Paleozoic-aged brine and authigenic helium preserved in an Ordovician shale aquiclude

Consideration of the geosphere for isolation of nuclear waste has generated substantial interest in the origin, age, and movement of fl uids and gases in low-permeability rock formations. Here, we present profi les of isotopes, solutes, and helium in porewaters recovered from 860 m of Cambrian to Devonian strata on the eastern fl ank of the Michigan Basin. Of particular interest is a 240-m-thick, halite-mineralized, Ordovician shale and carbonate aquiclude, which hosts Br–-enriched, post-dolomitic brine (5.8 molal Cl) originating as evaporated Silurian seawater. Authigenic helium that has been accumulating in the aquiclude for more than 260 m.y. is found to be isolated from underlying allochthonous, 3He-enriched helium that originated from the rifted base of the Michigan Basin and the Canadian Shield. The Paleozoic age and immobility of the pore fl uids in this Ordovician aquiclude considerably strengthen the safety case for deep geological repositories, but also provide new insights into the origin of deep crustal brines and opportunities for research on other components of a preserved Paleozoic porewater system.

Peak Last Glacial weathering intensity on the North American continent recorded by the authigenic Hf isotope composition of North Atlantic deep-sea sediments

We have retrieved radiogenic hafnium (Hf) isotope compositions (ɛHf) from authigenic Fe–Mn oxyhydroxides of deep northwest Atlantic sediments deposited over the past 26 ka to investigate the oceanic evidence of changes in dissolved weathering inputs from NE America during the last deglaciation. The extraction of seawater-derived Hf isotopic compositions from Fe–Mn oxyhydroxides is not a standard procedure. Comparisons between the Al/Hf ratios and Hf isotopic compositions of the chemically extracted authigenic phase on the one hand, and those of the corresponding detrital fractions on the other, provide evidence that the composition of past seawater has been reliably obtained for most sampled depths with our leaching procedures. This is endorsed most strongly by data for a sediment core from 4250 m water depth at the deeper Blake Ridge, for which consistent replicates were produced throughout. The Hf isotopic composition of the most recent sample in this core also closely matches that of nearby present day central North Atlantic seawater. Comparison with previously published seawater Nd and Pb isotope compositions obtained on the same cores shows that both Hf and Pb were released incongruently during incipient chemical weathering, but responded differently to the deglacial retreat of the Laurentide Ice Sheet. Hafnium was released more congruently during peak glacial conditions of the Last Glacial Maximum (LGM) and changed to typical incongruent interglacial ɛHf signatures either during or shortly after the LGM. This indicates that some zircon-derived Hf was released to seawater during the LGM. Conversely, there is no clear evidence for an increase in the influence of weathering of Lu-rich mineral phases during deglaciation, possibly since relatively unradiogenic Hf contributions from feldspar weathering were superimposed. While the authigenic Pb isotope signal in the same marine sediment samples traced peak chemical weathering rates on continental North America during the transition to the Holocene a similar incongruent excursion is notably absent in the Hf isotope record. The early change towards more radiogenic ɛHf in relation to the LGM may provide direct evidence for the transition from a cold-based to a warm-based Laurentide Ice Sheet on the Atlantic sector of North America.

Molybdenum isotope fractionation in pelagic euxinia: Evidence from the modern Black and Baltic Seas

Here we present stable isotope data for vertical profiles of dissolved molybdenum of the modern euxinic water columns of the Black Sea and two deeps of the Baltic Sea. Dissolved molybdenum in all water samples is depleted in salinity-normalized concentration and enriched in the heavy isotope (δ98Mo values up to + 2.9‰) compared to previously published isotope data of sedimentary molybdenum from the same range of water depths. Furthermore, δ98Mo values of all water samples from the Black Sea and anoxic deeps of the Baltic Sea are heavier than open ocean water. The observed isotope fractionation between sediments and the anoxic water column of the Black Sea are in line with the model of thiomolybdates that scavenge to particles under reducing conditions. An extrapolation to a theoretical pure MoS42− solution indicates a fractionation constant between MoS42− and authigenic solid Mo of 0.5 ± 0.3‰. Measured waters with all thiomolybdates coexisting in various proportions show larger but non-linear fractionation. The best explanation for our field observations is Mo scavenging by the thiomolybdates, dominantly — but not exclusively — present in the form of MoS42−. The Mo isotopic compositions of samples from the sediments and anoxic water column of the Baltic Sea are in overall agreement with those of the Black Sea at intermediate depth and corresponding sulphide concentrations. The more dynamic changes of redox conditions in the Baltic deeps complicate the Black Sea-derived relationship between thiomolybdates and Mo isotopic composition. In particular, the occasional flushing/mixing, of the deep waters, affects the corresponding water column and sedimentary data. δ98Mo values of the upper oxic waters of both basins are higher than predicted by mixing models based on salinity variations. The results can be explained by non-conservative behaviour of Mo under suboxic to anoxic conditions in the shallow bottom parts of the basin, most pronounced on the NW shelf of the Black Sea.

Dynamics of the last four glacial terminations recorded in Lake Van, Turkey

A well-dated suite of Lake Van climate-proxy data covering the last 360 ka documents environmental changes over 4 glacial/interglacial cycles in Eastern Anatolia, Turkey. The picture of cold and dry glacials and warm and wet interglacials emerging from pollen, organic carbon, authigenic carbonate content, elemental profiling by XRF and lithological analyses is inconsistent with classical interpretation of ox- ygen isotopic composition of carbonates pointing to a more complex pattern in Lake Van region. Detailed analysis of glacial terminations allows for the constraining of a depositional model explaining different patterns observed in all the proxies. We hypothesize that variations in relative contribution of rainfall, snowmelt and glacier meltwater recharging the basin have a very important role for all sedimentary processes in Lake Van. Lake level of glacial Lake Van, predominantly fed by snowmelt, was low, the water column was oxic, and carbonates precipitating in the epilimnion recorded the light isotopic signature of inflow. During terminations, increasing rainfall and significant supply of mountain glaciers' meltwater contributed to lake level rise. Increased rainfall enhanced density gradients in the water column, and hindered mixing leading to development of bottom-water anoxia. Carbonates precipitating during terminations show large fluctuations in their isotopic composition. Full interglacial conditions in Lake Van are characterized by high or slowly falling lake level. Rainfall and snowmelt feed the lake but due to re-established mixing, the isotopic composition of authigenic carbonates is heavier and closer to that of evaporation-influenced lake water than that of runoff representing snowmelt and atmospheric precipitation.

Provenance versus weathering control on the composition of tropical river mud (southern Africa)

This study presents an integrated mineralogical-geochemical data base on fine-grained sediments transported by all major rivers of southern Africa, including the Zambezi, Okavango, Limpopo, Olifants, Orange and Kunene. Clay mineralogy, bulk geochemistry, Sr and Nd isotopic signatures of river mud, considered as proxy of suspended load, are used to investigate the influence of source-rock lithology and weathering intensity on the composition of clay and silt produced in subequatorial to subtropical latitudes. Depletion in mobile alkali and alkaline-earth metals, minor in arid Namibia, is strong in the Okavango, Kwando and Upper Zambezi catchments, where recycling is also extensive. Element removal is most significant for Na, and to a lesser extent for Sr. Depletion in K, Ca and other elements, negligible in Namibia, is moderate elsewhere. The most widespread clay minerals are smectite, dominant in muds derived from Karoo or Etendeka flood basalts, or illite and chlorite, dominant in muds derived from metasedimentary rocks of the Damara Orogen or Zimbabwe Craton. Kaolinite represents 30-40% of clay minerals only in Okavango and Upper Zambezi sediments sourced in humid subequatorial Angola and Zambia. After subtracting the effects of recycling and of local accumulation of authigenic carbonates in soils, the regional distribution of clay minerals and chemical indices consistently reflect weathering intensity primarily controlled by climate. Bulk geochemistry identifies most clearly volcaniclastic sediments and mafic sources in general, but cannot discriminate the other sources of detritus in detail. Instead, Sr and Nd isotopic fingerprints are insensitive to weathering, and thus mirror faithfully the tectonic structure of the southern African continent. Isotopic tools thus represent a much firmer basis than bulk geochemistry or clay mineralogy in the provenance study of mudrocks.

Diagenesis of a light, tight-oil chert reservoir at the Ediacaran/Cambrian boundary, Sultanate of Oman

The Al Shomou Silicilyte Member (Athel Formation) in the South Oman Salt Basin shares many of the characteristics of a light, tight-oil (LTO) reservoir: it is a prolifi c source rock mature for light oil, it produces light oil from a very tight matrix and reservoir, and hydraulic fracking technology is required to produce the oil. What is intriguing about the Al Shomou Silicilyte, and different from other LTO reservoirs, is its position related to the Precambrian/Cambrian Boundary (PCB) and the fact that it is a ‘laminated chert‘ rather than a shale. In an integrated diagenetic study we applied microstructural analyses (SEM, BSE) combined with state-of-the-art stable isotope and trace element analysis of the silicilyte matrix and fractures. Fluid inclusion microthermometry was applied to record the salinity and minimum trapping temperatures. The microstructural investigations reveal a fi ne lamination of the silicilyte matrix with a mean lamina thickness of ca. 20 μm consisting of predominantly organic matter-rich and fi nely crystalline quartz-rich layers, respectively. Authigenic, micron-sized idiomorphic quartz crystals are the main matrix components of the silicilyte. Other diagenetic phases are pyrite, apatite, dolomite, magnesite and barite cements. Porosity values based on neutron density logs and core plug data indicate porosity in the silicilyte ranges from less than 2% to almost to 40%. The majority of the pore space in the silicilyte is related to (primary) inter-crystalline pores, with locally important oversized secondary pores. Pore casts of the silica matrix show that pores are extremely irregular in three dimensions, and are generally interconnected by a complex web or meshwork of fi ne elongate pore throats. Mercury injection capillary data are in line with the microstructural observations suggesting two populations of pore throats, with an effective average modal diameter of 0.4 μm. The acquired geochemical data support the interpretation that the primary source of the silica is the ambient seawater rather than hydrothermal or biogenic. A maximum temperature of ca. 45°C for the formation of microcrystalline quartz in the silicilyte is good evidence that the lithifi cation and crystallization of quartz occurred in the fi rst 5 Ma after deposition. Several phases of brittle fracturing and mineralization occurred in response to salt tectonics during burial. The sequences of fracture-fi lling mineral phases (dolomite - layered chalcedony – quartz – apatite - magnesite I+II - barite – halite) indicates a complex fl uid evolution after silicilyte lithifi cation. Primary, all-liquid fl uid inclusions in the fracturefi lling quartz are good evidence of growth beginning at low temperatures, i.e. ≤ 50ºC. Continuous precipitation during increasing temperature and burial is documented by primary two-phase fl uid inclusions in quartz cements that show brines at 50°C and fi rst hydrocarbons at ca. 70°C. The absolute timing of each mineral phase can be constrained based on U-Pb geochronometry, and basin modelling. Secondary fl uid inclusions in quartz, magnesite and barite indicate reactivation of the fracture system after peak burial temperature during the major cooling event, i.e. uplift, between 450 and 310 Ma. A number of fi rst-order trends in porosity and reservoir-quality distribution are observed which are strongly related to the diagenetic and fl uid history of the reservoir: the early in-situ generation of hydrocarbons and overpressure development arrests diagenesis and preserves matrix porosity. Chemical compaction by pressure dissolution in the fl ank areas could be a valid hypothesis to explain the porosity variations in the silicilitye slabs resulting in lower porosity and poorer connectivity on the fl anks of the reservoir. Most of the hydrocarbon storage and production comes from intervals characterized by Amthor et al. 114488 preserved micropores, not hydrocarbon storage in a fracture system. The absence of oil expulsion results in present-day high oil saturations. The main diagenetic modifi cations of the silicilyte occurred and were completed relatively early in its history, i.e. before 300 Ma. An instrumental factor for preserving matrix porosity is the diffi culty for a given slab to evacuate all the fl uids (water and hydrocarbons), or in other words, the very good sealing capacity of the salt embedding the slab.

The sediment record of the past 200 years in a Swiss high-alpine lake: Hagelseewli (2339 ma.s.l.)

Sediment cores spanning the last two centuries were taken in Hagelseewli, a high-elevation lake in the Swiss Alps. Contiguous 0.5 cm samples were analysed for biological remains, including diatoms, chironomids, cladocera, chrysophyte cysts, and fossil pigments. In addition, sedimentological and geochemical variables such as loss-on-ignition, total carbon, nitrogen, sulphur, grain-size and magnetic mineralogy were determined. The results of these analyses were compared to a long instrumental air temperature record that was adapted to the elevation of Hagelseewli by applying mean monthly lapse rates. During much of the time, the lake is in the shadow of a high cliff to the south, so that the lake is ice-covered during much of the year and thus decoupled from climatic forcing. Lake biology is therefore influenced more by the duration of ice-cover than by direct temperature effects during the short open-water season. Long periods of ice-cover result in anoxic water conditions and dissolution of authigenic calcites, leading to carbonate-free sediments. The diversity of chironomid and cladoceran assemblages is extremely low, whereas that of diatom and chrysophyte cyst assemblages is much higher. Weak correlations were observed between the diatom and chrysophyte cyst assemblages on the one hand and summer or autumn air temperatures on the other, but the proportion of variance explained is low, so that air temperature alone cannot account for the degree of variation observed in the paleolimnological record. Analyses of mineral magnetic parameters, spheroidal carbonaceous particles and lead suggest that atmospheric pollution has had a significant effect on the sediments of Hagelseewli, but little effect on the water quality as reflected in the lake biota.

Northern Mediterranean climate since the Middle Pleistocene: a 637 ka stable isotope record from Lake Ohrid (Albania/Macedonia)

Lake Ohrid (Macedonia/Albania) is an ancient lake with unique biodiversity and a site of global significance for investigating the influence of climate, geological, and tectonic events on the generation of endemic populations. Here, we present oxygen (δ18O) and carbon (δ13C) isotope data from carbonate over the upper 243 m of a composite core profile recovered as part of the Scientific Collaboration on Past Speciation Conditions in Lake Ohrid (SCOPSCO) project. The investigated sediment succession covers the past ca. 637 ka. Previous studies on short cores from the lake (up to 15 m, < 140 ka) have indicated the total inorganic carbon (TIC) content of sediments to be highly sensitive to climate change over the last glacial–interglacial cycle. Sediments corresponding to warmer periods contain abundant endogenic calcite; however, an overall low TIC content in glacial sediments is punctuated by discrete bands of early diagenetic authigenic siderite. Isotope measurements on endogenic calcite (δ18Oc and δ13Cc) reveal variations both between and within interglacials that suggest the lake has been subject to palaeoenvironmental change on orbital and millennial timescales. We also measured isotope ratios from authigenic siderite (δ18Os and δ13Cs) and, with the oxygen isotope composition of calcite and siderite, reconstruct δ18O of lake water (δ18Olw) over the last 637 ka. Interglacials have higher δ18Olw values when compared to glacial periods most likely due to changes in evaporation, summer temperature, the proportion of winter precipitation (snowfall), and inflow from adjacent Lake Prespa. The isotope stratigraphy suggests Lake Ohrid experienced a period of general stability from marine isotope stage (MIS) 15 to MIS 13, highlighting MIS 14 as a particularly warm glacial. Climate conditions became progressively wetter during MIS 11 and MIS 9. Interglacial periods after MIS 9 are characterised by increasingly evaporated and drier conditions through MIS 7, MIS 5, and the Holocene. Our results provide new evidence for long-term climate change in the northern Mediterranean region, which will form the basis to better understand the influence of major environmental events on biological evolution within Lake Ohrid.

Human–climate interactions in the central Mediterranean region during the last millennia: The laminated record of Lake Butrint (Albania)

Lake Butrint (39°47 N, 20°1 E) is a ca. 21 m deep, coastal lagoon located in SW Albania where finely-laminated sediments have been continuously deposited during the last millennia. The multi-proxy analysis (sedimentology, high-resolution elemental geochemistry and pollen) of a 12 m long sediment core, supported by seven AMS radiocarbon dates and 137Cs dating, enable a precise reconstruction of the environmental change that occurred in the central Mediterranean region during the last ∼4.5 cal kyrs BP. Sediments consist of triplets of authigenic carbonates, organic matter and clayey laminae. Fluctuations in the thickness and/or presence of these different types of seasonal laminae indicate variations in water salinity, organic productivity and runoff in the lake's catchment, as a result of the complex interplay of tectonics, anthropogenic forcing and climate variability. The progradation of the Pavllo river delta, favoured by variable human activity from the nearby ancient city of Butrint, led to the progressive isolation of this hydrological system from the Ionian Sea. The system evolved from an open bay to a restricted lagoon, which is consistent with archaeological data. An abrupt increase in mass-wasting activity between 1515 and 1450 BC, likely caused by nearby seismic activity, led to the accumulation of 24 homogenites, up to 17 cm thick. They have been deposited during the onset of finely laminated sedimentation, which indicates restricted, anoxic bottom water conditions and higher salinity. Periods of maximum water salinity, biological productivity, and carbonate precipitation coincide with warmer intervals, such as the early Roman Warm Period (RWP) (500 BC–0 AD), the Medieval Climate Anomaly (MCA) (800–1400 AD) and recent times (after 1800 AD). Conversely, lower salinity and more oxic conditions, with higher clastic input were recorded during 1400–500 BC, the Late Roman and the Early Medieval periods (0–800 AD) and during the Little Ice Age (1400–1800 AD). Hydrological fluctuations recorded in Butrint are in phase with most central and western Mediterranean records and correlate with NAO variability. In contrast, opposite hydrological patterns have been recorded in the Eastern Balkans and the Levant during the last millennium, emphasizing a complex spatial variability in the region. Phases of maximum settlement intensity in Butrint (Roman-Late Antique) coincide with warmer and/or stable climate periods (0–800 AD and MCA, respectively), indicating a long-term influence of climatic conditions on human activities. The Late Holocene sedimentary record of Lake Butrint demonstrates the complex interplay of climate variability, tectonics and human impact in the recent evolution of coastal Mediterranean regions.

Mineral-magnetic record of Late Quaternary climatic changes in a high Alpine lake

The magnetic properties of a sediment core from a high altitude lake in the Swiss Alps were compared with palynological and geochemical data to link climatic and mineral magnetic variations. According to pollen data, the sediments extend from the present to the Younger Dryas, i.e., they cover more than 10,000 years of environmental change in the Alps. The major change in magnetic properties corresponds to the climatic warming of the early Holocene. High-coercivity magnetic minerals that characterize the Late Glacial period almost disappeared during the Holocene and the concentration of ferrimagnetic minerals increased sharply. The contribution of superparamagnetic grains also decreased in the Holocene sediments. Similar variations in {SP} content and coercivity, of smaller magnitude, are found in the Holocene and are interpreted to represent minor climatic variations. Comparison with the historical record of the last 1000 years confirms this interpretation. The magnetic mineralogy, the superparamagnetic contents, and the {IRM} intensity in the coarse-grained, Late Glacial sediments are similar to those measured in the catchment bedrock. This indicates a detrital origin. The different properties and the higher concentration of magnetic minerals in the Holocene sediments are due to authigenic phases. Magnetic properties provide a high resolution record of climatic change. They are sensitive even to small variations that are not recorded in the pollen or {LOI} data. Magnetic parameters show fine-scale variation and constitute a valuable supplement to conventional climatic indicators.