ALBERT

Description: Heme b is an iron-containing co-factor in hemoproteins. Heme b concentrations are low (〈1 pmol L-1) in iron limited phytoplankton in cultures and in the field. Here, we determined heme b in marine particulate material (〉0.7 μm) from the North Atlantic Ocean (GEOVIDE cruise – GEOTRACES section GA01), which spanned several biogeochemical regimes. We examined the relationship between heme b abundance and the microbial community composition, and its utility for mapping iron limited phytoplankton. Heme b concentrations ranged from 0.16 to 5.1 pmol L-1 (median = 2.0 pmol L-1, n = 62) in the surface mixed layer (SML) along the cruise track, driven mainly by variability in biomass. However, in the Irminger Basin, the lowest heme b levels (SML: median = 0.53 pmol L-1, n = 12) were observed, whilst the biomass was highest (particulate organic carbon, median = 14.2 μmol L-1, n = 25; chlorophyll a: median = 2.0 nmol L-1, n = 23) pointing to regulatory mechanisms of the heme b pool for growth conservation. Dissolved iron (DFe) was not depleted (SML: median = 0.38 nmol L-1, n = 11) in the Irminger Basin, but large diatoms (Rhizosolenia sp.) dominated. Hence, heme b depletion and regulation is likely to occur during bloom progression when phytoplankton class-dependent absolute iron requirements exceed the available ambient concentration of DFe. Furthermore, high heme b concentrations found in the Iceland Basin and Labrador Sea (median = 3.4 pmol L-1, n = 20), despite having similar DFe concentrations to the Irminger Basin, were attributed to an earlier growth phase of the extant phytoplankton populations. Thus, heme b provides a snapshot of the cellular activity in situ and could both be used as indicator of iron limitation and contribute to understanding phytoplankton adaptation mechanisms to changing iron supplies.

Description: Trace metal micronutrients are integral to the functioning of marine ecosystems and the export of particulate carbon to the deep ocean. Although much progress has been made in mapping the distributions of metal micronutrients throughout the ocean over the last 30 years, there remain information gaps, most notable during seasonal transitions and in remote regions. The next challenge is to develop in situ sensing technologies necessary to capture the spatial and temporal variabilities of micronutrients characterized with short residence times, highly variable source terms, and sub-nanomolar concentrations in open ocean settings. Such an effort will allow investigation of the biogeochemical processes at the necessary resolution to constrain fluxes, residence times, and the biological and chemical responses to varying metal inputs in a changing ocean. Here, we discuss the current state of the art and analytical challenges associated with metal micronutrient determinations and highlight existing and emerging technologies, namely in situ chemical analyzers, electrochemical sensors, passive preconcentration samplers, and autonomous trace metal clean samplers, which could form the basis of autonomous observing systems for trace metals within the next decade. We suggest that several existing assets can already be deployed in regions of enhanced metal concentrations and argue that, upon further development, a combination of wet chemical analyzers with electrochemical sensors may provide the best compromise between analytical precision, detection limits, metal speciation, and longevity for autonomous open ocean determinations. To meet this goal, resources must be invested to: (1) improve the sensitivity of existing sensors including the development of novel chemical assays; (2) reduce sensor size and power requirements; (3) develop an open-source “Do-It-Yourself” infrastructure to facilitate sensor development, uptake by end-users and foster a mechanism by which scientists can rapidly adapt commercially available technologies to in situ applications; and (4) develop a community-led standardized protocol to demonstrate the endurance and comparability of in situ sensor data with established techniques. Such a vision will be best served through ongoing collaborations between trace metal geochemists, analytical chemists, the engineering community, and commercial partners, which will accelerate the delivery of new technologies for in situ metal sensing in the decade following OceanObs’19.