Analytical performance during ratiometric long-term imaging of pH in bioturbated sediments

In this study, the long-term analytical performance of a high-resolution ratiometric imaging sensor for pH was quantitatively determined. The sensor was applied in an experimental microcosm to illustrate biogeochemical consequences from mining activities by the chemosymbiotic bivalve Thyasira sarsi. Utilizing time-correlated pixel-by-pixel calibration protocols during imaging, close to 90% of the pixels were associated with a precision (S.D.) of <0.05 pH units at the end of an experimental period of 17 days. For comparison, a precision of <0.05 pH units was achieved for less than 50% of the pixels throughout experiments using conventional pre-sample calibration procedures. The average standard deviation of pixels was 0.01 pH units. Image analysis of single pixel derivatives and pH measurements over time suggested that T. sarsi affect pH distributions and general sediment geochemistry more than would be expected based on the small size of the bivalves. A significant decrease of pH in the overlying water suggested a considerable release of reduced compounds from the exhalent stream of the thyasirids. Strong pH gradients were demonstrated not only across the sediment-water interface but, also associated with bioturbation activities immediately adjacent to T. sarsi burrowing tracts, inhalant tubes and pedal tracts in the sediment matrix. Gradients of up to 1.16 pH units per mm were observed.