Continuous 25-years aerosol records at coastal Antarctica: Part I. Variability and climate implications of ionic compounds

The aerosol climatology at the coastal Antarctic Neumayer Station (NM) was investigated based on continuous, 25-yr long observations of biogenic sulphur components (methanesulfonate and non-sea salt sulphate), sea salt and nitrate. Although significant long-term trends could only be detected for nitrate (-3.6 ± 2.5% per year between 1983 and 1993 and +4.0 ± 3.2% per year from 1993-2007), non-harmonic periodicities between 2 and 5 yr were typical for all species. Dedicated time series analyses revealed that relations to sea ice extent and various circulation indices are weak at best or not significant. In particular, no consistent link between sea ice extent and sea salt loadings was evident suggesting only a rather local relevance of the NM sea salt record. Nevertheless, a higher Southern Annular Mode index tended to entail a lower biogenic sulphur signal. In examining the spatial uniformity of the NM findings we contrasted them to respective 17 yr records from the coastal Dumont d'Urville Station. We found similar long-term trends for nitrate, indicating an Antarctic-wide but not identifiable atmospheric signal, although any significant impact of solar activity or pollution could be ruled out. No inter-site variability on the multiannual scale was evident for the other ionic compounds.

Probability inundation map for a scenario combining storm surge and sea-level rise

Coastal managers require reliable spatial data on the extent and timing of potential coastal inundation, particularly in a changing climate. Most sea level rise (SLR) vulnerability assessments are undertaken using the easily implemented bathtub approach, where areas adjacent to the sea and below a given elevation are mapped using a deterministic line dividing potentially inundated from dry areas. This method only requires elevation data usually in the form of a digital elevation model (DEM). However, inherent errors in the DEM and spatial analysis of the bathtub model propagate into the inundation mapping. The aim of this study was to assess the impacts of spatially variable and spatially correlated elevation errors in high-spatial resolution DEMs for mapping coastal inundation. Elevation errors were best modelled using regression-kriging. This geostatistical model takes the spatial correlation in elevation errors into account, which has a significant impact on analyses that include spatial interactions, such as inundation modelling. The spatial variability of elevation errors was partially explained by land cover and terrain variables. Elevation errors were simulated using sequential Gaussian simulation, a Monte Carlo probabilistic approach. 1,000 error simulations were added to the original DEM and reclassified using a hydrologically correct bathtub method. The probability of inundation to a scenario combining a 1 in 100 year storm event over a 1 m SLR was calculated by counting the proportion of times from the 1,000 simulations that a location was inundated. This probabilistic approach can be used in a risk-aversive decision making process by planning for scenarios with different probabilities of occurrence. For example, results showed that when considering a 1% probability exceedance, the inundated area was approximately 11% larger than mapped using the deterministic bathtub approach. The probabilistic approach provides visually intuitive maps that convey uncertainties inherent to spatial data and analysis.

Direct visualization of solute locations in laboratory ice samples, links to videos

Many important chemical reactions occur in polar snow, where solutes may be present in several reservoirs, including at the air-ice interface and in liquid-like regions within the ice matrix. Some recent laboratory studies suggest chemical reaction rates may differ in these two reservoirs. While investigations have examined where solutes are found in natural snow and ice, similar research has not identified solute locations in laboratory samples, nor the possible factors controlling solute segregation. To address this, we examined solute locations in ice samples prepared from either aqueous cesium chloride (CsCl) or Rose Bengal solutions that were frozen using several different methods. Samples frozen in a laboratory freezer had the largest liquid-like inclusions and air bubbles, while samples frozen in a custom freeze chamber had somewhat smaller air bubbles and inclusions; in contrast, samples frozen in liquid nitrogen showed much smaller concentrated inclusions and air bubbles, only slightly larger than the resolution limit of our images (~2 µm). Freezing solutions in plastic versus glass vials had significant impacts on the sample structure, perhaps because the poor heat conductivity of plastic vials changes how heat is removed from the sample as it cools. Similarly, the choice of solute had a significant impact on sample structure, with Rose Bengal solutions yielding smaller inclusions and air bubbles compared to CsCl solutions frozen using the same method. Additional experiments using higher-resolution imaging of an ice sample show that CsCl moves in a thermal gradient, supporting the idea that the solutes in ice are present in liquid-like regions. Our work shows that the structure of laboratory ice samples, including the location of solutes, is sensitive to freezing method, sample container, and solute characteristics, requiring careful experimental design and interpretation of results.

Annual-layer thickness, d18O and sodium values on Akademii Nauk ice core (AD 900-1998) based on core chronology AN 2012

Understanding recent Arctic climate change requires detailed information on past changes, in particular on a regional scale. The extension of the depth-age relation of the Akademii Nauk (AN) ice core from Severnaya Zemlya (SZ) to the last 1100 yr provides new perspectives on past climate fluctuations in the Barents and Kara seas region. Here, we present the easternmost high-resolution ice-core climate proxy records (d18O and sodium) from the Arctic. Multi-annual AN d18O data as near-surface air-temperature proxies reveal major temperature changes over the last millennium, including the absolute minimum around 1800 and the unprecedented warming to a double-peak maximum in the early 20th century. The long-term cooling trend in d18O is related to a decline in summer insolation but also to the growth of the AN ice cap as indicated by decreasing sodium concentrations. Neither a pronounced Medieval Climate Anomaly nor a Little Ice Age are detectable in the AN d18O record. In contrast, there is evidence of several abrupt warming and cooling events, such as in the 15th and 16th centuries, partly accompanied by corresponding changes in sodium concentrations. These abrupt changes are assumed to be related to sea-ice cover variability in the Barents and Kara seas region, which might be caused by shifts in atmospheric circulation patterns. Our results indicate a significant impact of internal climate variability on Arctic climate change in the last millennium.

Iridium and other element concentrations and magnetostratigraphy across the Cretaceous/Tertiarty boundary in ODP Hole 122-761C

Samples from Ocean Drilling Program Hole 761C, collected on both sides of the Cretaceous/Tertiary boundary have been analyzed for their chemical and mineralogical content. The sediment consists of nannofossil ooze with variable amounts of clay. The boundary is marked by a color change associated with a nearly step-like decrease of the carbonate fraction. Paleomagnetic data and the drop of the carbonate content indicate that a strong reduction of the sedimentation rate occurred at the boundary and persisted for million of years. An iridium anomaly of 80 ng/cm**2, together with overabundances of Cr and Fe, are found in close coincidence with the planktonic crisis. These enrichments can be explained by the infall of =0.16 g/cm2 of Cl-like chondritic material. Co and Ni enrichments and a great quantity of Ni-rich magnetites are also observed in the basal Danian. These elements and minerals excepted, the composition of the insoluble fraction appears to be nearly unchanged across the boundary. Chemical and mineralogical observations support a cosmic origin for the Cretaceous/Tertiary event but do not reveal the presence of any significant impact ejecta.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

Stable oxygen isotope. Mg/Ca and Temperature record of Caribbean and Pacific sediments

The final phase of the closure of the Panamanian Gateway and the intensification of Northern Hemisphere Glaciation (NHG) both occurred during the Late Pliocene. Glacial-interglacial (G-IG) variations in sea level might, therefore, have had a significant impact on the remaining connections between the East Pacific and the Caribbean. Here, we present combined foraminiferal Mg/Ca and d18O measurements from Ocean Drilling Program (ODP) Site 1241 from the East Pacific and ODP Site 999 from the Caribbean. The studied time interval covers the first three major G-IG Marine Isotope Stages (MIS 95-100, ~2.5 Ma) after the intensification of NHG. Analyses were performed on the planktonic foraminifera Neogloboquadrina dutertrei and Globigerinoides sacculifer, representing water mass properties in the thermocline and the mixed-layer, respectively. Changes in sea water temperature, relative salinity, and water column stratification strongly suggest that the Panamanian Gateway temporarily closed during glacial MIS 98 and 100, as a result of changes in ice volume equivalent to a drop in sea level of 60-90 m. Reconstructed sea surface temperatures (SST) from G. sacculifer show a glacial decrease of 2.5°C at Site 1241, but increases of up to 3°C at Site 999 during glacial MIS 98 and 100 suggesting that the Panamanian Gateway closed during these glacial periods. The Mg/Ca-temperatures of N. dutertrei remain relatively stable in the East Pacific, but do show a 3°C warming in the Caribbean at the onset of these glacial periods suggesting that the closing of the gateway also changed the water column stratification. We infer that the glacial closure of the gateway allowed the Western Atlantic Warm Pool to extend into the southern Caribbean, increasing SST (G. sacculifer) and deepening the thermocline (N. dutertrei). Additionally, ice volume appears to have become large enough during MIS 100 to survive the relatively short lasting interglacial MIS 99 so that the gateway remained closed. Towards the end of MIS 98, during MIS 97 and into MIS 96 temperatures on both sides are mostly similar suggesting water masses exchanged again. Additionally, Caribbean variations in SST and d18Owater follow a precession-like cyclicity rather than the obliquity-controlled variations characteristic of the East-Pacific and many other tropical areas, suggesting that regional atmospheric processes related to the trade winds and the Intertropical Convergence Zone (ITCZ) had a dominant impact in the Caribbean.

Atmospheric nitrate concentrations and isotope composition for samples collected in the marine boundary layer in 2006 and 2007

The comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the d15N of nitrate mostly deriving from anthropogenically emitted NOx is found to be significantly different (from 0 to 6 per mil) from nitrate sampled in locations influenced by natural NOx sources (-4 ± 2) per mil. The effects on d15N(NO3-) of different NOx sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (D17O = d17O - 0.52 × d18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NOx sinks. Different D17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low d15N values (down to -40 per mil) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NOx from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores.

Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

Sponge bioerosion accelerated by ocean acidification across species and latitudes?

In many marine biogeographic realms, bioeroding sponges dominate the internal bioerosion of calcareous substrates such as mollusc beds and coral reef framework. They biochemically dissolve part of the carbonate and liberate so-called sponge chips, a process that is expected to be facilitated and accelerated in a more acidic environment inherent to the present global change. The bioerosion capacity of the demosponge Cliona celata Grant, 1826 in subfossil oyster shells was assessed via alkalinity anomaly technique based on 4 days of experimental exposure to three different levels of carbon dioxide partial pressure (pCO2) at ambient temperature in the cold-temperate waters of Helgoland Island, North Sea. The rate of chemical bioerosion at present-day pCO2 was quantified with 0.08-0.1 kg/m**2/year. Chemical bioerosion was positively correlated with increasing pCO2, with rates more than doubling at carbon dioxide levels predicted for the end of the twenty-first century, clearly confirming that C. celata bioerosion can be expected to be enhanced with progressing ocean acidification (OA). Together with previously published experimental evidence, the present results suggest that OA accelerates sponge bioerosion (1) across latitudes and biogeographic areas, (2) independent of sponge growth form, and (3) for species with or without photosymbionts alike. A general increase in sponge bioerosion with advancing OA can be expected to have a significant impact on global carbonate (re)cycling and may result in widespread negative effects, e.g. on the stability of wild and farmed shellfish populations, as well as calcareous framework builders in tropical and cold-water coral reef ecosystems.

Tough as a rock-boring urchin: adult Echinometra sp. EE from the Red Sea show high resistance to ocean acidification over long-term exposures

Ocean acidification, a process caused by the continuous rise of atmospheric CO2 levels, is expected to have a profound impact on marine invertebrates. Findings of the numerous studies conducted in this field indicate high variability in species responses to future ocean conditions. This study aimed at understanding the effects of long-term exposure to elevated pCO2 conditions on the performance of adult Echinometra sp. EE from the Gulf of Aqaba (Red Sea). During an 11-month incubation under high pCO2 (1,433 µatm, pHNBS 7.7) and control (435 µatm, pHNBS 8.1) conditions, we examined the urchins' somatic and gonadal growth, gametogenesis and skeletal microstructure. Somatic and gonadal growths were exhibited with no significant differences between the treatments. In addition, all urchins in the experiment completed a full reproductive cycle, typical of natural populations, with no detectable impact of increased pCO2 on the timing, duration or progression of the cycle. Furthermore, scanning electron microscopy imaging of urchin tests and spines revealed no signs of the usual observed effects of acidosis, such as skeletal dissolution, widened stereom pores or non-smoothed structures. Our results, which yielded no significant impact of the high pCO2 treatment on any of the examined processes in the urchins studied, suggest high resistance of adult Echinometra sp. EE to near future ocean acidification conditions. With respect to other findings in this area, the outcome of this study provides an example of the complicated and diverse responses of echinoids to the predicted environmental changes.

(Table T1) Permeability, electrical resistivity and density of ODP Hole 193-1188A and Site 193-1189 minicores, PACMANUS field

Magmatic fluids, heat fluxes, and fluid/rock interactions associated with hydrothermal systems along spreading centers and convergent margins have a significant impact on the genesis of major sulfide deposits and biological communities. Circulation of hydrothermal fluids is one of the most fundamental processes associated with localized mineralization and is controlled by inherent porous and permeable properties of the ocean crust. Heat from magmatic intrusions drives circulation of seawater through permeable portions of the oceanic crust and upper mantle, discharging at the seafloor as both focused high-temperature (250°-400°C) fluids and diffuse lower-temperature (<250°C) fluids. This complex interaction between the circulating hydrothermal fluids and the oceanic basement greatly influences the physical properties and the composition of the crust (Thompson, 1983; Jacobson, 1992, doi:10.1029/91RG02811; Johnson and Semyan, 1994, doi:10.1029/93JB00717). During Ocean Drilling Program (ODP) Leg 193, 13 holes were drilled in the PACMANUS hydrothermal system (Binns, Barriga, Miller, et al., 2002, doi:10.2973/odp.proc.ir.193.2002). The hydrothermal system consists of isolated hydrothermal deposits lined along the main crest of the Pual Ridge, a 500- to 700-m-high felsic neovolcanic ridge in the eastern Manus Basin. The principal drilling targets were the Snowcap (Site 1188) and Roman Ruins (Site 1189) active hydrothermal fields. Samples from these two sites were used for a series of permeability, electrical resistivity, and X-ray computed tomography measurements.

Sea-surface temperature reconstruction of sediment cores from the Skagerrak

We attempt a reconstruction of salinity levels of the central Baltic Sea based on diatom assemblages, the isotopic composition of organic matter and sedimentological expression of anoxia over the last 10 000 years. We use the data to investigate the dependence of salinity levels on climate evolution and isostasy. Changes in salinity of surface and deep waters were most pronounced from 8400 to approximately 5000 cal. BP. Density stratification between salty deep and fresher surface waters caused the frequent development of anoxic conditions and deposition of laminated sediments on large parts of the sea floor in the central Baltic Sea, and dramatic changes in organic carbon-accumulation rates. From 5000 to 3100 cal. BP, the salinity of the basin decreased, oxygenation of deep sea floors was improved, and fertility of the sea surface was significantly reduced. This is reflected by low accumulation rates of organic carbon in bioturbated sediments. Since 2800 cal. BP, salinity rose again and anoxic periods were more common. Even though the major steps in environmental evolution in the Baltic Sea coincide with known patterns of climatic change of the North Atlantic realm over the last 10 000 years, we find no conclusive evidence for synchronous changes or linear responses on submillennial timescales. However, we note that major variations in our salinity records agree with temporal patterns of reconstructed summer warmth and winter precipitation in southern Scandinavia. Both types of record suggest that climate in the mid-Holocene was far from stable. Our data also confirm that climate evolution over the late Holocene had significant impact on environmental conditions in the Baltic Sea.