This study assessed changes in the phytoplankton community related to macronutrient and bioactive trace metal distribution in surface waters of the Atlantic sector of the Southern Ocean, between Cape Town and Antarctica along the GEOTRACES GIPY_05 (mainly along prime meridian) transect in summer 2014-2015. Several general community structure features were reaffirmed, such as the restriction of cyanobacteria to the northern Subtropical Zone, while haptophytes, such as Phaeocystis, along with diatoms, dominate the community north of the Polar Front, and diatoms clearly dominate south of the Polar Front. These community structure changes were often linked with macro-and micro-nutrient composition changes. For example, the concentration of diatoms increased southwards with the availability of silica whereas the cyanobacterial contribution in the northern Subtropical Zone appeared to be linked with labile cobalt depletion. However, these links were not consistent along the entire transect, i.e., no individual nutrient, such as silica or iron, was linked to community composition changes across all water masses. Each station showed a rather unique combination of nutrient and community compositions. Our findings also indicated impacts on the phytoplankton community through trace metal distributions that could be related to a deep mixing event at ∼54 • S and to ice melt at ∼65 and 68 • S. The timing of sampling after such trace metal fluxes proved to be an important consideration, particularly where iron appeared to be preferentially depleted to near-limiting concentrations, possibly driving utilization of other metals. The study highlights the importance of considering a suite of trace metals when assessing controls of phytoplankton variability in the open ocean and emphasizes the need for higher resolution trace metal sampling and multi-element incubation studies to further study the complex relationships between phytoplankton and nutrients.
The quantification of dissolved metals in seawater requires pre-treatment before the measurement can be done, posing a risk of contamination, and requiring a time-consuming procedure. Despite the development of automated preconcentration units and sophisticated instruments, the entire process often introduces inaccuracies in quantification, especially for low-metal seawaters. This study presents a robust method for measuring dissolved metals from seawater accurately and precisely using a seaFAST and quadrupole Inductively Coupled Plasma Mass Spectrometer (ICPMS), employed in both offline (2016–2018) and online (2020–2021) setups. The proposed method shows data processing, including the re-calculation of metals after eliminating the instrumental signals caused by polyatomic interferences. Here, we report the blank concentration of Fe below 0.02 nmol kg−1, somewhat lower values than that have been previously reported using high-resolution and triple-quad ICPMS. The method allows for the accurate determination of Cd and Fe concentrations in low-metal seawaters, such as GEOTRACES GSP, using a cost-effective quadrupole ICPMS (Cdconsensus: 2 ± 2 pmol kg−1, Cdmeasured: 0.99 ± 0.35 pmol kg−1; Feconsensus: 0.16 ± 0.05 nmol kg−1, Femeasured: 0.21 ± 0.03 nmol kg−1). Between two setups, online yields marginally lower blank values for metals based on short-term analysis. However, the limit of detection is comparable between the two, supporting optimal instrumental sensitivity of the ICPMS over 4+ years of analysis.
Winter distributions of dissolved cadmium (dCd) and particulate cadmium (pCd) were measured for the first time in the Indian sector of the Southern Ocean thereby contributing a unique spatial and seasonal dataset. Seven depth profiles, between 41°S and 58°S, were collected along the 30°E longitude during the 2017 austral winter to investigate the biogeochemical cycling of cadmium during a period characterized by contrasting upper water column dynamics compared to summer. Our results support an important role for biological uptake during winter months albeit weaker compared to summer. Distinct, biologically driven changes in cadmium cycling across the transect were observed. For example, surface ratios of pCd to phosphorus (P; pCd:P) increased from 0.37 to 1.07 mmol mol–1 between the subtropical zone (STZ) and the Antarctic zone (AAZ) reflecting increased Cd requirements for diatoms at higher latitudes which, in turn, was driven by a complex relationship between the availability of dCd and dissolved iron (dFe), zinc (dZn) and manganese (dMn). Vertical profiles of pCd:P displayed near-surface maxima consistent with (1) P occurring in two phases with different labilities and the lability of Cd being somewhere in-between and (2) increasing dCd to phosphate (PO4; dCd:PO4) ratios with depth at each station. North of the Antarctic Polar Front (APF), a secondary, deeper pCd:P maximum may reflect an advective signal associated with northward subducting Antarctic Intermediate Water (AAIW). The strong southward increase in surface dCd and dCd:PO4, from approximately 10–700 pmol kg–1 and 40–400 μmol mol–1, respectively, reflected the net effect of preferential uptake and regeneration of diatoms with high Cd content and the upwelling of Cd enriched water masses in the AAZ. Furthermore, distinct dCd versus PO4 relationships were observed in each of the intermediate and deep water masses suggesting that dCd and PO4 distributions at depth are largely the result of physical water mass mixing.
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