Inorganic carbon and geochemistry measurements from landfast sea ice in Resolute Passage, Nunavut, Canada, as part of the Arctic-ICE project, May - June 2010

We conducted a six-week investigation of the sea ice inorganic carbon system during the winter-spring transition in the Canadian Arctic Archipelago. Samples for the determination of sea ice geochemistry were collected in conjunction with physical and biological parameters as part of the 2010 Arctic-ICE (Arctic - Ice-Covered Ecosystem in a Rapidly Changing Environment) program, a sea ice-based process study in Resolute Passage, Nunavut. The goal of Arctic-ICE was to determine the physical-biological processes controlling the timing of primary production in Arctic landfast sea ice and to better understand the influence of these processes on the drawdown and release of climatically active gases. The field study was conducted from 1 May to 21 June, 2010.

(Table 1) Horizontal and vertical ice flow velocities for seven markers around Vostok Station

Combined geodetic, geophysical and glaciological in situ measurements are interpreted regarding surface height changes over subglacial Lake Vostok and the local mass balance of the ice sheet at Vostok station. Repeated GPS observations spanning 5 years and long-term surface accumulation data show that the height of the lake surface has not changed over the observation period. The application of the mass conservation equation to purely observational data yields an ice mass balance for Vostok station close to equilibrium.

Flow rates, hydraulic conductivities and permeabilities of sediments from ODP Holes 190-1173A and 190-1174B

Understanding the role of fluids in active accretionary prisms requires quantitative knowledge of parameters such as permeability. We report here the results of permeability tests on four samples from Ocean Drilling Program Leg 190 at the Nankai Trough accretionary prism-two from Site 1173 and two from Site 1174. Volcanic ash is present in one of the samples; otherwise, the material is hemipelagic mud. A constant-rate-of-flow technique was used at various effective pressures and rates of flow. The permeability of the four samples ranges between 10**-15 and 10**-18 m**2, with the ash-bearing sample showing the highest values.

Coral-algae metabolism and diurnal changes in the CO2-carbonate system of bulk sea water

Precise measurements were conducted in continuous flow seawater mesocosms located in full sunlight that compared metabolic response of coral, coral-macroalgae and macroalgae systems over a diurnal cycle. Irradiance controlled net photosynthesis (Pnet), which in turn drove net calcification (Gnet), and altered pH. Pnet exerted the dominant control on [CO3]2- and aragonite saturation state (Omega arag) over the diel cycle. Dark calcification rate decreased after sunset, reaching zero near midnight followed by an increasing rate that peaked at 03:00 h. Changes in Omega arag and pH lagged behind Gnet throughout the daily cycle by two or more hours. The flux rate Pnet was the primary driver of calcification. Daytime coral metabolism rapidly removes dissolved inorganic carbon (DIC) from the bulk seawater and photosynthesis provides the energy that drives Gnet while increasing the bulk water pH. These relationships result in a correlation between Gnet and Omega arag, with Omega arag as the dependent variable. High rates of H+ efflux continued for several hours following mid-day peak Gnet suggesting that corals have difficulty in shedding waste protons as described by the Proton Flux Hypothesis. DIC flux (uptake) followed Pnet and Gnet and dropped off rapidly following peak Pnet and peak Gnet indicating that corals can cope more effectively with the problem of limited DIC supply compared to the problem of eliminating H+. Over a 24 h period the plot of total alkalinity (AT) versus DIC as well as the plot of Gnet versus Omega arag revealed a circular hysteresis pattern over the diel cycle in the coral and coral-algae mesocosms, but not the macroalgae mesocosm. Presence of macroalgae did not change Gnet of the corals, but altered the relationship between Omega arag and Gnet. Predictive models of how future global changes will effect coral growth that are based on oceanic Omega arag must include the influence of future localized Pnet on Gnet and changes in rate of reef carbonate dissolution. The correlation between Omega arag and Gnet over the diel cycle is simply the response of the CO2-carbonate system to increased pH as photosynthesis shifts the equilibria and increases the [CO3]2- relative to the other DIC components of [HCO3]- and [CO2]. Therefore Omega arag closely tracked pH as an effect of changes in Pnet, which also drove changes in Gnet. Measurements of DIC flux and H+ flux are far more useful than concentrations in describing coral metabolism dynamics. Coral reefs are systems that exist in constant disequilibrium with the water column.

Seawater carbonate chemistry, mortality and hatching rate, size and mass of Clupea harengus during experiments, 2011

Due to atmospheric accumulation of anthropogenic CO2 the partial pressure of carbon dioxide (pCO2) in surface seawater increases and the pH decreases. This process known as ocean acidification might have severe effects on marine organisms and ecosystems. The present study addresses the effect of ocean acidification on early developmental stages, the most sensitive stages in life history, of the Atlantic herring (Clupea harengus L.). Eggs of the Atlantic herring were fertilized and incubated in artificially acidified seawater (pCO2 1260, 1859, 2626, 2903, 4635 µatm) and a control treatment (pCO2 480 µatm) until the main hatch of herring larvae occurred. The development of the embryos was monitored daily and newly hatched larvae were sampled to analyze their morphometrics, and their condition by measuring the RNA/DNA ratios. Elevated pCO2 neither affected the embryogenesis nor the hatch rate. Furthermore the results showed no linear relationship betweenpCO2 and total length, dry weight, yolk sac area and otolith area of the newly hatched larvae. For pCO2 and RNA/DNA ratio, however, a significant negative linear relationship was found. The RNA concentration at hatching was reduced at higher pCO2 levels, which could lead to a decreased protein biosynthesis. The results indicate that an increased pCO2 can affect the metabolism of herring embryos negatively. Accordingly, further somatic growth of the larvae could be reduced. This can have consequences for the larval fish, since smaller and slow growing individuals have a lower survival potential due to lower feeding success and increased predation mortality. The regulatory mechanisms necessary to compensate for effects of hypercapnia could therefore lead to lower larval survival. Since the recruitment of fish seems to be determined during the early life stages, future research on the factors influencing these stages are of great importance in fisheries science.

Seawater carbonate chemistry and hatching rate, malformation rate, metamorphosis rate and shell growth of the Pacific abalone in a laboratory experiment

The hatching process of the Pacific abalone Haliotis discus hannai was prolonged at a pH of 7.6 and pH 7.3, and the embryonic developmental success was reduced. The hatching rate at pH 7.3 was significantly (10.8%) lower than that of the control (pH 8.2). The malformation rates at pH 7.9 and pH 8.2 were less than 20% but were 53.8% and 77.3% at pH 7.6 and pH 7.3, respectively. When newly hatched larvae were incubated for 48 h at pH 7.3, only 2.7% of the larvae settled, while more than 70% of the larvae completed settlement in the other three pH treatments. However, most 24 h old larvae could complete metamorphosis in all four pH treatments. Overall, a 0.3-unit reduction in water pH will produce no negative effect on the early development of the Pacific abalone, but further reduction in pH to the values predicted for seawater by the end of this century will have strong detrimental effects.

Seawater carbonate chemistry and resource allocation and extracellular acid-base status in the sea urchin Strongylocentrotus droebachiensis during experiments, 2012

Anthropogenic CO2 emission will lead to an increase in seawater pCO2 of up to 80-100 Pa (800-1000 µatm) within this century and to an acidification of the oceans. Green sea urchins (Strongylocentrotus droebachiensis) occurring in Kattegat experience seasonal hypercapnic and hypoxic conditions already today. Thus, anthropogenic CO2 emissions will add up to existing values and will lead to even higher pCO2 values >200 Pa (>2000 µatm). To estimate the green sea urchins' potential to acclimate to acidified seawater, we calculated an energy budget and determined the extracellular acid base status of adult S. droebachiensis exposed to moderately (102 to 145 Pa, 1007 to 1431 µatm) and highly (284 to 385 Pa, 2800 to 3800 µatm) elevated seawater pCO2 for 10 and 45 days. A 45 - day exposure to elevated pCO2 resulted in a shift in energy budgets, leading to reduced somatic and reproductive growth. Metabolic rates were not significantly affected, but ammonium excretion increased in response to elevated pCO2. This led to decreased O:N ratios. These findings suggest that protein metabolism is possibly enhanced under elevated pCO2 in order to support ion homeostasis by increasing net acid extrusion. The perivisceral coelomic fluid acid-base status revealed that S. droebachiensis is able to fully (intermediate pCO2) or partially (high pCO2) compensate extracellular pH (pHe) changes by accumulation of bicarbonate (maximum increases 2.5 mM), albeit at a slower rate than typically observed in other taxa (10 day duration for full pHe compensation). At intermediate pCO2, sea urchins were able to maintain fully compensated pHe for 45 days. Sea urchins from the higher pCO2 treatment could be divided into two groups following medium-term acclimation: one group of experimental animals (29%) contained remnants of food in their digestive system and maintained partially compensated pHe (+2.3 mM HCO3), while the other group (71%) exhibited an empty digestive system and a severe metabolic acidosis (-0.5 pH units, -2.4 mM HCO3). There was no difference in mortality between the three pCO2 treatments. The results of this study suggest that S. droebachiensis occurring in the Kattegat might be pre-adapted to hypercapnia due to natural variability in pCO2 in its habitat. We show for the first time that some echinoderm species can actively compensate extracellular pH. Seawater pCO2 values of >200 Pa, which will occur in the Kattegat within this century during seasonal hypoxic events, can possibly only be endured for a short time period of a few weeks. Increases in anthropogenic CO2 emissions and leakages from potential sub-seabed CO2 storage (CCS) sites thus impose a threat to the ecologically and economically important species S. droebachiensis.

Seawater carbonate chemistry, fertilization and early development of the coral eating crown-of-thorns starfish, Acanthaster planci in a laboratory experiment

Outbreaks of crown-of-thorns starfish (COTS), Acanthaster planci, contribute to major declines of coral reef ecosystems throughout the Indo-Pacific. As the oceans warm and decrease in pH due to increased anthropogenic CO2 production, coral reefs are also susceptible to bleaching, disease and reduced calcification. The impacts of ocean acidification and warming may be exacerbated by COTS predation, but it is not known how this major predator will fare in a changing ocean. Because larval success is a key driver of population outbreaks, we investigated the sensitivities of larval A. planci to increased temperature (2-4 °C above ambient) and acidification (0.3-0.5 pH units below ambient) in flow-through cross-factorial experiments (3 temperature × 3 pH/pCO2 levels). There was no effect of increased temperature or acidification on fertilization or very early development. Larvae reared in the optimal temperature (28 °C) were the largest across all pH treatments. Development to advanced larva was negatively affected by the high temperature treatment (30 °C) and by both experimental pH levels (pH 7.6, 7.8). Thus, planktonic life stages of A. planci may be negatively impacted by near-future global change. Increased temperature and reduced pH had an additive negative effect on reducing larval size. The 30 °C treatment exceeded larval tolerance regardless of pH. As 30 °C sea surface temperatures may become the norm in low latitude tropical regions, poleward migration of A. planci may be expected as they follow optimal isotherms. In the absence of acclimation or adaptation, declines in low latitude populations may occur. Poleward migration will be facilitated by strong western boundary currents, with possible negative flow-on effects on high latitude coral reefs. The contrasting responses of the larvae of A. planci and those of its coral prey to ocean acidification and warming are considered in context with potential future change in tropical reef ecosystems.

Impact of medium-term exposure to elevated pCO2 levels on the physiological energetics of the mussel Mytilus chilensis

This study evaluated the impact of medium-term exposure to elevated pCO2 levels (750-1200 ppm) on the physiological processes of juvenile Mytilus chilensis mussels over a period of 70 d in a mesocosm system. Three equilibration tanks filled with filtered seawater were adjusted to three pCO2 levels: 380 (control), 750 and 1200 ppm by bubbling air or an air-CO2 mixture through the water. For the control, atmospheric air (with aprox. 380 ppm CO2) was bubbled into the tank; for the 750 and 1200 ppm treatments, dry air and pure CO2 were blended to each target concentration using mass flow controllers for air and CO2. No impact on feeding activity was observed at the beginning of the experiment, but a significant reduction in clearance rate was observed after 35 d of exposure to highly acidified seawater. Absorption rate and absorption efficiency were reduced at high pCO2 levels. In addition, oxygen uptake fell significantly under these conditions, indicating a metabolic depression. These physiological responses of the mussels resulted in a significant reduction of energy available for growth (scope for growth) with important consequences for the aquaculture of this species during medium-term exposure to acid conditions. The results of this study clearly indicate that high pCO2 levels in the seawater have a negative effect on the health of M. chilensis. Therefore, the predicted acidification of seawater associated with global climate change could be harmful to this ecologically and commercially important mussel.

Time series of air chemistry measurements at Georg-von-Neumayer station, Dronning Maud Land, Antarctica in the years 1982 to 1991

The first Air Chemistry Observatory at the German Antarctic station Georg von Neumayer (GvN) was operated for 10 years from 1982 to 1991. The focus of the established observational programme was on characterizing the physical properties and chemical composition of the aerosol, as well as on monitoring the changing trace gas composition of the background atmosphere, especially concerning greenhouse gases. The observatory was designed by the Institut für Umweltphysik, University of Heidelberg (UHEIIUP). The experiments were installed inside the bivouac lodge, mounted on a sledge and put upon a snow hill to prevent snow accumulation during blizzards. All experiments were under daily control and daily performance protocols were documented. A ventilated stainless steel inlet stack (total height about 3-4 m above the snow surface) with a 50% aerodynamic cut-off diameter around 7-10 µm at wind velocities between 4-10 m/s supplied all experiments with ambient air. Contamination free sampling was realized by several means: (i) The Air Chemistry Observatory was situated in a clean air area about 1500 m south of GvN. Due to the fact that northern wind directions are very rare, contamination from the base can be excluded for most of the time. (ii) The power supply (20 kW) is provided by a cable from the main station, thus no fuel-driven generator is operated in the very vicinity. (iii) Contamination-free sampling is controlled by the permanently recorded wind velocity, wind direction and by condensation particle concentration. Contamination was indicated if one of the following criteria were given: Wind direction within a 330°-30° sector, wind velocity <2.2 m/s or >17.5 m/s, or condensation particle concentrations >2500/cm**3 during summer, >800/cm**3 during spring/autumn and >400/cm**3 during winter. If one or a definable combination of these criteria were given, high volume aerosol sampling and part of the trace gas sampling were interrupted. Starting at 1982 through 1991-01-14 surface ozone was measured with an electrochemical concentration cell (ECC). Surface ozone mixing ratio are given in ppbv = parts per 10**9 by volume. The averaging time corresponds to the given time intervals in the data sheet. The accuracy of the values are better than ±1 ppbv and the detection limit is around 1.0 ppbv. Aerosols were sampled on two Whatman 541 cellulose filters in series and analyzed by ion chromatography at the UHEI-IUP. Generally, the sampling period was seven days but could be up to two weeks on occasion. The air flow was around 100 m**3/h and typically 10000-20000 m**3 of ambient air was forced through the filters for one sample. Concentration values are given in nanogram (ng) per 1 m**3 air at standard pressure and temperature (1013 mbar, 273.16 K). Uncertainties of the values were approximately ±10% to ±15% for the main components MSA, chloride, nitrate, sulfate and sodium, and between ±20% and ±30% for the minor species bromide, ammonium, potassium, magnesium and calcium.

Seawater carbonate chemistry and biological processes during experiments with postlarvae of barnacle of Semibalanus balanoides and Elminius modestus, 2010

Ocean acidification and global warming are occurring concomitantly, yet few studies have investigated how organisms will respond to increases in both temperature and CO2. Intertidal microcosms were used to examine growth, shell mineralogy and survival of two intertidal barnacle post-larvae, Semibalanus balanoides and Elminius modestus, at two temperatures (14 and 19°C) and two CO2 concentrations (380 and 1,000 ppm), fed with a mixed diatom-flagellate diet at 15,000 cells ml-1 with flow rate of 10 ml-1 min-1. Control growth rates, using operculum diameter, were 14 ± 8 µm day-1 and 6 ± 2 µm day-1 for S. balanoides and E. modestus, respectively. Subtle, but significant decreases in E. modestus growth rate were observed in high CO2 but there were no impacts on shell calcium content and survival by either elevated temperature or CO2. S. balanoides exhibited no clear alterations in growth rate but did show a large reduction in shell calcium content and survival under elevated temperature and CO2. These results suggest that a decrease by 0.4 pH(NBS) units alone would not be sufficient to directly impact the survival of barnacles during the first month post-settlement. However, in conjunction with a 4-5°C increase in temperature, it appears that significant changes to the biology of these organisms will ensue.