Electron Transfer Between Sulfide and Humic Acid: Electrochemical Evaluation of the Reactivity of Sigma-Aldrich Humic Acid Toward Sulfide

Little is known of potential reactivity and redox properties of reduced dissolved organic matter (DOM), although DOM in anoxic environments, e.g., groundwater, peat soils, or lake sediments, can be expected to differ from DOM of oxidized environments. We therefore investigated the impact of electrochemical and wet chemical [hydrogen (H₂)/Pd catalyst] reduction in Sigma-Aldrich humic acid (HA) as a model DOM for high salinity, high ionic strength, or iron-rich systems on its reactivity toward sulfide. Mediated electrochemical measurement showed that the reactivity of HA toward sulfide decreased in the order non-reduced HA > electrochemically reduced (?0.1 V) HA > H₂/Pd-reduced HA > electrochemically reduced (?0.4 V) HA. Results indicated that measured initial values of electron-accepting capacities of HA had a strongly positive correlation with the sulfide transformation, except for the H₂/Pd treatment of HA. This latter treatment obviously changed HA structures and lead to a different reactivity toward sulfide, limiting a direct comparison to electrochemically reduced organic matter. Our result confirmed that reduced HA was still reactive toward sulfide, although to a lower extent compared with oxidized HA. Compared to electrochemical reduction, H₂/Pd pre-treatment of HA alters redox properties and reactivity of organic matter and may therefore lead to results that cannot be transferred to natural systems.     

Rainfall thresholds for the possible landslide occurrence in Sicily (Southern Italy) based on the automatic reconstruction of rainfall events

Review of the literature on the reconstruction of the rainfall responsible for slope failures reveals that criteria for the identification of rainfall events are lacking or somewhat subjective. To overcome this problem, we developed an algorithm for the objective and reproducible reconstruction of rainfall events and of rainfall conditions responsible for landslides. The algorithm consists of three distinct modules for (i) the reconstruction of distinct rainfall events, in terms of duration (D, in h) and cumulated event rainfall (E, in mm), (ii) the identification of multiple ED rainfall conditions responsible for the documented landslides, and (iii) the definition of critical rainfall thresholds for possible landslide occurrences. The algorithm uses pre-defined parameters to account for different seasonal and climatic settings. We applied the algorithm in Sicily, southern Italy, using rainfall measurements obtained from a network of 169 rain gauges, and information on 229 rainfall-induced landslides occurred between July 2002 and December 2012. The algorithm identified 29,270 rainfall events and reconstructed 472 ED rainfall conditions as possible triggers of the observed landslides. The algorithm exploited the multiple rainfall conditions to define objective and reproducible empirical rainfall thresholds for the possible initiation of landslide in Sicily. The calculated thresholds may be implemented in an operational early warning system for shallow landslide forecasting.     

Identifying landslide preconditions in Swedish quick clays—insights from integration of surface geophysical,core sample- and downhole property measurements

Quick-clay landslides are a serious geohazard in Canada, Norway and Sweden. Identification and mapping of quick clays are essential endeavours because the damage caused by an individual landslide can be large and costly, with potentially fatal consequences. We collected geophysical borehole and soil core data from an area prone to quick-clay landslides in southwestern Sweden. Methodologies included in situ and laboratory measurements, providing information about natural gamma radiation, sonic velocities, electrical conductivity, pH, physical grain size, elemental and mineral composition, magnetic properties, cation exchange capacity and fossil content. A stratigraphic thickness of almost 60 m enables us to study quick clays and their host environment in Sweden at unusually high resolution. Results identify the origin and location of reflections in nearby seismic lines and assign physico-chemical properties to the geological units present in the area. We show that coarse-grained layers are sandwiched between marine clays (some of which are quick clays). These layers function as a conduit for relatively fresh water that infiltrates the marine clays and chemically destabilizes them by leaching out their salts. The salinity distribution in the boreholes indicate that the groundwater movement is downwards, through the coarse-grained layer and towards the Göta river. The presence of these materials is important for the development of quick clays, although not a prerequisite. With the help of surface geophysical methods, the location of the coarse-grained layers can be known faster and more economically, which could be relevant for studying the potential for quick-clay landslide occurrence over large areas.     

Measurements and modelling of the advection of suspended sediment in the swash zone by solitary waves

Novel laboratory experiments and numerical modelling have been performed to study the advection scales of suspended sediment in the swash zone. An experiment was designed specifically to measure only the sediment picked up seaward of the swash zone and during bore collapse. The advection scales and settling of this sediment were measured during the uprush along a rigid sediment-free beach face by a sediment trap located at varying cross-shore positions. Measurements were made using a number of repeated solitary broken waves or bores. Approximately 25% of the pre-suspended sediment picked up by the bores reaches the mid-swash zone (50% of the horizontal run-up distance), indicating the importance of the sediment advection in the lower swash zone. The pre-suspended sediment is sourced from a region seaward of the shoreline (still water line) which has a width of about 20% of the run-up distance. An Eulerian–Lagrangian numerical model is used to model the advection scales of the suspended sediment. The model resolves the hydrodynamics by solving the non-linear shallow water equations in an Eulerian framework and then solves the advection–diffusion equation for turbulence and suspended sediment in a Lagrangian framework. The model provides good estimates of the measured mass and distribution of sediment advected up the beach face. The results suggest that the correct modelling of turbulence generation prior to and during bore collapse and the advection of the turbulent kinetic energy into the lower swash is important in resolving the contribution of pre-suspended sediment to the net sediment transport in the swash zone.     

High-precision late Aptian Pb/U age for the Punta del Barco Formation (Baqueró Group), Santa Cruz Province,Argentina

The Baqueró Group holds a rich fossil flora including macrofloristic and palynological remains that characterize the Early Cretaceous vegetation of Argentina. The age of the upper part of the Group, known as Punta del Barco Formation, has been a topic of several discussions in the past. The type locality of this stratigraphic unit exposes fossiliferous tuffs together with muddy tuffs and tuffaceous sandstones beds. However, there have been no reliable age constraints for the fossil assemblages. ²⁰⁶Pb/²³⁸U analyses of zircon crystals yielded an age of 114.67 ± 0.18 Ma. This age control makes possible an improved analysis and comparison of the floras in the southern region.     

Modeling a tsunami from the Nicoya,Costa Rica,seismic gap and its potential impact in Puntarenas

Although subduction zones around the world are known to be the source of earthquakes and/or tsunamis, not all segments of these plate boundaries generate destructive earthquakes and catastrophic tsunamis. Costa Rica, in Central America, has subduction zones on both the Pacific and the Caribbean coasts and, even though large earthquakes (Mw = 7.4–7.8) occur in these convergent margins, they do not produce destructive tsunamis. The reason for this is that the seismogenic zones of the segments of the subduction zones that produce large earthquakes in Costa Rica are located beneath land (Nicoya peninsula, Osa peninsula and south of Limón) and not off shore as in most subduction zones around the world. To illustrate this particularity of Costa Rican subduction zones, we show in this work the case for the largest rupture area in Costa Rica (under the Nicoya peninsula), capable of producing Mw ～ 7.8 earthquakes, but the tsunamis it triggers are small and present little potential for damage even to the largest port city in Costa Rica.The Nicoya seismic gap, in NW Costa Rica, has passed its ～50-year interseismic period and therefore a large earthquake will have to occur there in the near future. The last large earthquake, in 1950 generated a tsunami which slightly affected the southwest coast of the Nicoya Peninsula. We present here a simulation to study the possible consequences that a tsunami generated by the next Nicoya earthquake could have for the city of Puntarenas. Puntarenas has a population of approximately eleven thousand people and is located on a 7.5 km long sand bar with a maximum height of 2 m above the mean sea level. This condition makes Puntarenas vulnerable to tsunamis.     

530 Ma syntectonic syenites and granites in NW Namibia — Their relation with collision along the junction of the Damara and Kaoko belts

The Lower Ugab and Goantagab structural domains are located at the junction between the N–S trending Kaoko and the E–W trending Damara belts (NW Namibia), where Neoproterozoic metavolcano-sedimentary sequences were intruded by several syenitic/granitic plutons. We present here new U–Pb ages on zircon grains from the Voetspoor and Doros plutons. Together with petrological, geochemical and structural data we evaluate the timing of the deformation and relation to the geodynamics during the final stage of Gondwana amalgamation.The plutons are composed of three main rock types: hornblende quartz-syenite, syenodiorite and biotite granite. The two former are predominant and show genetic correlation such as magma mingling structures and similar geochemical signatures. The biotite granite occurs in the SW parts of the intrusions and clearly cuts the syenitic rocks. Although the plutons are mainly isotropic, the structures around them demonstrate that their intrusion occurred during a second deformation phase (D2) with a component of sinistral solid state rotation with respect to the wall rocks in response to D2 transpression. Four samples were dated using U–Pb SHRIMP methodology in single zircon grains. A hornblende monzodiorite from the Voetspoor pluton yielded an age of 534 ± 4.5 Ma. A hornblende monzonite from the Doros pluton produced an age of 528 ± 5 Ma. The biotite granite facies was sampled in the Doros intrusion and yielded an age of 530 ± 4.5 Ma. In addition, a granitic vein folded by D2 close to the northeastern contact of the Doros pluton with the encasing phyllites (Amis River Formation) was also dated, yielding an age of 533 ± 6 Ma. The data show that all granite–syenite from Doros and Voetspoor intrusions are contemporaneous and crystallized in the period between 539 and 522 Ma within the errors. D1–D2 deformational phases took place under greenschist facies (biotite zone) conditions and during D3 the metamorphic grade was slightly lower. We interpret that the plutons are coeval to peak metamorphism of the region (530–520 Ma) and that D2 and D3 sinistral transpressional phases are due to collision in the Damara Belt. The E–W compressional event and second metamorphic episode in the Kaoko Belt occurred between 580 and 560 Ma and are apparently unrelated to the thermo-tectonic evolution described here, although D1 might be partially related to this event. The sinistral transpressional D2 phase resulted probably from the position of the area considered at the junction between the belts, and not in the frontal Damara collision further to the east. This new interpretation is consistent with the Ar–Ar ages for the region (about 500 Ma), interpreted to reflect cooling of the orogen. The enrichment in LREE, K, Rb, Ba and Sr, and depletion in Nb of these basic to intermediate alkalic rocks could indicate that they partially derived from melting of a subcontinental lithospheric mantle that was affected by subduction and the granitic rock types represent lower crust contamination. We interpret that they could be related to heating in the mantle caused by asthenosphere influx in a zone of slab-breakoff during collision between Kalahari and Congo cratons.