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.

137Cs and 90Sr depositions, and 137Cs/90Sr ratios of samples from the Kraton-3 underground nuclear explosion site, Russia

Strontium-90 activity concentrations in surface soils and areal deposition densities have been studied at a site contaminated by an accidental release to atmosphere from the underground nuclear explosion 'Kraton-3' conducted near the Polar Circle (65.9°N, 112.3°E) within the territory of the former USSR in 1978. In 2001-2002, the ground surface contamination at 14 plots studied ranged from 20 to 15000 kBq/m**2, which significantly exceeds the value of 0.44 kBq/m**2 deduced for three background plots. The zone with substantial radiostrontium contamination extends, at least, 2.5 km in a north-easterly direction from the borehole. The average 137Cs/90Sr ratio in the ground contamination originated from the 'Kraton-3' fallout was estimated to be 0.55, which is significantly different from the ratio of 2.05 evaluated for background plots contaminated mostly from global fallout. Although vertical migration of 90Sr in all undisturbed soil profiles studied is more rapid than that for 137Cs, the depth of percolation of both radionuclides into the ground is mostly limited to the top 10-20 cm, which may be explained, primarily, by permafrost conditions. The horizontal migration rate of radiostrontium in the aqueous phase exceeds the radiocaesium migration rate by many times. This phenomenon seems to be a reason for the significant enrichment of the soil surface layers by radiostrontium at some sites, with variations occurring in accordance with small-scale irregularities of landscape.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.

Degradation of [14C]GlcDGD in the marine sediment by monitoring radioactivity in the aqueous and gas phase using liquid scintillation counting (LSC) techniques

An experiment was conceived in which we monitored degradation of GlcDGD. Independent of the fate of the [14C]glucosyl headgroup after hydrolysis from the glycerol backbone, the 14C enters the aqueous or gas phase whereas the intact lipid is insoluble and remains in the sediment phase. Total degradation of GlcDGD then is obtained by combining the increase of radioactivity in the aqueous and gaseous phases. We chose two different sediment to perform this experiment. One is from microbially actie surface sediment sampled in February 2010 from the upper tidal flat of the German Wadden Sea near Wremen (53° 38' 0N, 8° 29' 30E). The other one is deep subsurface sediments recovered from northern Cascadia Margin during Integrated Ocean Drilling Program Expedition 311 [site U1326, 138.2 meters below seafloor (mbsf), in situ temperature 20 °C, water depth 1,828 m. We performed both alive and killed control experiments for comparison. Surface and subsurface sediment slurry were incubated in the dark at in situ temperature, 4 °C and 20 °C for 300 d, respectively. The sterilized slurry was stored at 20 °C. All incubations were carried out under N2 headspace to ensure anaerobic conditions. The sampling frequency was high during the first half-month, i.e., after 1, 2, 7, and 14 d; thereafter, the sediment slurry was sampled every 2 months. At each time point, samples were taken in triplicate for radioactivity measurements. After 300 d of incubation, no significant changes of radioactivity in the aqueous phase were detected. This may be the result of either the rapid turnover of released [14C] glucose or the relatively high limit of detection caused by the slight solubility (equivalent to 2% of initial radioactivity) of GlcDGD in water. Therefore, total degradation of GlcDGD in the dataset was calculated by combining radioactivity of DIC, CH4, and CO2, leading to a minimum estimate.

Delta 13C measured on alkenones of surface sediment samples GeoB1008-6 to GeoB3603-1 from the South Atlantic

We have analyzed the stable carbon isotopic composition of the diunsaturated C37 alkenone in 29 surface sediments from the equatorial and South Atlantic Ocean. Our study area covers different oceanographic settings, including sediments from the major upwelling regions off South Africa, the equatorial upwelling, and the oligotrophic western South Atlantic. In order to examine the environmental influences on the sedimentary record the alkenone-based carbon isotopic fractionation (Ep) values were correlated with the overlying surface water concentrations of aqueous CO2 ([CO2(aq)]), phosphate, and nitrate. We found Ep positively correlated with 1/[CO2(aq)] and negatively correlated with [PO43-] and [NO3-]. However, the relationship between Ep and 1/[CO2(aq)] is opposite of what is expected from a [CO2(aq)] controlled, diffusive uptake model. Instead, our findings support the theory of Bidigare et al. (1997, doi:10.1029/96GB03939) that the isotopic fractionation in haptophytes is related to nutrient-limited growth rates. The relatively high variability of the Ep-[PO4] relationship in regions with low surface water nutrient concentrations indicates that here other environmental factors also affect the isotopic signal. These factors might be variations in other growth-limiting resources such as light intensity or micronutrient concentrations.