Geochemistry of the Kimmeridge Clay Formation, Dorset Coast

The Kimmeridge Clay Formation (KCF) and its equivalents worldwide represent one of the most prolonged periods of organic carbon accumulation of the Mesozoic. In this study, we use the molybdenum (Mo) stable isotope system in conjunction with a range of trace metal paleoredox proxies to assess how seawater redox varied both locally and globally during the deposition of the KCF. Facies with lower organic carbon contents (TOC 1-7 wt %) were deposited under mildly reducing (suboxic) conditions, while organic-rich facies (TOC >7 wt %) accumulated under more strongly reducing (anoxic or euxinic) local conditions. Trace metal abundances are closely linked to TOC content, suggesting that the intensity of reducing conditions varied repeatedly during the deposition of the KCF and may have been related to orbitally controlled climate changes. Long-term variations in d98/95Mo are associated with the formation of organic-rich intervals and are related to third-order fluctuations in relative sea level. Differences in the mean d98/95Mo composition of the organic-rich intervals suggest that the global distribution of reducing conditions was more extensive during the deposition of the Pectinatites wheatleyensis and lower Pectinatites hudlestoni zones than during the deposition of the upper Pectinatites hudlestoni and Pectinatites pectinatus zones. The global extent of reducing conditions during the Kimmerigidan was greater than today but was less widespread than during the Toarcian (Early Jurassic) oceanic anoxic event. This study also demonstrates that the Mo isotope system in Jurassic seawater responded to changes in redox conditions in a manner consistent with its behavior in present-day sedimentary environments.

Stable isotope record, and abundances of ice rafted debris and Neogloboquadrina pachyderma in sediments of the Iberian margin

This paper documents the migration of the Polar Front (PF) over the Iberian margin during some of the cold climatic extremes of the last 45 ka. It is based on a compilation of robust and coherent paleohydrological proxies obtained from eleven cores distributed between 36 and 42°N. Planktonic delta18O (Globigerina bulloides), ice-rafted detritus concentrations, and the relative abundance of the polar foraminifera Neogloboquadrina pachyderma sinistral were used to track the PF position. These three data sets, compared from core to core, show a consistent evolution of the sea surface paleohydrology along the Iberian margin over the last 45 ka. We focused on five time slices representative of cold periods under distinct paleoenvironmental forcings: the 8.2 ka event and the Younger Dryas (two recent cold events occurring within high values of summer insolation), Heinrich events 1 and 4 (reflecting major episodes of massive iceberg discharges into the North Atlantic), and the Last Glacial Maximum (typifying the highest ice volume accumulated in the Northern Hemisphere). For each event, we generated schematic maps mirroring past sea surface hydrological conditions. The maps revealed that the Polar Front presence along the Iberian margin was restricted to Heinrich events. The sea surface conditions during the Last Glacial Maximum were close to those at present day, except for the northern sites which briefly experienced subarctic conditions.

Present day and paleo-geographic coordinates, thicknesses and isopach area of the Early Eocene +19 ash layer (Table 1)

23 layers of altered volcanic ash (bentonites) originating from the North Atlantic Igneous Province have been recorded in early Eocene deposits of the Austrian Alps, about 1,900 km away from the source area. The Austrian bentonites are distal equivalents of the ''main ash-phase'' in Denmark and the North Sea basin. We have calculated the total eruption volume of this series as 21,000 km**3, which occurred in 600,000 years. The most powerful single eruption of this series took place 54.0 million years ago (Ma) and ejected ca. 1,200 km**3 of ash material, which makes it one of the largest basaltic pyroclastic eruptions in geological history. The clustering of eruptions must have significantly affected the incoming solar radiation in the early Eocene by the continuous production of stratospheric dust and aerosol clouds. This hypothesis is corroborated by oxygen isotope values, which indicate a global decrease of sea surface temperatures between 1 and 2 C during this major phase of explosive volcanism.

Chlorophyll-a concentrations in phytoplankton fractions in waters of the Black Sea

Comparison of daily and diel variability of chlorophyll-a concentration at three long-term stations in meso- and eutrophic regions indicates that their values are similar. Daily patterns of deviation in chlorophyll concentration in small and large phytoplankton fraction from average daily values are presented. In conformity with a hypothesis of daily removal rhythms correlated with changes in diel light-dark periods, it was concluded that the mesotrophic region during the dark period is characterized by predominance of grazing on large phytoplankton in the upper layers and accumulation of detritus from cell fragments in the lower layer, while during the light period smaller phytoplankton predominantly grazed. The eutrophic region is characterized by predominance of grazing on small phytoplankton fraction in the upper layers during the dark period and settling out of fecal pellets containing chlorophyll into deeper depths; but during the light period, large phytoplankton predominantly grazed throughout the whole water layer.

Geochemistry of sediments of stage 5 of the Nordic seas

Stable isotope, foraminifera and ice rafted detritus (IRD) records covering the last interglacial (the Eemian) from 7 sediment cores in a transect from the Norwegian to the Greenland Sea are presented. The percentages of Neogloboquadrina pachyderma (s.) and Globigerina quinqueloba, foraminiferal content, and to some extent planktonic stable isotope records, demonstrate marked, regional changes in surface water conditions. Importantly, the variability in the abundances of subpolar foraminifera and foraminiferal content are not coherent, implying that these two types of proxies fluctuated independently of each other and most likely reflect changes in sea surface temperature and surface water carbonate productivity, respectively. Paleoceanographic reconstructions demonstrate significant movements of the oceanographic fronts. At the warmest periods, the Arctic front was located far west of the present-day location, at least within the Iceland Sea region. At 126-125 ka, this was most probably due to a stronger or more westerly located Norwegian current. Within the later warm intervals, higher heat flux to the western part of the basin reflects a combination of a stronger Irminger current and/or a weaker east Greenland current. During the main cold spell at ~124 ka, a diffuse Arctic front had a more southeasterly location than today, and intrusion of Atlantic surface waters was probably limited to a narrow corridor in the Eastern Norwegian Sea. A general correspondence between minima in sea surface temperatures and light benthic delta18O may indicate enhanced influx of freshwater to the basin within the cold events. At least in the Norwegian Sea, we find some evidence that the changes in surface water conditions are associated with changes in deep water ventilation. The majority of the fluctuations may be related to occasional breakdown or reduction of the thermohaline circulation within the Nordic seas. In the earliest Eemian, this could result from meltwater forcing. During the remaining part of the last interglacial the fine balance between temperature and salinity, which the deep water formation is depending on, may have been disturbed by periodic increases in fresh water supply or variable influx of warm Atlantic surface waters.

Dissolved iron measured along surface transects of the CARUSO-EISENEX experiment

Measurements of Fe(II) and H2O2 were carried out in the Atlantic sector of the Southern Ocean during EisenEx, an iron enrichment experiment. Iron was added on three separate occasions, approximately every 8 days, as a ferrous sulfate (FeSO4) solution. Vertical profiles of Fe(II) showed maxima consistent with the plume of the iron infusion. While H2O2 profiles revealed a corresponding minima showing the effect of oxidation of Fe(II) by H2O2, observations showed detectable Fe(II) concentrations existed for up to 8 days after an iron infusion. H2O2 concentrations increased at the depth of the chlorophyll maximum when iron concentrations returned to pre-infusion concentrations (<80 pM) possibly due to biological production related to iron reductase activity. In this work, Fe(II) and dissolved iron were used as tracers themselves for subsequent iron infusions when no further SF6 was added. EisenEx was subject to periods of weak and strong mixing. Slow mixing after the second infusion allowed significant concentrations of Fe(II) and Fe to exist for several days. During this time, dissolved and total iron in the infusion plume behaved almost conservatively as it was trapped between a relict mixed layer and a new rain-induced mixed layer. Using dissolved iron, a value for the vertical diffusion coefficient Kz=6.7±0.7 cm**2/s was obtained for this 2-day period. During a subsequent surface survey of the iron-enriched patch, elevated levels of Fe(II) were found in surface waters presumably from Fe(II) dissolved in the rainwater that was falling at this time. Model results suggest that the reaction between uncomplexed Fe(III) and O2? was a significant source of Fe(II) during EisenEx and helped to maintain high levels of Fe(II) in the water column. This phenomenon may occur in iron enrichment experiments when two conditions are met: (i) When Fe is added to a system already saturated with regard to organic complexation and (ii) when mixing processes are slow, thereby reducing the dispersion of iron into under-saturated waters.

Distribution of planktonic foraminifera and paleotemperature reconstruction for the Subantarctic Zone of the South Atlantic

Pleistocene summer sea-surface temperatures (SSST) have been reconstructed on a composite core section recovered in the Subantarctic Zone of the Southern Ocean from planktonic foraminifers applying the Modern Analog Technique. The composite consists of Core PS2489-2 and the sections recovered at ODP Site 1090, and documents the last 1.83 Ma. Three distinct climatic periods can be identified that mirror the Pleistocene development of the Southern Ocean hydrography. Cold climatic conditions prevailed at 43°S during glacial as well as during interglacial periods during the early Pleistocene (1.83-0.87 Ma), indicating a northward shift of isotherms that characterize the present-day Polar Front Zone by about 7° of latitude. Evidence shows a strong linkage between Southern Ocean and low latitude climate during that interval time. Between the Mid-Pleistocene Revolution (ca. 0.9 Ma) and the Mid-Brunhes Event (ca. 0.4 Ma), we observe higher amplitude fluctuations in the SSST between glacial and interglacial periods, corresponding to the temperature range between the present Polar Front and Subantarctic Front. These climatic variations have been related to changes in the northern hemisphere ice sheets. The past 0.4 Ma are characterized by strong SSST variations, of up to 8°C, between glacials and interglacials. Only during the climatic optima (stages 11.3, 9.3, 7.5, 7.1, 5.5, and the early Holocene), SSST exceeded present SSST at the core locality (10.2°C). Although the carbonate dissolution record exhibits high variability during the Pleistocene, it can be shown that SSST estimates were not significantly biased. The Mid-Brunhes dissolution cycle as well as the Mid-Pleistocene enhanced carbonate preservation appear to belong to a global long-term variability in carbonate preservation.

Paleotemperature reconstructions of the Atlantic Sector of the Southern Ocean

Diatom assemblages from ODP Leg 177 sites 1093, 1094 and core PS2089-2, from the present Antarctic sea ice free zone and close to the Polar Front, were analyzed in order to reconstruct the climate development around the Mid-Brunhes Event 400 000 yr ago, as reflected by summer sea surface temperature (SSST) and sea ice distribution. Dense sample spacing allows a mean temporal resolution during Marine Isotope Stage (MIS) 11 (423-362 ka) of 300-400 yr. SSST values were estimated from diatom assemblages using a transfer function technique. The distribution pattern of sea ice diatoms indicates that the present-day ice free Antarctic Zone was seasonally covered by sea ice during the cold MIS 12 and MIS 10. These glacial periods are characterized by sea ice fluctuations with a periodicity of 3 and 1.85 kyr, suggesting the occurrence of Dansgaard-Oeschger-style millennial-scale oscillations in the Atlantic sector of the Southern Ocean during the glacial stages MIS 12 and MIS 10. Termination V (MIS 12/11) is characterized by a distinct temperature increase of 4-6°C, intersected especially at the southern site 1094 and core PS2089-2 by two distinct cooling events reminiscent of the Younger Dryas, which are associated with a northward shift of the winter sea ice edge in the Antarctic Zone. The SSST record is characterized by distinct temperature intervals bounded by stepwise, rapid changes. Maximum temperatures were reached during Termination V and the early MIS 11, exceeding modern values by 2°C over a period of 8 kyr. This pattern indicates a very early response of the Southern Ocean to global climate on Milankovitch-driven climate variability. The SSST optimum is marked by millennial-scale temperature oscillations with an amplitude of ca. 1°C and periodicities of ca. 1.85 and 1.47 kyr, probably reflecting changes in the ocean circulation system. The SSSTs during the MIS 11 temperature optimum do not exceed values obtained from other interglacial optima such as the early periods of MIS 5 or MIS 1 from the Antarctic Zone. However, the total duration of the warmest period was distinctly longer than observed from other interglacials. The comparison of the South Atlantic climate record with a high-resolution record from ODP Leg 162, site 980from the North Atlantic shows a strong conformity in the climate development during the studied time interval.

(Table 1) Content of sand fraction components in sediments of the interglacial MIS 7 optimum from Core LV28-42-4

Distribution of diatoms, radiolarians, planktonic and benthic foraminifers, and sediment components in fraction >0.125 mm was analyzed in a core obtained from the central Sea of Okhotsk within frameworks of the Russian-German KOMEX Project. The core section characterizes the period 190-350 ka, which corresponds to marine-isotopic stages (MIS) 7 to 10. During glacial MIS 10 and MIS 8, the basin accumulated terrigenous material lacking microfossils or containing them in low abundance, which reflects, along with their composition, heavy sea-ice conditions, suppressed bioproductivity, and bottom environment aggressive toward calcium carbonate. Interglacial MIS 9 was characterized by elevated bioproductivity with accumulation of diatomaceous ooze during the climatic optimum (328 to 320 ka). Water exchange with the Pacific was maximal from 328 to 324 ka ago. Environment became moderate and close to the present-day one at the end of the optimum exhibiting possible existence of a dichothermal layer with substantial amounts of surface Pacific water still flowing into the basin. Similar to interglacial MIS 5e and MIS 1, ''old'' Pacific water determined near-bottom environment in the central Sea of Okhotsk during that period, although influx of terrigenous material was higher, probably reflecting more humid climate of the region. Slight warming marked the terminal MIS 8 (approximately 260 ka ago). Paleoceanographic situation during the interglacial MIS 7 was highly variable: from warm-water to almost glacial. The main climatic optimum of MIS 7 occurred within 220-210 ka, when subsurface stratification increased and the dichothermal layer developed. Bottom environment during the studied time interval, except for the optimum of interglacial MIS 9, resembled those characteristic of glacial periods: actively formed ''young'' Okhotsk water displaced ''old'' Pacific deep water.

(Figure 2) Mean discharge per day (total and baseflow part) of the San Francisco River and daily precipitation at station ECPL (Planta), in 2007

We investigated controls on the water chemistry of a South Ecuadorian cloud forest catchment which is partly pristine, and partly converted to extensive pasture. From April 2007 to May 2008 water samples were taken weekly to biweekly at nine different subcatchments, and were screened for differences in electric conductivity, pH, anion, as well as element composition. A principal component analysis was conducted to reduce dimensionality of the data set and define major factors explaining variation in the data. Three main factors were isolated by a subset of 10 elements (Ca2+, Ce, Gd, K+, Mg2+, Na+, Nd, Rb, Sr, Y), explaining around 90% of the data variation. Land-use was the major factor controlling and changing water chemistry of the subcatchments. A second factor was associated with the concentration of rare earth elements in water, presumably highlighting other anthropogenic influences such as gravel excavation or road construction. Around 12% of the variation was explained by the third component, which was defined by the occurrence of Rb and K and represents the influence of vegetation dynamics on element accumulation and wash-out. Comparison of base- and fast flow concentrations led to the assumption that a significant portion of soil water from around 30 cm depth contributes to storm flow, as revealed by increased rare earth element concentrations in fast flow samples. Our findings demonstrate the utility of multi-tracer principal component analysis to study tropical headwater streams, and emphasize the need for effective land management in cloud forest catchments.

Geochemistry of the water column of southern lake Baikal during 1967-2005

At present, when the influence of human economic activity is progressively increasing, significant attention is devoted to the state of water ecosystems. All researchers engaged in these problems agree that the state of the water system (pollution and eutrophication) can only be estimated on the basis of long-term researches. Systemic monitoring (at least once per month) of ionic components (Ca2+, Mg2+, Na+, K+, bicarbonates, sulfates, and chlorides) in unfiltered water of Lake Baikal and its tributaries had been carried out under the supervision of Votintsev since 1947. Based on the analysis of systematic data on trophic components obtained during 1965-2005, we tried to estimate the present-day trophic status of the pelagic zone in the lake, define the trend of long-term changes of trophic components and understand the reasons of the distortion of cyclicity in the development of spring diatom algae, which create a favorable environment in any water basin. It should be noted that the station near Cape Polovinnyi is located 20 km away from the town of Baikal'sk. Wastewaters of the Baikal'sk pulp and paper mill is the main source of dioxins and furans in Baikal. Based on the significant difference between sulfate contents in wastewaters of the plant (>300 mg/l), tributaries of Baikal (7.5 mg/l), and waters in the southern part of the lake (3.9 mg/l), we defined the following periods: (i) period of natural seasonal patterns until 1967-1968 (prior to putting the Baikal'sk Mill into operation; (ii) period of weak anthropogenic pollution (1969-1985); and (iii) period of strong anthropogenic pollution since 1986.