Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates

This study presents magnesium stable-isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species, seawater samples collected from the western Dutch Wadden Sea, and reference materials. The aim of this study is to explore the influence of mineralogy, taxonomy and environmental factors (e.g., seawater isotopic composition, temperature, salinity) on magnesium-isotopic (δ²⁶Mg) ratios of skeletal carbonates. Using high-precision multi-collector inductively coupled plasma mass spectrometry, we observed that the magnesium-isotopic composition of seawater from the semi-enclosed Dutch Wadden Sea is identical to that of open marine seawater. We further found that a considerable component of the observed variability in δ²⁶Mg values of marine skeletal carbonates can be attributed to differences in mineralogy. Furthermore, magnesium-isotope fractionation is species-dependent, with all skeletal carbonates being isotopically lighter than seawater. While δ²⁶Mg values of skeletal aragonite and high-magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences, the δ²⁶Mg values of echinoids, brachiopods and bivalves likely result from a taxon-specific level of control on Mg-isotope incorporation during biocalcification. Moreover, no resolvable salinity and temperature effect were observed for coralline red algae and echinoids. In contrast, Mg-isotope data of bivalves yield ambiguous results, which require further validation. The data presented here, point to a limited use of Mg isotopes as temperature proxy, but highlight the method’s potential as tracer of seawater chemistry through Earth’s history.     

A high‐resolution relative time scale for the Viséan Stage (Carboniferous) of the Kulm Basin (Rhenish Mountains,Germany)

The Viséan (Carboniferous) sedimentary succession of the basinal Kulm facies (Rhenish Mountains) was investigated in detail in order to achieve a high‐resolution stratigraphic subdivision and correlation. Additionally, the ranges of fossil index taxa (ammonoids), fossil marker beds, volcaniclastic horizons and sedimentary features (e.g. colour changes) were integrated in the correlation. As a result, a comprehensive database was compiled, which contains 190 stratigraphic events of the Viséan interval of this area. Several sections are almost completely composed of shales, which are regarded to represent a slow but constant basinal background sedimentation of the Kulm facies. The thickness of lithological homogeneous sections thus indicates an approximately linear record of time and the average thicknesses of biozones and positions of stratigraphic events can easily be calculated from the compiled database. The result is an approximately time‐linear biostratigraphic scale for the Viséan Stage of the Kulm Basin. Given a numerical length of the Viséan Stage of ca. 19 Ma, 190 stratigraphic events give a mean resolution of 100 000 years. This is unique in Palaeozoic stratigraphy. Copyright © 2008 John Wiley & Sons, Ltd.     

IR calibrations for water determination in olivine,r-GeO<Subscript>2</Subscript>, and SiO<Subscript>2</Subscript> polymorphs

Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO₂ polymorphs, and GeO₂ with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering, confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO₂ system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith the peak position (quartz ε = 89,000 ± 15,000  \textl \textmol_{\textH2\textO}^-1 \textcm^-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}), but it varies as a function of structure (coesite ε = 214,000 ± 14,000  \textl \textmol_{\textH2\textO}^-1 \textcm^-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}; stishovite ε = 485,000 ± 109,000  \textl \textmol_{\textH2\textO}^-1 \textcm^-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling the Earth’s deep water cycle.     

Empirical Relationships for Debris Flows

The assessment of the debris flow hazard potential has to rely on semi-quantitative methods. Due to the complexity of the debris-flow process, numerical simulation models of debris flows are still limited with regard to practical applications. Thus, an overview is given of empirical relationships that can be used to estimate the most important parameters of debris-flow behavior. In a possible procedure, an assessment of a maximum debris-flow volume may be followed by estimates of the peak discharge, the mean flow velocity, the total travel distance, and the runout distance on the fan. The applicability of several empirical equations is compared with available field and laboratory data, and scaling considerations are used to discuss the variability of the parameters over a large range of values. Some recommendations are made with regard to the application of the presented relationships by practicing engineers, apart from advocating field reconnaissance and searching for historic events wherever possible.     

Internal morphology, habit and U-Th-Pb microanalysis of amphibolite-to-granulite facies zircons: geochronology of the Ivrea Zone (Southern Alps)

Several types of growth morphologies and alteration mechanisms of zircon crystals in the high-grade metamorphic Ivrea Zone (IZ) are distinguished and attributed to magmatic, metamorphic and fluid-related events. Anatexis of pelitic metasediments in the IZ produced prograde zircon overgrowths on detrital cores in the restites and new crystallization of magmatic zircons in the associated leucosomes. The primary morphology and Th-U chemistry of the zircon overgrowth in the restites show a systematic variation apparently corresponding to the metamorphic grade: prismatic (prism-blocked) low-Th/U types in the upper amphibolite facies, stubby (fir-tree zoned) medium-Th/U types in the transitional facies and isometric (roundly zoned) high-Th/U types in the granulite facies. The primary crystallization ages of prograde zircons in the restites and magmatic zircons in the leucosomes cannot be resolved from each other, indicating that anatexis in large parts of the IZ was a single and short lived event at 299 ± 5 Ma (95% c. l.). Identical U/Pb ages of magmatic zircons from a metagabbro (293 ± 6 Ma) and a metaperidotite (300 ± 6 Ma) from the Mafic Formation confirm the genetic context of magmatic underplating and granulite facies anatexis in the IZ. The U-Pb age of 299 ± 5 Ma from prograde zircon overgrowths in the metasediments also shows that high-grade metamorphic (anatectic) conditions in the IZ did not start earlier than 20 Ma after the Variscan amphibolite facies metamorphism in the adjacent Strona–Ceneri Zone (SCZ). This makes it clear that the SCZ cannot represent the middle to upper crustal continuation of the IZ. Most parts of zircon crystals that have grown during the granulite facies metamorphism became affected by alteration and Pb-loss. Two types of alteration and Pb-loss mechanisms can be distinguished by cathodoluminescence imaging: zoning-controlled alteration (ZCA) and surface-controlled alteration (SCA). The ZCA is attributed to thermal and/or decompression pulses during extensional unroofing in the Permian, at or earlier than 249 ± 7 Ma. The SCA is attributed to the ingression of fluids at 210 ± 12 Ma, related to hydrothermal activity during the breakup of the Pangaea supercontinent in the Upper Triassic/Lower Jurassic. Received: 7 July 1998 / Accepted: 4 November 1998     

Sorption and Chemical Reactions of PAHs with Dissolved Humic Substances and Related Model Polymers

Sorption coefficients measured for PAHs on dissolved humic substances by SPME and FQT were found to be inevitably different and method‐dependent – SPME provides activity‐based and FQT concentration‐based sorption coefficients. Poly(acrylic acid) esters as well‐defined model polymers were used in sorption experiments, leading to the conclusion that short aliphatic chains are more effective in binding PAHs than aromatic moieties. FQT was inappropriate to measure sorption coefficients for the interaction of pyrene with poly(acrylic acid) esters but the experiments revealed a characteristic shift in the fluorescence spectrum. Using pyrene as a probe for the molecular environment in the sorbed state, the observed spectral shift indicated a highly hydrophobic microenvironment. The empirical relationships between lg K_DOC and lg K_OW were generalized on the basis of a modified Flory‐Huggins concept. Introducing only one sorbent‐specific parameter, the solubility parameter δ_DOM, the calculation of sorption coefficients became possible for a wide range of HOCs using fundamental data readily available from the literature. Long‐term experiments showed that reactive PAHs (such as acenaphthylene and 9‐methylanthracene) are able to react with HAs under strictly abiotic and anoxic conditions, whereas less reactive PAHs (such as naphthalene and dihydroanthracene) do not form bound residues. The HA reveals two functions in the interaction, behaving as a reaction partner and as a protecting ligand.     

Prograded foredunes of Western Australia's macro‐tidal coast – implications for Holocene sea‐level change and high‐energy wave impacts

The Holocene evolution of the Canning Coast of Western Australia has largely been overlooked so far mainly due to its remoteness and low population density. We report on new data from a sequence of foredunes inside the macro‐tidal Admiral Bay, 110 km southwest of Broome. Based on sediment cores, differential global positioning system (dGPS)‐based elevation transects, and stratigraphical analyses on outcrops of the relict foredunes, we aim at reconstructing Holocene coastal changes and relative sea levels (RSLs), as well as identifying and dating imprints of extreme‐wave events. Sedimentary analyses comprise the documentation of bedding structures, foraminiferal content and macrofaunal remains, grain size distribution, and organic matter. The chronological framework is based on 26 carbon‐14 accelerator mass spectrometry (¹⁴C‐AMS) datings. Marine flooding of the pre‐Holocene surface landward of the 2.5 km‐wide foredune barriers occurred 7400–7200 cal bp , when mangroves colonized the area. After only 200–400 years, a high‐energy inter‐tidal environment established and prevailed until c. 4000 cal bp , before turning into the present supralittoral mudflat. During that time, coastal regression led to beach progradation and the formation of aligned foredunes. Drivers of progradation were a stable RSL or gradual RSL fall after the mid‐Holocene and a positive sand budget. The foredunes overlie upper beach deposits located up to >2 m above the present upper beach level and provide evidence for a higher mid‐Holocene RSL. Discontinuous layers of coarse shells and sand are intercalated in the foredunes, indicating massive coastal flooding events. One such layer was traced over three dune ridges and dated to c. 1700–1550 cal bp . However, it seems that most tropical cyclones induce net erosion rather than deposition at aligned foredunes and thus, they are only suitable for reconstructing temporal variability if erosional features or sedimentation reliably tied to these events can be identified and dated accurately. Copyright © 2014 John Wiley & Sons, Ltd.     

Compositional zoning of garnet porphyroblasts from the polymetamorphic Wölz Complex, Eastern Alps

We employ garnet isopleth thermobarometry to derive the P–T conditions of Permian and Cretaceous metamorphism in the Wölz crystalline Complex of the Eastern Alps. The successive growth increments of two distinct growth zones of the garnet porphyroblasts from the Wölz Complex indicate garnet growth in the temperature interval of 540°C to 560°C at pressures of 400 to 500 MPa during the Permian and temperatures ranging from 550°C to 570°C at pressures in the range of 700 to 800 MPa during the Cretaceous Eo-Alpine event. Based on diffusion modelling of secondary compositional zoning within the outermost portion of the first garnet growth zone constraints on the timing of the Permian and the Eo-Alpine metamorphic events are derived. We infer that the rocks remained in a temperature interval between 570°C and 610°C over about 10 to 20 Ma during the Permian, whereas the high temperature stage of the Eo-Alpine event only lasted for about 0.2 Ma. Although peak metamorphic temperatures never exceeded 620°C, the prolonged thermal annealing during the Permian produced several 100 µm wide alteration halos in the garnet porphyroblasts and partially erased their thermobarometric memory. Short diffusion profiles which evolved around late stage cracks within the first garnet growth zone constrain the crack formation to have occurred during cooling below about 450°C after the Eo-Alpine event.