RESUMEN
Current water quality monitoring for heavy metal contaminants largely results in analytical snapshots at a particular time and place. Therefore, we have been interested in miniaturized and inexpensive sensors suitable for long-term, real-time monitoring of the drinking water distribution grid, industrial wastewater effluents, and even rivers and lakes. Among the biggest challenges for such sensors are the issues of in-field device calibration and sample pretreatment. Previously, we have demonstrated use of coulometric stripping analysis for calibration-free determination of copper and mercury. For more negatively reduced metals, O2 reduction interferes with stripping analysis; hence, most electroanalysis techniques rely on pretreatments to remove dissolved oxygen (DO). Current strategies for portable DO removal offer limited practicality, because of their complexity, and often cause inadvertent sample alterations. Therefore, we have designed an indirect in-line electrochemical DO removal device (EDOR), utilizing a silver cathode to reduce DO in a chamber that is fluidically isolated from the sample stream by an O2-permeable membrane. The resulting concentration gradient supports passive DO diffusion from the sample stream into the deoxygenation chamber. The DO levels in the sample stream were determined by cyclic voltammetry (CV) and amperometry at a custom thin-layer cell (TLC) detector. Results show removal of 98% of the DO in a test sample at flow rates approaching 50 µL/min and power consumption as low as 165 mW h L(-1) at steady state. Besides our specific stripping application, this device is well-suited for LOC applications where miniaturized DO removal and/or regulation are desirable.
Asunto(s)
Técnicas Electroquímicas/métodos , Oxígeno/química , Agua Potable/análisis , Técnicas Electroquímicas/instrumentación , Electrodos , Monitoreo del Ambiente , Técnicas Analíticas Microfluídicas/instrumentación , Oxidación-ReducciónRESUMEN
Remote unattended sensor networks are increasingly sought after to monitor the drinking water distribution grid, industrial wastewater effluents, and even rivers and lakes. One of the biggest challenges for application of such sensors is the issue of in-field device calibration. With this challenge in mind, we report here the use of anodic stripping coulometry (ASC) as the basis of a calibration-free micro-fabricated electrochemical sensor (CF-MES) for heavy metal determinations. The sensor platform consisted of a photo-lithographically patterned gold working electrode on SiO2 substrate, which was housed within a custom stopped-flow thin-layer cell, with a total volume of 2-4 µL. The behavior of this platform was characterized by fluorescent particle microscopy and electrochemical studies utilizing Fe(CN)6(3-/4-) as a model analyte. The average charge obtained for oxidation of 500 µM ferrocyanide after 60s over a 10 month period was 176 µC, corresponding to a volume of 3.65 µL (RSD = 2.4%). The response of the platform to copper concentrations ranging from 50 to 7500 ppb was evaluated, and the ASC results showed a linear dependence of charge on copper concentrations with excellent reproducibility (RSD ≤ 2.5%) and accuracy for most concentrations (≤ 5-10% error). The platform was also used to determine copper and mercury mixtures, where the total metallic content was measurable with excellent reproducibility (RSD ≤ 4%) and accuracy (≤ 6% error).