Halogen deposition in polar snow and ice

The atmospheric chemistry of iodine and bromine in polar regions is of interest due to the key role of halogens in many atmospheric processes, particularly tropospheric ozone destruction. Bromine is emitted from the open ocean but is enriched above first-year sea ice during springtime bromine explosion events, whereas iodine is emitted from biological communities hosted by sea ice. It has been previously demonstrated that bromine and iodine are present in Antarctic ice over glacial-interglacial cycles. Here we investigate seasonal variability of bromine and iodine in polar snow and ice, to evaluate their emission, transport and deposition in Antarctica and the Arctic and better understand potential links to sea ice. We find that bromine enrichment (relative to sea salt content) and iodine concentrations in polar ice do vary seasonally in Arctic snow and Antarctic ice and we relate such variability to satellite-based observations of tropospheric halogen concentrations. Peaks of bromine enrichment in Arctic snow and Antarctic ice occur in spring and summer, when sunlight is present. Iodine concentrations are largest in winter Antarctic ice strata, contrary to contemporary observations of summer maxima in iodine emissions.

Stable isotope record, Mg/Ca ratios and sea surface reconstruction for sediment core MD06-3067

We present sea surface, upper thermocline, and benthic d18O data, as well as temperature and paleoproductivity proxy data, from the International Marine Global Change Study Program (IMAGES) Core MD06-3067 (6°31'N, 126°30'E, 1575 m water depth), located in the western equatorial Pacific Ocean within the flow path of the Mindanao Current. Our records reveal considerable glacial-interglacial and suborbital variability in the Mindanao Dome upwelling over the last 160 kyr. Dome activity generally intensified during glacial intervals resulting in cooler thermocline waters, whereas it substantially declined during interglacials, in particular in the early Holocene and early marine oxygen isotope stage (MIS) 5e, when upwelling waters did not reach the thermocline. During MIS 3 and MIS 2, enhanced surface productivity together with remarkably low SST and low upper ocean thermal contrast provide evidence for episodic glacial upwelling to the surface, whereas transient surface warming marks periodic collapses of the Mindanao Dome upwelling during Heinrich events. We attribute the high variability during MIS 3 and MIS 2 to changes in the El Niño Southern Oscillation state that affected boreal winter monsoonal winds and upper ocean circulation. Glacial upwelling intensified when a strong cyclonic gyre became established, whereas El Niño-like conditions during Heinrich events tended to suppress the cyclonic circulation, reducing Ekman transport. Thus, our findings demonstrate that variations in the Mindanao Dome upwelling are closely linked to the position and intensity of the tropical convection and also reflect far-field influences from the high latitudes.

Data compilation of ESOP

The work in this sub-project of ESOP focuses on the advective and convective transforma-tion of water masses in the Greenland Sea and its neighbouring areas. It includes observational work on the sub-mesoscale and analysis of hydrographic data up to the gyre-scale. Observations of active convective plumes were made with a towed chain equipped with up to 80 CTD sensors, giving a horizontal and vertical resolution of the hydrographic fields of a few metres. The observed scales of the penetrative convective plumes compare well with those given by theory. On the mesoscale the structure of homogeneous eddies formed as a result of deep convection was observed and the associated mixing and renewal of the intermediate layers quantified. The relative importance and efficiency of thermal and haline penetrative convection in relation to the surface boundary conditions (heat and salt fluxes and ice cover) and the ambient stratification are studied using the multi year time series of hydro-graphic data in the central Greenland Sea. The modification of the water column of the Greenland Sea gyre through advection from and mixing with water at its rim is assessed on longer time scales. The relative contributions are quantified using modern water mass analysis methods based on inverse techniques. Likewise the convective renewal and the spreading of the Arctic Intermediate Water from its formation area is quantified. The aim is to budget the heat and salt content of the water column, in particular of the low salinity surface layer, and to relate its seasonal and interannual variability to the lateral fluxes and the fluxes at the air-sea-ice interface. This will allow to estimate residence times for the different layers of the Greenland Sea gyre, a quantity important for the description of the Polar Ocean carbon cycle.

Geochemistry, isotopic ratios and aldehyde concentrations of frost flowers, snow and ice near Barrow, Alaska

Frost flowers, intricate featherlike crystals that grow on refreezing sea ice leads, have been implicated in lower atmospheric chemical reactions. Few studies have presented chemical composition information for frost flowers over time and many of the chemical species commonly associated with Polar tropospheric reactions have never been reported for frost flowers. We undertook this study on the sea ice north of Barrow, Alaska to quantify the major ion, stable oxygen and hydrogen isotope, alkalinity, light absorbance by soluble species, organochlorine, and aldehyde composition of seawater, brine, and frost flowers. For many of these chemical species we present the first measurements from brine or frost flowers. Results show that major ion and alkalinity concentrations, stable isotope values, and major chromophore (NO3- and H2O2) concentrations are controlled by fractionation from seawater and brine. The presence of these chemical species in present and future sea ice scenarios is somewhat predictable. However, aldehydes, organochlorine compounds, light absorbing species, and mercury (part 2 of this research and Sherman et al. (2012, doi:10.1029/2011JD016186)) are deposited to frost flowers through less predictable processes that probably involve the atmosphere as a source. The present and future concentrations of these constituents in frost flowers may not be easily incorporated into future sea ice or lower atmospheric chemistry scenarios. Thinning of Arctic sea ice will likely present more open sea ice leads where young ice, brine, and frost flowers form. How these changing ice conditions will affect the interactions between ice, brine, frost flowers and the lower atmosphere is unknown.

Radiocarbon ages, dose rates, water isotopic composition and hydrochemistry of samples from Komakuk Beach and Herschel Island

Terrestrial permafrost archives along the Yukon Coastal Plain (northwest Canada) have recorded landscape development and environmental change since the Late Wisconsinan at the interface of unglaciated Beringia (i.e. Komakuk Beach) and the northwestern limit of the Laurentide Ice Sheet (i.e. Herschel Island). The objective of this paper is to compare the late glacial and Holocene landscape development on both sides of the former ice margin based on permafrost sequences and ground ice. Analyses at these sites involved a multi-proxy approach including: sedimentology, cryostratigraphy, palaeoecology of ostracods, stable water isotopes in ground ice, hydrochemistry, and AMS radiocarbon and infrared stimulated luminescence (IRSL) dating. AMS and IRSL age determinations yielded full glacial ages at Komakuk Beach that is the northeastern limit of ice-free Beringia. Herschel Island to the east marks the Late Wisconsinan limit of the northwest Laurentide Ice Sheet and is composed of ice-thrust sediments containing plant detritus as young as 16.2 cal ka BP that might provide a maximum age on ice arrival. Late Wisconsinan ice wedges with sediment-rich fillings on Herschel Island are depleted in heavy oxygen isotopes (mean d18O of -29.1 per mil); this, together with low d-excess values, indicates colder-than-modern winter temperatures and probably reduced snow depths. Grain-size distribution and fossil ostracod assemblages indicate that deglaciation of the Herschel Island ice-thrust moraine was accompanied by alluvial, proluvial, and eolian sedimentation on the adjacent unglaciated Yukon Coastal Plain until ~11 cal ka BP during a period of low glacio-eustatic sea level. The late glacial-Holocene transition was marked by higher-than-modern summer temperatures leading to permafrost degradation that began no later than 11.2 cal ka BP and caused a regional thaw unconformity. Cryostructures and ice wedges were truncated while organic matter was incorporated and soluble ions were leached in the thaw zone. Thermokarst activity led to the formation of ice-wedge casts and deposition of thermokarst lake sediments. These were subsequently covered by rapidly accumulating peat during the early Holocene Thermal Maximum. A rising permafrost table, reduced peat accumulation, and extensive ice-wedge growth resulted from climate cooling starting in the middle Holocene until the late 20th century. The reconstruction of palaeolandscape dynamics on the Yukon Coastal Plain and the eastern Beringian edge contributes to unraveling the linkages between ice sheet, ocean, and permafrost that have existed since the Late Wisconsinan.

Age determination and stable isotope records of sediment core M78/1_235-1

Paleoenvironmental studies and climate models demonstrate that fluvial runoff and moisture availability in the Caribbean hinterland react very sensitively to climatic variations. Late Pleistocene and Holocene climate records document pronounced dry and wet periods over tropical South America mainly caused by shifts of the Intertropical Convergence Zone (ITCZ). However, forcing mechanisms for changes in the ITCZ position remain controversial. Here we present high-resolution foraminiferal Ba/Ca and d18Oseawater records from a core located within the Orinoco River outflow documenting abrupt hydrological changes in the Orinoco catchment area during the deglacial and Holocene. Our data, obtained from the surface-dwelling foraminifera Globigerinoides ruber (pink), show an abrupt increase in Ba/Ca ratios in the early Holocene, starting ~600 yr after the end of the Younger Dryas (YD) cold interval at ca. 10.8 ka and suggesting a massive reorganization of moisture sources in northern South America. In contrast, the salinity dependent d18Oseawater from the same samples shows a gradual decrease starting at the end of the YD. The offset of our Ba/Ca peak excludes meltwater release in conjunction with the northern Andean glacier retreat well before the end of the YD as a forcing mechanism. We suggest that the Ba/Ca record documents an abrupt increase in Ba-rich waters of a northern Andean source caused by the insolation-driven shift of the ITCZ and/or enhanced monsoon activity.

Stable oxygen isotope and Mg/Ca ratios of planktonic foraminifera from the Caribbean and North Atlantic

Variations in the strength of the North Atlantic Ocean thermohaline circulation have been linked to rapid climate changes during the last glacial cycle through oscillations in North Atlantic Deep Water formation and northward oceanic heat flux. The strength of the thermohaline circulation depends on the supply of warm, salty water to the North Atlantic, which, after losing heat to the atmosphere, produces the dense water masses that sink to great depths and circulate back south. Here we analyse two Caribbean Sea sediment cores, combining Mg/Ca palaeothermometry with measurements of oxygen isotopes in foraminiferal calcite in order to reconstruct tropical Atlantic surface salinity during the last glacial cycle. We find that Caribbean salinity oscillated between saltier conditions during the cold oxygen isotope stages 2, 4 and 6, and lower salinities during the warm stages 3 and 5, covarying with the strength of North Atlantic Deep Water formation. At the initiation of the Bølling/Allerød warm interval, Caribbean surface salinity decreased abruptly, suggesting that the advection of salty tropical waters into the North Atlantic amplified thermohaline circulation and contributed to high-latitude warming.

Results of a sediment profile and water analyses from Lake Hancza in northeastern Poland

We investigated the sedimentary record of Lake Hancza (northeastern Poland) using a multi-proxy approach, focusing on early to mid-Holocene climatic and environmental changes. AMS 14C dating of terrestrial macrofossils and sedimentation rate estimates from occasional varve thickness measurements were used to establish a chronology. The onset of the Holocene at c. 11600 cal. a BP is marked by the decline of Lateglacial shrub vegetation and a shift from clastic-detrital deposition to an autochthonous sedimentation dominated by biochemical calcite precipitation. Between 10000 and 9000 cal. a BP, a further environmental and climatic improvement is indicated by the spread of deciduous forests, an increase in lake organic matter and a 1.7% rise in the oxygen isotope ratios of both endogenic calcite and ostracod valves. Rising d18O values were probably caused by a combination of hydrological and climatic factors. The persistence of relatively cold and dry climate conditions in northeastern Poland during the first one and a half millennia of the Holocene could be related to a regional eastern European atmospheric circulation pattern. Prevailing anticyclonic circulation linked to a high-pressure cell above the retreating Scandinavian Ice Sheet might have blocked the influence of warm and moist Westerlies and attenuated the early Holocene climatic amelioration in the Lake Hancza region until the final decay of the ice sheet.

Geochemistry of Globigerinoides ruber from ODP Hole 130-806B

A sea surface temperature (SST) record based on planktonic foraminiferal magnesium/calcium ratios from a site in the western equatorial Pacific warm pool reveals that glacial-interglacial oscillations in SST shifted from a period of 41,000 to 100,000 years at the mid-Pleistocene transition, 950,000 years before the present. SST changes at both periodicities were synchronous with eastern Pacific cold-tongue SSTs but preceded changes in continental ice volume. The timing and nature of tropical Pacific SST changes over the mid-Pleistocene transition implicate a shift in the periodicity of radiative forcing by atmospheric carbon dioxide as the cause of the switch in climate periodicities at this time.

Geochemistry of hydrate gas and water at DSDP Hole 84-570

Molecular and isotopic measurements of gas and water obtained from a gas hydrate at Site 570, DSDP Leg 84, are reported. The hydrate appeared to be Structure I and was composed of a solid framework of water molecules enclosing methane and small amounts of ethane and carbon dioxide. Carbon isotopic values for the hydrate-bound methane, ethane, and carbon dioxide were -41 to about -44, -27, and -2.9 per mil, respectively. The d13C-C1 values are consistent with void gas values that were determined to have a biogenic source. A significant thermogenic source was discounted because of high C1/C2 ratios and because the d13C-CO2 values in these sections were also anomalously heavy (or more positive) isotopically, suggesting that the methane was formed biogenically by reduction of heavy CO2 . The isotopically heavy hydrate d13C-C2 is also similar to void gas isotopic compositions and is either a result of low-temperature diagenesis producing heavy C2 in these immature sediment sections or upward migration of deeper thermogenic gas. The salinity of the hydrate water was 2.6 per mil with dDH2O and d18OH2O values of +1 and +2.2 per mil, respectively.

Stable isotopic composition of bottom water and benthic foraminifera from Hakon Mosby Mud Vulcano

To investigate the use of benthic foraminifera as a means to document ancient methane release, we determined the stable isotopic composition of tests of live (Rose Bengal stained) and dead specimens of epibenthic Fontbotia wuellerstorfi, preferentially used in paleoceanographic reconstructions, and of endobenthic high-latitude Cassidulina neoteretis and Cassidulina reniforme from a cold methane-venting seep off northern Norway. We collected foraminiferal tests from three push cores and nine multiple cores obtained with a remotely operated vehicle and a video-guided multiple corer, respectively. All sampled sites except one control site are situated at the Håkon Mosby mud volcano (HMMV) on the Barents Sea continental slope in 1250 m water depth. At the HMMV in areas densely populated by pogonophoran tube worms, d13C values of cytoplasm-containing epibenthic F. wuellerstorfi are by up to 4.4 per mil lower than at control site, thus representing the lowest values hitherto reported for this species. Live C. neoteretis and C. reniforme reach d13C values of -7.5 and -5.5 per mil Vienna Pee Dee Belemnite (VPDB), respectively, whereas d13C values of their empty tests are higher by 4 per mil and 3 per mil. However, d13C values of empty tests are never lower than those of stained specimens, although they are still lower than empty tests from the control site. This indicates that authigenic calcite precipitates at or below the sediment surface are not significantly influencing the stable isotopic composition of foraminiferal shells. The comparatively high d13C results rather from upward convection of pore water and fluid mud during active methane venting phases at these sites. These processes mingle tests just recently calcified with older ones secreted at intermittent times of less or no methane discharge. Since cytoplasm-containing specimens of suspension feeder F. wuellerstorfi are almost exclusively found attached to pogonophores, which protrude up to 3 cm above the sediment, and d13C values of bottom-water-dissolved inorganic carbon (DIC) are not significantly depleted, we conclude that low test d13C values of F. wuellerstorfi are the result of incorporation of heavily 13C-depleted methanotrophic biomass that these specimens feed on rather than because of low bottom water d13CDIC. Alternatively, the pogonophores, which are rooted at depth in the upper sediment column, may serve as a conduit for depleted d13CDIC that ultimately influences the calcification process of F. wuellerstorfi attached to the pogonophoran tube well above the sediment/water interface. The lowest d13C of live specimens of the endobenthic C. neoteretis and C. reniforme are within the range of pore water d13CDIC values, which exceed those that could be due to organic matter decomposition, and thus, in fact, document active methane release in the sediment.

Oceanography and stable isotopes on planktonic foraminifera from the North Atlantic

With the examination of multinet catches (63 µm mesh size), the present study analyzes the distribution of planktonic foraminifera in Polar regions: the Labrador Sea, Greenland Sea at 75°N and Fram Strait at 80°N. The community of the planktonic foraminifera, which in the study area mainly consists of six species: left and right-coiling N. pachyderma, T. quinqueloba, G. bulloides, G. glutinata and G. uvula, is primarily controlled by the temperature in the different water masses. Besides hydrographic parameters, the changes in the horizontal and vertical distribution of N. pachyderma (s.) and T. quinqueloba as well as their shell size distribution in the study area are primarily influenced by the synchrone reproduction, which is coupled to the lunar cycle. Detailed examinations of the isotope signal in dependency on the shell size and weight for N. pachyderma (s.) and T. quinqueloba from plankton tows, indicated the weight or degree of calcification to not be the primary factor controlling the isotope signal of encrusted specimens.The d18O vital effect is primarily caused by the thermal stratification of the water column, whereas the d13C vital effect mainly results from the ontogenetic development.

Methane and stable isotope record of ice core EDML from Dronning Maud Land, Antarctica

Precise knowledge of the phase relationship between climate changes in the two hemispheres is a key for understanding the Earth's climate dynamics. For the last glacial period, ice core studies have revealed strong coupling of the largest millennial-scale warm events in Antarctica with the longest Dansgaard-Oeschger events in Greenland through the Atlantic meridional overturning circulation. It has been unclear, however, whether the shorter Dansgaard-Oeschger events have counterparts in the shorter and less prominent Antarctic temperature variations, and whether these events are linked by the same mechanism. Here we present a glacial climate record derived from an ice core from Dronning Maud Land, Antarctica, which represents South Atlantic climate at a resolution comparable with the Greenland ice core records. After methane synchronization with an ice core from North Greenland, the oxygen isotope record from the Dronning Maud Land ice core shows a one-to-one coupling between all Antarctic warm events and Greenland Dansgaard-Oeschger events by the bipolar seesaw. The amplitude of the Antarctic warm events is found to be linearly dependent on the duration of the concurrent stadial in the North, suggesting that they all result from a similar reduction in the meridional overturning circulation.

Stable isotope ratios and paleoceanaographic reconstructions from sediment cores 80-548 and 161-978A

Largely continuous millennial-scale records of benthic d18O, Mg/Ca-based temperature, and salinity variations in bottom waters were obtained from Deep Sea Drilling Project Site 548 (eastern Atlantic continental margin south of Ireland, 1250 m water depth) for the period between 3.7 and 3.0 million years ago. This site monitored mid-Pliocene changes in Mediterranean Outflow Water (MOW) documented by continuously high Nd values between -10.7 and -9. Site 978 (Alboran Sea, 1930 m water depth) provides a complementary record of bottom water variability in the westernmost Mediterranean Sea, which is taken to represent MOW composition at its source. Both sites are marked by a singular and persistent rise in bottom water salinities by 0.7-1.4 psu and in densities by ~1 kg m-3 from 3.5 to 3.3 Ma, which is matched by an average 3 °C increase in bottom water temperatures at Site 548. This event suggests the onset of strongly enhanced deep-water convection in the Mediterranean Sea and a related strengthened MOW flow, which implies a major aridification of the Mediterranean source region. In harmony with model suggestions, the enhanced MOW flow has possibly intensified Upper North Atlantic Deep Water formation.

Late Pliocene variations of the Mediterranean outflow

Late Pliocene changes in the advection of Mediterranean Outflow Water (MOW) derivates were reconstructed at northeast Atlantic DSDP/ODP sites 548 and 982 and compared to records of WMDW at West Mediterranean Site 978. Neodymium isotope (epsilon-Nd) values more positive than ~10.5/~ 11 reflect diluted MOW derivates that spread almost continuously into the northeast Atlantic from 3.7 to 2.55 Ma, reaching Rockall Plateau Site 982 from 3.63 to 2.75 Ma. From 3.4 to 3.3 Ma average MOW temperature and salinity increased by 2°-4 °C and ~1 psu both at proximal Site 548 and distal Site 982. The rise implies a rise in flow strength, coeval with a long-term rise in both west Mediterranean Sea surface salinity by almost 2 psu and average bottom water salinity (BWS) by ~1 psu, despite inherent uncertainties in BWS estimates. The changes were linked with major Mediterranean aridification and a drop in African monsoon humidity. In contrast to model expectations, the rise in MOW salt discharge after 3.4 Ma did not translate into improved ventilation of North Atlantic Deep Water, since it possibly was too small to significantly influence Atlantic Meridional Overturning Circulation. Right after ~2.95 Ma, with the onset of major Northern Hemisphere Glaciation, long-term average bottom water temperature (BWT) and BWS at Site 548 dropped abruptly by ~5 °C and ~1-2 psu, in contrast to more distal Site 982, where BWT and BWS continued to oscillate at estimates of ~2 °C and 1.5-2.5 psu higher than today until ~2.6 Ma. We relate the small-scale changes both to a reduced MOW flow and to enhanced dilution by warm waters of a strengthened North Atlantic Current temporarily replacing MOW derivates at Rockall Plateau.