On the accuracy of upper ocean particulate organic carbon export fluxes estimated from 234Th/ 238U disequilibrium

Abstract

An analysis of the 234Th method for determining the export flux of particulate organic carbon ( P POC) from the upper ocean using in situ pumps or water bottles shows that the accuracy of the method (the ratio of the experimental value of P POC divided by the true POC flux, F POC), defined as the p-ratio, is equal to the mean settling velocity of particulate 234Th divided by that of POC. Therefore, P POC is equivalent to the true POC flux ( F POC) and the p-ratio is equal to unity if, and only if, POC and particulate 234Th have the same mean sinking velocities. A simple particle settling model is discussed that invokes Stokes’ Law settling velocities, volume:surface area ( V:SA) fractionation of C: 234Th and two assemblages of particles having different sizes and densities. The model is used to illustrate the ranges of parameter values that conform to values of the p-ratio sufficiently close to unity that the experimentally determined POC flux can be considered to be an accurate representation of the true POC flux. Despite the over-simplification of real systems implicit in the model, the results suggest that p-ratios<1, equivalent to an under-estimate of the POC flux, are representative of single particle settling regimes in which the larger particles dominate the vertical flux. This follows from the assumption that the ratio of C/ 234Th on particles is governed by the volume to surface area ( V:SA) ratio of the particles. This results in a greater proportion of 234Th compared to C being associated with the smaller, more slowly settling particles and, as a result, normalization of the POC flux to the 234Th flux provides an under-estimate of the former quantity. However, when the smaller particle assemblage dominates the vertical flux, as could occur in open ocean regimes having high aeolian inputs of dense, rapidly settling, inorganic particles, then the p-ratio could exceed unity ( p-ratio >1) resulting in an over-estimate of the POC flux using the 234Th method. High levels of flocculation associated with phytoplankton blooms in productive regions of the ocean are likely to produce p-ratios approaching unity, because flocs would tend to preserve the V:SA partitioning of the original particle size distribution and thereby minimize differences in the mean settling speeds of POC and particulate 234Th (Waite, A.W., Hill, P.S., 2006. Flocculation, phytoplankton and the accuracy of 234Th-based estimates of the vertical flux of particulate organic carbon in the sea. Marine Chemistry in press). Selective sampling of the large particle fraction using, for example, 53-μm screens can produce a more accurate estimate of the true POC flux, but may not entirely shift the p-ratio to a value of unity.