ALBERT

Description: The aim of this paper is to analyze and compare mineralogy and geochemistry of copper-zinc sulfide ores from the Logachev-2 and Rainbow hydrothermal fields of the Mid-Atlantic Ridge (MAR) confined to serpentinite protrusions. It was found that Zn(Fe) and Cu, Fe(Zn) sulfides had been deposited in black smokers pipes almost simultaneously from intermittently flowing, nonequilibrium H2S-low solutions of different temperatures. Pb isotope composition confirmed that the deep oceanic crust had been a source of lead. The ores from the Rainbow field are 20-fold higher in Co than ores restricted to basalts and show a high ratio of Co/Ni=46. The ores from the Rainbow field are enriched in 34S isotope (aver. d34S=10 per mil) because of constant flow of cold sea water into the subsurface zone of the hydrothermal system. Ores from the Logachev-2 field are 8 times higher in gold compared to other MAR regions. Sulfide ores from the Rainbow and Logachev-2 fields have no analogues among MAR ore occurrences in terms of enrichment in valuable components (Zn, Cd, Co, and Au).

Description: Composition of ore minerals in MAR sulflde occurrences related to ultramaflc rocks was studied using methods of mineragraphy, electron microscopy, microprobe analysis, and X-ray analysis. Objects are located at various levels of maturity of sulflde mounds owing to differences in age, duration and degree of activity of the following hydrothermal systems: generally inactive Logatchev-1 field (up to 66.5 ka old), inactive Logatchev-2 field (3.9 ka), and generally active Rainbow field (up to 23 ka). Relative to MAR submarine ore occurrences in the basalt substrate, mineralization in the hydrothermal fields mentioned above is characterized by high contents of Au, Cd, Co, and Ni, along with presence of accessory minerals of Co and Ni. The studied mounds differ in quantitative ratios of major minerals and structural-textural features of ores that suggest their transformation. Ores in the Logatchev-1 field are characterized by the highest Cu content and development of a wide range of multistage contrast exsolution structures of isocubanite and bornite. In the Logatchev-2 field, sphalerite-chalcopyrite and gold-arsenic exsolution structures are present, but isocubanite exsolution structures are less diverse and contrast. The Rainbow field is marked by presence of homogenous isocubanite and the subordinate development of exsolution structures. The authors have identified four new phases in the Cu-Fe-S system. Phases X and Y (close to chalcopyrite and isocubanite, respectively) make up lamellae among isocubanite exsolution products in the Logatchev-1 and Logatchev-2 fields. Phase Y includes homogenous zones in zonal chimneys of the Rainbow field. Phases A and B formed in the orange bornite domain at low-temperature alteration of chalcopyrite in the Logatchev-1 field. Mineral assemblages of the Cu-S system are most abundant and diverse in the Logatchev-1 field, but their development is minimal in the Logatchev-2 field where mainly Cu-poor sulfides of the geerite-covellite series have been identified. Specific features of mineral assemblages mentioned above reflect the maturity grade of sulfide mounds and can serve as indicators of maturity.

Description: Soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs) in marine river fan sediments have a potential use for determining changes in the mean annual temperature (MAT) and pH of the river watershed soils. Prior to their incorporation in marine sediments, the compounds are transported to the marine system by rivers. However, emerging evidence suggests that the brGDGTs in freshwater systems can be derived from both soil run-off and in situ production. The production of brGDGTs in the river system can complicate the interpretation of the brGDGT signal delivered to the marine system. Therefore, we studied the distribution of brGDGT lipids in suspended particulate matter (SPM) of the Yenisei River. Chromatographic improvements allowed quantification of the recently described hexamethylated brGDGT isomer, characterized by having two methyl groups at the 6/6' instead of the 5/5' positions, in an environmental dataset for the first time. This novel compound was the most abundant brGDGT in SPM from the Yenisei. Its fractional abundance correlated well with that of the 6-methyl isomer of the hexamethylated brGDGT that contains one cyclopentane moiety. The Yenisei River watershed is characterized by large differences in MAT (〉11 °C) as it spans a large latitudinal range (46-73°N), which would be expected to be reflected in brGDGT distributions of its soils. However, the brGDGT distributions in its SPM show little variation. Furthermore, the reconstructed pH values are high compared to the watershed soil pH. We, therefore, hypothesize that the brGDGTs in the Yenisei River SPM are predominantly produced in situ and not primarily derived from erosion of soil. This accounts for the absence of a change in the temperature signal, as the river water temperature is more stable. Using a lake calibration, the reconstructed temperature values agree with the mean summer temperatures (MST) recorded. The brGDGTs delivered to the sea by the Yenisei River during this season are thus not soil-derived, possibly complicating the use of brGDGTs in marine sediments for palaeoclimate reconstructions.

Description: The distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in soils has been shown to correlate with pH and mean annual air temperature. Because of this dependence brGDGTs have found an application as palaeoclimate proxies in coastal marine sediments, based on the assumption that their distribution is not altered during the transport from soils to marine systems by rivers. To study the processes acting on the brGDGT distributions, we analysed the full suite of brGDGTs, including the recently described 6-Me brGDGTs, in both the suspended particulate matter (SPM) of the Siberian Yenisei River and the SPM and sediments of its outflow in the Kara Sea. The brGDGT distribution in the SPM of the Yenisei River was fairly constant and characterized by high abundances of the 6-Me brGDGTs, reflecting their production at the neutral pH of the river water. However, the brGDGT distribution showed marked shifts in the marine system. Firstly, in the Yenisei River Mouth, the fractional abundance of the 6-Me brGDGTs decreases sharply. The brGDGT signature in the Yenisei River Mouth possibly reflects brGDGTs delivered during the spring floods that may carry a different distribution. Also, coastal cliffs were shown to contain brGDGTs and to influence especially those sites without major river inputs (e.g. Khalmyer Bay). Further removed from the river mouth, in-situ production of brGDGTs in the marine system influences the distribution. However, also the fractional abundance of the tetramethylated brGDGT Ia increases, resulting in a distribution that is distinct from in-situ produced signals at similar latitudes (Svalbard). We suggest that this shift may be caused by preferential degradation of labile (riverine in-situ produced) brGDGTs and the subsequent enrichment in less labile (soil) material. The offshore distribution indeed agrees with the brGDGT distribution encountered in a lowland peat. This implies that the offshore Kara Sea sediments possibly carry a soil-dominated signal, indicating potential for palaeoclimate reconstructions at this site. Both in the river system and coastal cliffs, brGDGTs were much more abundant than crenarchaeol, an archaeal isoprenoid GDGT, resulting in high (〉0.93) Branched and Isoprenoid Tetraether (BIT) index values. Moving downstream in the marine sediments, a decrease in brGDGT concentrations, coeval with an increase in crenarchaeol, resulted in decreasing BIT index values. This decrease correlates with changes in bulk proxies for terrigenous input (d13Corg, C/N), confirming the use of the BIT index to trace the delivery of river-transported and coastal cliff-derived terrigenous organic matter.

Description: Bacteriohopanepolyols (BHPs) are ubiquitous bacterial membrane lipids, encountered in soils, river and marine suspended particulate matter (SPM) and sediments. Their abundance and distribution provides a direct means to identify bacterial inputs and can be used to trace soil-derived bacterial organic matter (OM) and in some cases the presence of bacterial groups and their activities in aquatic systems. We have studied the BHP distribution in the SPM of a major Siberian River (Yenisei River) that crosses a large latitudinal gradient, draining a large part of Mongolia and Siberian Russia. The Yenisei River is the main river to flow into the Kara Sea, a shelf sea of the Arctic Ocean. We show that the BHP distribution and concentration of SPM and surface sediments of the Yenisei Outflow in the Kara Sea allow to trace soil-marker BHPs and evaluate the performance of the R'soil index, a proxy developed to trace bacterial soil-derived OM. Soil-marker BHPs are present in the Yenisei River, and their concentration decreases from the Yenisei River Outflow into the offshore marine sediments. The R'soil correlates well with an independent proxy for bacterial OM, the BIT-index (r**2 = 0.82) and has a moderate correlation with the d13Corg values, a bulk OM proxy for terrigenous input (r**2 = 0.44). Consequently, the R'soil index performs well in the Kara Sea, strengthening its application for tracing bacterial OM in the Arctic Ocean, both in modern and downcore sediments. Furthermore, a suite of BHPs that are characteristic for methanotrophic bacteria, i.e. 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) and 35-aminobacteriohopane-31,32,33,34-tetrol (aminotetrol), is encountered in the Yenisei Outflow sediments. These components are partly sourced from terrigenous sources, but are likely also produced in-situ in the marine sediments. The distribution of the pentafunctionalized cyclitol ether BHP in the marine systems is noteworthy, and indicates that it can possibly be applied as a marker for cyanobacterial biomass in marine sediments.