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An important factor for predicting the effect of increased CO2 on future acidification of the ocean is a proper understanding of the interactions controlling production and dissolution of calcium carbonate minerals (CaCO3). The production and dissolution of CaCO3 in the ocean can be assessed over large spatial scales by measuring seawater calcium concentrations and total alkalinity (AT), yet past studies suggest that there could be large discrepancies between calcium and AT-based balances of the CaCO3 cycle in the North Pacific and Indian Oceans. Here, we analyse water column samples collected along transects in the North Pacific, Southern Ocean, tropical Indian Ocean and Red Sea for their concentrations of calcium, nutrients, and AT. We find that there is an excess calcium over AT anomaly in the top 1000 m of the tropical Indian Ocean water-column. The source of this anomaly is the dissolution of subsurface gypsum deposits in the Red Sea. We find no evidence for calcium-over-AT anomalies in the North Pacific, in contrast to previous studies. Our results show that, in most cases, calcium and AT data agree well and can be used to reconstruct the marine CaCO3 cycle.

Knowledge of Southern Ocean carbon cycling is limited by a paucity of phytoplankton primary productivity (PP) and spectral absorption data in this globally-important region. We measured 13C-based PP in the Indian sector of Southern Ocean (ISSO) during austral summer 2017, examining its link with spectral absorption coefficients and phytoplankton size structure derived from an absorption-based global model. Phytoplankton productivity was assessed at both coastal (60°S-69°S) and frontal stations (40°S-60°S), characterized by silicate- replete and -deplete water masses, respectively (indicated by measured nutrient ratios) to capture a range of phytoplankton growth conditions. Bio-optical relationships were used as indicators of phytoplankton community size structure and to assess the extent of cellular pigment packaging - a phenomenon reported previously for phytoplankton in this region. Blue-Red (B/R) ratios of phytoplankton absorption (aph) spectra indicated that microphytoplankton (more prone to “package effects”) were the dominant size class at most sites sampled. Overall, PP was better explained by aph (R2 = 0.85) than total chlorophyll-a (R2 = 0.64) in surface waters. The a*ph (675)-chlorophyll-a relationship explained package effects more effectively in frontal regions (R2 = 0.63) than stations further south (R2 = 0.30). The global absorption-based model captured smaller (pico, nano) phytoplankton size classes but failed to identify larger microphytoplankton, underscoring the need for region-specific algorithm modifications. Our findings improve existing understanding of spatio-temporal trends in PP and bio-optical variability within the Indian Sector of the Southern Ocean (ISSO) – knowledge that is essential to improve capacity to retrieve PP from satellite-based models in this region.

An important factor for predicting the effect of increased CO2 on future acidification of the ocean is a proper understanding of the interactions controlling production and dissolution of calcium carbonate minerals (CaCO3). The production and dissolution of CaCO3 in the ocean can be assessed over large spatial scales by measuring seawater calcium concentrations and total alkalinity (AT), yet past studies suggest that there could be large discrepancies between calcium and AT-based balances of the CaCO3 cycle in the North Pacific and Indian Oceans. Here, we analyse water column samples collected along transects in the North Pacific, Southern Ocean, tropical Indian Ocean and Red Sea for their concentrations of calcium, nutrients, and AT. We find that there is an excess calcium over AT anomaly in the top 1000 m of the tropical Indian Ocean water-column. The source of this anomaly is the dissolution of subsurface gypsum deposits in the Red Sea. We find no evidence for calcium-over-AT anomalies in the North Pacific, in contrast to previous studies. Our results show that, in most cases, calcium and AT data agree well and can be used to reconstruct the marine CaCO3 cycle.

Iodine chemistry has noteworthy impacts on the oxidising capacity of the marine boundary layer (MBL) through the depletion of ozone (O3) and changes to HOx (OH=HO2) and NOx (NO=NO2) ratios. Hitherto, studies have shown that the reaction of atmospheric O3 with surface seawater iodide (I-) contributes to the flux of iodine species into the MBL mainly as hypoiodous acid (HOI) and molecular iodine (I2). Here, we present the first concomitant observations of iodine oxide (IO), O3 in the gas phase, and sea surface iodide concentrations. The results from three field campaigns in the Indian Ocean and the Southern Ocean during 2015 2017 are used to compute reactive iodine fluxes in the MBL. Observations of atmospheric IO by multi-axis differential optical absorption spectroscopy (MAX-DOAS) show active iodine chemistry in this environment, with IO values up to 1 pptv (parts per trillion by volume) below latitudes of 40° S. In order to compute the sea-to-air iodine flux supporting this chemistry, we compare previously established global sea surface iodide parameterisations with new regionspecific parameterisations based on the new iodide observations. This study shows that regional changes in salinity and sea surface temperature play a role in surface seawater iodide estimation. Sea air fluxes of HOI and I2, calculated from the atmospheric ozone and seawater iodide concentrations (observed and predicted), failed to adequately explain the detected IO in this region. This discrepancy highlights the need to measure direct fluxes of inorganic and organic iodine species in the marine environment. Amongst other potential drivers of reactive iodine chemistry investigated, chlorophyll a showed a significant correlation with atmospheric IO (R D 0:7 above the 99 % significance level) to the north of the polar front. This correlation might be indicative of a biogenic control on iodine sources in this region.

Observations of iodine oxide (IO) were made in the Indian Ocean and the Southern Ocean marine boundary layer (MBL) during the 8th Indian Southern Ocean Expedition. IO was observed almost ubiquitously in the open ocean with larger mixing ratios south of the Polar Front (PF). Contrary to previous reports, IO was not positively correlated to sea surface temperature (SST)/salinity, or negatively to chlorophyll a. Over the whole expedition, SST showed a weak negative correlation with respect to IO while chl a was positively correlated. North of the PF, chl a showed a strong positive correlation with IO. The computed HOI and I fluxes do not show any significant correlation with atmospheric IO. Simulations with the global CAM-Chem model show a reasonably good agreement with observations north of the PF but the model fails to reproduce the elevated IO south of the PF indicating that the current emission parametrizations are not sufficient to explain iodine chemistry in the Southern Indian Ocean.