement approach enabled in situ determination of the apparent pKa of MOPS (3-(N-morpholino)propanesulfonic acid) buffer at ambient conditions. The dynamic and combinatory approach presented here holds large potential also for other pH-active analytes.