Metal contents of phytoplankton and labile particulate material in the North Atlantic Ocean

Phytoplankton contribute significantly to global C cycling and serve as the base of ocean food webs. Phytoplankton require trace metals for growth and also mediate the vertical distributions of many metals in the ocean. We collected bulk particulate material and individual phytoplankton cells from the upper water column (<150 m) of the North Atlantic Ocean as part of the US GEOTRACES North Atlantic Zonal Transect cruise (GEOTRACES GA03). Particulate material was first leached to extract biogenic and potentially-bioavailable elements, and the remaining refractory material was digested in strong acids. The cruise track spanned several ocean biomes and geochemical regions. Particulate concentrations of metals associated primarily with lithogenic phases (Fe, Al, Ti) were elevated in surface waters nearest North America, Africa and Europe, and elements associated primarily with biogenic material (P, Cd, Zn, Ni) were also found at higher concentrations near the coasts. However metal/P ratios of labile particulate material were also elevated in the middle of the transect for Fe, Ni, Co, Cu, and V. P-normalized cellular metal quotas measured with synchrotron X-ray fluorescence (SXRF) were generally comparable to ratios in bulk labile particles but did not show mid-basin increases. Manganese and Fe ratios and cell quotas were higher in the western part of the section, nearest North America, and both elements were more enriched in bulk particles, relative to P, than in cells, suggesting the presence of labile oxyhydroxide particulate phases. Cellular Fe quotas thus did not increase in step with aeolian dust inputs, which are highest near Africa; these data suggest that the dust inputs have low bioavailability. Copper and Ni cell quotas were notably higher nearest the continental margins. Overall mean cellular metal quotas were similar to those measured in the Pacific and Southern Oceans except for Fe, which was approximately 3-fold higher in North Atlantic cells. Cellular Fe quotas are in-line with those measured in laboratory cultures at comparable Fe concentrations. Particulate Zn, Cu, Ni, and Co are primarily associated with cellular material, but less than 30% of labile particulate Fe and Mn are biogenic. Particulate Al was primarily associated with lithogenic material, but the labile fraction was highly correlated with P, as well as with biogenic silica, suggesting that some particulate Al (perhaps around 20%) may occur adsorbed to biogenic material. Cellular element maps indicate that externally scavenged Fe was not a significant fraction of the metal associated with live phytoplankton, but adsorbed or precipitated phases are likely to be important in particulate detrital material. Such abiotic scavenging, along with differential remineralization of cellular nutrients in the water column, results in estimates of cellular metal/nutrient ratios from dissolved concentrations that significantly underestimate the ratios in phytoplankton. These data demonstrate the response of phytoplankton to the unique metal inputs to the North Atlantic Ocean.