An evaluation of electrode insertion techniques for measurement of redox potential in estuarine sediments

Eh measurements by electrodes are commonly used to characterize redox status of sediments in freshwater, marine and estuarine studies, due to the relative ease and rapidity of data collection. In our studies of fine-grained estuarine seabeds, we observed that Eh values measured in intact sediment cores were influenced by different electrode insertion techniques. Sediment Eh measurements generated via lateral insertion of platinum electrodes through silicone-filled ports in acrylic cores were systematically more positive (on the order of 10-100 mV) than profiles generated via vertical insertion of platinum electrodes downward through the sediment-water interface of the same cores. A review of the literature indicated that while researchers routinely use both insertion techniques to measure Eh, no discrepancy in output has previously been reported. We discuss the results of three experiments conducted to determine if the discrepancy in output was caused by electrode poisoning by sulfides during the stepwise vertical insertion technique, or was caused by contact of the electrode with the silicone plug during the lateral insertion technique. We conclude that contact between the platinum surface of the electrode and the silicone plug biases the Eh measurements, resulting in erroneously positive Eh values. Insertion of electrodes into sediment through silicone plugs produced Eh values that were an average of 105.6 mV (±10.4 SE) more positive than values generated upon electrode insertion directly into sediment. Thus, we recommend against using an insertion technique where the platinum electrode remains in contact with the silicone plug, as this method results in misclassification of sediment redox state and estimated depth of the redoxcline.