(Table 1) Nutrient concentrations and carbon isotopes of sea ice segments and brine sampled during Nathaniel B. Palmer cruises NBP98-07 and NBP06-08, Ross Sea

We examined controls on the carbon isotopic composition of sea ice brines and organic matter during cruises to the Ross Sea, Antarctica in November/December 1998 and November/December 2006. Brine samples were analyzed for salinity, nutrients, total dissolved inorganic carbon (sum CO2), and the 13C/12C ratio of Sum CO2 (d13C(sum CO2)). Particulate organic matter from sea ice cores was analyzed for percent particulate organic carbon (POC), percent total particulate nitrogen (TPN), and stable carbon isotopic composition (d13C(POC)). Sum CO2 in sea ice brines ranged from 1368 to 7149 µmol/kg, equivalent to 1483 to 2519 µmol/kg when normalized to 34.5 psu salinity (s sum CO2), the average salinity of Ross Sea surface waters. Sea ice primary producers removed up to 34% of the available sum CO2, an amount much higher than the maximum removal observed in sea ice free water. Carbonate precipitation and CO2 degassing may reduce s sum CO2 by a similar amount (e.g., 30%) in the most hypersaline sea ice environments, although brine volumes are low in very cold ice that supports these brines. Brine d13C(sum CO2) ranged from -2.6 to +8.0 per mil while d13C(POC) ranged from -30.5 to -9.2 per mil. Isotopic enrichment of the sum CO2 pool via net community production accounts for some but not all carbon isotopic enrichment of sea ice POC. Comparisons of s sum CO2, d13C(sum CO2), and d13C(POC) within sea ice suggest that epsilon p (the net photosynthetic fractionation factor) for sea ice algae is ~8 per mil smaller than the epsilon p observed for phytoplankton in open water regions of the Ross Sea. These results have implications for modeling of carbon uptake and transformation in the ice-covered ocean and for reconstruction of past sea ice extent based on stable isotopic composition of organic matter in sediment cores.

Particulate organic carbon flux of moored sediment traps

We report primary production of organic matter and organic carbon removal from three subtropical open ocean time-series stations, two located in the Atlantic and one in the Pacific, to quantify the biological components of the oceanic carbon pump. We find that within subtropical gyres, export production varies considerably despite similar phytoplankton biomass and productivity. We provide evidence that the removal of organic carbon is linked to differences in nutrient input into the mixed layer, both from eddy induced mixing and dinitrogen fixation. These findings contribute to our knowledge of the spatial heterogeneity of the subtropical oceans, which make up more than 50% of all ocean area and are thought to spread in the course of CO2- induced global warming.

Impact of CO2 enrichment on organic matter dynamics during nutrient induced coastal phytoplankton blooms

A mesocosm experiment was conducted to investigate the impact of rising fCO2 on the build-up and decline of organic matter during coastal phytoplankton blooms. Five mesocosms (~38 m³ each) were deployed in the Baltic Sea during spring (2009) and enriched with CO2 to yield a gradient of 355-862 µatm. Mesocosms were nutrient fertilized initially to induce phytoplankton bloom development. Changes in particulate and dissolved organic matter concentrations, including dissolved high-molecular weight (>1 kDa) combined carbohydrates, dissolved free and combined amino acids as well as transparent exopolymer particles (TEP), were monitored over 21 days together with bacterial abundance, and hydrolytic extracellular enzyme activities. Overall, organic matter followed well-known bloom dynamics in all CO2 treatments alike. At high fCO2, higher dPOC:dPON during bloom rise, and higher TEP concentrations during bloom peak, suggested preferential accumulation of carbon-rich components. TEP concentration at bloom peak was significantly related to subsequent sedimentation of particulate organic matter. Bacterial abundance increased during the bloom and was highest at high fCO2. We conclude that increasing fCO2 supports production and exudation of carbon-rich components, enhancing particle aggregation and settling, but also providing substrate and attachment sites for bacteria. More labile organic carbon and higher bacterial abundance can increase rates of oxygen consumption and may intensify the already high risk of oxygen depletion in coastal seas in the future.

Impact of elevated levels of CO2 on animal mediated ecosystem function: The modification of sediment nutrient fluxes by burrowing urchins

A mesocosm experiment was conducted to quantify the relationships between the presence and body size of two burrowing heart urchins (Brissopsis lyrifera and Echinocardium cordatum) and rates of sediment nutrient flux. Furthermore, the impact of seawater acidification on these relationships was determined during this 40-day exposure experiment. Using carbon dioxide (CO2) gas, seawater was acidified to pHNBS 7.6, 7.2 or 6.8. Control treatments were maintained in natural seawater (pH = 8.0). Under normocapnic conditions, burrowing urchins were seen to reduce the sediment uptake of nitrite or nitrate whilst enhancing the release of silicate and phosphate. In acidified (hypercapnic) treatments, the biological control of biogeochemical cycles by urchins was significantly affected, probably through the combined impacts of high CO2 on nitrifying bacteria, benthic algae and urchin behaviour. This study highlights the importance of considering biological interactions when predicting the consequences of seawater acidification on ecosystem function.

Increased feeding and nutrient excretion of adult antarctic krill, Euphausia superba, exposed to enhanced carbon dioxide (CO2)

Ocean acidification has a wide-ranging potential for impacting the physiology and metabolism of zooplankton. Sufficiently elevated CO2 concentrations can alter internal acid-base balance, compromising homeostatic regulation and disrupting internal systems ranging from oxygen transport to ion balance. We assessed feeding and nutrient excretion rates in natural populations of the keystone species Euphausia superba (Antarctic krill) by conducting a CO2 perturbation experiment at ambient and elevated atmospheric CO2 levels in January 2011 along the West Antarctic Peninsula (WAP). Under elevated CO2 conditions (~672 ppm), ingestion rates of krill averaged 78 µg C/individual/d and were 3.5 times higher than krill ingestion rates at ambient, present day CO2 concentrations. Additionally, rates of ammonium, phosphate, and dissolved organic carbon (DOC) excretion by krill were 1.5, 1.5, and 3.0 times higher, respectively, in the high CO2 treatment than at ambient CO2 concentrations. Excretion of urea, however, was ~17% lower in the high CO2 treatment, suggesting differences in catabolic processes of krill between treatments. Activities of key metabolic enzymes, malate dehydrogenase (MDH) and lactate dehydrogenase (LDH), were consistently higher in the high CO2 treatment. The observed shifts in metabolism are consistent with increased physiological costs associated with regulating internal acid-base equilibria. This represents an additional stress that may hamper growth and reproduction, which would negatively impact an already declining krill population along the WAP.

On the Southern Ocean CO2 uptake and the role of the biological carbon pump in the 21st century, links to supplementary material

We use a suite of eight ocean biogeochemical/ecological general circulation models from the MAREMIP and CMIP5 archives to explore the relative roles of changes in winds (positive trend of Southern Annular Mode, SAM) and in warming- and freshening-driven trends of upper ocean stratification in altering export production and CO2 uptake in the Southern Ocean at the end of the 21st century. The investigated models simulate a broad range of responses to climate change, with no agreement ona dominance of either the SAM or the warming signal south of 44° S. In the southernmost zone, i.e., south of 58° S, they concur on an increase of biological export production, while between 44 and 58° S the models lack consensus on the sign of change in export. Yet, in both regions, the models show an enhanced CO2 uptake during spring and summer. This is due to a larger CO 2 (aq) drawdown by the same amount of summer export production at a higher Revelle factor at the end of the 21st century. This strongly increases the importance of the biological carbon pump in the entire Southern Ocean. In the temperate zone, between 30 and 44° S all models show a predominance of the warming signal and a nutrient-driven reduction of export production. As a consequence, the share of the regions south of 44° S to the total uptake of the Southern Ocean south of 30° S is projected to increase at the end of the 21st century from 47 to 66% with a commensurable decrease to the north. Despite this major reorganization of the meridional distribution of the major regions of uptake, the total uptake increases largely in line with the rising atmospheric CO2. Simulations with the MITgcm-REcoM2 model show that this is mostly driven by the strong increase of atmospheric CO2, with the climate-driven changes of natural CO2 exchange offsetting that trend only to a limited degree (~10%) and with negligible impact of climate effects on anthropogenic CO2 uptake when integrated over a full annual cycle south of 30° S.

Data compilation on the biological response to ocean acidification: environmental and experimental context of data sets and related literature

The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

(Table 1) Cadmium and nutrient concentration of surface waters sampled during POLARSTERN cruise ANT-XXIV/III

The High Nutrient Low Chlorophyll (HNLC) Southern Ocean plays a key role in regulating the biological pump and the global carbon cycle. Here we examine the efficacy of stable cadmium (Cd) isotope fractionation for detecting differences in biological productivity between regions. Our results show strong meridional Cd isotope and concentration gradients modulated by the Antarctic Fronts, with a clear biogeochemical divide located near 56°S. The coincidence of the Cd isotope divide with the Southern Boundary of the Antarctic Circumpolar Current (ACC),together with evidence for northward advection of the Cd signal in the ACC, demonstrate that Cd isotopes trace surface ocean circulation regimes. The relationships between Cd isotope ratios and concentrations display two negative correlations, separating the ACC and Weddell Gyre into two distinct Cd isoscapes. These arrays are consistent with Rayleigh fractionation and imply a doubling of the isotope effect due to biological consumption of Cd during water transport from the Weddell Gyre into the ACC. The increase in magnitude of Cd isotope fractionation can be accounted for by differences in the phytoplankton biomass, community composition, and their physiological uptake mechanisms in the Weddell Gyre and ACC, thus linking Cd isotope fractionation to primary production and the global carbon cycle.