Extraction of Nd isotopes from bulk deep sea sediments for paleoceanographic studies on Cenozoic time scales

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.     

Reassessing the uranium decay constants for geochronology using ID-TIMS U-Pb data

As the internal precision of radiometric dates approaches the 0.1% level, systematic biases between different methods have become apparent. Many workers have suggested that calibrating other decay constants against the U-Pb system is a viable solution to this problem. We test this assertion empirically and quantitatively by analyzing U-Pb systematics of zircon and xenotime on the single- to sub-grain scale by high-precision ID-TIMS geochronology on 11 rock samples ranging from 0.1 to 3.3 Ga. Large statistically equivalent datasets give ²⁰⁷Pb/²⁰⁶Pb dates that are systematically older than ²⁰⁶Pb/²³⁸U dates by ∼0.15% in Precambrian samples to as much as ∼3.3% in Mesozoic samples, suggesting inaccuracies in the mean values of one or both of the U decay constants. These data are used to calculate a ratio of the U decay constants that is lower than the accepted ratio by 0.09% and is a factor of 5 more precise. Four of the samples are used to augment existing data from which the U-Pb and ⁴⁰Ar/³⁹Ar systems can be compared. The new data support most previous observations that U-Pb and ²⁰⁷Pb/²⁰⁶Pb dates are older than ⁴⁰Ar/³⁹Ar by ?1%, though scatter in the amount of offset in samples as a function of age suggests that the bias is not entirely systematic, and may incorporate interlaboratory biases and/or geologic complexities. Studies that calibrate other decay schemes against U-Pb should include an assessment of inaccuracies in the U decay constants in addition to other systematic biases and non-systematic geologic uncertainty.     

U–Pb systematics of the McClure Mountain syenite: thermochronological constraints on the age of the 40Ar/39Ar standard MMhb

Recent advances in U–Pb geochronology allow unprecedented levels of precision in the determination of geological ages. However, increased precision has also illuminated the importance of understanding subtle sources of open-system behavior such as Pb-loss, inheritance, intermediate daughter product disequilibria, and the accuracy of the model assumptions for initial Pb. Deconvolution of these effects allows a much richer understanding of the power and limitations of U–Pb geochronology and thermochronology. In this study, we report high-precision ID-TIMS U–Pb data from zircon, baddelleyite, titanite and apatite from the McClure Mountain syenite, from which the ⁴⁰Ar/³⁹Ar hornblende standard MMhb is derived. We find that excess ²⁰⁶Pb in zircon due to inclusions of high-Th minerals and elevated Th/U in titanite and apatite jeopardize the utility of the ²³⁸U–²⁰⁶Pb system in this rock. Strongly air-abraded zircons give dates that are younger than chemical-abraded zircons, which yield a statistically robust ²⁰⁷Pb/²³⁵U date of 523.98±0.12 Ma that is interpreted as the crystallization age. We explore the best method of Pb_c correction in titanite and apatite by analyzing the U–Pb isotopes of K-feldspar and using 2-D and 3-D regression methods—the latter of which yields the best results in each case. However, the calculated compositions of Pb_c for titanite, apatite and K-feldspar are different, implying that using a single Pb_c correction for multiple U–Pb thermochronometers may be inaccurate. The U–Pb thermochronological results are used to predict a closure time for Ar in hornblende of 522.98±1.00 Ma. Widely cited K–Ar and ⁴⁰Ar/³⁹Ar dates overlap with the U–Pb date, and relatively large errors make it impossible to verify whether U–Pb dates are systematically ≤1% older than K–Ar and ⁴⁰Ar/³⁹Ar dates.     

Topographic, geologic and cavity effects on the harmonic content of tidal strain

Summary. The combined effects of topography, geology and cavities upon the measurements of tidal strains are considered. A theoretical model is proposed in which the topography and geology are modelled with finite elements, and the cavity (assumed to be elliptical) modelled using the analytical theory. The three effects are then superimposed to form a total model. Previous experimental results obtained for the solid tidal strain in Eastern Australia (Blair & Sydenham) are compared with the present theoretical model and reasonable agreement is found assuming values of the Love numbers for the Gutenberg—Bullen A earth model in which h = 0.61 and l = 0.08 (Farrell). Further experimental results are presented for two strain meters, only one of which is not significantly influenced by the cavity. The relative difference, in harmonic content between the recordings of both strain meters is compared with that predicted by the theoretical model.     

The Frequency Content of Ground Vibration

A detailed examination of the frequency content of ground vibration is presented in terms of the so-called instantaneous frequency and time-frequency analysis. These techniques, and others, are applied to the surface vibration from a mass blast that triggered a large seismic event and to an earthquake vibration measured in the walls of a massive dam. As an associated issue it is shown that the relationship between peak levels of acceleration and velocity also reveals information on the frequency content of ground vibration. It is demonstrated quite clearly that the popular zero-crossing method cannot be used to obtain the frequency associated with the peak vibration level. In fact it is a false notion that one particular frequency can be associated with the peak level except for the ideal (and impractical) case of a single sinusoid. Realistically, there is a distribution of frequencies associated with the peak level, and a technique of sliding filters is suggested in order to examine the dependence of the peak level upon this frequency content. In light of the sliding filter approach, a new frequency dependent criterion for allowable levels of vibration is presented. This criterion is a completely continuous and well-defined function of frequency and so is more realistic than the current criteria which are only piecewise continuous and based upon an ill-defined frequency. The new criterion is applied to vibration data obtained from quarries and underground operations and is also applied to a model of resonant vibrations in urban dwellings.     

Early diagenetic remineralization of sedimentary organic C in the Gulf of Papua deltaic complex (Papua New Guinea): Net loss of terrestrial C and diagenetic fractionation of C isotopes

Oceania supplies ∼40% of the global riverine flux of organic carbon, approximately half of which is injected onto broad continental shelves and processed in shallow deltaic systems. The Gulf of Papua, on the south coast of the large island of New Guinea, is one such deltaic clinoform complex. It receives ∼4 Mt yr⁻¹ particulate terrestrial organic carbon with initial particle C_org loading ∼0.7 mg m⁻². C_org loading is reduced to ∼0.3 mg m⁻² in the topset-upper foreset zones of the delta despite additional inputs of mangrove and planktonic detritus, and high net sediment accumulation rates of 1-4 cm yr⁻¹. Carbon isotopic analyses (δ¹³C, Δ¹⁴C) of ΣCO₂ and C_org demonstrate rapid (<100 yr) remineralization of both terrestrial (δ¹³C <−28.6) and marine C_org (δ¹³C ∼−20.5) ranging in average age from modern (bomb) (Δ¹⁴C ∼60) to ∼1000 yr (Δ¹⁴C ∼−140). Efficient and rapid remineralization in the topset-upper foreset zone is promoted by frequent physical reworking, bioturbation, exposure, and reoxidation of deposits. The seafloor in these regions, particularly <20 m, apparently functions as a periodically mixed, suboxic batch reactor dominated by microbial biomass. Although terrestrial sources can be the primary metabolic substrates at inshore sites, relatively young marine C_org often preferentially dominates pore water ΣCO₂ relative to bulk C_org in the upper foreset. Thus a small quantity of young, rapidly recycled marine organic material is often superimposed on a generally older, less reactive terrestrial background. Whereas the pore water ΣCO₂ reflects both rapidly cycled marine and terrestrial sources, terrestrial material dominates the slower overall net loss of C_org from particles in the topset-upper foreset zone (i.e. recycled marine C_org leaves little residue). Preferential utilization of C_org subpools and diagenetic fractionation of C isotopes supports the reactive continuum model as a conceptual basis for net decomposition kinetics. Early diagenetic fractionation of C isotopes relative to the bulk sedimentary C_org composition can produce changes in ¹⁴C activity independent of radioactive decay. In the Gulf of Papua topset-upper foreset, Δ¹⁴C of pore water ΣCO₂ averaged ∼ 300‰ greater than C_org sediment between ∼1-3 m depth in deposits. Diagenetic fractionation and decomposition aging of sedimentary C_org compromises simple application of ¹⁴C for determination of sediment accumulation rates in diagenetically reactive deposits.     

Comparison of physical and chemical properties of maceral groups separated by density dradient centrifugation

Eight coals have been selected for study of the physical and chemical properties of the maceral group . The density-gradient centrifugation technique was employed to affect maceral group separation. The maximum reflectance method of Ting and Lo was used for estimating the reflectance of very small coal particles. The reflectograms were used to characterize the separated maceral fractions. The density, elemental composition, reflectance, NMR parameters of aromaticity, protonated aromatic carbon content and ƒ_stuggereda^stuggeredH of the maceral groups were compared. Variations in the aromatic structure of the maceral groups are discussed as well as the observation that ƒ_stuggereda and ƒ_stuggereda^stuggeredH change with particle density.     

Basin and petroleum system modelling of the East Coast Basin,New Zealand: a test of overpressure scenarios in a convergent margin

In the East Coast Basin (ECB), an active convergent margin of the North Island, New Zealand, the smectite‐rich Eocene Wanstead Formation forms an effective regional seal, creating high overpressure in the underlying Cretaceous through Palaeocene units due to disequilibrium compaction. This study examines the evolution of pore pressure and porosity in Hawke Bay of the ECB based on stepwise structural reconstruction of a stratigraphic and structural framework derived from interpretation of a regional two‐dimensional seismic line. This framework is incorporated into a basin and petroleum system model to predict the generation, distribution, and dissipation of overpressure, and examine the influence of faults, erosion, structural thickening, and seal effectiveness of the Wanstead Formation on pore pressure evolution. We find that natural hydraulic fracturing is likely occurring in sub‐Wanstead source rocks, which makes it a favourable setting for potential shale gas plays. We use poroelastic modelling to investigate the impact of horizontal bulk shortening due to tectonic compression on pore pressure and the relative order of principal stresses. We find that shortening modestly increases pore pressure. When 5% or greater shortening occurs, the horizontal stress may approach and exceed vertical stress in the last 4 Myr of the basin's history. Shortening impacts both the magnitude and relative order of principal stresses through geological time. Due to the overpressured nature of the basin, we suggest that subtle changes in stress regime are responsible for the significant changes in structural deformational styles observed, enabling compressional, extensional, and strike‐slip fault regimes to all occur during the tectonic history and, at times, simultaneously.     

ASCA observations of deep ROSAT fields — II. The 2–10 keV AGN luminosity function

The explosion mechanism associated with thermonuclear supernovae (SNIa) is still a matter of debate. There is a wide agreement that high amounts of radioactive nuclei are produced during these events and they are expected to be strong γ-ray emitters. In the past, several authors have investigated the use of this γ-ray emission as a diagnostic tool. In this paper we have performed a complete study of the γ-ray spectra associated with all the different scenarios currently proposed. This includes detonation, delayed detonation, deflagration and the off-centre detonation. We have performed accurate simulations for this complete set of models in order to determine the most promising spectral features that could be used to discriminate among the different models. Our study is not limited to qualitative arguments. Instead, we have quantified the differences among the spectra and established distance limits for their detection. The calculations have been performed considering the best current response estimations of the SPI and IBIS instruments aboard INTEGRAL in such a way that our results can be used as a guideline to evaluate the capabilities of INTEGRAL in the study of Type Ia supernovae. For the purpose of completeness we have also investigated the nuclear excitation and spallation reactions as a possible secondary source of γ-rays present in some supernova scenarios. We conclude that this mechanism can be neglected because of its small contribution.     

GHR1 Zircon – A New Eocene Natural Reference Material for Microbeam U‐Pb Geochronology and Hf Isotopic Analysis of Zircon

We present multitechnique U‐Pb geochronology and Hf isotopic data from zircon separated from rapakivi biotite granite within the Eocene Golden Horn batholith in Washington, USA. A weighted mean of twenty‐five Th‐corrected ²⁰⁶Pb/²³⁸U zircon dates produced at two independent laboratories using chemical abrasion‐isotope dilution‐thermal ionisation mass spectrometry (CA‐ID‐TIMS) is 48.106 ± 0.023 Ma (2s analytical including tracer uncertainties, MSWD = 1.53) and is our recommended date for GHR1 zircon. Microbeam ²⁰⁶Pb/²³⁸U dates from laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS) laboratories are reproducible and in agreement with the CA‐ID‐TIMS date to within < 1.5%. Solution multi‐collector ICP‐MS (MC‐ICP‐MS) measurements of Hf isotopes from chemically purified aliquots of GHR1 yield a mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.283050 ± 17 (2s, n = 10), corresponding to a εHf₀ of +9.3. Hafnium isotopic measurements from two LA‐ICP‐MS laboratories are in agreement with the solution MC‐ICP‐MS value. The reproducibility of ²⁰⁶Pb/²³⁸U and ¹⁷⁶Hf/¹⁷⁷Hf ratios from GHR1 zircon across a variety of measurement techniques demonstrates their homogeneity in most grains. Additionally, the effectively limitless reserves of GHR1 material from an accessible exposure suggest that GHR1 can provide a useful reference material for U‐Pb geochronology of Cenozoic zircon and Hf isotopic measurements of zircon with radiogenic ¹⁷⁶Hf/¹⁷⁷Hf.