Real-Time Determination of Picomolar Free Cu(II) in Seawater Using a Fluorescence-Based Fiber Optic Biosensor

We report real-time, in situ determination of free copper ion at picomolar levels in seawater using a fluorescence-based fiber optic biosensor. The sensor transducer is a protein molecule, site-specifically labeled with a fluorophore that is attached to the distal end of an optical fiber, which binds free Cu(II) with high affinity and selectivity. The transducer reports the metalʹs concentration as a change in fluorescence intensity or lifetime, using a frequency domain approach. The transducerʹs response time is diffusion-limited, with a typical measurement requiring 30 s. The sensor demonstrates a detection limit of 0.1 pM free Cu(II) in a seawater model. Accuracy and precision of the sensor were at least comparable to cathodic ligand exchange/adsorptive cathodic stripping voltammetry. Measurements of tidal flushing of a copper-contaminated inlet are shown.