Timescales and mechanisms of REE and Hf uptake in fossil bones

Rare earth element (REE) patterns of fossil bones and teeth are widely used as proxies for provenance, taphonomy, and palaeoenvironment. In order to investigate if fossil bones behave as closed systems over geologic time, REE profiles were analysed by LA-ICPMS along cross sections of 54 bones from various well-characterised and well-dated settings. These include terrestrial and marine diagenetic environments, covering Early Triassic to Holocene ages. In general, all fossil bones exhibit the highest REE concentrations at the outer rim, gradually decreasing by up to four orders of magnitude toward the inner bone cortex. Intra-bone REE concentration gradients decrease significantly from Quaternary via Tertiary to Mesozoic specimens, suggesting long term REE uptake and open system behaviour of fossil bone. This view is further corroborated by ¹⁷⁶Lu-¹⁷⁶Hf dating of selected samples, all yielding significantly younger ages than the known chronostratigraphic ages. Hence, there is clear evidence for long term open system behaviour of fossil bones with respect to REE, which is in marked contrast to currently accepted models suggesting that REE uptake is only early diagenetic. Although unexpected, statistically significant four to seven point isochrons are observed for four fossil dinosaur bone samples and one Upper Triassic Mastodonsaurus tooth with MSWDs ranging from 0.083 to 4.5. Notably, mobility of Lu alone cannot account for the observed age patterns. Assuming constant Lu uptake rates over time, the radiometric ages should only be as low as half of the chronostratigraphic age. However, a six-point isochron defined by subsamples of a single Upper Triassic Mastodonsaurus tooth yields an age of 65.2 ± 1.1 Ma (MSWD = 0.68), much younger than half of the stratigraphic age (ca. 234 Ma). Hence, Hf must also undergo late diagenetic exchange. Likely mechanisms to account for the presence of statistically meaningful isochrons as well as for the late diagenetic exchange of both REE and Hf are diffusion, adsorption, and dissolution-reprecipitation processes.     

Rare earth element composition of Paleogene vertebrate fossils from Toadstool Geologic Park,Nebraska, USA

Fossil bones and teeth from terrestrial environments encode unique rare earth and trace element (REE and TE) signatures as a function of redox conditions, pH, concentrations of complexing ligands, and water-colloid interactions. This signature is set early in the fossilization process and serves as a paleoenvironmental and paleoclimatic proxy. These signatures can also be used to interpret temporal and spatial averaging within vertebrate accumulations, and can help relocate displaced fossil bones back into stratigraphic context. Rare earth elements in vertebrate fossils from upper Eocene and Oligocene strata of Toadstool Geologic Park, northwestern Nebraska, record mixing and evolution of Paleogene vadose or groundwaters and variations in paleoenvironments. REE signatures indicate that HREE-enriched alkaline groundwater reacted with LREE- and MREE-enriched sediments to produce 3-component mixtures. REE signatures become increasingly LREE- and MREE-enriched toward the top of the studied section as the paleoenvironment became cooler and drier, suggesting that REE signatures may be climate proxies. Time series analysis suggests that REE ratios are influenced by cycles of ca. 1050, 800, 570, 440, and 225 ka, similar to some previously determined Milankovitch astronomical and climate periodicities.     

Models of diffusion-limited uptake of trace elements in fossils and rates of fossilization

Many fossils are assumed to take up trace elements by a process of combined diffusion plus adsorption (DA), yet in principle composition profiles can be explained by several different diffusion-limited processes, including diffusion plus reaction or recrystallization (DR) and double-medium diffusion (DMD). The DA and DMD models are supported by REE and U composition profiles across fossil teeth, measured by laser-ablation ICP-MS, that show error-function - like diffusion profiles into enamel from the dentine-enamel interface and concentrations in the interior of enamel that are at original biogenic levels or higher. Published composition and age profiles in some Pleistocene bones may be better explained by a DR model. All three diffusion models imply linear behavior between age and distance squared, vastly simplifying U-series dating methods for Pleistocene fossils. Modeled uptake rates for fossil teeth yield a strict minimum bound on durations of about one decade to one century. The similarity of diffusion profiles in teeth, irrespective of depositional ages ranging from ∼30 ka to >30 Ma, implies that uptake occurred quickly, with a maximum duration of a few tens of kyr for typical fossil enamel; faster uptake is implied for typical fossil bone and dentine. Disparities in these uptake estimates compared to some archeological bone may reflect sampling and preservation bias for paleontological vs. archeological materials.     

The effect of tissue structure and soil chemistry on trace element uptake in fossils

Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H₂O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO₃. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element “plumes” down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ∼5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients (K_d’s). Although acid leaches and bulk digestion of soils yield comparable fossil-soil K_d’s among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H₂O leachates instead reveal radically different K_d’s in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE K_d’s and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading K_d’s for many trace elements, especially the REE, and H₂O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.     

Nd and Sr isotope compositions in modern and fossil bones - Proxies for vertebrate provenance and taphonomy

Rare earth elements (REE), while not essential for the physiologic functions of animals, are ingested and incorporated in ppb concentrations in bones and teeth. Nd isotope compositions of modern bones of animals from isotopically distinct habitats demonstrate that the ¹⁴³Nd/¹⁴⁴Nd of the apatite can be used as a fingerprint for bedrock geology or ambient water mass. This potentially allows the provenance and migration of extant vertebrates to be traced, similar to the use of Sr isotopes. Although REE may be enriched by up to 5 orders of magnitude during diagenesis and recrystallization of bone apatite, in vivo¹⁴³Nd/¹⁴⁴Nd may be preserved in the inner cortex of fossil bones or enamel. However, tracking the provenance of ancient or extinct vertebrates is possible only for well-preserved archeological and paleontological skeletal remains with in vivo-like Nd contents at the ppb-level. Intra-bone and -tooth REE analysis can be used to screen for appropriate areas. Large intra-bone Nd concentration gradients of 10¹-10³ are often measured. Nd concentrations in the inner bone cortex increase over timescales of millions of years, while bone rims may be enriched over millenial timescales. Nevertheless, ε_Nd values are often similar within one ε_Nd unit within a single bone. Larger intra-bone differences in specimens may either reflect a partial preservation of in vivo values or changing ε_Nd values of the diagenetic fluid during fossilization. However, most fossil specimens and the outer rims of bones will record taphonomic ¹⁴³Nd/¹⁴⁴Nd incorporated post mortem during diagenesis. Unlike REE patterns, ¹⁴³Nd/¹⁴⁴Nd are not biased by fractionation processes during REE-uptake into the apatite crystal lattice, hence the ε_Nd value is an important tracer for taphonomy and reworking. Bones and teeth from autochthonous fossil assemblages have small variations of ±1 ε_Nd unit only. In contrast, fossil bones and teeth from over 20 different marine and terrestrial fossil sites have a total range of ε_Nd values from -13.0 to 4.9 (n = 80), often matching the composition of the embedding sediment. This implies that the surrounding sediment is the source of Nd in the fossil bones and that the specimens of this study seem not to have been reworked. Differences in ε_Nd values between skeletal remains and embedding sediment may either indicate reworking of fossils and/or a REE-uptake from a diagenetic fluid with non-sediment derived ε_Nd values. The latter often applies to fossil shark teeth, which may preserve paleo-seawater values. Complementary to ε_Nd values, ⁸⁷Sr/⁸⁶Sr can help to further constrain the fossil provenance and reworking.     

Geochemical trends through time and lateral variability of diatom floras in the Pleistocene Olorgesailie Formation, southern Kenya Rift Valley

The Olorgesailie Formation (1.2-0.49 Ma) consists of fluvial and lacustrine rift sediments that have yielded abundant Acheulean artifacts and a fossil hominin (Homo cf. erectus). In testing prior understandings of the paleoenvironmental context, we define nine new geochemical zones. A Chemical Index of Alteration suggests increased catchment weathering during deposition of Members 1, 2, 7, 11, and 13. Biophile elements (Br, S) peak in M8-9 and lower M13 possibly reflecting increased input from soil erosion. REE data show that the Magadi Trachytes supplied most siliciclastic grains. Sixteen diatom stages indicate conductivities of 200-16,000 μS cm^− 1 and pH of 7.5-9.5 for five deep-water lakes, ten shallow lakes and sixteen wetlands. These results are compared with diatom data from other sections in the basin and show aquatic spatial variability over km-scale distances. Similar floras are traceable over several kilometers for M2, M3 and M9, indicating broadly homogeneous lacustrine conditions during these times, but diatoms in other members imply variable conditions, some related to local tectonic controls. This lateral and temporal variability emphasizes the importance of carrying out stratigraphic sampling at multiple sites within a basin in efforts to define the environmental context relevant to human evolution.     

Stable isotope chemistry of fossil bone as a new paleoclimate indicator

During fossilization, bone is thought to recrystallize and alter chemically on timescales of kyr to a few tens of kyr, i.e., similar to the timescale for formation of soils. Therefore, C- and O-isotope compositions of bone apatite should correlate with trends in soil water composition and aridity, and serve as paleoclimate indicators. This hypothesis was tested by analyzing C- and O-isotope compositions of the CO₃ component of fossil bone apatite from mid-Oligocene through late Pleistocene units in Oregon and western Idaho, including the John Day (19.4-30.0 Ma), Mascall (15.2-15.8 Ma), and Rattlesnake (7.2-7.8 Ma) Formations, whose paleosol sequences have been studied in detail, and the Juntura (10-11 Ma), Hagerman (3.2 Ma), and Fossil Lake (<23-650 ka) fossil localities. Tooth enamel δ¹⁸O values provide a baseline of meteoric water compositions. Stable isotope compositions of bone CO₃ do change in response to broad climatic trends, but show poor correlation with compositions of corresponding paleosol CO₃ at specific horizons. Instead, compositional deviations between bone and paleosol CO₃ correlate with compositional deviations with the next higher paleosol; this suggests that the timescale for fossilization exceeds one paleosol cycle. Based on stratigraphic evidence and simple alteration models, fossilization timescales are estimated at 20-50 kyr, indicating that bone CO₃ will prove most useful for sequences spanning >100 kyr. C-isotopes show negative and strong positive deviations during wet and dry climates respectively, and short-term trends correspond well with changes in aridity within the Mascall and Rattlesnake Formations, as inferred from paleosols. A proposed correction to δ¹⁸O values based on δ¹³C anomalies implies a small, ∼1.5‰ increase in meteoric water δ¹⁸O during the late Oligocene global warming event, consistent with a minimum temperature increase of ∼4 °C. A strong inferred decrease in δ¹⁸O of 4-5‰ after 7 Ma closely parallels compositional changes in tooth enamel, and reflects a doubling in the height of the Cascade Range.     

Petrographical and geochemical investigation of the Triassic marbles associated with Menderes massif metamorphics,Kavaklıdere,Muğla,SW Turkey

Vast marble deposits occur in a cover sequence of the Menderes Massif, SW Turkey. Four major marble deposits are recognized in Mu?la province based on the stratigraphic levels. These are Permo-Carboniferous aged black marbles (1), Triassic aged marbles (2), Upper Cretaceous aged marbles (3), and Paleocene aged pelagic marbles (4). This study deals with Triassic aged marbles of the southern part of the Menderes Massif. The Triassic marbles from SW Turkey consist of two big marble horizons in the Çayboyu (ÇM) and Kestanecik (KM) regions. The characteristic samples are collected from different stratigraphic levels in marble deposits in the ÇM and KM horizons. Mineralogical and major, trace, and rare earth element (REE) analyses of marble, limestone, and schist were conducted on these samples to reveal their petrographical and geochemical characteristics. The ÇM horizon is represented by calcitic marble layers. Nickel, cobalt, manganese, and iron elements filled in fractures, fissures, and intergranular spaces of calcite crystals and these elements give the pinky colour to the marble from the ÇM horizon. KM marbles were deformed, metamorphosed, and recrystallized under greenschist facies P–T conditions. As a result of the metasomatic reaction of magnesium and manganese rich fluids with marbles, dolomite, and manganese, minerals such as rhodochrosite and pyrolusite have crystallized along vein walls and layers in the KM horizon. Dolomitization was determined in KM marbles, whereas ÇM marbles show the character of limestone. MgO, MnO, Fe₂O₃, Ni, and Zn contents of marbles from the KM horizon are higher than those of ÇM marbles due to metasomatic reactions. The Sr content in white coloured marbles ranges between 11.20 ppm and 112.20 ppm and this concentration reaches up to 272.70 ppm due to metasomatic reactions and fluid intake. The REE content of Triassic marbles is independent of the abundance of carbonate and the REE enrichment observed due to syn-metamorphic fluid flow. The significant negative Eu anomaly in REE patterns indicates that the protoliths of Triassic marbles are carbonate rocks of sedimentary origin.     

Depositional Age of a Fossil Whale Bone from São Paulo Ridge,South Atlantic Ocean,Based on Os Isotope Stratigraphy of a Ferromanganese Crust

Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (¹⁸⁷Os/¹⁸⁸Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. ¹⁸⁷Os/¹⁸⁸Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.     

Source and origin of active and fossil thermal spring systems,northern Upper Rhine Graben,Germany

Thermal water samples and related young and fossil mineralization from a geothermal system at the northern margin of the Upper Rhine Graben have been investigated by combining hydrochemistry with stable and Sr isotope geochemistry. Actively discharging thermal springs and mineralization are present in a structural zone that extends over at least 60 km along strike, with two of the main centers of hydrothermal activity being Wiesbaden and Bad Nauheim. This setting provides the rare opportunity to link the chemistry and isotopic signatures of modern thermal waters directly with fossil mineralization dating back to at least 500–800 ka. The fossil thermal spring mineralization can be classified into two major types: barite-(pyrite) fracture filling associated with laterally-extensive silicification; and barite, goethite and silica impregnation mineralization in Tertiary sediments. Additionally, carbonatic sinters occur around active springs. Strontium isotope and trace element data suggest that mixing of a hot (>100 °C), deep-sourced thermal water with cooler groundwater from shallow aquifers is responsible for present-day thermal spring discharge and fossil mineralization. The correlation between both Sr and S isotope ratios and the elevation of the barite mineralization relative to the present-day water table in Wiesbaden is explained by mixing of deep-sourced thermal water having high ⁸⁷Sr/⁸⁶Sr and low δ³⁴S with shallow groundwater of lower ⁸⁷Sr/⁸⁶Sr and higher δ³⁴S. The Sr isotope data demonstrate that the hot thermal waters originate from an aquifer in the Variscan crystalline basement at depths of 3–5 km. The S isotope data show that impregnation-type mineralization is strongly influenced by mixing with SO₄ that has high δ³⁴S values. The fracture style mineralization formed by cooling of the thermal waters, whereas impregnation-type mineralization precipitated by mixing with SO₄-rich groundwater percolating through the sediments.     

Vestoid cosmic spherules from the South Pole Water Well and Transantarctic Mountains (Antarctica): A major and trace element study

We present major and trace element data of five glass cosmic spherules (CS) with differentiated compositions recovered in the South Pole Water Well and the Transantarctic Mountains, Antarctica. The differentiated CS were first identified using Fe/Mg and Fe/Mn ratios and we have now added high Rare Earth Element concentrations (5 < REE_N < 14), and low siderophile element abundances (e.g. Ni = 25 ± 27 ppm) as characteristics. We propose that the siderophile depletions observed in differentiated CS result from the segregation of these elements into the core of their parent body during differentiation. Then, the high Fe/Mg ratios of differentiated CS result from their low MgO contents. Combined with their high level of REE enrichment, this indicates that the precursors formed through basaltic melt extraction from the asteroid/planetary source. As Fe/Mn and Fe/Mg ratios cannot distinguish between a Martian or Vestoid origin, we measured trace elements (zinc, cobalt, and vanadium) whose chemical behavior depends on oxidation state, known to be higher in the Martian than in the Vestoid environment. The compositions of the differentiated CS studied in this work share the characteristics of eucrites for all these indicators, providing further evidence that these differentiated CS are samples of a Vesta-like asteroid. However, their precursors show a considerable diversity in their mineralogy when compared to eucrites, that results in a wider range of major (Ca and Al) and trace element (Ba, Sr, Sc, and V) composition in differentiated CS.     

The timing of sea-level high-stands during Marine Isotope Stages 7.5 and 9: Constraints from the uranium-series dating of fossil corals from Henderson Island

Direct dating of fossil coral reefs using the U-series chronometer provides an important independent test of the Milankovitch orbital forcing theory of climate change. However, well-dated fossil corals pre-dating the last interglacial period (>130 thousand years ago; ka) are scarce due to, (1) a lack of sampling localities, (2) insufficient analytical precision in U-series dating methods, and (3) diagenesis which acts to violate the assumption of closed-system U-series isotopic decay in fossil corals. Here we present 50 new high-precision U-series age determinations for fossil corals from Henderson Island, an emergent coral atoll in the central South Pacific. U-series age determinations associated with the Marine Isotope Stage (MIS) 9 interglacial and MIS 7.5 interstadial periods are reported. The fossil corals show relatively little open-system U-series behaviour in comparison to other localities with fossil coral reefs formed prior to the last glacial cycle, however, open-system U-series behaviour is still evident in most of the dated corals. In particular, percent-level shifts in the [²³⁰Th/²³⁸U]_act composition are observed, leading to conventional U-series ages that are significantly younger or older than the true sample age. This open-system U-series behaviour is not accounted for by any of the open-system U-series models, indicating that new models should be derived. The new U-series ages reported here support and extend earlier findings reported in Stirling et al. (2001), providing evidence of prolific coral reef development on Henderson Island at ∼320 ka, most likely correlated with MIS 9.3, and subsequent reef development at ∼307 ka during MIS 9.1, while relative sea-level was potentially ∼20 m lower than during MIS 9.3. The U-series ages for additional well-preserved fossil corals are suggestive of minor reef development on Henderson Island during MIS 7.5 (245-230 ka) at 240.3 ± 0.8 and 234.7 ± 1.3 ka. All U-series observations are consistent with the Milankovitch theory of climate change, in terms of the timing of onset and termination of the dated interglacial and interstadial periods. The best preserved samples also suggest that the oceanic ²³⁴U/²³⁸U during MIS 9 and MIS 7.5 was within five permil of the modern open ocean composition.     

Optical ages on loess derived from outwash surfaces constrain the advance of the Laurentide Ice Sheet out of the Lake Superior Basin,USA

We present textural and thickness data on loess from 125 upland sites in west-central Wisconsin, which confirm that most of this loess was derived from the sandy outwash surfaces of the Chippewa River and its tributaries, which drained the Chippewa Lobe of the Laurentide front during the Wisconsin glaciation (MIS 2). On bedrock uplands southeast of the widest outwash surfaces in the Chippewa River valley, this loess attains thicknesses > 5 m. OSL ages on this loess constrain the advance of the Laurentide ice from the Lake Superior basin and into west-central Wisconsin, at which time its meltwater started flowing down the Chippewa drainage. The oldest MAR OSL age, 23.8 ka, from basal loess on bedrock, agrees with the established, but otherwise weakly constrained, regional glacial chronology. Basal ages from four other sites range from 13.2 to 18.5 ka, pointing to the likelihood that these sites remained geomorphically unstable and did not accumulate loess until considerably later in the loess depositional interval. Other OSL ages from this loess, taken higher in the stratigraphic column but below the depth of pedoturbation, range to nearly 13 ka, suggesting that the Chippewa River valley may have remained a loess source for several millennia.     

Mineralogical control of rare earth elements in acid sulfate soils

Major, trace and rare earth element concentrations were measured in porewater, surface water and sediments at an acid sulfate soil site. The concentrations of La and Ce in porewater are up to 1-3 ppm. There is a strong correlation between REE concentration and acidity, except that the maximum concentrations were consistently found below the horizon of maximum acidity, associated with an increase in pH (to ca. 4) and change in mineralogy from jarosite-dominated to goethite-dominated mottles. Jarosite replacement by goethite is as expected with the rise in pH, which in turn is due to the occurrence of a fossil shell bed just below. The rare earth element patterns in the porewaters are enriched in the MREE with respect to Post-Archaean Australian Shale (PAAS). Measurements and calculations show that this is in accord with experiments on low-degree partial dissolution of jarosite, even when the jarosite itself is highly enriched in LREE. There is a clear fractionation in the patterns between the clay-rich soil matrix, which is slightly depleted in the LREE when normalized to PAAS (La/Yb_PAAS ∼0.5), and the secondary mineral phase jarosite, which is enriched in the LREE (La/Yb_PAAS = 15-50). The REE pattern in the porewater changes with the transition from jarosite- to goethite-rich mottles, becoming relatively more enriched in the LREE compared to the HREE, which is consistent with the incongruent dissolution of jarosite to form goethite and the release of greater amounts of jarosite REE to solution, including proportionately more of the jarosite-compatible LREE.Maximum surface water REE concentrations in acidic water were 100-200 ppb La and Ce. REE patterns in surface water were very similar to the porewater transition zone, enriched in the MREE, but asymmetric, relatively enriched in the LREE compared to the HREE.     

Rates of trace metal and nutrient diagenesis in an intertidal creek bank

Carbon mineralization in marine sediments is a key process involved in the cycling of carbon, nutrients and trace metals. However, as marine sediments are usually diffusion dominated, the pace of element and nutrient cycling is slow, because consumption of oxidants and/or nutrients in the pore waters via microbial activity often outpaces resupply. Adding an advective flow component to such a system should change the biogeochemical dynamics considerably. Numerical simulations show that shallow coastal aquifers affected by tidal forces can establish ground water velocities of up to 7 cm h⁻¹, driving a circulation of sea water through the sediments with subsequent discharge. Although known to enhance solute exchange, the impact of advection on early diagenesis has not received much attention.To address this issue we mapped the interstitial water chemistry down to 2.5 m sediment depth along a transect on an intertidal creek bank that is subject to a periodic advective flow. Additionally a recently developed hydrogeological simulation of the creek bank was applied to calculate ages of the sampled pore waters. Sample ages obtained were used to quantify (flow path integrated) production or depletion rates for trace metals, nutrients, and sulphate.We find young sea water percolating relatively fast through sediments close to the creek showing strong signs of alteration, whereas pore waters from diffusion dominated regions are less altered. The increase in inorganic nutrients and some trace elements along the flow path requires high rates of turnover. Sulphate, molybdenum, and uranium are almost completely depleted after 200 days, while dissolved inorganic carbon (DIC), ammonia, and manganese increase. Averaged production rates for DIC appear to be three times higher when advection dominated the subsurface flow regime. Our results demonstrate that sites dominated by advection generally show signs of faster rates of diagenetic reactions.     

The coupled release of REE and Pb to the soil labile pool with time by weathering of accessory phases, Wind River Mountains, WY

Rare earth element (REE) distributions and Pb isotope compositions were explored in soils varying in age from ca. 0.4 to ?300 ka, developed on moraines in the Wind River Mountains, Wyoming. Soil extracts (0.6 M HCl) were used to examine the soil labile pool while the major element distribution in soil profiles was used to determine the extent of weathering at different soil depths. The results show that the chondrite-normalized REE patterns of the deepest bulk soil within each profile reflects the composition of the moraine till, except for the oldest soil. Up to ca. 12 ka, the soil extract fraction is enriched in light REE, indicating early release of light REE to the soil labile pool while that of the two oldest soils are relatively enriched in heavy REE. In the soil extracts the La/Sm ratio normalized to the deepest soil (La_D/Sm_D) decreases systematically with soil age. Similarly, the Eu-anomaly in the deepest soil from each profile (Eu_D/Eu_D*) decreases slightly with soil age in the three young soils; however, Eu_D/Eu_D* increases with soil age in the older soils. The systematic trends of these two ratios indicate the depletion of light REE in young soils and the enrichment of Eu and heavy REE in the older soils. Based on the Pb isotope ratios, the relative contribution of Pb to the soil labile pool via mineral weathering of U- or Th-rich phases was assessed for the different stages of weathering. The whole-soil profile ²⁰⁸Pb/²⁰⁴Pb ratio was found to decrease with soil age and with La_D/Sm_D, whereas it increased with the Eu_D/Eu_D* ratio. In each horizon, Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb) ratio generally decrease with soil age. In order to overcome possible effects from parent material heterogeneity, the amount of radiogenic Pb as compared to the whole-soil composition was calculated and this was found to decrease systematically with soil age.     

Geochemical constraints on the genesis of the Bayan Obo Fe-Nb-REE deposit in Inner Mongolia, China

Trace element and isotopic compositions of carbonate from ore bodies, country rock which hosts the ore bodies (H8 dolomite), a carbonatite dyke exposed in Dulahala near Bayan Obo, and rare earth element (REE)-rich dolomite in Bayan Obo have been determined to understand the genesis of the Bayan Obo Fe-Nb-REE ore deposit, the world’s largest resource of REE. The REE and trace element distribution patterns of samples from the REE-rich carbonatite dykes are identical to those of mineralized carbonate rocks, indicating a genetic linkage between the REE-rich carbonatite and mineralization in this region. By contrast, carbon and oxygen isotopes in the mineralized carbonate varied significantly, δ¹³C = −7.98‰ to −1.12‰, δ¹⁸O = 8.60-25.69‰, which are distinctively different from those in mantle-derived carbonatite. Abnormal isotopic fractionations between dolomite and calcite suggest that these two minerals are in disequilibrium in the carbonatite dyke, ore bodies, and H8 marble from Bayan Obo. This isotopic characteristic is also found in mineralized sedimentary marine micrite from Heinaobao, ∼25 km southeast of the Bayan Obo Fe-Nb-REE ore deposit. These facts imply that the carbonate minerals in the Bayan Obo deposit have resulted from sedimentary carbonate rocks being metasomatised by mantle-derived fluids, likely derived from a REE-enriched carbonatitic magma. The initial Nd isotope values of ore bodies and carbonatite dykes are identical, indicating that ore bodies, carbonatite dykes and veins may have a similar REE source.     

Trace element mobility in dolomitic argillites of the Mesoproterozoic Belt-Purcell Supergroup, Western North America

The Belt-Purcell Supergroup comprises dolomite-rich stratigraphic units in a dominantly siliciclastic succession, where sedimentation spans 1400-1470 Ma. Dolomitic units are variable mixtures of co-sedimented argillite and primary carbonate post-depositionally converted to secondary dolomite. Based on rare earth element (REE) relationships three distinct REE patterns are identified in the dolomite-rich units: Type 1 (T1d; d = dolomitic sample) with REE patterns parallel to post-Archean Upper Continental Crust (PA-UCC), albeit at lower absolute abundances due to dilution by carbonate content; Type 2 (T2d) with Heavy REE (HREE) enrichment but Light REE (LREE) depletion relative to T1d; and Type 3 (T3d) with enrichment in LREE and HREE relative to T1d, but erratic Middle REE (MREE) patterns. There is a progressive increase of ΣREE from T1d through T2d to T3d, whereas for ΣLREE/ΣHREE T2d < T1d < T3d. T1d-T2d and T3d represent three different “snapshots” of a continuous process.In terms of timing, dolomitization of calcite primary sediment in all samples likely took place broadly during burial diagenesis, as inferred for most Proterozoic dolomites. T1d is easily explained by provenance: however, T2d and T3d cannot be related to provenance, weathering or sedimentary sorting processes to explain higher concentrations of HREE referenced to PA-UCC and consequently developed in the sediment from a T1d precursor. The same three REE signatures have been described in previous studies in counterpart siliciclastic counterparts throughout the Belt-Purcell Supergroup at three different locations. Mobility of normally stable REE is accompanied by mobility of normally isochemical high field strength elements (HFSE) in T2d and T3d to give REE/REE, HFSE/HFSE, REE/HFSE and Y/HREE fractionations. No specific REE-HFSE signatures are apparent in the carbonate-rich units as compared to their non-dolomitic siliciclastic counterparts. This unusual mobility of REE and HFSE reflected in T2d and T3d is attributed to alkaline oxidizing post-depositional brines. Salinity was derived from seawater-sediment reactions, dissolution of evaporite minerals, and the smectite-illite transformation, whereas alkaline oxidizing conditions were promoted by groundwater interaction with mafic units in the basin, CO₂ introduced into the system during episodic rifting with mantle degassing, and interaction of syn-sedimentary mafic intrusions with carbonate units at early stages of BPS deposition. Intermittent brine activity, inducing T2d and T3d patterns, spanned >1 Ga as recorded by secondary monazite grains with age distributions that correspond to large scale tectono-thermal events in Laurentia.Post-depositional processes and redistribution of carbonate can have an impact on transitional stratigraphic contacts between dolomitic and siliciclastic units which may have been incorrectly described as primary due to sedimentary environment changes.     

Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (∼15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ∼15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H₂S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ∼90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ∼15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS⁻ production.