Solubilization of particles in sediment traps: revising the stoichiometry of mixed layer export

Sinking particles, once caught in sediment trap jars, release dissolved elements into the surrounding medium through leaching from their pore fluids, chemical dissolution and the activity of free exoenzymes. This results in an increase in dissolved elements in the trap jar supernatant. Elemental fluxes as traditionally measured by sediment traps underestimate total export when this particle-associated dissolved flux is not considered. The errors introduced are variable and alter both the absolute levels of flux as well as the stoichiometry of export. These errors have been quantified and corrections applied for samples from sediment traps in the North Atlantic based on measurements of excess dissolved carbon, nitrogen, phosphorus, silica and calcium in the supernatant of the collection cups. At the base of the winter mixed layer, on average 90 +/- 6% of phosphorus fluxes are found as excess phosphate whereas for carbon and nitrogen dissolved concentrations account for 30 (+/- 8)% and 47(+/- 11)% of total fluxes respectively. Excess dissolved silica is on average 61 (+/- 17)% of total biogenic silica flux. Little (< 10%) of calcium is solubilized. The proportion of dissolved to total flux decreases with trap deployment depth. Calculations of the C: N: P ratios for particles only are well above the Redfield ratios of 106: 16: 1 (Redfield et al., 1963), although the mid-water dissolved N: P and N: Si values as well as the C: N: P ratios of remineralisation along isopycnals conform to the Redfield ratios at this site. Accounting for dissolved fluxes of all these elements brings the stoichiometry of export in agreement with the Redfield Ratio and with other geochemical estimates of winter mixed layer export. A factor of 3 to 4 higher ratios of organic: inorganic carbon export also implies that the net atmospheric CO2 sequestration by the biological pump is about 50% higher at this site when the dissolved elemental fluxes are considered. Solubilization is thus a process that should be accounted for in protocols used to measure vertical fluxes with sediment traps.