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.     

Earthquake forewarning — A multidisciplinary challenge from the ground up to space

Most destructive earthquakes nucleate at between 5–7 km and about 35–40 km depth. Before earthquakes, rocks are subjected to increasing stress. Not every stress increase leads to rupture. To understand pre-earthquake phenomena we note that igneous and high-grade metamorphic rocks contain defects which, upon stressing, release defect electrons in the oxygen anion sublattice, known as positive holes. These charge carriers are highly mobile, able to flow out of stressed rocks into surrounding unstressed rocks. They form electric currents, which emit electromagnetic radiation, sometimes in pulses, sometimes sustained. The arrival of positive holes at the ground-air interface can lead to air ionization, often exclusively positive. Ionized air rising upward can lead to cloud condensation. The upward flow of positive ions can lead to instabilities in the mesosphere, to mesospheric lightning, to changes in the Total Electron Content (TEC) at the lower edge of the ionosphere, and electric field turbulences. Advances in deciphering the earthquake process can only be achieved in a broadly multidisciplinary spirit.     

Geological evolution of the West Luzon Basin (South China Sea,Philippines)

Interpretation of deep 2-D multi-channel seismic data sheds insights into the geological evolution of the West Luzon Basin, Philippines. This basin is a sediment-filled trough that is located between the island of Luzon and the outer arc high of the west Luzon subduction zone. High-amplitude, low-frequency reflection bands mark the acoustic basement. The basement, at about 6 s (TWT), is dissected by normal faults with some of them being inverted in a later phase of deformation. The sedimentary successions, overlying the basement are stratified with partly chaotic structures and discontinuous reflectors. Five regional unconformities separate major stratigraphic units. Grid calculations of our seismic data reveal variations in the sedimentation pattern of the basin with a shift of the deposition centre from east to west and backwards during formation. A distinct bottom-simulating reflector is commonly observed. Because the northern boundary of the continental fragments to the South of the West Luzon Basin is unclear we speculate that the basin may be (partly) underlain by continental crust. The continental crust was affected by rifting prior to and during the opening of the South China Sea and the basin was overprinted at a later stage by a forearc structural setting when subduction was initiated.     

Ries crater and suevite revisited—Observations and modeling Part I: Observations

We report results of an interdisciplinary project devoted to the 26 km‐diameter Ries crater and to the genesis of suevite. Recent laboratory analyses of “crater suevite” occurring within the central crater basin and of “outer suevite” on top of the continuous ejecta blanket, as well as data accumulated during the past 50 years, are interpreted within the boundary conditions imposed by a comprehensive new effort to model the crater formation and its ejecta deposits by computer code calculations (Artemieva et al. 2013). The properties of suevite are considered on all scales from megascopic to submicroscopic in the context of its geological setting. In a new approach, we reconstruct the minimum/maximum volumes of all allochthonous impact formations (108/116 km³), of suevite (14/22 km³), and the total volume of impact melt (4.9/8.0 km³) produced by the Ries impact event prior to erosion. These volumes are reasonably compatible with corresponding values obtained by numerical modeling. Taking all data on modal composition, texture, chemistry, and shock metamorphism of suevite, and the results of modeling into account, we arrive at a new empirical model implying five main consecutive phases of crater formation and ejecta emplacement. Numerical modeling indicates that only a very small fraction of suevite can be derived from the “primary ejecta plume,” which is possibly represented by the fine‐grained basal layer of outer suevite. The main mass of suevite was deposited from a “secondary plume” induced by an explosive reaction (“fuel‐coolant interaction”) of impact melt with water and volatile‐rich sedimentary rocks within a clast‐laden temporary melt pool. Both melt pool and plume appear to be heterogeneous in space and time. Outer suevite appears to be derived from an early formed, melt‐rich and clast‐poor plume region rich in strongly shocked components (melt ? clasts) and originating from an upper, more marginal zone of the melt pool. Crater suevite is obviously deposited from later formed, clast‐rich and melt‐poor plumes dominated by unshocked and weakly shocked clasts and derived from a deeper, central zone of the melt pool. Genetically, we distinguish between “primary suevite” which includes dike suevite, the lower sublayer of crater suevite, and possibly a basal layer of outer suevite, and “secondary suevite” represented by the massive upper sublayer of crater suevite and the main mass of outer suevite.     

The use of tracers to assess drill-mud penetration depth into sandstone cores during deep drilling: method development and application

For the utilization of deep saline aquifers in the frame of geotechnical use, such as geological sequestration of CO₂, H₂ or energy storage, a baseline characterization of pristine reservoir rock cores is required to monitor changes in the indigenous microbial communities and pore fluids, and to study alterations in rock characteristics resulting from interaction with geological storage technologies. However, drilling procedures and technical fluids, particularly drill mud, are sources of core contamination. To measure the penetration of drill mud into the cores, three tracers (fluorescein, microspheres, and 4′,6-diamidino-2-phenylindole stained bacteria) were tested under laboratory conditions. The flow of drill mud into core samples was induced by applying uniaxial pressure differentials to the core, and the penetration depth was microscopically determined for each tracer. Fluorescein was extracted from the rock samples and quantified fluorometrically. The results indicate that all tested tracers are suitable for tracking drill-mud penetration. The actual penetration depth seems to be related to differences in mineral composition and texture as well as microfractures. Among all tested tracers, fluorescein labelling is the simplest, cheapest and most accurate method for analyzing the contamination of rock cores by technical fluids. The application of this tracer was successfully applied during two deep drilling campaigns at the CO₂ storage pilot site in Ketzin, Germany. The results highlight that the use of tracers is indispensable to ensure the quality of core samples for microbiological and biogeochemical analysis.     

Altitude variation of the plasmapause signature in the main ionospheric trough

The projection of the plasmapause magnetic-field lines to low altitudes, where the light-ion chemistry is dominated by O⁺, tends to occur near the minimum electron density in the main (midlatitude) electron density trough at night. With increasing altitude in the trough, where H⁺ emerges as the dominant ion on the low-latitude boundary, we have found cases where the plasmapause field lines are located on the sharp low-latitude side of the trough as expected if this topside ionosphere H⁺ distribution varies in step with the plasmapause gradient in the distant plasmasphere. These conclusions are based on near-equatorial crossings of the plasmapause (corresponding to the steep gradient in the dominant species H⁺) by the Explorer-45 satellite as determined from electric-field measurements by Maynard and Cauffman in the early 1970s and ISIS-2 ionospheric topside-sounder measurements. The former data have now been converted to digital form and made available at http://nssdcftp.gsfc.nasa.gov. The latter provide samples of nearly coincident observations of ionospheric main trough crossings near the same magnetic-field lines of the Explorer 45-determined equatorial plasmapause. The ISIS-2 vertical electron density profiles are used to infer where the F-region transitions from an O⁺ to a H⁺ dominated plasma through the main trough boundaries.     

Stable carbon isotope distribution of particulate organic matter in the ocean: a model study

The stable carbon isotopic composition of particulate organic matter in the ocean, δ¹³C_POC, shows characteristic spatial variations with high values in low latitudes and low values in high latitudes. The lowest δ¹³C_POC values (−32‰ to −35‰) have been reported in the Southern Ocean, whereas in arctic and subarctic regions δ¹³C_POC values do not drop below −27‰. This interhemispheric asymmetry is still unexplained. Global gradients in δ¹³C_POC are much greater than in δ¹³C_DIC, suggesting that variations in isotopic fractionation during organic matter production are primarily responsible for the observed range in δ¹³C_POC. Understanding the factors that control isotope variability is a prerequisite when applying δ¹³C_POC to the study of marine carbon biogeochemistry. The present model study attempts to reproduce the δ¹³C_POC distribution pattern in the ocean. The three-dimensional (3D) Hamburg Model of the Oceanic Carbon Cycle version 3.1 (HAMOCC3.1) was combined with two different parametrizations of the biological fractionation of stable carbon isotopes. In the first parametrization, it is assumed that the isotopic fractionation between CO₂ in seawater and the organic material produced by algae, _P, is a function of the ambient CO₂ concentration. The two parameters of this function are derived from observations and are not based on an assumption of any specific mechanism. Thus, this parametrization is purely empirical. The second parametrization is based on fractionation models for microalgae. It is supported by several laboratory experiments. Here the fractionation, _P, depends on the CO₂ concentration in seawater and on the (instantaneous) growth rates, μ_i, of the phytoplankton. In the Atlantic Ocean, where most field data are available, both parametrizations reproduce the latitudinal variability of the mean δ¹³C_POC distribution. The interhemispheric asymmetry of δ¹³C_POC can mostly be attributed to the interhemispheric asymmetry of CO₂ concentration in the water. However, the strong seasonal variations of δ¹³C_POC as reported by several authors, can only be explained by a growth rate-dependent fractionation, which reflects variations in the cellular carbon demand.     

Focal Mechanisms and Stress Field in The Region Vogtland/Western Bohemia

We calculated focal mechanisms for 30 of the strongest events (1.5 M _L 3.3) in distinct subregions of Vogtland/Western Bohemia between 1990 and 1998. Our investigations are concerned with events of the swarms near Bad Elster (1991), Haingrün (1991), Nový Kostel (1994 and 1997) and Zwickau (1998), two events from a group of earthquakes near Klingenthal (1997) and eight single events. Seismograms were provided by the digital station networks of the Geophysical Observatory of the University of Munich, the Technical University of Freiberg, the Academy of Sciences of the Czech Republic in Prague, the Masaryk University in Brno and some nearby stations of the German Regional Seismic Network (GRSN). To calculate focal mechanisms two inversion methods were applied. The inferred focal mechanisms do not show a simple, uniform pattern of seismic dislocation. All possible dislocation types – strike-slip, normal and thrust faulting - are represented. The prevailing mechanisms are normal and strike-slip faulting. Considerable differences in the fault plane solutions are noted for the individual subregions as well as in some cases among the individual events of a single swarm. For the Nový Kostel area we succeeded to resolve a change in the orientations of the nodal planes for the two successive swarms of December 1994 and January 1997. Besides this we also observe a change in the mechanisms, namely from strike-slip and normal faulting (December 1994) to strike-slip and thrust faulting (January 1997). Based on the inferred focal mechanisms the stress field was estimated. It turned out, that the dominating stress field in the region Vogtland/Western Bohemia does not substantially differ from the known stress field of West and Central Europe, being characterized by a SE-NW direction of the maximum compressive horizontal stress. We conclude that the seismicity in the Vogtland/Western Bohemia region is not predominantly caused by an independent local stress field, but rather controlled by the dominating stress regime in Central Europe.