Some hydrophysical and hydrochemical parameters of the upper part of the hydrogen sulfide zone in the Black Sea, September 11-22, 1994

Features of spatial variability of hydrogen sulfide in the northeastern part of the Black Sea are estimated. Some technical aspects of H2S concentration determination in the anoxic zone are discussed: in its upper part at H2S concentration <30 µmol/l, the photometric method is recommended, while for deeper layers the iodometric method should be used. With linearity of vertical distribution of hydrogen sulfide and ammonium taken into account their vertical gradients are estimated as 0.49+/-0.04 µmol/m and 0.19+/-0.06 µmol/m respectively. It is shown that the upper boundary of the H2S layer corresponds to the isopycnal surface with Sigma_t = 16.19+/-0.05 arbitrary units. Special attention is paid to relationship of hydrogen sulfide distribution with hydrophysical features in the region under study, in particular in the coastal zone. It is shown that hydrodynamic conditions control spatial distribution of hydrogen sulfide. On the basis of isopycnal treatment of the H2S field existence of a coastal convergence zone is proved, and peculiarities are recognized of vertical circulation in the main Black Sea gyre and coastal anticyclonic eddies; here hydrogen sulfide serves as a tracer of hydrophysical mixing processes.

Geomicrobiology, bulk sediment characteristics and pore water chemistry of sediment cores from Laguna Potrok Aike, southern Patagonia

Authigenic minerals can form in the water column and sediments of lakes, either abiotically or mediated by biological activity. Such minerals have been used as paleosalinity and paleoproductivity indicators and reflect trophic state and early diagenetic conditions. They are also considered potential indicators of past and perhaps ongoing microbial activity within sediments. Authigenic concretions, including vivianite, were described in late glacial sediments of Laguna Potrok Aike, a maar lake in southernmost Argentina. Occurrence of iron phosphate implies specific phosphorus sorption behavior and a reducing environment, with methane present. Because organic matter content in these sediments was generally low during glacial times, there must have been alternative sources of phosphorus and biogenic methane. Identifying these sources can help define past trophic state of the lake and diagenetic processes in the sediments. We used scanning electron microscopy, phosphorus speciation in bulk sediment, pore water analyses, in situ ATP measurements, microbial cell counts, and measurements of methane content and its carbon isotope composition (d13C CH4) to identify components of and processes in the sediment. The multiple approaches indicated that volcanic materials in the catchment are important suppliers of iron, sulfur and phosphorus. These elements influence primary productivity and play a role in microbial metabolism during early diagenesis. Authigenic processes led to the formation of pyrite framboids and revealed sulfate reduction. Anaerobic oxidation of methane and shifts in pore water ion concentration indicated microbial influence with depth. This study documents the presence of active microbes within the sediments and their relationship to changing environmental conditions. It also illustrates the substantial role played by microbes in the formation of Laguna Potrok Aike concretions. Thus, authigenic minerals can be used as biosignatures in these late Pleistocene maar sediments.

Physical, chemical and biological characteristics of disturbed and undisturbed Arctic lakes, Northwest Territories

1. Global warming is predicted to cause changes in permafrost cover and stability in the Arctic. Zones of high ion concentration in regions of ice-rich permafrost are a reservoir of chemicals that can potentially be transferred to fresh waters during thawing. Consequently, input of enriched runoff from the thaw and sediment and vegetation from the landscape could alter lakes by affecting their geochemistry and biological production. 2. Three undisturbed lakes and five lakes disturbed by retrogressive permafrost thaw slumps were sampled during late summer of 2006 to assess the potential effects of thermokarst shoreline slumping on water and sediment chemistry, the underwater light regime, and benthic macrophyte biomass and community structure. 3. Undisturbed lakes had sediments rich in organic material and selected micronutrients, while disturbed lakes had sediments richer in calcium, magnesium and strontium, greater transparency of the water column, and a well-developed submerged macrophyte community. 4. It is postulated that enriched runoff chemistry may alter nutrient availability at the sediment-water interface and also the degradation of organic material, thus affecting lake transparency and submerged macrophytes. The results suggest that retrogressive permafrost slumping can significantly affect food webs in arctic tundra lakes through an increase in macrophyte biomass and development of a more complex benthic habitat.

Carbonate concentrations of ODP Leg 115 samples

We measured carbonate concentrations in Pleistocene and Pliocene sediments deposited at Sites 709, 710, and 711. Carbonate concentrations exhibit low-amplitude, long-wave length (300-400 k.y. period) variations at the shallowest sites (709 and 710). Before 2.47 Ma, all three sites exhibit higher frequency (100 k.y. period) variations. The deepest site (711) exhibited low-amplitude variations and very low concentrations up to the Gauss/Matuyama magnetic reversal (2.47 Ma), then concentrations abruptly increased. After 2.47 Ma, carbonate concentrations at Site 711 exhibited the same periodic changes as at Site 709. Although a long wave-length periodicity (260-280 k.y.) occurs at these sites after 2.47 Ma, the 100 k.y. period is absent. The dominant periods observed in these data are those found in the eccentricity component of the earth's orbital geometry. Estimates of carbonate accumulation at Sites 709 and 710 document that surface-water productivity decreased near the Gauss/Matuyama magnetic reversal whereas accumulation at Site 711 increased. These results indicate that the rate of carbonate preservation in the deep Indian Ocean increased at that time. This increase in preservation may have re- sulted from a decrease in the production rate of carbonate in tropical oceans of the world. Carbonate accumulation esti- mated from sediments in shallow locations (~3000-3800 m) of the Atlantic and Pacific oceans also indicates that carbonate production decreased at this time. A consequence of lowered surface-water productivity is increased carbonate ion concentration of the deep ocean and better preservation of carbonate on the seafloor.

Middle Miocene stable carbon and oxygen isotope record of foraminifera of ODP Hole 120-747A

Paleoceanographic variability at southern high latitude Ocean Drilling Program (ODP) Site 747 was investigated in this study through the interval which spans the Middle Miocene Climate Transition (MMCT). Between 15.0 and 12.2 million years ago (Ma), foraminiferal d18O records derived from both benthic (Cibicidoides spp.) and planktonic taxa (Globorotalia praescitula and Globigerina bulloides) reveal a history of changes in water column thermal and salinity structure and a strong imprint of seasonality. Prior to the MMCT, in the interval between 14.35 and 13.9 Ma, G. bulloides displays relatively high d18O values similar to those of G. praescitula, interpreted to indicate weakening of the thermocline and/or increased seasonality with cooler early-spring and/or late-fall temperatures. Following this interval, G. bulloidesd18O values diverge significantly from benthic and G. praescitula values, with G. bulloides values remaining relatively low for at least 600 kyr following the benthic foraminiferal d18O shift during the MMCT at ~13.9 Ma. This divergence in d18O records occurs in direct association with the Mi3 cooling and glaciation event and may suggest: (1) a strengthening of the vertical temperature gradient, with greater cooling of deep waters than surface waters, (2) changes in the depth habitat of G. bulloides, (3) changes in the dominant season of G. bulloides calcification, (4) modification of surface-water d18O values in association with enhanced sea-ice formation, (5) increased surface-water carbonate ion concentration, and/or (6) a significant decrease in surface-water salinity across the MMCT. The first of these possible scenarios is not likely, particularly in light of recent Mg/Ca evidence for significant surface-water cooling in the Southern Ocean associated with the MMCT. Of the remaining possibilities, we favor a change in surface salinity to explain the observed trends in d18O values and hypothesize that surface salinity may have decreased by up to 2 salinity units at ~13.9 Ma. In this scenario, the development of a lower-salinity Antarctic surface layer coincided with regional cooling of both surface and deep waters of the Southern Ocean during the Mi3 glaciation of East Antarctica, and contributed into the dominance of Neogloboquadrina spp. between 13.8 and 13.2 Ma. Additionally, the distinct patterns observed in planktonic foraminiferal d18O records spanning the MMCT correspond with changes in the vertical d13C gradient between planktonic and benthic foraminiferal records and major changes in planktonic foraminiferal assemblages at Site 747, providing further evidence of the environmental significance of this climatic transition.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.