Description: Harde (2017) proposes an alternative accounting scheme for the modern carbon cycle and concludes that only 4.3% of today's atmospheric CO2 is a result of anthropogenic emissions. As we will show, this alternative scheme is too simple, is based on invalid assumptions, and does not address many of the key processes involved in the global carbon cycle that are important on the timescale of interest. Harde (2017) therefore reaches an incorrect conclusion about the role of anthropogenic CO2 emissions. Harde (2017) tries to explain changes in atmospheric CO2 concentration with a single equation, while the most simple model of the carbon cycle must at minimum contain equations of at least two reservoirs (the atmosphere and the surface ocean), which are solved simultaneously. A single equation is fundamentally at odds with basic theory and observations. In the following we will (i) clarify the difference between CO2 atmospheric residence time and adjustment time, (ii) present recently published information about anthropogenic carbon, (iii) present details about the processes that are missing in Harde (2017), (iv) briefly discuss shortcoming in Harde's generalization to paleo timescales, (v) and comment on deficiencies in some of the literature cited in Harde (2017).

Description: The physical and biological carbon pumps in the different hydrographic and biogeochemical regimes of the Atlantic Sector of the Southern Ocean are controlled by a series of coupled physical, chemical and biological processes and a project named Eddy-Pump was designed to study them. The Eddy Pump field campaign was carried out during RV Polarstern Cruise ANT-XXVIII/3 between January and March 2012. Particular emphasis was laid on the differences which occur along the axis of the Antarctic Circumpolar Current (ACC) with its associated mesoscale eddy field. The study sites were selected in order to represent: 1) the central ACC with its regular separation in different frontal jets, investigated by a meridional transect along 10°E; 2) a large-scale bloom west of the Mid-Atlantic Ridge which lasted several months with conspicuous chlorophyll-poor waters to its immediate east studied by a three-dimensional mesoscale survey centred at 12°40'W; and 3) the Georgia Basin north of the island of South Georgia, which regularly features an extended and dense phytoplankton bloom, was investigated by a mesoscale survey centred at 38°12'W. While Eddy-Pump represents an interdisciplinary project by design, we here focus on describing the variable physical environment within which the different biogeochemical regimes developed. For describing the physical environment we use measurements of temperature, salinity and density, of mixed-layer turbulence parameters, of dynamic heights and horizontal current vectors, and of flow trajectories obtained from surface drifters and submerged floats. This serves as background information for the analyses of biological and chemical processes and of biogeochemical fluxes addressed by other papers in this issue. The Section along 10°E between 44°S and 53°S showed a classical ACC structure with well-known hydrographic fronts, the Subantarctic Front (SAF) at 46.5°S, the Antarctic Polar Front (APF) split in two, at 49.25°S and 50.5°S, and the Southern Polar Front (SPF) at 52.5°S. Each front was associated with strong eastward flows. The West Mid-Atlantic Ridge Survey showed a weak and poorly resolved meander structure between the APF and the SPF. During the first eight days of the survey the oceanographic conditions at the Central Station at 12°40’W remained reasonably constant. However after that, conditions became more variable in the thermocline with conspicuous temperature inversions and interleavings and also a decrease in temperature in the surface layer. At the very end of the period of observation the conditions in the thermocline returned to being similar to those observed during the early part of the period with however the mixed layer temperature raised. The period of enhanced thermohaline variability was accompanied by increased currents . The Georgia Basin Survey showed a very strong zonal jet at its northern edge which connects to a large cyclonic meander that itself joins an anticyclonic eddy in the southeastern quadrant. The water mass contrasts in this survey were stronger than in the West Mid-Atlantic Ridge Survey, but similar to those met along 10°E with the exception that the warm and saline surface water typical of the northern side of the SAF was not covered by the Georgia Basin Survey. Mixed layers found during Eddy-Pump were typically deep, but varied between the three survey areas; the mean depths and standard variations of the mixed layer along the 10°E were 77.2 ± 24.7 m, at the West Mid-Atlantic Ridge 66.7 ± 17.7 m, and in the Georgia Basin 36.8 ± 10.7 m.

Description: Stratospheric ozone depletion and emission of greenhouse gases lead to a trend of the Southern Annular Mode (SAM) towards its high-index polarity. The positive phase of the SAM is characterised by stronger than usual westerly winds that induce changes in the physical carbon transport. Changes in the natural carbon budget of the upper 100 m of the Southern Ocean in response to a positive SAM phase are explored with a coupled ecosystem-general circulation model and regression analysis. Previously overlooked processes that are important for the upper ocean carbon budget during a positive SAM period are identified, namely export production and downward transport of carbon north of the Polar Front (PF) as large as the upwelling in the south. The limiting micronutrient iron is brought into the surface layer by upwelling and stimulates phytoplankton growth and export production, but only in summer. This leads to a drawdown of carbon and less summertime outgassing (or more uptake) of natural CO2. In winter, biological mechanisms are inactive and the surface ocean equilibrates with the atmosphere by releasing CO2. In the annual mean, the upper ocean region south of the PF loses more carbon by additional export production than by the release of CO2 into the atmosphere, highlighting the role of the biological carbon pump in response to a positive SAM event.

Description: Ikaite (CaCO3�6H2O) has recently been discovered in sea ice, providing first direct evidence of CaCO3 precipitation in sea ice. However, the impact of ikaite precipitation on phosphate (PO4) concentration has not been considered so far. Experiments were set up at pH from 8.5 to 10.0, salinities from 0 to 105, temperatures from 24°C to 0°C, and PO4 concentrations from 5 to 50 mmol kg-1 in artificial sea ice brine so as to understand how ikaite precipitation affects the PO4 concentration in sea ice under different conditions. Our results show that PO4 is coprecipitated with ikaite under all experimental conditions. The amount of PO4 removed by ikaite precipitation increases with increasing pH. Changes in salinity (S 〉=35) as well as temperature have little impact on PO4 removal by ikaite precipitation. The initial PO4 concentration affects the PO4 coprecipitation. These findings may shed some light on the observed variability of PO4 concentration in sea ice.

Description: The effects of pH and phosphate on the precipitation of calcium carbonate polymorphs from aqueous solution were investigated. Experiments were carried out at near-freezing temperature and two different pH conditions (pH 13.4 and 9.0). At each pH condition, solutions having different concentrations of CaCl2 and NaHCO3 were mixed to achieve Ca/CO3 ratios of 1:1 and 10:1 at different pumping rates with and without phosphate. Results showed that, at pH 13.4, only ikaite was formed, independent of pumping rate, Ca/CO3 ratio, and phosphate. At pH 9.0, the precipitate was predominantly vaterite in the absence of phosphate and ikaite in the presence of phosphate regardless of the ratio of Ca/CO3. These results indicate that at low temperatures and moderate alkaline conditions (pH 9.0), phosphate can act as a switch between ikaite and vaterite polymorphs. Contrastingly, at higher alkaline conditions (pH 13.4) phosphate is not prerequisite and the high pH in itself is enough to trigger ikaite formation over vaterite.

Description: Ongoing global warming induced by anthropogenic emissions has opened the debate as to whether geoengineering is a 'quick fix' option. Here we analyse the intended and unintended effects of one specific geoengineering approach, which is enhanced weathering via the open ocean dissolution of the silicate-containing mineral olivine. This approach would not only reduce atmospheric CO2 and oppose surface ocean acidification, but would also impact on marine biology. If dissolved in the surface ocean, olivine sequesters 0.28 g carbon per g of olivine dissolved, similar to land-based enhanced weathering. Silicic acid input, a byproduct of the olivine dissolution, alters marine biology because silicate is in certain areas the limiting nutrient for diatoms. As a consequence, our model predicts a shift in phytoplankton species composition towards diatoms, altering the biological carbon pumps. Enhanced olivine dissolution, both on land and in the ocean, therefore needs to be considered as ocean fertilization. From dissolution kinetics we calculate that only olivine particles with a grain size of the order of 1 μm sink slowly enough to enable a nearly complete dissolution. The energy consumption for grinding to this small size might reduce the carbon sequestration efficiency by ~30%.

Description: Chemical weathering is an integral part of both the rock and carbon cycles and is being affected by changes in land use, particularly as a result of agricultural practices such as tilling, mineral fertilization, or liming to adjust soil pH. These human activities have already altered the chemical terrestrial cycles and land-ocean flux of major elements, although the extent remains difficult to quantify. When deployed on a grand scale, Enhanced Weathering (a form of mineral fertilization), the application of finely ground minerals over the land surface, could be used to remove CO2 from the atmosphere. The release of cations during the dissolution of such silicate minerals would convert dissolved CO2 to bicarbonate, increasing the alkalinity and pH of natural waters. Some products of mineral dissolution would precipitate in soils or taken up by ecosystems, but a significant portion would be transported to the coastal zone and the open ocean, where the increase in alkalinity would partially counteract “ocean acidification” associated with the current marked increase in atmospheric CO2. Other elements released during this mineral dissolution, like Si, P or K, could stimulate biological productivity, further helping to remove CO2 from the atmosphere. On land, the terrestrial carbon-pool would likely increase in response to Enhanced Weathering in areas where ecosystem growth rates are currently limited by one of the nutrients that would be released during mineral dissolution. In the ocean, the biological carbon pumps (which export organic matter and CaCO3 to the deep ocean) may be altered by the resulting influx of nutrients and alkalinity to the ocean. This review merges current interdisciplinary knowledge about Enhanced Weathering, the processes involved, and the applicability as well as some of the consequences and risks of applying the method.

Description: Ikaite (CaCO3·6H2O) has only recently been discovered in sea ice, in a study that also provided first direct evidence of CaCO3 precipitation in sea ice. However, little is as yet known about the impact of physico-chemical processes on ikaite precipitation in sea ice. Our study focused on how the changes in pH, salinity, temperature and phosphate (PO4) concentration affect the precipitation of ikaite. Experiments were set up at pH from 8.5 to 10.0, salinities from 0 to 105 (in both artificial seawater (ASW) and NaCl medium), temperatures from 0 to −4 °C andPO4 concentrations from0 to 50 μmol kg−1. The results show that in ASW, calcium carbonate was precipitated as ikaite under all conditions. In the NaCl medium, the precipitates were ikaite in the presence of PO4 and vaterite in the absence of PO4. The onset time (τ) at which ikaite precipitation started, decreased nonlinearly with increasing pH. In ASW, τ increased with salinity. In the NaCl medium, τ first increased with salinity up to salinity 70 and subsequently decreased with a further increase in salinity; it was longer in ASW than in the NaCl medium under the same salinity. τ did not vary with temperature or PO4 concentration. These results indicate that ikaite is very probably the only phase of calcium carbonate formed in sea ice. PO4 is not, as previously postulated, crucial for ikaite formation in sea ice. The change in pH and salinity is the controlling factor for ikaite precipitation in sea ice. Within the ranges investigated in this study, temperature and PO4 concentration do not have a significant impact on ikaite precipitation.