Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

Physical oceanography, pore water chemistry and water column methane turover rates during POLARSTERN cruise ANT-XXIX/4

Recent studies have suggested that the marine contribution of methane from shallow regions and melting marine terminating glaciers may have been underestimated. Here we report on methane sources and potential sinks associated with methane seeps in Cumberland Bay, South Georgia's largest fjord system. The average organic carbon content in the upper 8 meters of the sediment is around 0.65 wt.%; this observation combined with Parasound data suggest that the methane gas accumulations probably originate from peat-bearing sediments currently located several tens of meters below the seafloor. Only one of our cores indicates upward advection; instead most of the methane is transported via diffusion. Sulfate and methane flux estimates indicate that a large fraction of methane is consumed by anaerobic oxidation of methane (AOM). Carbon cycling at the sulfate-methane transition (SMT) results in a marked fractionation of the d13C-CH4 from an estimated source value of -65 per mil to a value as low as -96 per mil just below the SMT. Methane concentrations in sediments are high, especially close to the seepage sites (~40 mM); however, concentrations in the water column are relatively low (max. 58 nM) and can be observed only close to the seafloor. Methane is trapped in the lowermost water mass, however, measured microbial oxidation rates reveal very low activity with an average turnover of 3.1 years. We therefore infer that methane must be transported out of the bay in the bottom water layer. A mean sea-air flux of only 0.005 nM/m²/s confirms that almost no methane reaches the atmosphere.

Radium 228 and Radium 226 in surface water of the Kara Sea and Laptev Sea

The surface water in the Transpolar Drift in the Arctic Ocean has a strong signature of 228Ra. In an earlier study of 228Ra in the open Arctic we showed that the major 228Ra source had to be in the Siberian shelf seas, but only a single shelf station was published so far. Here we investigate the sources of this signal on the Siberian shelves by measurements of 228Ra and 226Ra in surface waters of the Kara and Laptev Sea, including the Ob, Yenisey and Lena estuaries. In the Ob and Lena rivers we found an indication for a very strong and unexpected removal of both isotopes in the early stage of estuarine mixing, presumably related to flocculation of organic-rich material. Whereas 226Ra behaves conservatively on the shelf, the distribution of 228Ra is governed by large inputs on the shelves, although sources are highly variable. In the Kara Sea the maximum activity was found in the Baydaratskaya Bay, where tidal resonance and low freshwater supply favour 228Ra accumulation. The Laptev Sea is a stronger source for 228Ra than the Kara Sea. Since a large part of Kara Sea water flows through the Laptev Sea, the 228Ra signal in the Transpolar Drift can be described as originating on the Laptev shelf. The combined freshwater inputs from the Eurasian shelves thus produce a common radium signature with a 228Ra/226Ra activity ratio of 4.0 at 20% river water. The radium signals of the individual Siberian rivers and shelves cannot be separated, but their signal is significantly different from the signal produced on the Canadian shelf (Smith et al., in press). In this respect, the radium tracers add to the information given by Barium. Moreover, with the 5.8 year half-life of 228Ra, they have the potential to serve as a tracer for the age of a water mass since its contact with the shelves.

Gas, water and volume characteristics during controlled degassing experiments on ODP Leg 164 PCS cores

A pressurized core with CH4 hydrate or dissolved CH4 should evolve gas volumes in a predictable manner as pressure is released over time at isothermal conditions. Incremental gas volumes were collected as pressure was released over time from 29 pressure core sampler (PCS) cores from Sites 994, 995, 996, and 997 on the Blake Ridge. Most of these cores were kept at or near 0ºC with an ice bath, and many of these cores yielded substantial quantities of CH4. Volume-pressure plots were constructed for 20 of these cores. Only five plots conform to expected volume and pressure changes for sediment cores with CH4 hydrate under initial pressure and temperature conditions. However, other evidence suggests that sediment in these five and at least five other PCS cores contained CH4 hydrate before core recovery and gas release. Detection of CH4 hydrate in a pressurized sediment core through volume-pressure relationships is complicated by two factors. First, significant quantities of CH4-poor borehole water fill the PCS and come into contact with the core. This leads to dilution of CH4 concentration in interstitial water and, in many cases, decomposition of CH4 hydrate before a degassing experiment begins. Second, degassing experiments were conducted after the PCS had equilibrated in an ice-water bath (0ºC). This temperature is significantly lower than in situ values in the sediment formation before core recovery. Our results and interpretations for PCS cores collected on Leg 164 imply that pressurized containers formerly used by the Deep Sea Drilling Project (DSDP) and currently used by ODP are not appropriately designed for direct detection of gas hydrate in sediment at in situ conditions through volume-pressure relationships.

Planktic foraminifera of sediment core GeoB1710-3

In this study, we test various parameters in deep-sea sediments (bulk sediment parameters and changes in microfossil abundances and preservation character) which are generally accepted as indicators of calcium carbonate dissolution. We investigate sediment material from station GeoB 1710-3 in the northern Cape Basin (eastern South Atlantic), 280 km away from the Namibian coast, well outside today's coastal upwelling. As northern Benguela upwelling cells were displaced westward and periodically preceded the core location during the past 245 kyr (Volbers et al., submitted), GeoB 1710-3 sediments reflect these changes in upwelling productivity. Results of the most commonly used calcium carbonate dissolution proxies do not only monitor dissolution within these calcareous sediments but also reflect changes in upwelling intensity. Accordingly, these conventional proxy parameters misrepresent, to some extent, the extent of calcium carbonate dissolution. These results were verified by an independent dissolution proxy, the Globigerina bulloides dissolution index (BDX') (Volbers and Henrich, 2002, doi:10.1016/S0025-3227(02)00333-X). The BDX' is based on scanning electronic microscope ultrastructural investigation of planktonic foraminiferal tests and indicates persistent good carbonate preservation throughout the past 245 kyr, with the exception of one pronounced dissolution event at early oxygen isotopic stage (OIS) 6. The early OIS 6 is characterized by calcium carbonate contents, sand contents, and planktonic foraminiferal concentrations all at their lowest levels for the last 245 kyr. At the same time, the ratio of radiolarian to planktonic foraminiferal abundances and the ratio of benthic to planktonic foraminiferal tests are strongly increased, as are the rain ratio, the fragmentation index, and the BDX'. The sedimentary calcite lysocline rose above the core position and GeoB 1710-3 sediments were heavily altered, as attested to by the unusual accumulation of pellets, aggregates, sponge spicules, radiolaria, benthic foraminifera, and planktonic foraminiferal assemblages. Solely the early OIS 6 dissolution event altered the coarse fraction intensely, and is therefore reflected by all conventional calcium carbonate preservation proxies and the BDX'. We attribute the more than 1000 m rise of the sedimentary calcite lysocline to the combination of two processes: (a) a prominent change in the deep-water mass distribution within the South Atlantic and (b) intense degradation of organic material within the sediment (preserved as maximum total organic carbon content) creating microenvironments favorable for calcium carbonate dissolution.

Physical oceanography and processed 2 minutes-averaged continuous VM-ADCP profiles during POLARSTERN cruise ANT-XXVIII/3

The physical and biological carbon pumps in the different hydrographic and biogeochemical regimes of the Atlantic Sector of the Southern Ocean are controlled by a series of coupled physical, chemical and biological processes and a project named Eddy-Pump was designed to study them. The Eddy Pump field campaign was carried out during RV Polarstern Cruise ANT-XXVIII/3 between January and March 2012. Particular emphasis was laid on the differences which occur along the axis of the Antarctic Circumpolar Current (ACC) with its associated mesoscale eddy field. The study sites were selected in order to represent (1) the central ACC with its regular separation in different frontal jets, investigated by a meridional transect along 10°E; (2) a large-scale bloom west of the Mid-Atlantic Ridge which lasted several months with conspicuous chlorophyll-poor waters to its immediate east studied by a three-dimensional mesoscale survey centred at 12°40'W; and (3) the Georgia Basin north of the island of South Georgia, which regularly features an extended and dense phytoplankton bloom, was investigated by a mesoscale survey centred at 38°12'W. While Eddy-Pump represents an interdisciplinary project by design, we here focus on describing the variable physical environment within which the different biogeochemical regimes developed. For describing the physical environment we use measurements of temperature, salinity and density, of mixed-layer turbulence parameters, of dynamic heights and horizontal current vectors, and of flow trajectories obtained from surface drifters and submerged floats. This serves as background information for the analyses of biological and chemical processes and of biogeochemical fluxes addressed by other papers in this issue. The section along 10°E between 44°S and 53°S showed a classical ACC structure with well-known hydrographic fronts, the Subantarctic Front (SAF) at 46.5°S, the Antarctic Polar Front (APF) split in two, at 49.25°S and 50.5°S, and the Southern Polar Front (SPF) at 52.5°S. Each front was associated with strong eastward flows. The West Mid-Atlantic Ridge Survey showed a weak and poorly resolved meander structure between the APF and the SPF. During the first eight days of the survey the oceanographic conditions at the Central Station at 12°40'W remained reasonably constant. However after that, conditions became more variable in the thermocline with conspicuous temperature inversions and interleavings and also a decrease in temperature in the surface layer. At the very end of the period of observation the conditions in the thermocline returned to being similar to those observed during the early part of the period with however the mixed layer temperature raised. The period of enhanced thermohaline variability was accompanied by increased currents. The Georgia Basin Survey showed a very strong zonal jet at its northern edge which connects to a large cyclonic meander that itself joins an anticyclonic eddy in the southeastern quadrant. The water mass contrasts in this survey were stronger than in the West Mid-Atlantic Ridge Survey, but similar to those met along 10°E with the exception that the warm and saline surface water typical of the northern side of the SAF was not covered by the Georgia Basin Survey. Mixed layers found during Eddy-Pump were typically deep, but varied between the three survey areas; the mean depths and standard variations of the mixed layer along the 10°E were 77.2±24.7 m, at the West Mid-Atlantic Ridge 66.7±17.7 m, and in the Georgia Basin 36.8±10.7 m.

Physical oceanography from the TRACTOR project

Primary Objectives - Describe and quantify the present strength and variability of the circulation and oceanic processes of the Nordic Seas regions using primarily observations of the long term spread of a tracer purposefully released into the Greenland Sea Gyre in 1996. - Improve our understanding of ocean processes critical to the thermaholine circulation in the Nordic Seas regions so as to be able to predict how this region may respond to climate change. - Assess the role of mixing and ageing of water masses on the carbon transport and the role of the thermohaline circulation in carbon storage using water transports and mixing coefficients derived from the tracer distribution. Specific Objectives Perform annual hydrographic, chemical and SF6 tracer surveys into the Nordic regions in order to: - Measure lateral and diapycnal mixing rates in the Greenland Sea Gyre and in the surrounding regions. - Document the depth and rates of convective mixing in the Greenland Sea using the SF6 and the water masses characteristics. - Measure the transit time and transport of water from the Greenland Sea to surrounding seas and outflows. Document processes of water mass transformation and entrainment occurring to water emanating from the central Greenland Sea. - Measure diapycnal mixing rates in the bottom and margins of the Greenland Sea basin using the SF6 signal observed there. Quantify the potential role of bottom boundary-layer mixing in the ventilation of the Greenland Sea Deep Water in absence of deep convection. Monitor the variability of the entrainment of water from the Greenland Sea using time series auto-sampler moorings at strategic positions i.e., sill of the Denmark Strait, Labrador Sea, Jan Mayen fracture zone and Fram Strait. Relate the observed variability of the tracer signal in the outflows to convection events in the Greenland Sea and local wind stress events. Obtain a better description of deepwater overflow and entrainment processes in the Denmark Strait and Faeroe Bank Channel overflows and use these to improve modelling of deepwater overflows. Monitor the tracer invasion into the North Atlantic using opportunistic SF6 measurements from other cruises: we anticipate that a number of oceanographic cruises will take place in the north-east Atlantic and the Labrador Sea. It should be possible to get samples from some cruises for SF6 measurements. Use process models to describe the spread of the tracer to achieve better parameterisation for three-dimensional models. One reason that these are so resistant to prediction is that our best ocean models are as yet some distance from being good enough, to predict climate and climate change.

Planktonic foraminifera in the latest Maastrichtian of Walvis Ridge, South Atlantic

An abrupt global warming of 3-4°C occurred near the end of the Maastrichtian at 65.45-65.10 Ma. The environmental effects of this warm event are here documented based on stable isotopes and quantitative analysis of planktonic foraminifera at the South Atlantic DSDP Site 525A. Stable isotopes of individual species mark a rapid increase in temperature and a reduction in the vertical water mass stratification that is accompanied by a decrease in niche habitats, reduced species diversity and/or abundance, smaller species morphologies or dwarfing, and reduced photosymbiotic activity. During the warm event, the relative abundance of a large number of species decreased, including tropical-subtropical affiliated species, whereas typical mid-latitude species retained high abundances. This indicates that climate warming did not create favorable conditions for all tropical-subtropical species at mid-latitudes and did not cause a massive retreat in the local mid-latitude population. A noticeable exception is the ecological generalist Heterohelix dentata Stenestad that dominated during the cool intervals, but significantly decreased during the warm event. However, dwarfing is the most striking response to the abrupt warming and occurred in various species of different morphologies and lineages (e.g. biserial, trochospiral, keeled globotruncanids). Dwarfing is a typical reaction to environmental stress conditions and was likely the result of increased reproduction rates. Similarly, photosymbiotic activity appears to have been reduced significantly during the maximum warming, as indicated by decreased delta13C values. The foraminiferal response to climate change is thus multifaceted resulting in decreased species diversity, decreased species populations, increased competition due to reduced niche habitats, dwarfing and reduced photosymbiotic activity.

Ground truthing the Cd/Ca-carbon isotope relationship in foraminifera of the Greenland-Iceland-Norwegian Seas

In order to examine whether the paleoceanographic nutrient proxies, d13C and cadmium/calcium in foraminiferal calcite, are well coupled to nutrients in the region of North Atlantic Deep Water formation, we present da ta from two transects of the Greenland-Iceland-Norwegian Seas. Along Transect A (74.3°N, 18.3°E to 75.0°N, 12.5°W, 15 stations), we measured phosphate and Cd concentrations of modern surface sea water. Along Transect B (64.5°N, 0.7°W to 70.4°N, 18.2°W, 14 stations) we measured Cd/Ca ratios and d13C of the planktonic foraminifera Neogloboquadrina pachyderma sinistral in core top sediments. Our results indicate that Cd and phosphate both vary with surface water mass and are well correlated along Transect A. Our planktonic foraminiferal d13C data indicate similar nutrient variation with water mass along Transect B. Our Cd/Ca data hint at the same type of nutrient variability, but interpretations are hampered by low values close to the detection limit of this technique and therefore relatively large error bars. We also measured Cd and phosphate concentrations in water depth profiles at three sites along Transect A and the d13C of the benthic foraminifera Cibicidoides wuellerstorfi along Transect B. Modern sea water depth profiles along Transect A have nutrient depletions at the surface and then constant values at depths greater than 100 meters. The d13C of planktonic and benthic foraminifera from Transect B plotted versus depth also reflect surface nutrient depletion and deep nutrient enrichment as seen at Transect A, with a small difference between intermediate and deep waters. Overall we see no evidence for decoupling of Cd/Ca ratio and d13C in foraminiferal calcite from water column nutrient concentrations along these transects in a region of North Atlantic Deep Water formation.

Age model and Nd isotope ratios of DSDO Hole 43-386 and ODP Hole 210-1276A

Modern thermohaline circulation plays a role in latitudinal heat transport and in deep-ocean ventilation, yet ocean circulation may have functioned differently during past periods of extreme warmth, such as the Cretaceous. The Late Cretaceous (100-65 Ma) was an important period in the evolution of the North Atlantic Ocean, characterized by opening ocean gateways, long-term climatic cooling and the cessation of intermittent periods of anoxia (oceanic anoxic events, OAEs). However, how these phenomena relate to deep-water circulation is unclear. We use a proxy for deep-water mass composition (neodymium isotopes; e-Nd) to show that, at North Atlantic ODP Site 1276, deep waters shifted in the early Campanian (~78-83 Ma) from e-Nd values of ~-7 to values of ~-9, consistent with a change in the style of deep-ocean circulation but >10 Myr after a change in bottom water oxygenation conditions. A similar, but more poorly dated, trend exists in e-Nd data from DSDP Site 386. The Campanian e-Nd transition observed in the North Atlantic records is also seen in the South Atlantic and proto-Indian Ocean, implying a widespread and synchronous change in deep-ocean circulation. Although a unique explanation does not exist for the change at present, we favor an interpretation that invokes Late Cretaceous climatic cooling as a driver for the formation of Southern Component Water, which flowed northward from the Southern Ocean and into the North Atlantic and proto-Indian Oceans.

Nd, Pb, and Be isotopes of ferromanaganese crusts of the Atlantic Ocean

The isotopic composition of Nd in present-day deep waters of the central and northeastern Atlantic Ocean is thought to fingerprint mixing of North Atlantic Deep Water with Antarctic Bottom Water. The central Atlantic Romanche and Vema Fracture Zones are considered the most important pathways for deep water exchange between the western and eastern Atlantic basins today. We present new Nd isotope records of the deepwater evolution in the fracture zones obtained from ferromanganese crusts, which are inconsistent with simple water mass mixing alone prior to 3 Ma and require additional inputs from other sources. The new Pb isotope time series from the fracture zones are inexplicable by simple mixing of North Atlantic Deep Water and Antarctic Bottom Water for the entire past 33 Myr. The distinct and relatively invariable Nd and Pb isotope records of deep waters in the fracture zones appear instead to have been controlled to a large extent by contributions from Saharan dust and the Orinoco/Amazon Rivers. Thus the previously observed similarity of Nd and Pb isotope time series from the western and eastern North Atlantic basins is better explainable by direct supply of Labrador Seawater to the eastern basin via a northern pathway rather than by advection of North Atlantic Deep Water via the Romanche and Vema Fracture Zones.

Physical oceanography in the Western Bransfield Strait and Gerlache Strait during Austral summer 1995/96

n the framework of the FRUELA project, two oceanographic surveys were conducted by R/V Hespérides in the eastern Bellingshausen Sea, western basin of the Bransfield Strait and Gerlache Strait area during December 1995 and January 1996. The main hydrographic structures of the study domain were the Southern Boundary of the ACC and the Bransfield Front. The characteristics and zonation of local water masses are discussed in terms of temperature, salinity, dissolved oxygen, nutrient and inorganic carbon concentrations. Concentration intervals for water mass labelling, on the basis of chemical parameters in addition to the common theta/S-based classification, are defined. Silicate seems to be a very good discriminator for local water masses.

(Table T1) Radiolaria abundance of ODP Hole 175-1082A

A primary objective of Leg 175 was to investigate the upwelling history of the Benguela Current. Upwelling along the coast is found over the shelf in several well-established cells, as well as along the shelf-slope break, and extends over the 1000-m isobath. Streaming filaments along the coast also carry upwelled water off shore (Shannon, 1985). The upwelled nutrient-rich waters are sourced from the South Atlantic central water mass, which is a mixture of subtropical and subantarctic water masses. Below the central water mass lies Antarctic intermediate water (Shannon and Hunter, 1988, doi:10.2989/025776188784480735; Stramma and Peterson, 1989, doi:10.1175/1520-0485(1989)019<1440:GTITBC>2.0.CO;2). The upwelling system supports a robust marine community (Shannon and Pillar, 1986) where radiolarians are abundant (Bishop et al., 1978, doi:10.1016/0146-6291(78)90010-3). The endemic nature of radiolarians makes them useful in reconstructing the paleocirculation patterns. The biogeographic distribution of many species is limited by water-mass distribution. In a given geographic region, species may also have discrete depth habitats. However, their depth of occurrence can change worldwide because the depths of water masses vary with latitude (Boltovskoy, 1999). Consequently, species found at shallow depths at high latitudes (cold-water fauna) are observed deeper in the water column at lower latitudes. The low-latitude submergence of cold-water species broadens their distribution, resulting in species distributions that can cover multiple geographic regions (Kling, 1976, doi:10.1016/0011-7471(76)90880-9; Casey, doi:10.1016/0031-0182(89)90017-5; 1971; Boltovskoy, 1987, doi:10.1016/0377-8398(87)90014-4). Since radiolarian distribution is closely related to water-mass distribution and controlled by climatic conditions rather than geographic regions, similar assemblages characterize the equatorial, subtropical, transition, subpolar, and polar regions of ocean basins (Petrushevskaya, 1971a; Casey, 1989, doi:10.1016/0031-0182(89)90017-5; Boltovskoy, 1999). Numerous radiolarian species found in water masses in the Angola and Benguela Current systems have also been observed in plankton net samples, sediment traps, and surface-sediment studies in the Atlantic sector of the Southern Ocean, where they exhibited particular water-mass affinities (Abelmann, 1992a, doi:10.1007/BF00243107; Abelmann 1992b, doi:10.1007/BF00243108; Abelmann and Gowing, 1997, doi:10.1016/S0377-8398(96)00021-7). This report presents data on the radiolarian fauna recovered from Site 1082 sediments in the form of a survey of species reflecting the latitudinal migration of the Angola-Benguela Front and upwelling. The data constitute a time series of relative radiolarian abundances at very high resolution (every 20 cm) of the upper 12 m of Hole 1082A.

(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.