Continuous flow analysis method for determination of dissolved reactive phosphorus in ice cores.

Phosphorus (P) is an essential macronutrient for all living organisms. Phosphorus is often present in nature as the soluble phosphate ion PO4(3-) and has biological, terrestrial, and marine emission sources. Thus PO4(3-) detected in ice cores has the potential to be an important tracer for biological activity in the past. In this study a continuous and highly sensitive absorption method for detection of dissolved reactive phosphorus (DRP) in ice cores has been developed using a molybdate reagent and a 2-m liquid waveguide capillary cell (LWCC). DRP is the soluble form of the nutrient phosphorus, which reacts with molybdate. The method was optimized to meet the low concentrations of DRP in Greenland ice, with a depth resolution of approximately 2 cm and an analytical uncertainty of 1.1 nM (0.1 ppb) PO4(3-). The method has been applied to segments of a shallow firn core from Northeast Greenland, indicating a mean concentration level of 2.74 nM (0.26 ppb) PO4(3-) for the period 1930-2005 with a standard deviation of 1.37 nM (0.13 ppb) PO4(3-) and values reaching as high as 10.52 nM (1 ppb) PO4(3-). Similar levels were detected for the period 1771-1823. Based on impurity abundances, dust and biogenic particles were found to be the most likely sources of DRP deposited in Northeast Greenland.

Continuous flow analysis of labile iron in ice-cores.

The important active and passive role of mineral dust aerosol in the climate and the global carbon cycle over the last glacial/interglacial cycles has been recognized. However, little data on the most important aeolian dust-derived biological micronutrient, iron (Fe), has so far been available from ice-cores from Greenland or Antarctica. Furthermore, Fe deposition reconstructions derived from the palaeoproxies particulate dust and calcium differ significantly from the Fe flux data available. The ability to measure high temporal resolution Fe data in polar ice-cores is crucial for the study of the timing and magnitude of relationships between geochemical events and biological responses in the open ocean. This work adapts an existing flow injection analysis (FIA) methodology for low-level trace Fe determinations with an existing glaciochemical analysis system, continuous flow analysis (CFA) of ice-cores. Fe-induced oxidation of N,N'-dimethyl-p-pheylenediamine (DPD) is used to quantify the biologically more important and easily leachable Fe fraction released in a controlled digestion step at pH ~1.0. The developed method was successfully applied to the determination of labile Fe in ice-core samples collected from the Antarctic Byrd ice-core and the Greenland Ice-Core Project (GRIP) ice-core.

Optimization of high-resolution continuous flow analysis for transient climate signals in ice cores.

Over the past two decades, continuous flow analysis (CFA) systems have been refined and widely used to measure aerosol constituents in polar and alpine ice cores in very high-depth resolution. Here we present a newly designed system consisting of sodium, ammonium, dust particles, and electrolytic meltwater conductivity detection modules. The system is optimized for high-resolution determination of transient signals in thin layers of deep polar ice cores. Based on standard measurements and by comparing sections of early Holocene and glacial ice from Greenland, we find that the new system features a depth resolution in the ice of a few millimeters which is considerably better than other CFA systems. Thus, the new system can resolve ice strata down to 10 mm thickness and has the potential of identifying annual layers in both Greenland and Antarctic ice cores throughout the last glacial cycle.

Sulfate spikes in the deep layers of EPICA-Dome C ice core: evidence of glaciological artifacts.

A detailed ionic component record was performed on EPICA Dome C ice core (East Antarctica) to a depth of 3190 m using Ion Chromatography and Fast Ion Chromatography (FIC). At depths greater than 2800 m, the sulfate profile shows intense, sharp spikes which are not expected due to the smoothing of sulfate peaks by diffusion processes. Moreover, these spikes show an "anomalous" chemical composition (e.g., unusually low acidity, high Mg(2+) concentration and high Mg(2+)/Ca(2+) ratio). These peaks and the surrounding layers also exhibit good Mg(2+) vs SO(4)(2-) and Cl(-) vs Na(+) correlations through both glacial and interglacial periods. Furthermore, the high-resolution analysis of two horizontally contiguous ice sections showed that some fraction of the impurities are characterized by a heterogeneous distribution. Altogether, these results suggest the occurrence of long-term postdepositional processes involving a rearrangement of impurities via migration in the vein network, characterized by sulfuric acidity and leading to the formation of soluble particles of magnesium sulfate salts, along with ionic association of ions in the liquid films along boundaries. This evidence should be taken into consideration when inferring information on for rapid climatic and environmental changes from ice core chemical records at great depths. At Dome C, the depth threshold was found to be 2800 m.

An improved continuous flow analysis system for high-resolution field measurements on ice cores.

Continuous flow analysis (CFA) is a well-established method to obtain information about impurity contents in ice cores as indicators of past changes in the climate system. A section of an ice core is continuously melted on a melter head supplying a sample water flow which is analyzed online. This provides high depth and time resolution of the ice core records and very efficient sample decontamination as only the inner part of the ice sample is analyzed. Here we present an improved CFA system which has been totally redesigned in view of a significantly enhanced overall efficiency and flexibility, signal quality, compactness, and ease of use. These are critical requirements especially for operations of CFA during field campaigns, e.g., in Antarctica or Greenland. Furthermore, a novel deviceto measure the total air content in the ice was developed. Subsequently, the air bubbles are now extracted continuously from the sample water flow for subsequent gas measurements.

Proxies and measurement techniques for mineral dust in Antarctic ice cores.

To improve quantitative interpretation of ice core aeolian dust records, a systematic methodological comparison was made. This involved methods for water-insoluble particle counting (Coulter counter and laser-sensing particle detector), soluble ion analysis (ion chromatography and continuous flow analysis), elemental analysis (inductively coupled plasma mass spectroscopy at pH 1 and after full acid digestion), and water-insoluble elemental analysis (proton induced X-ray emission). Antarctic ice core samples covering the last deglaciation from the EPICA Dome C (EDC) and the EPICA Dronning Maud Land (EDML) cores were used. All methods correlate very well among each other, but the ratios of glacial age to Holocene concentrations, which are typically a factor approximately 100, differ between the methods by up to a factor of 2 with insoluble particles showing the largest variability. The recovery of ICP-MS measurements depends on the digestion method and is differentfor different elements and during different climatic periods. EDC and EDML samples have similar dust composition, which suggests a common dust source or a common mixture of sources for the two sites. The analyzed samples further reveal a change of dust composition during the last deglaciation.

High-resolution Greenland ice core data show abrupt climate change happens in few years.

The last two abrupt warmings at the onset of our present warm interglacial period, interrupted by the Younger Dryas cooling event, were investigated at high temporal resolution from the North Greenland Ice Core Project ice core. The deuterium excess, a proxy of Greenland precipitation moisture source, switched mode within 1 to 3 years over these transitions and initiated a more gradual change (over 50 years) of the Greenland air temperature, as recorded by stable water isotopes. The onsets of both abrupt Greenland warmings were slightly preceded by decreasing Greenland dust deposition, reflecting the wetting of Asian deserts. A northern shift of the Intertropical Convergence Zone could be the trigger of these abrupt shifts of Northern Hemisphere atmospheric circulation, resulting in changes of 2 to 4 kelvin in Greenland moisture source temperature from one year to the next.

Eight glacial cycles from an Antarctic ice core.

The Antarctic Vostok ice core provided compelling evidence of the nature of climate, and of climate feedbacks, over the past 420,000 years. Marine records suggest that the amplitude of climate variability was smaller before that time, but such records are often poorly resolved. Moreover, it is not possible to infer the abundance of greenhouse gases in the atmosphere from marine records. Here we report the recovery of a deep ice core from Dome C, Antarctica, that provides a climate record for the past 740,000 years. For the four most recent glacial cycles, the data agree well with the record from Vostok. The earlier period, between 740,000 and 430,000 years ago, was characterized by less pronounced warmth in interglacial periods in Antarctica, but a higher proportion of each cycle was spent in the warm mode. The transition from glacial to interglacial conditions about 430,000 years ago (Termination V) resembles the transition into the present interglacial period in terms of the magnitude of change in temperatures and greenhouse gases, but there are significant differences in the patterns of change. The interglacial stage following Termination V was exceptionally long--28,000 years compared to, for example, the 12,000 years recorded so far in the present interglacial period. Given the similarities between this earlier warm period and today, our results may imply that without human intervention, a climate similar to the present one would extend well into the future.