Search

The cold (−13.4°C), cryoencapsulated, anoxic, interstitial brine of the >27 m thick ice of Lake Vida (Victoria Valley, Antarctica) contains 49 µg · L−1 of perchlorate and 11 µg · L−1 of chlorate. Lake Vida brine (LVBr) may provide an analog for potential oxychlorine-rich subsurface brine on Mars. LVBr volatiles were analyzed by solid-phase microextraction (SPME) gas chromatography–mass spectrometry (GC-MS) with two different SPME fibers. With the exception of volatile organic sulfur compounds, most other volatiles observed were artifacts produced in the GC injector when the thermal decomposition products of oxychlorines reacted with reduced carbon derived from LVBr and the SPME fiber phases. Analysis of MilliQ water with perchlorate (40 µg · L−1) showed low level of organic artifacts, reflecting carbon limitation. In order to observe sample-derived organic compounds, both in analog samples and on Mars, the molar abundance of reduced carbon in a sample must exceed those of O2 and Cl2 produced during decomposition of oxychlorines. This suggests that the abundance of compounds observed by the Sample Analysis at Mars (SAM) instruments in Sheepbed samples (CB-3, CB5, and CB6) may be controlled by an increase in the reduced-carbon/oxychlorine ratio of these samples. To increase chances of in situ detection of Martian organics during pyrolysis-GC-MS, we propose that the derivatization agents stored on SAM may be used as an external source of reduced carbon, increasing artificially the reduced-carbon to perchlorate ratio during pyrolysis, allowing the expression of more abundant and perhaps more diverse Martian organic matter.

Carbon isotopic compositions of suspended organic matter and biomarker compounds were determined for 59 samples filtered from Southern Ocean surface waters in January 1994 along two north-south transects (WOCE SR3 from Tasmania to Antarctica, and across the Princess Elizabeth Trough (PET) east of Prydz Bay, Antarctica). Along the SR3 line, bulk organic matter show generally decreasing 13C contents southward, which are well correlated with increasing dissolved molecular carbon dioxide concentrations, CO2(aq). This relationship does not hold along the PET transect. Using concentrations and isotopic compositions of molecular compounds, we evaluate the relative roles of several factors affecting the δ13C of Southern Ocean suspended particulate organic matter. Along the WOCE SR3 transect, the concentration of CO2(aq) plays an important role. It is well described by a supply versus demand model for the extent of cellular CO2 utilization and its associated linear dependence of isotopic fractionation (EP) on the reciprocal of CO2(aq). An equally important factor appears to be changes in algal assemblages along the SR3 transect, with their contribution to isotopic fractionation also well described by the supply and demand model, when formulated to include the cell surface/volume control of supply. Changes in microalgal growth rates appear to have a minor effect on EP. Along the PET transect, algal assemblage changes and possibly changes in microalgal growth rates appear to strongly affect the carbon isotopic variations of suspended organic matter. These results can be used to improve the formulation of modern carbon cycle models that include phytoplankton carbon isotopic fractionation.

We present the first results of U37K′ and ealkenone from Emiliania huxleyi grown in chemostat cultures at constant temperature but at variable growth rates. A small change in U37K′ with growth rate was found for a noncalcifying strain of E. huxleyi, whereas results from a calcifying strain showed no systematic variation between U37K′ and growth rate. We conclude that nutrient-limited growth rate effects will not produce serious errors in paleotemperature determinations using U37K′ or U37K′. However, U37K′ values for the two strains differed significantly and apparent temperatures calculated using unsaturation ratios obtained from chemostat experiments are very different from those derived from batch culture experiments. Results of isotopic analyses of alkenones and bulk cells indicate no effect of growth rate on ealkenone (ealkenone=4.2±0.2‰). Constancy of ealkenone values is a requirement for environmental and paleoenvironmental interpretations. These results indicate that isotopic analyses of alkenones are ideal markers for paleo-[CO2(aq)] determinations.

Measurements of the U(37)(K') index and the absolute abundance of alkenones in marine sediments are increasingly used in paleoceanographic research as proxies of past sea surface temperature and haptophyte (mainly coccolith-bearing species) primary productivity, respectively. An important aspect of these studies is to be able to compare reliably data obtained by different laboratories from a wide variety of locations. Hence the intercomparability of data produced by the research community is essential. Here we report results from an anonymous interlaboratory comparison study involving 24 of the leading laboratories that carry out alkenone measurements worldwide. The majority of laboratories produce data that are intercomparable within the considered confidence limits. For the measurement of alkenone concentrations, however, there are systematic biases between laboratories, which might be related to the techniques employed to quantify the components. The maximum difference between any two laboratories for any two single measurements of U(37)(K') in sediments is estimated, with a probability of 95% to be C. In addition, the overall within-laboratory precision for the U(37)(K') temperature estimates is estimated to be C (95% probability). Similarly, from the analyses of alkenone concentrations the interlaboratory reproducibility is estimated at 32%, and the repeatability is estimated at 24%. The former is compared to a theoretical estimate of reproducibility and found to be excessively high. Hence there is certainly scope and a demonstrable need to improve reproducibility and repeatability of U(37)(K') and especially alkenone quantification data across the community of scientists involved in alkenone research.