Electron paramagnetic resonance spectroscopy: A suggested approach to trace metal analysis in marine environments

Electron paramagnetic resonance (EPR) spectroscopy analysis of marine samples from different environments appears to differentiate between adsorbed and structural Mn (II) and Fe (III) sites in the sediment. This suggests that EPR may provide a means of distinguishing different environmental influences on sediment. Acid extract solutions from sediment samples exhibit clearly defined EPR spectra due to Mn(II), Ti(III), Fe(III), and VO(IV), which are amenable to qualitative and quantitative analysis at concentrations below one part per million. Spectra of several shellfish vary considerably, both between species, and within a species, depending on sampling localities. Resonances from Mn(II), Mo(V), and Fe(III) can be obtained. Mn(II) is substituted for Ca(II) in the calcite structure of some shells. The low detection limits, small sample size, required and identification of oxidation states by EPR complement other analytical techniques and may prove useful in marine systems.     

Origin of the Blue Ridge escarpment along the passive margin of Eastern North America

The Blue Ridge escarpment is a rugged landform situated within the ancient Appalachian orogen. While similar in some respects to the great escarpments along other passive margins, which have evolved by erosion following rifting, its youthful topographic expression has inspired proposals of Cenozoic tectonic rejuvenation in eastern North America. To better understand the post‐orogenic and post‐rift geomorphic evolution of passive margins, we have examined the origin of this landform using low‐temperature thermochronometry and manipulation of topographic indices. Apatite (U–Th)/He and fission‐track analyses along transects across the escarpment reveal a younging trend towards the coast. This pattern is consistent with other great escarpments and fits with an interpretation of having evolved by prolonged erosion, without the requirement of tectonic rejuvenation. Measured ages are also comparable specifically to those measured along other great escarpments that are as much as 100 Myr younger. This suggests that erosional mechanisms that maintain rugged escarpments in the early post‐rift stages may remain active on ancient passive margins for prolonged periods. The precise erosional evolution of the escarpment is less clear, however, and several end‐member models can explain the data. Our preferred model, which fits with all data, involves a significant degree of erosional escarpment retreat in the Cenozoic. Although this suggests that early onset of topographic stability is not required of passive margin evolution, more data are required to better constrain the details of the escarpment's development.     

A study of arctic sea ice and sea‐level pressure using POP and neural network methods

Abstract

We examine Arctic sea‐ice concentration (SIC) and sea‐level pressure (SLP) data using principal oscillation pattern (POP) and neural network methods. The POP method extracts oscillating patterns from multivariate time series, each pattern being characterized by an oscillation period and a decay time. Predictions can be made for patterns whose decay time is comparable with the period. For both the SIC and SLP, however, the decay times are much shorter than the oscillation periods, and therefore the forcast skill is poor. A neural network is a model of the learning behaviour of a living neural system. Presented with training data, a neural network can learn the linear or non‐linear rules embedded in the data. We trained neural networks with sea‐ice and sea‐level pressure data, and estimated the forecast skill using a cross‐validation technique. The neural networks did not exhibit forecast skill significantly better than that of persistence. We contrast the Arctic situation with previous studies in which POP and neural networks were successfully used to forecast El Niño at lead times up to 6 months. Reasons for the lack of skill in both methods are discussed.     

Reconstruction of contaminant trends in a salt wedge estuary with sediment cores dated using a multiple proxy approach

The Taunton River is a partially mixed tidal estuary in southeastern Massachusetts (USA) which has received significant contaminant inputs, yet little information exists on the history of discharge and the subsequent fate of these contaminants. Three sediment cores taken along a transect were analyzed, reconstructing the spatial and temporal trends of pollution in the estuary. A combination of radiometric dating, contaminant markers, and storm layers from major hurricanes were used to establish age models and sedimentation rates. Age estimates obtained from the different dating methods compared well, establishing an accurate history of contaminant release to the estuary. Polycyclic aromatic hydrocarbons (PAHs) were present in one core at depths corresponding to the early 1860s, earlier than previously established dates of introduction. Temporal and spatial trends of Cr, Cu, Hg and Pb indicated multiple sources of varying input to the river. Polychlorinated biphenyls (PCBs) were present in each of the cores from the 1930s onward, with elevated levels still present in surficial sediments at several sites. A unique organic compound, Topanol, which was produced locally was used as a tracer to track contaminant transport in the river. Tracer data indicates that contaminants are still being transported and deposited to surficial sediments at high concentrations well after their discharge. This reconstruction demonstrates the utility of using multiple dating proxies where often the sole use of radiometric dating techniques is not an option and provides insights into the fate of contaminants discharged decades ago but continue to represent environmental risks.     

In search of a hidden long-term isolated sub-chondritic Nd/Nd reservoir in the deep mantle: Implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic ¹⁴²Nd/¹⁴⁴Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic ¹⁴³Nd/¹⁴⁴Nd and high ²⁰⁷Pb/²⁰⁶Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic ¹⁴²Nd/¹⁴⁴Nd.High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable ¹⁴²Nd/¹⁴⁴Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle.We then evaluate mass balance in the Earth with respect to both ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε¹⁴³Nd estimates of the reservoirs in the μ¹⁴²Nd = 0 Earth, where μ¹⁴²Nd is ((measured ¹⁴²Nd/¹⁴⁴Nd/terrestrial standard ¹⁴²Nd/¹⁴⁴Nd)−1 * 10⁻⁶) and the μ¹⁴²Nd = 0 Earth is the proportion of the silicate Earth with ¹⁴²Nd/¹⁴⁴Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd unless the μ¹⁴²Nd = 0 Earth has a ε¹⁴³Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age ¹⁴²Nd-¹⁴³Nd isochron for the Earth intersects μ¹⁴²Nd = 0 at ε¹⁴³Nd of +8 ± 2 providing a minimum ε¹⁴³Nd for the μ¹⁴²Nd = 0 Earth. The high ε¹⁴³Nd of the μ¹⁴²Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε¹⁴³Nd.If the EER formed early after solar system formation (0-70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ¹⁴²Nd = 0 Earth must have a bulk ε¹⁴³Nd more radiogenic than DMM and additional high ε¹⁴³Nd material is required to balance the Nd isotope systematics of the Earth.     

Periglacial climate at the 2.5 Ma onset of Northern Hemisphere glaciation inferred from the Whippoorwill Formation, northern Missouri, USA

The Whippoorwill Formation is a gleyed diamicton that is present locally within bedrock depressions beneath the oldest glacial till in northern Missouri, USA. Stratigraphy, paleomagnetism, and cosmogenic-nuclide burial ages show that it was deposited between the Matuyama-Gauss magnetostratigraphic boundary at 2.58 Ma and the first advance of the Laurentide ice sheet into Missouri at 2.47 ± 0.19 Ma. High cosmogenic-nuclide concentrations also show that the constituents of the Whippoorwill Formation experienced long exposure at a stable landscape surface with erosion rates of 1-2 m/Ma. However, cosmogenic-nuclide concentrations are invariant with depth below the Whippoorwill Formation surface, indicating active mixing of the soil profile shortly before burial by till. The Whippoorwill Formation retains numerous features indicative of cryoturbation. Therefore, we interpret it as a buried Gelisol, a soil formed under periglacial conditions in the presence of permafrost. At the onset of Northern Hemisphere glaciation, climate cooling established permafrost conditions and accelerated erosion by inducing landscape instability. Thus, weathered regolith materials were mobilized and redeposited by gelifluction shortly before the ice sheet overrode the landscape.     

Diagenetic model of carbonate rocks of Guri Member of Mishan Formation (Lower to Middle Miocene) SE Zagros basin,Iran

In order to understand the post-depositional history of carbonate rocks of Guri Member (Lower to Middle Miocene), three stratigraphic sections were selected in north Bandar-Abbas in southeast of Iran. Sampling was carried out, analyzed for selective parameters such as oxygen and carbon isotopic compositions (δ¹⁸O and δ¹³C) and interpreted in the present study. We recognized several diagenetic processes including micritization, cementation, neomorphism, compaction, dissolution, silicification, dolomitization, fracturing and vein filling. Some of the diagenetic processes occurred at different conditions, so in order to achieve precise interpretation, samples from different carbonate components such as, micrite, fracture cement, solution pore cement, intergranular cement, and some biotic allochems were analyzed. In this study micrite samples were subdivided into two groups including micro-spary and micrite. They were recognized under Cathodoluminescence microscope. In addition, micrite samples were classified into five groups based on their depositional environments: supratidal, lagoon, coral bar, open sea, and open basin. There were minor changes in stable isotope ratios based on the sedimentary environments, stratigraphy successions, and micro-spary or micrite properties. In this study, similar calcite cements in petrography studies were differentiated by stable isotope data. Those calcite cements have formed in different diagenetic environments such as meteoric and burial cements. Paragenetic sequence of carbonate rocks were interpreted by integration of petrographic and isotopic studies. We have reconstructed diagenetic models of Guri Member into four stages including marine, meteoric, burial, and uplifting.