Techniques for determination of trace metals in small samples of size-fractionated particulate matter: phytoplankton metals off central California

Abstract

The oceanic biogeochemical cycles of many trace elements are dominated by their association with the growth, death, consumption and sinking of phytoplankton. The trace element content of marine phytoplankton reflects nutritional status, species composition, surface area to volume ratios, and interactions with bioactive and toxic elements in the ambient seawater. Despite the ecological and environmental importance of trace element assimilation by autotrophs, there are few modern measurements of trace elements in phytoplankton assemblages from the natural environment. Here we introduce a new method for collection and analysis of size-fractionated particulate samples from practical seawater volumes. We pay particular attention to accurate determination of trace element filter blanks which are typically the limiting factor for analysis of such samples. Metals were determined at very low detection limits by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for 11 elements (Ag, Al, Cd, Co, Cr, Cu, Fe, Mn, U, Zn and P, which is used as a biomass normalizer) in three types of polymer filters (0.45, 5.0, and 53 μm pore size) and a quartz fiber filter (0.8 μm pore size). To place these new determinations in a practical context, results are presented for a vertical profile of samples filtered from 1–4 l of coastal seawater (0.3–1.0 mg total solid dry weight) at a station off central California. The results demonstrate that the blanks of the evaluated filter types, precleaned appropriately, are sufficiently low to allow accurate determination of the trace metal content of three size-classes of phytoplankton. At the Pacific station, measured phytoplankton Zn content (as Zn/P) agrees with values predicted from single-species culture studies growing at seawater Zn concentrations expected for coastal waters. The new method has utility as a generally applicable and simple size fractionation technique, and allows determination of natural and pollutant elements in small samples of phytoplankton and particles in coastal, estuarine and offshore marine regimes.