Dating groundwater in the Bohemian Cretaceous Basin: Understanding tracer variations in the subsurface

The northern section of the Bohemian Cretaceous Basin has been the site of intensive U exploitation with harmful impacts on groundwater quality. The understanding of groundwater flow and age distribution is crucial for the prediction of the future dispersion and impact of the contamination. State of the art tracer methods (3H, 3He, 4He, 85Kr, 39Ar and 14C) were, therefore, used to obtain insights to ageing and mixing processes of groundwater along a north–south flow line in the centre of the two most important aquifers of Cenomanian and middle Turonian age. Dating of groundwater is particularly complex in this area as: (i) groundwater in the Cenomanian aquifer is locally affected by fluxes of geogenic and biogenic gases (e.g. CO2, CH4, He) and by fossil brines in basement rocks rich in Cl and SO4; (ii) a thick unsaturated zone overlays the Turonian aquifer; (iii) a periglacial climate and permafrost conditions prevailed during the Last Glacial Maximum (LGM), and iv) the wells are mostly screened over large depth intervals. Large disagreements in 85Kr and 3H/3He ages indicate that processes other than ageing have affected the tracer data in the Turonian aquifer. Mixing with older waters (>50 a) was confirmed by 39Ar activities. An inverse modelling approach, which included time lags for tracer transport throughout the unsaturated zone and degassing of 3He, was used to estimate the age of groundwater. Best fits between model and field results were obtained for mean residence times varying from modern up to a few hundred years. The presence of modern water in this aquifer is correlated with the occurrence of elevated pollution (e.g. nitrates). An increase of reactive geochemical indicators (e.g. Na) and radiogenic 4He, and a decrease in 14C along the flow direction confirmed groundwater ageing in the deeper confined Cenomanian aquifer. Radiocarbon ages varied from a few hundred years to more than 20 ka. Initial 14C activity for radiocarbon dating was calibrated by means of 39Ar measurements. The 14C age of a sample recharged during the LGM was further confirmed by depleted stable isotope signatures and near freezing point noble gas temperature. Radiogenic 4He accumulated in groundwater with concentrations increasing linearly with 14C ages. This enabled the use of 4He to validate the dating range of 14C and extend it to other parts of this aquifer. In the proximity of faults, 39Ar in excess of modern concentrations and 14C dead CO2 sources, elevated 3He/4He ratios and volcanic activity in Oligocene to Quaternary demonstrate the influence of gas of deeper origin and impeded the application of 4He, 39Ar and 14C for groundwater dating.

Radiocarbon dates of sediments from ODP Site 161-976

Multiproxy paleoenvironmental records (pollen and planktonic isotope) from Ocean Drilling Program Site 976 (Alboran Sea) document rapid ocean and climate variations during the last glacial that follow the Dansgaard-Oeschger climate oscillations seen in the Greenland ice core records, thus suggesting a close link of the Mediterranean climate swings with North Atlantic climates. Continental conditions rapidly oscillated through cold-arid and warm-wet conditions in the course of stadial-interstadial climate jumps. At the time of Heinrich events, i.e., maximum meltwater flux to the North Atlantic, western Mediterranean marine microflora and microfauna show rapid cooling correlated with increasing continental dryness. Enhanced aridity conceivably points to prolonged wintertime stability of atmospheric high-pressure systems over the southwestern Mediterranean in conjunction with cooling of the North Atlantic.

Chronostratigraphic framework at sites GeoB14403 and GeoB14414 from the Gela Basin, Sicily Channel

A multi-proxy chronological framework along with sequence-stratigraphic interpretations unveils composite Milankovitch cyclicity in the sedimentary records of the Last GlacialeInterglacial cycle at NE Gela Basin on the Sicilian continental margin. Chronostratigraphic data (including foraminifera-based eco-biostratigraphy and d18O records, tephrochronological markers and 14C AMS radiometric datings) was derived from the shallow-shelf drill sites GeoB14403 (54.6 m recovery) and GeoB14414 (27.5 m), collected with both gravity and drilled MeBo cores in 193 m and 146 m water depth, respectively. The recovered intervals record Marine Isotope Stages and Substages (MIS) from MIS 5 to MIS 1, thus comprising major stratigraphic parts of the progradational deposits that form the last 100-ka depositional sequence. Calibration of shelf sedimentary units with borehole stratigraphies indicates the impact of higher-frequency (20-ka) sea level cycles punctuating this 100-ka cycle. This becomes most evident in the alternation of thick interstadial highstand (HST) wedges and thinner glacial forced-regression (FSST) units mirroring seaward shifts in coastal progradation. Albeit their relatively short-lived depositional phase, these subordinate HST units form the bulk of the 100-ka depositional sequence. Two mechanisms are proposed that likely account for enhanced sediment accumulation ratios (SAR) of up to 200 cm/ka during these intervals: (1) intensified activity of deep and intermediate Levantine Intermediate Water (LIW) associated to the drowning of Mediterranean shelves, and (2) amplified sediment flux along the flooded shelf in response to hyperpycnal plumes that generate through extreme precipitation events during overall arid conditions. Equally, the latter mechanism is thought to be at the origin of undulated features resolved in the acoustic records of MIS 5 Interstadials, which bear a striking resemblance to modern equivalents forming on late-Holocene prodeltas of other Mediterranean shallow-shelf settings.

A comparison between multi-proxy and historical data of drift-ice conditions on the East Greenland shelf

The reduction in sea ice along the SE Greenland coast during the last century has severely impacted ice-rafting to this area. In order to reconstruct ice-rafting and oceanographic conditions in the area of Denmark Strait during the last ~150 years, we conducted a multiproxy study on three short (20 cm) sediment cores from outer Kangerdlugssuaq Trough (~300 m water depth). The proxy-based data obtained have been compared with historical and instrumental data to gain a better understanding of the ice sheet-ocean interactions in the area. A robust chronology has been developed based on 210Pb and 137Cs measurements on core PO175GKC#9 (~66.2°N, 32°W) and expanded to the two adjacent cores based on correlations between calcite weight percent records. Our proxy records include sea-ice and phytoplankton biomarkers, and a variety of mineralogical determinations based on the <2 mm sediment fraction, including identification with quantitative x-ray diffraction, ice-rafted debris counts on the 63-150 µm sand fraction, and source identifications based on the composition of Fe oxides in the 45-250 µm fraction. A multivariate statistical analysis indicated significant correlations between our proxy records and historical data, especially with the mean annual temperature data from Stykkishólmur (Iceland) and the storis index (historical observations of sea-ice export via the East Greenland Current). In particular, the biological proxies (calcite weight percent, IP25, and total organic carbon %) showed significant linkage with the storis index. Our records show two distinct intervals in the recent history of the SE Greenland coast. The first of these (ad 1850-1910) shows predominantly perennial sea-ice conditions in the area, while the second (ad 1910-1990) shows more seasonally open water conditions.

Micro-facies and µXRF element scanning data of Dead Sea sediment cores DSEn and 5017-1

Laminated lake sediments from the Dead Sea basin provide high-resolution records of climatic variability in the eastern Mediterranean region, which is especially sensitive to changing climatic conditions. In this study, we aim on detailed reconstruction of climatic fluctuations and related changes in the frequency of flood and dust deposition events at ca. 3300 and especially at 2800 cal. yr BP from high-resolution sediment records of the Dead Sea basin. A ca. 4-m-thick, mostly varved sediment section from the western margin of the Dead Sea (DSEn - Ein Gedi profile) was analysed and correlated to the new International Continental Scientific Drilling Program (ICDP) Dead Sea Deep Drilling Project core 5017-1 from the deep basin. To detect even single event layers, we applied a multi-proxy approach of high-resolution microscopic thin section analyses, micro-X-ray fluorescence (µ-XRF) element scanning and magnetic susceptibility measurements, supported by grain size data and palynological analyses. Based on radiocarbon and varve dating, two pronounced dry periods were detected at ~3500-3300 and ~3000-2400 cal. yr BP which are differently expressed in the sediment records. In the shallow-water core (DSEn), the older dry period is characterised by a thick sand deposit, whereas the sedimentological change at 2800 cal. yr BP is less pronounced and characterised mainly by an enhanced frequency of coarse detrital layers interpreted as erosion events. In the 5017-1 deep-basin core, both dry periods are depicted by halite deposits. The onset of the younger dry period coincides with the Homeric Grand Solar Minimum at ca. 2800 cal. yr BP. Our results suggest that during this period, the Dead Sea region experienced an overall dry climate, superimposed by an increased occurrence of flash floods caused by a change in synoptic weather patterns.

INTCAL98

The focus of this paper is the conversion of radiocarbon ages to calibrated (cal) ages for the interval 24,00-0 cal BP (Before Present, 0 cal BP = AD 1950), based upon a sample set of dendrochronologically dated tree rings, uranium-thorium dated corals, and varve-counted marine sediment. The 14C age-cal age information, produced by many laboratories, is converted to 14C profiles and calibration curves, for the atmosphere as well as the oceans. We discuss offsets in measured 14C ages and the errors therein, regional 14C age diferences, tree-coral 14C age comparisons and the time dependence of marine reservoir ages, and evaluate decadal vs. single-year 14C results. Changes in oceanic deepwater circulation, especialy for the 16,00-1,00 cal BP interval, are reflected in the Delta14C values of INTCAL98.

Holocene sedimentation in the Strait of Otranto, Mediterranean Sea

An extensive radiograph study of 24 undisturbed, up to 206-cm long box and gravity cores from the western part of the Strait of Otranto revealed a great variety of primary bedding structures and secondary burrowing features. The regional distribution of the sediments according to their structural, textural, and compositional properties reflects the major morphologic subdivisions of the strait into shelf, slope, and trough bottom (e.g., the bottom of the northern end of the Corfu-Kephallinia Trough, which extends from the northeastern Ionian Sea into the Strait of Otranto): (1) The Apulian shelf (0 to -170m) is only partly covered by very poorly sorted, muddy sands without layering. These relict(?) sands are rich in organic carbonate debris and contain glauconite and reworked (?Pleistocene) ooids. (2) The slope sediments (-170 to -1,000 m) are poorly sorted, sandy muds with a high degree of burrowing. One core (OT 5) is laminated and shows slump structures. An origin of these slumped sediment masses from older deposits higher on the slope was inferred from their abnormal compaction, color, texture, organic content, and mineral composition. (3) Cores from the northern end of the Corfu-Kephallinia Trough (-980 to -1,060 m) display a few graded sand layers, 2-5 cm (maximum 30 cm) thick with parallel and ripple-cross-laminations, deposited by oceanic bottom or small-scale turbidity currents. They are intercalated with homogeneous lutite. (4) Hemipelagic sediments prevail in the more southerly part of the Corfu-Kephallinia Trough and on the "Apulian-Ionian Ridge", the southern submarine extension of the Apulian Peninsula. Below a core depth of 160 cm, these cores have a laminated ("varved") zone, representing an Early Holocene (Boreal-Atlanticum) "stagnation layer" (14C age approximately 9,000 years). The terrigenous components of the surface sediments as well as those of the deeper sand layers can be derived from the Apulian shelf and the Italian mainland (Cretaceous Apulian Plateau and Gargano Mountains, southern Apennines, volcanic province of the Monte Vulture). Indicated by the heavy mineral glaucophane, a minor proportion of the sedimentary material is probably of Alpine origin. If this portion is considered to be first-cycle clastic material it reaches the Strait of Otranto after a longitudinal transport of 700 km via the Adriatic Sea. The lack of phyllosilicates in the coarse- to medium-grained shelf samples might be explained by the activity of the "Apulian Current" (surface velocities up to 4 knots) which in the past possibly has affected the bottom almost down to depths of the shelf edge. The percentage of planktonic organisms, and also the plankton: benthos ratio in the sediments is a useful indicator for bathymetry (depth zonation).

Carbon and Lead chemistry of sediments from the Middle Atlantic Bight

A mass budget was constructed for organic carbon on the upper slope of the Middle Atlantic Bight, a region thought to serve as a depocenter for fine-grained material exported from the adjacent shelf. Various components of the budget are internally consistent, and observed differences can be attributed to natural spatial variability or to the different time scales over which measurements were made. The flux of organic carbon to the sediments in the core of the depocenter zone, at a water depth of 1000 m, was measured with sediment traps to be 65 mg C m**-2 day**-1, of which 6-24 mg C m**-2 day**-1 is buried. Oxygen fluxes into the sediments, measured with incubation chambers attached to a free vehicle lander, correspond to total carbon remineralization rates of 49-70 mg C m**-2 day**-1. Carbon remineralization rates estimated from gradients of Corg within the mixed layer, and from gradients of dissolved ammonia and phosphate in pore waters, sum to only 4-6 mg C m**-2 day**-1. Most of the Corg remineralization in slope sediments is mediated by bacteria and takes place within a few mm of the sediment-water interface. Most of the Corg deposited on the upper slope sediments is supplied by lateral transport from other regions, but even if all of this material were derived from the adjacent shelf, it represents <2% of the mean annual shelf productivity. This value is further lowered by recognizing that as much as half of the Corg deposited on the slope is refractory, having originated by reworking from older deposits. Refractory Corg arrives at the sea bed with an average 14C age 600-900 years older than the pre-bomb 14C age of DIC in seawater, and has a mean life in the sediments with respect to biological remineralization of at least 1000 years. Labile carbon supplied to the slope, on the other hand, is rapidly and (virtually) completely remineralized, with a mean life of < 1 year. Carbon-14 ages of fine-grained carbonate and organic carbon present within the interstices of shelf sands are consistent with this material acting as a source for the old carbon supplied to the slope. Winnowing and export of reworked carbon may contribute to the often-described relationship between organic carbon preservation and accumulation rate of marine sediments.

Postglacial deposition of sand in the Eckernfoerder Bay, western Baltic Sea

At the NW-slope of Eckernforder Bay (Western Baltic) between 14 and 21 m water depth 7 sand cores were taken with a vibrocorer. The cores were between 85 and 250 cm long. The sand was analysed for grain size distribution, proportions of organic carbon and carbonate, and contents of microfossils. The radiometric age and stable carbon isotope ratios were determined on organic material from 14 sample. With regard to benthic foraminifera and other microorganisms four different types of depositional conditions could be distinguished: Types 1 and 2: two types of offshore sand areas. Type 3: lagoon and nearshore. Type 4: subaerial or limnic. Using sedimentological and geochemical parameters two formation areas could be distinguished with the aid of a discriminant analysis: offshore (types 1 and 2) and nearshore (types 3 and 4). A juxtaposition of core sections indicated two distinct profiles. Their ages fit into the picture of the assumed postglacial sea-level rise. The lagoon- and nearshore sands are interpreted as the result of sea-level stagnation at 17-18 m below present sea-level. The accumulation rates of the sand in the offshore areas are, with a maximum of 0.15 mm/yr., an order of magnitude smaller than in the mud areas, located several hundred metres away.

Geochemistry and diatom proxy record of ODP Site 127-797

Late Quaternary sediments of the Japan Sea are characterized by centimeter- to meter-scale alternations of dark and light layers which are synchronous basinwide. High-resolution analyses of the sediments from Ocean Drilling Program site 797 reveal that deposition of the meter-scale alternations reflect variations in paleoceanographic conditions which were closely associated with glacio-eustatic sea level changes through the modulation of the volume and character of the influx to the sea through the Tsushima Strait. The centimeter- to decimeter-scale alternations reflect millennial-scale variations which are possibly associated with Dansgaard-Oeschger (D-O) cycles, with each dark layer appearing to correspond to an interstadial. This variability is attributed to the development of a humid climate in central to eastern Asia and the consequent increase in discharge from the Huanghe and Changjiang Rivers during interstadials. This caused expansion of the East China Sea coastal water (ECSCW), which penetrated more strongly into the Japan Sea. The increased influence of the lower-salinity, nutrient-enriched ECSCW reduced deep water ventilation and enhanced the surface productivity, leading to the development of anoxic bottom waters and deposition of the dark layers. Thus the centimeter- to decimeter-scale alternations of the dark and light layers record wet and dry cycles in central to eastern Asia possibly associated with D-O cycles.

Isotopic composition of terrestrial plant waxes (dD and d13C of n-alkanes) of sediment core SO188_342 from the Northern Bay of Bengal for the last 18 ka

The Indian Summer Monsoon (ISM) is a major global climatic phenomenon. Long-term precipitation proxy records of the ISM, however, are often fragmented and discontinuous, impeding an estimation of the magnitude of precipitation variability from the Last Glacial to the present. To improve our understanding of past ISM variability, we provide a continuous reconstructed record of precipitation and continental vegetation changes from the lower Ganges-Brahmaputra-Meghna catchment and the Indo-Burman ranges over the last 18,000 years (18 ka). The records derive from a marine sediment core from the northern Bay of Bengal (NBoB), and are complemented by numerical model results of spatial moisture transport and precipitation distribution over the Bengal region. The isotopic composition of terrestrial plant waxes (dD and d13C of n-alkanes) are compared to results from an isotope-enabled general atmospheric circulation model (IsoCAM) for selected time slices (pre-industrial, mid-Holocene and Heinrich Stadial 1). Comparison of proxy and model results indicate that past changes in the dD of precipitation and plant waxes were mainly driven by the amount effect, and strongly influenced by ISM rainfall. Maximum precipitation is detected for the Early Holocene Climatic Optimum (EHCO; 10.5-6 ka BP), whereas minimum precipitation occurred during the Heinrich Stadial 1 (HS1; 16.9-15.4 ka BP). The IsoCAM model results support the hypothesis of a constant moisture source (i.e. the NBoB) throughout the study period. Relative to the pre-industrial period the model reconstructions show 20% more rain during the mid-Holocene (6 ka BP) and 20% less rain during the Heinrich Stadial 1 (HS1), respectively. A shift from C4-plant dominated ecosystems during the glacial to subsequent C3/C4-mixed ones during the interglacial took place. Vegetation changes were predominantly driven by precipitation variability, as evidenced by the significant correlation between the dD and d13C alkane records. When compared to other records across the ISM domain, precipitation and vegetation changes inferred from our records and the numerical model results provide evidence for a coherent regional variability of the ISM from the Last Glacial to the present.

Planktic foraminiferal Mg/Ca and oxygen isotopes, plus estimated d18Oseawater and ice volume corrected d18Oseawater for the past 35000 years of sediment core GeoB10069-3

Evidence from geologic archives suggests that there were large changes in the tropical hydrologic cycle associated with the two prominent northern hemisphere deglacial cooling events, Heinrich Stadial 1 (HS1; ~19 to 15 kyr BP; kyr BP = 1000 yr before present) and the Younger Dryas (~12.9 to 11.7 kyr BP). These hydrologic shifts have been alternatively attributed to high and low latitude origin. Here, we present a new record of hydrologic variability based on planktic foraminifera-derived d18O of seawater (d18Osw) estimates from a sediment core from the tropical Eastern Indian Ocean, and using 12 additional d18Osw records, construct a single record of the dominant mode of tropical Eastern Equatorial Pacific and Indo-Pacific Warm Pool (IPWP) hydrologic variability. We show that deglacial hydrologic shifts parallel variations in the reconstructed interhemispheric temperature gradient, suggesting a strong response to variations in the Atlantic Meridional Overturning Circulation and the attendant heat redistribution. A transient model simulation of the last deglaciation suggests that hydrologic changes, including a southward shift in the Intertropical Convergence Zone (ITCZ) which likely occurred during these northern hemisphere cold events, coupled with oceanic advection and mixing, resulted in increased salinity in the Indonesian region of the IPWP and the eastern tropical Pacific, which is recorded by the d18Osw proxy. Based on our observations and modeling results we suggest the interhemispheric temperature gradient directly controls the tropical hydrologic cycle on these time scales, which in turn mediates poleward atmospheric heat transport.

Radiocarbon ages and plateau definitions of sediments from the abyssal ocean

Ice core records demonstrate a glacial-interglacial atmospheric CO2 increase by ~100 ppm, while 14C calibration efforts document a strong decrease in atmospheric 14C concentration during this period. A calculated transfer of ~530 Gt of 14C depleted carbon is required to produce the deglacial coeval rise of carbon in the atmosphere and terrestrial biosphere. This amount is usually ascribed to oceanic carbon release, although the actual mechanisms remained elusive, since an adequately old and carbon-enriched deep-ocean reservoir seemed unlikely. Here we present a new, though still fragmentary, ocean-wide d14C dataset showing that during the Last Glacial Maximum (LGM) and Heinrich Stadial 1 (HS-1) the maximum 14C age difference between ocean deep waters and the atmosphere exceeded the modern values by up to 1500 14C yr, in the extreme reaching 5100 14C yr. Below 2000 m depth the 14C ventilation age of modern ocean waters is directly linked to the concentration of dissolved inorganic carbon (DIC). We propose as working hypothesis that the modern regression of DIC vs d14C also applies for LGM times, which implies that a mean LGM aging by ~600 14C yr corresponded to a global rise of ~85-115 µmol DIC/kg in the deep ocean. Thus, the prolonged residence time of ocean deep waters may indeed have made it possible to absorb an additional ~730-980 Gt DIC, one third of which possibly originated from intermediate waters. We also infer that LGM deep-water O2 dropped to suboxic values of <10µmol/kg in the Atlantic sector of the Southern Ocean, possibly also in the subpolar North Pacific. The outlined deglacial transfer of the extra aged, deep-ocean carbon to the atmosphere via the dynamic ocean-atmosphere carbon exchange would be sufficient to account for two trends observed, (1) for the increase in atmospheric CO2 and (2) for the 190-permil drop in atmospheric d14C during the so-called HS-1 'Mystery Interval', when atmospheric 14C production rates were largely constant.

Stable isotope record of the Okhotsk Sea

Stable isotope data on benthic foraminifera from more than 30 cores on the northern Emperor Seamounts and in the Okhotsk Sea are synthesized in paleohydrographic profiles spanning the depth range 1000-4000 m. Holocene (core-top) benthic foraminiferal d18O and d13C data are calibrated to modern hydrographic properties through measurements of d13C of SumCO2 and d18O of seawater. Cibicidoides stable isotope ratios are close to the d13C and equilibrium d18O of seawater, whereas Uvigerina d18O and d13C are variably offset from Cibicidoides. Glacial maximum d13C of Cibicidoides displays a different vertical profile than that of the Holocene. When results are adjusted by +0.32 per mil to account for the secular change in d13C during the last glacial maximum, the data coincide with the modern seawater and foraminiferal curves deeper than ~2 km. However, at shallower depths d13C gradually increases by as much as 1 per mil above the modern value. Furthermore, above 2 km the benthic d18O decreases by ~0.5 per mil. These results are consistent with a benthic front at ~2 km in the North Pacific (see Herguera et al., 1992), but they differ from interpretations based on trace metal data which indicate a source of nutrient-depleted deep water during glaciation. The isotopic data suggest that during glaciation there was a better ventilated watermass at intermediate depths in the far northwestern Pacific, it was relatively fresher than deep waters there, and deep waters were as nutrient-rich as today.

Deep water formation in the North Pacific and deglacial CO2 rise

Deep water formation in the North Atlantic and Southern Ocean is widely thought to influence deglacial CO2 rise and climate change; here we suggest that deep water formation in the North Pacific may also play an important role. We present paired radiocarbon and boron isotope data from foraminifera from sediment core MD02-2489 at 3640 m in the North East Pacific. These show a pronounced excursion during Heinrich Stadial 1, with benthic-planktic radiocarbon offsets dropping to ~350 years, accompanied by a decrease in benthic d11B. We suggest this is driven by the onset of deep convection in the North Pacific, which mixes young shallow waters to depth, old deep waters to the surface, and low-pH water from intermediate depths into the deep ocean. This deep water formation event was likely driven by an increase in surface salinity, due to subdued atmospheric/monsoonal freshwater flux during Heinrich Stadial 1. The ability of North Pacific Deep Water (NPDW) formation to explain the excursions seen in our data is demonstrated in a series of experiments with an intermediate complexity Earth system model. These experiments also show that breakdown of stratification in the North Pacific leads to a rapid ~30 ppm increase in atmospheric CO2, along with decreases in atmospheric d13C and D14C, consistent with observations of the early deglaciation. Our inference of deep water formation is based mainly on results from a single sediment core, and our boron isotope data are unavoidably sparse in the key HS1 interval, so this hypothesis merits further testing. However we note that there is independent support for breakdown of stratification in shallower waters during this period, including a minimum in d15N, younging in intermediate water 14C, and regional warming. We also re-evaluate deglacial changes in North Pacific productivity and carbonate preservation in light of our new data, and suggest that the regional pulse of export production observed during the Bølling-Allerød is promoted by relatively stratified conditions, with increased light availability and a shallow, potent nutricline. Overall, our work highlights the potential of NPDW formation to play a significant and hitherto unrealized role in deglacial climate change and CO2 rise.