Nanochemo-mechanical signature of organic-rich shales: a coupled indentation–EDX analysis

The organic–inorganic nature of organic-rich source rocks poses several challenges for the development of functional relations that link mechanical properties with geochemical composition. With this focus in mind, we herein propose a method that enables chemo-mechanical characterization of this highly heterogeneous source rock at the micron and submicron length scale through a statistical analysis of a large array of energy-dispersive X-ray spectroscopy (EDX) data coupled with nanoindentation data. The ability to include elemental composition to the indentation probe via EDX is shown to provide a means to identify pure material phases, mixture phases, and interfaces between different phases. Employed over a large array, the statistical clustering of this set of chemo-mechanical data provides access to the properties of the fundamental building blocks of clay-dominated organic-rich source rocks. The versatility of the approach is illustrated through the application to a large number of source rocks of different origin, chemical composition, and organic content. We find that the identified properties exhibit a unique scaling relation between stiffness and hardness. This suggests that organic-rich shale properties can be reduced to their elementary constituents, with several implications for the development of predictive functional relations between chemical composition and mechanical properties of organic-rich source rocks such as the intimate interplay between clay-packing, organic maturity, and mechanical properties of porous clay/organic phase.     

Simplified SMA-inspired 1-parameter SCS-CN model for runoff estimation

This study proposes a simplified 1-parameter SCS-CN model (M5) based on Mishra-Singh (2002) model and soil moisture accounting (SMA) procedure for surface runoff estimation and compares its performance with the existing SCS-CN method (SCS, 1956) (M1), Michel 1-P model (Water Resour Res 41:1-6, 2005) (M2), Sahu 1-P model (Hydrol Process 21:2872-2881, 2007) (M3), and Ajmal et al. model (J Hydrol 530:623-633, 2015) (M4) using large rainfall–runoff dataset of 48,763 events from123 USDA-ARS watersheds. The performance of models was evaluated using three statistical error indices such as Nash-Sutcliffe efficiency (NSE), root mean square error (RMSE), percentage bias (PBIAS), and rank and grading system (RGS). Based on the results obtained, the models can be ranked as follows: M5?>?M4?>?M3?>?M1?>?M2, i.e., model M5 outperformed all the remaining four models M1–M4 and hence is recommended for field applications.     

High-resolution isotope records of early Holocene rapid climate change from two coeval stalagmites of Katerloch Cave,Austria

Two coeval stalagmites from Katerloch Cave show pronounced intervals of low δ¹⁸O values around 8.2, 9.1, and 10.0 kyr (all ages are reported before the year 2000 AD) and represent an inorganic U–Th dated climate archive from the southeast of the European Alps, a region where only very few well-dated climate records exist. The O isotope curves, providing near-annual resolution, allow a direct comparison to the Greenland ice core records, as temperature was the primary factor controlling the O isotopic composition of Katerloch speleothems.The 8.2 kyr climate anomaly lasted about one century, from 8196 to 8100 yr, with a maximum amplitude of 1.1‰ at 8175 yr. The event is characterized by a rapid onset and a more gradual demise and U–Th data as well as annual lamina counting support a rapid climate change towards cooler conditions within 10–20 yr. There is no strong evidence that the 8.2 kyr anomaly was superimposed on a pronounced longer-term cooling episode, nor do the new data support two separate cooling events within the 8.2 kyr event as reported by other studies. Our record also shows a distinct climate anomaly around 9.1 kyr, which lasted 70–110 yr and showed a maximum amplitude of 1.0‰, i.e. it had a similar duration and amplitude as the (central) 8.2 kyr event. Compared to the 8.2 kyr event, the 9.1 kyr anomaly shows a more symmetrical structure, but onset and demise still occurred within a few decades only. The different progression of the 8.2 (asymmetrical) and 9.1 kyr anomaly (symmetrical) suggests a fundamental difference in the trigger and/or the response of the climate system. Moreover, both stalagmites show evidence of a climate anomaly around 10.0 kyr, which was of comparable magnitude to the two subsequent events.Using a well constrained modern calibration between air temperature and δ¹⁸O of precipitation for the study area and cave monitoring data (confirming speleothem deposition in Katerloch reflecting cave air temperature), a maximum cooling by ca 3 °C can be inferred at 8.2 and 9.1 kyr, which is similar to other estimates, e.g., from Lake Ammersee north of the Alps. The O isotopic composition of meteoric precipitation, however, is a complex tracer of the hydrological cycle and these temperature estimates do not take into account additional effects such as changes in the source area or synoptic shifts. Apart from that, the relative thickness of the seasonally controlled lamina types in the Katerloch stalagmites remains rather constant across the intervals comprising the isotopic anomalies, i.e. the stalagmite petrography argues against major shifts in seasonality during the early Holocene climate excursions.     

Iron and lithium isotope systematics of the Hekla volcano,Iceland — Evidence for Fe isotope fractionation during magma differentiation

In this study potential iron isotope fractionation by magmatic processes in the Earth's crust was systematically investigated. High precision iron isotope analyses by MC-ICP-MS were performed on a suite of rock samples representative for the volcanic evolution of the Hekla volcano, Iceland. The whole series of Hekla's rocks results from several processes. (i) Basaltic magmas rise and induce partial melting of meta-basalts in the lower part of the Icelandic crust. The resulting dacitic magma evolves to rhyolitic composition through crystal fractionation. During this differentiation the δ^56/54Fe_IRMM-014 values increase successively from 0.051 ± 0.021‰ for the primitive dacites to 0.168 ± 0.021‰ for the rhyolites. This increase can be described by a Rayleigh fractionation model using a constant bulk fractionation factor between all mineral phases (M) and the silicate liquid (L) of Δ^56/54Fe_M–L = ? 0.1‰. (ii) The basaltic magma itself differentiates by crystal fractionation to basaltic andesite composition. No Fe isotope fractionation was found in this series. All basalts and basaltic andesites have an average δ^56/54Fe_IRMM-014 value of 0.062 ± 0.042‰ (2SD, n = 9), identical to mean terrestrial basaltic values reported in previous studies. This observation is consistent with the limited removal of iron from the remaining silicate melt through crystal fractionation and small mineral-melt Fe isotope fractionation factors expected at temperatures in excess of 1050 °C. (iii) Andesites are produced by mixing of basaltic andesite with dacitic melts. The iron isotope composition of the andesites is matching that of the basaltic andesites and the less evolved dacites, in agreement with a mixing process. In the Hekla volcanic suite Li concentrations are positively correlated with indicators of magma differentiation. All Hekla rocks have δ⁷Li values typical for the upper mantle and demonstrate the absence of resolvable Li isotope fractionation during crystal fractionation. As a fluid-mobile trace element, Li concentrations and isotopes are a potential tracer of magma/fluid interaction. At Hekla, Li concentrations and isotope compositions do not indicate any extensive fluid exsolution. Hence, the heavy Fe isotope composition of the dacites and rhyolites can be predominately attributed to fractional crystallisation. Iron isotope analyses on single samples from other Icelandic volcanoes (Torfajökull, Vestmannaeyjar) confirm heavy Fe isotope enrichment in evolving magmas. Our results suggest that the iron isotope composition of highly evolved crust can be slightly modified by magmatic processes.     

The experimental calibration of the iron isotope fractionation factor between pyrrhotite and peralkaline rhyolitic melt

A first experimental study was conducted to determine the equilibrium iron isotope fractionation between pyrrhotite and silicate melt at magmatic conditions. Experiments were performed in an internally heated gas pressure vessel at 500 MPa and temperatures between 840 and 1000 °C for 120-168 h. Three different types of experiments were conducted and after phase separation the iron isotope composition of the run products was measured by MC-ICP-MS. (i) Kinetic experiments using ⁵⁷Fe-enriched glass and natural pyrrhotite revealed that a close approach to equilibrium is attained already after 48 h. (ii) Isotope exchange experiments—using mixtures of hydrous peralkaline rhyolitic glass powder (∼4 wt% H₂O) and natural pyrrhotites (Fe_1 − xS) as starting materials— and (iii) crystallisation experiments, in which pyrrhotite was formed by reaction between elemental sulphur and rhyolitic melt, consistently showed that pyrrhotite preferentially incorporates light iron. No temperature dependence of the fractionation factor was found between 840 and 1000 °C, within experimental and analytical precision. An average fractionation factor of Δ ⁵⁶Fe/⁵⁴Fe_{pyrrhotite-melt} = −0. 35 ± 0.04‰ (2SE, n = 13) was determined for this temperature range. Predictions of Fe isotope fractionation between FeS and ferric iron-dominated silicate minerals are consistent with our experimental results, indicating that the marked contrast in both ligand and redox state of iron control the isotope fractionation between pyrrhotite and silicate melt. Consequently, the fractionation factor determined in this study is representative for the specific Fe²⁺/ΣFe ratio of our peralkaline rhyolitic melt of 0.38 ± 0.02. At higher Fe²⁺/ΣFe ratios a smaller fractionation factor is expected. Further investigation on Fe isotope fractionation between other mineral phases and silicate melts is needed, but the presented experimental results already suggest that even at high temperatures resolvable variations in the Fe isotope composition can be generated by equilibrium isotope fractionation in natural magmatic systems.     

Identification of typical synoptic patterns causing heavy rainfall in the rainy season in Japan by a Self-Organizing Map

In order to systematically and visually understand well-known but qualitative and complex relationships between synoptic fields and heavy rainfall events in Kyushu Islands, southwestern Japan, during the BAIU season, these synoptic fields were classified using the Self-Organizing Map (SOM), which can convert complex non-linear features into simple two-dimensional relationships. It was assumed that the synoptic field patterns could be simply expressed by the spatial distribution of (1) wind components at the 850 hPa level and (2) precipitable water (PW) defined by the water vapor amount contained in a vertical column of the atmosphere. By the SOM algorithm and the clustering techniques of the U-matrix and the K-means, the synoptic fields could be divided into eight kinds of patterns (clusters). One of the clusters has the notable spatial features represented by a large PW content accompanied by strong wind components known as low-level jet (LLJ). The features of this cluster indicate a typical synoptic field pattern that frequently causes heavy rainfall in Kyushu during the rainy season.In addition, an independent data set was used for validating the performance of the trained SOM. The results indicated that the SOM could successfully extract heavy rainfall events related to typical synoptic field patterns of the BAIU season. Interestingly, one specific SOM unit was closely related to the occurrence of disastrous heavy rainfall events observed during both training and validation periods. From these results, the trained SOM showed good performance for identifying synoptic fields causing heavy rainfall also in the validation period. We conclude that the SOM technique may be an effective tool for classifying complicated non-linear synoptic fields and identifying heavy rainfall events to some degree.     

Twenty years of Belgian North Sea aerial surveillance: a quantitative analysis of results confirms effectiveness of international oil pollution legislation

Over the years many policy measures have been taken to prevent illegal oil discharges from ships, like the MARPOL 73/78 Convention (1983) and the Bonn Agreement (1969/1983). However, the number of discharges remained high, leading to chronic oiling of seabirds and sensitive coastlines, therefore further measures were taken. The aim of this study is to quantify the effectiveness of two key legislative regulations: the IMO-designation of the North Sea as MARPOL Special Area which took effect in 1999, and the adoption of the EU Directive on Port Reception Facilities in 2000. Under study is the heavily navigated Belgian Surveillance Area, monitored since 1991, characterised by shallow waters with ecologically important sandbanks. The aerial surveillance data from 1991 to 2010 show a stepwise decrease in ship-source oil pollution. Three time periods can be distinguished with two turning points coinciding with the actual implementation of these key legislative measures, confirming their effectiveness.