Modern sampling and analytical methods for the determination of trace elements in marine particulate material using...

Trace elements often limit phytoplankton growth in the ocean, and the quantification of particulate forms is essential to fully understand their biogeochemical cycling. There is presently a lack of reliable measurements on the trace elemental content of marine particles, in part due to the inadequacies of the sampling and analytical methods employed. Here we report on the development of a series of state-of-the-art trace metal clean methods to collect and process oceanic particulate material in open-ocean and sea ice environments, including sampling, size-fractionated filtration, particle digestions and analysis by magnetic sector inductively coupled plasma-mass spectrometry (ICP-MS). Particular attention was paid to the analysis of certified reference materials (CRMs) and field blanks, which are typically the limiting factor for the accurate analysis of low concentrations of trace metals in marine particulate samples. Theoretical detection limits (3 s of the blank) were low for all 17 elements considered, and varied according to filter material and porosity (sub-microg L(-1) for polycarbonate filters and 1-2 microg L(-1) for quartz and polyester filters). Analytical accuracy was verified using fresh water CRMs, with excellent recoveries noted (93-103%). Digestion efficiencies for various acid combinations were assessed using sediment and plankton CRMs. Using nitric acid only, good recoveries (79-90%) were achieved for Mo, Cd, Ba, Pb, Mn, Fe, Co, Ni, Cu, Zn and Ga. The addition of HF was necessary for the quantitative recovery of the more refractory trace elements such as U, Al, V and Cr. Bioactive elements such as P can also be analysed and used as a biomass normaliser. Our developed sampling and analytical methods proved reliable when applied during two major field programs in both the open Southern Ocean and Antarctic sea ice environments during the International Polar Year in 2007. Trace elemental data are presented for particulate samples collected in both suspended and sinking marine material, and also within sea ice cores.