The seasonal sea-ice zone in the glacial Southern Ocean as a carbon sink, supplementary datasets

Reduced surface-deep ocean exchange and enhanced nutrient consumption by phytoplankton in the Southern Ocean have been linked to lower glacial atmospheric CO2. However, identification of the biological and physical conditions involved and the related processes remains incomplete. Here we specify Southern Ocean surface-subsurface contrasts using a new tool, the combined oxygen and silicon isotope measurement of diatom and radiolarian opal, in combination with numerical simulations. Our data do not indicate a permanent glacial halocline related to melt water from icebergs. Corroborated by numerical simulations, we find that glacial surface stratification was variable and linked to seasonal sea-ice changes. During glacial spring-summer, the mixed layer was relatively shallow, while deeper mixing occurred during fall-winter, allowing for surface-ocean refueling with nutrients from the deep reservoir, which was potentially richer in nutrients than today. This generated specific carbon and opal export regimes turning the glacial seasonal sea-ice zone into a carbon sink.

Stable carbon isotope ratios of carbon dioxide from EDC and Berkner Island ice cores for 40-50 ka BP

The stable carbon isotopic signature of carbon dioxide (d13CO2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric d13CO2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble-clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO2 concentration values, presenting a worst-case test for d13CO2 reconstructions. Even so, the reconstructed atmospheric d13CO2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16 per mil magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of d13CO2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs.

Continuous measurement of carbon dioxid partial pressure in seawater in the region of the Iceland-Faroe Ridge (Table 1)

During the 14th expedition of the research vessel "Meteor" from the 2nd of July to the 7th of August 1968 continously recording instruments for measuring the CO2 partial pressure of seawater and atmospheric CO2 were developped by the Meteorological Institute, University of Frankfurt/M. During the Faroer expedition instrumental constants, such as relative and absolute accuracy, inertia and solvent power were tested. The performance of discontinous analyses of water samples was adopted to shipboard conditiones and correction factors depending on water volume, depth of sampling and water temperature were measured. After having computed average values of the continous records (atmosp. CO2 content, CO2 partial pressure, water temperature) geographical distribution, diurnal variation and dependence of diurnal averages were tested. At four different locations CO2 partial pressure was measured in various depths. During the voyage from the Faroer islands to Helgoland the measured concentrations of atmospheric CO2 content and CO2 partial pressure were tested with respect to a correlation of the geographical latitude.

Boron isotope and B/Ca ratios of planktonic foraminifera

Here a new analytical methodology is described for measuring the isotopic composition of boron in foraminifera using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). This new approach is fast (~10 samples analysed in duplicate per analytical session) and accurate (to better than 0.25 per mil at 95% confidence) with acceptable sample size requirements (1-3 mg of carbonate). A core top calibration of several common planktic and two benthic species from geographically widespread localities shows a very close agreement between the isotopic composition measured by MC-ICPMS and the isotopic composition of B(OH)-4 in seawater (as predicted using the recently measured isotopic equilibrium factor of 1.0272) at the depth of habitat. A down core and core top investigation of boron concentration (B/Ca ratio) shows that the partition coefficient is influenced by [CO2-3] complicating the application of this proxy. Nevertheless, it is demonstrated that these two proxies can be used to fully constrain the carbonate system of surface water in the Caribbean Sea (ODP Site 999A) over the last 130 kyr. This reconstruction shows that during much of the Holocene and the last interglacial period surface water at Site 999A was in equilibrium with the atmosphere with respect to CO2. During the intervening colder periods although the surface water pCO2 was lower than the Holocene, it was a minor to significant source of CO2 to the atmosphere possibly due to either an expansion of the eastern equatorial Atlantic upwelling zone, or a more local expansion of coastal upwelling in the southern Caribbean. Such reorganisation of the oceanic carbonate system in favour of a larger source of CO2 to the atmosphere from the equatorial ocean may require mechanisms responsible for lowering atmospheric CO2 during glacial periods to be more efficient than previously supposed.

Seawater carbonate chemistry and biological processes of zooplankton Amphiascoides atopus and Schizopera knabeni during experiments, 2010

Increased atmospheric CO2 concentrations are causing greater dissolution of CO2 into seawater, and are ultimately responsible for today's ongoing ocean acidification. We manipulated seawater acidity by addition of HCl and by increasing CO2 concentration and observed that two coastal harpacticoid copepods, Amphiascoides atopus and Schizopera knabeni were both more sensitive to increased acidity when generated by CO2. The present study indicates that copepods living in environments more prone to hypercapnia, such as mudflats where S. knabeni lives, may be less sensitive to future acidification. Ocean acidification is also expected to alter the toxicity of waterborne metals by influencing their speciation in seawater. CO2 enrichment did not affect the free-ion concentration of Cd but did increase the free-ion concentration of Cu. Antagonistic toxicities were observed between CO2 with Cd, Cu and Cu free-ion in A. atopus. This interaction could be due to a competition for H+ and metals for binding sites.

Seawater carbonate chemistry and calcification rate of eastern oyster Crassostrea virginica, 2011

Anthropogenic carbon dioxide (CO2) emissions reduce pH of marine waters due to the absorption of atmospheric CO2 and formation of carbonic acid. Estuarine waters are more susceptible to acidification because they are subject to multiple acid sources and are less buffered than marine waters. Consequently, estuarine shell forming species may experience acidification sooner than marine species although the tolerance of estuarine calcifiers to pH changes is poorly understood. We analyzed 23 years of Chesapeake Bay water quality monitoring data and found that daytime average pH significantly decreased across polyhaline waters although pH has not significantly changed across mesohaline waters. In some tributaries that once supported large oyster populations, pH is increasing. Current average conditions within some tributaries however correspond to values that we found in laboratory studies to reduce oyster biocalcification rates or resulted in net shell dissolution. Calcification rates of juvenile eastern oysters, Crassostrea virginica, were measured in laboratory studies in a three-way factorial design with 3 pH levels, two salinities, and two temperatures. Biocalcification declined significantly with a reduction of ~0.5 pH units and higher temperature and salinity mitigated the decrease in biocalcification.

Seawater carbonate chemistry, length, mass and otholith development of spiny damselfish Acanthochromis polyacanthus during experiments, 2011

Determining which marine species are sensitive to elevated CO2 and reduced pH, and which species tolerate these changes, is critical for predicting the impacts of ocean acidification on marine biodiversity and ecosystem function. Although adult fish are thought to be relatively tolerant to higher levels of environmental CO2, very little is known about the sensitivity of juvenile stages, which are usually much more vulnerable to environmental change. We tested the effects of elevated environmental CO2 on the growth, survival, skeletal development and otolith (ear bone) calcification of a common coral reef fish, the spiny damselfish Acanthochromis polyacanthus. Newly hatched juveniles were reared for 3 wk at 4 different levels of PCO2(seawater) spanning concentrations already experienced in near-reef waters (450 µatm CO2) to those predicted to occur over the next 50 to 100 yr in the IPCC A2 emission scenario (600, 725, 850 µatm CO2). Elevated PCO2 had no effect on juvenile growth or survival. Similarly, there was no consistent variation in the size of 29 different skeletal elements that could be attributed to CO2 treatments. Finally, otolith size, shape and symmetry (between left and right side of the body) were not affected by exposure to elevated PCO2, despite the fact that otoliths are composed of aragonite. This is the first comprehensive assessment of the likely effects of ocean acidification on the early life history development of a marine fish. Our results suggest that juvenile A. polyacanthus are tolerant of moderate increases in environmental CO2 and that further acidification of the ocean will not, in isolation, have a significant effect on the early life history development of this species, and perhaps other tropical reef fishes

Seawater carbonate chemistry and processes during experiments with benthic foraminifera Ammonia tepida

Evidence of increasing concentrations of dissolved carbon dioxide, especially in the surface ocean and its associated impacts on calcifying organisms, is accumulating. Among these organisms, benthic and planktonic foraminifera are responsible for a large amount of the globally precipitated calcium carbonate. Hence, their response to an acidifying ocean may have important consequences for future inorganic carbon cycling. To assess the sensitivity of benthic foraminifera to changing carbon dioxide levels and subsequent alteration in seawater carbonate chemistry, we cultured specimens of the shallow water species Ammonia tepida at two concentrations of atmospheric CO2 (230 and 1900 ppmv) and two temperatures (10 °C and 15 °C). Shell weights and elemental compositions were determined. Impact of high and low pCO2 on elemental composition are compared with results of a previous experiment were specimens were grown under ambient conditions (380 ppvm, no shell weight measurements of specimen grown under ambient conditions are, however, available). Results indicate that shell weights decrease with decreasing [CO3], although calcification was observed even in the presence of calcium carbonate under-saturation, and also decrease with increasing temperature. Thus both warming and ocean acidification may act to decrease shell weights in the future. Changes in [CO3] or total dissolved inorganic carbon do not affect the Mg distribution coefficient. On the contrary, Sr incorporation is enhanced under increasing [CO3]. Implications of these results for the paleoceanographic application of foraminifera are discussed.

Palynological counts (dinoflagellate cysts) and foraminiferal geochemistry (d18O, d18C, Mg/Ca) of the Pliocene-Pleistocene transition in the North Atlantic

The position of the North Atlantic Current (NAC) during the intensification of Northern Hemisphere glaciation (iNHG) has been evaluated using dinoflagellate cyst assemblages and foraminiferal geochemistry from a ~260 kyr interval straddling the base of the Quaternary System from two sites: eastern North Atlantic Deep Sea Drilling Project Site 610 in the path of the present NAC and central North Atlantic Integrated Ocean Drilling Program Site U1313 in the subtropical gyre. Stable isotope and foraminiferal Mg/Ca analyses confirm cooling near the marine isotope stage (MIS) G7-G6 transition (2.74 Ma). However, a continued dominance of the dinoflagellate cyst Operculodinium centrocarpum sensu Wall and Dale (1966) indicates an active NAC in the eastern North Atlantic for a further 140 kyr. At MIS 104 (~2.60 Ma), a profound dinoflagellate cyst assemblage turnover indicates NAC shutdown in the eastern North Atlantic, implying elevated atmospheric pressure over the Arctic and a resulting shift in the westerlies that would have driven the NAC. These findings challenge recent suggestions that there was no significant southward shift of the NAC or the Arctic Front during iNHG, and reveal a fundamental climatic reorganization near the base of the Quaternary.

Chemical composition and phytoplankton characteristics of water samples obtained during POLARSTERN cruise ANT-XXIV/3

The fixation of dissolved inorganic carbon (DIC) by marine phytoplankton provides an important feedback mechanism on concentrations of CO2 in the atmosphere. As a consequence it is important to determine whether oceanic primary productivity is susceptible to changing atmospheric CO2 levels Among numerous other factors, the acquisition of DIC by microalgae particularly in the polar seas is projected to have a significant effect on future phytoplanktonic production and hence atmospheric CO2 concentrations. Using the isotopic disequilibrium technique the contribution of different carbon species (CO2 and bicarbonate) to the overall DIC uptake and the extent to which external Carbonic Anhydrase (eCA) plays a role in facilitating DIC uptake was estimated. Simultaneous uptake of CO2 and HCO3- was observed in all cases, but the proportions in which different DIC species contributed to carbon assimilation varied considerably between stations. Bicarbonate as well as CO2 could be the major DIC source for local phytoplankton assemblages. There was a positive correlation between the contribution of CO2 to total DIC uptake and ambient concentration of CO2 in seawater suggesting that Southern Ocean microalgae could increase the proportion of CO2 uptake under future high atmospheric CO2 levels. Results will be discussed in view of metabolic costs related to DIC acquisition of Southern Ocean phytoplankton.

Calcification repsonse of m,arione bivalves to changed carbonate chemistry

Bivalve calcification, particularly of the early larval stages, is highly sensitive to the change in ocean carbonate chemistry resulting from atmospheric CO2 uptake. Earlier studies suggested that declining seawater [CO32-] and thereby lowered carbonate saturation affect shell production. However, disturbances of physiological processes such as acid-base regulation by adverse seawater pCO2 and pH can affect calcification in a secondary fashion. In order to determine the exact carbonate system component by which growth and calcification are affected it is necessary to utilize more complex carbonate chemistry manipulations. As single factors, pCO2 had no effects and [HCO3-] and pH had only limited effects on shell growth, while lowered [CO32-] strongly impacted calcification. Dissolved inorganic carbon (CT) limiting conditions led to strong reductions in calcification, despite high [CO32-], indicating that [HCO3-] rather than [CO32-] is the inorganic carbon source utilized for calcification by mytilid mussels. However, as the ratio [HCO3-] / [H+] is linearly correlated with [CO32-] it is not possible to differentiate between these under natural seawater conditions. An equivalent of about 80 µmol kg-1 [CO32-] is required to saturate inorganic carbon supply for calcification in bivalves. Below this threshold biomineralization rates rapidly decline. A comparison of literature data available for larvae and juvenile mussels and oysters originating from habitats differing substantially with respect to prevailing carbonate chemistry conditions revealed similar response curves. This suggests that the mechanisms which determine sensitivity of calcification in this group are highly conserved. The higher sensitivity of larval calcification seems to primarily result from the much higher relative calcification rates in early life stages. In order to reveal and understand the mechanisms that limit or facilitate adaptation to future ocean acidification, it is necessary to better understand the physiological processes and their underlying genetics that govern inorganic carbon assimilation for calcification.

(Table S2) The reconstructed sea surface temperature (SST) over the eastern equatorial Pacific

Abundant hydroclimatic evidence from western Amazonia and the adjacent Andes documents wet conditions during Heinrich Stadial 1 (HS1, 18-15 ka), a cold period in the high latitudes of the North Atlantic. This precipitation anomaly was attributed to a strengthening of the South American summer monsoon due to a change in the Atlantic interhemispheric sea surface temperature (SST) gradient. However, the physical viability of this mechanism has never been rigorously tested. We address this issue by combining a thorough compilation of tropical South American paleorecords and a set of atmosphere model sensitivity experiments. Our results show that the Atlantic SST variations alone, although leading to dry conditions in northern South America and wet conditions in northeastern Brazil, cannot produce increased precipitation over western Amazonia and the adjacent Andes during HS1. Instead, an eastern equatorial Pacific SST increase (i.e., 0.5-1.5 °C), in response to the slowdown of the Atlantic Meridional Overturning Circulation during HS1, is crucial to generate the wet conditions in these regions. The mechanism works via anomalous low sea level pressure over the eastern equatorial Pacific, which promotes a regional easterly low-level wind anomaly and moisture recycling from central Amazonia towards the Andes.

The role of coccolithophore calcification in bioengineering their environment.

Coccolithophorids are enigmatic plankton that produce calcium carbonate coccoliths, which over geological time have buried atmospheric CO2 into limestone, changing both the atmosphere and geology of the Earth. However, the role of coccoliths for the proliferation of these organisms remains unclear; suggestions include roles in anti-predation, enhanced photosynthesis and sun-screening. Here we test the hypothesis that calcification stabilizes the pH of the seawater proximate to the organisms, providing a level of acidification countering the detrimental basification that occurs during net photosynthesis. Such bioengineering provides a more stable pH environment for growth and fits the empirical evidence for changes in rates of calcification under different environmental conditions. Under this scenario, simulations suggest that the optimal production ratio of inorganic to organic particulate C (PIC : POCprod) will be lower (by approx. 20%) with ocean acidification and that overproduction of coccoliths in a future acidified ocean, where pH buffering is weaker, presents a risk to calcifying cells.

The role of coccolithophore calcification in bioengineering their environment.

Coccolithophorids are enigmatic plankton that produce calcium carbonate coccoliths, which over geological time have buried atmospheric CO2 into limestone, changing both the atmosphere and geology of the Earth. However, the role of coccoliths for the proliferation of these organisms remains unclear; suggestions include roles in anti-predation, enhanced photosynthesis and sun-screening. Here we test the hypothesis that calcification stabilizes the pH of the seawater proximate to the organisms, providing a level of acidification countering the detrimental basification that occurs during net photosynthesis. Such bioengineering provides a more stable pH environment for growth and fits the empirical evidence for changes in rates of calcification under different environmental conditions. Under this scenario, simulations suggest that the optimal production ratio of inorganic to organic particulate C (PIC : POCprod) will be lower (by approx. 20%) with ocean acidification and that overproduction of coccoliths in a future acidified ocean, where pH buffering is weaker, presents a risk to calcifying cells.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07