Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Assessing the reliability of probabilistic flood inundation model predictions

An ability to quantify the reliability of probabilistic flood inundation predictions is a requirement not only for guiding model development but also for their successful application. Probabilistic flood inundation predictions are usually produced by choosing a method of weighting the model parameter space, but previous study suggests that this choice leads to clear differences in inundation probabilities. This study aims to address the evaluation of the reliability of these probabilistic predictions. However, a lack of an adequate number of observations of flood inundation for a catchment limits the application of conventional methods of evaluating predictive reliability. Consequently, attempts have been made to assess the reliability of probabilistic predictions using multiple observations from a single flood event. Here, a LISFLOOD‐FP hydraulic model of an extreme (>1 in 1000 years) flood event in Cockermouth, UK, is constructed and calibrated using multiple performance measures from both peak flood wrack mark data and aerial photography captured post‐peak. These measures are used in weighting the parameter space to produce multiple probabilistic predictions for the event. Two methods of assessing the reliability of these probabilistic predictions using limited observations are utilized; an existing method assessing the binary pattern of flooding, and a method developed in this paper to assess predictions of water surface elevation. This study finds that the water surface elevation method has both a better diagnostic and discriminatory ability, but this result is likely to be sensitive to the unknown uncertainties in the upstream boundary condition. Copyright © 2015 John Wiley & Sons, Ltd.     

Assessing the effects of land cover and future climate conditions on the provision of hydrological services in a medium‐sized watershed of Portugal

The separated and combined effects of land‐cover scenarios and future climate on the provision of hydrological services were evaluated in Vez watershed, northern Portugal. Soil and Water Assessment Tool was calibrated against daily discharge, sediments and nitrates, with good agreements between model predictions and field observations. Four hypothetical land‐cover scenarios were applied under current climate conditions (eucalyptus/pine, oak, agriculture/vine and low vegetation). A statistical downscaling of four General Circulation Models, bias‐corrected with ground observations, was carried out for 2021–2040 and 2041–2060, using representative concentration pathway 4.5 scenario. Also, the combined effects of future climate conditions were evaluated under eucalyptus/pine and agriculture/vine scenario. Results for land cover revealed that eucalyptus/pine scenario reduced by 7% the annual water quantity and up to 17% in the summer period. Although climate change has only a modest effect on the reduction of the total annual discharge (?7%), the effect on the water levels during summer was more pronounced, between ?15% and ?38%. This study shows that climate change can affect the provision of hydrological services by reducing dry season flows and by increasing flood risks during the wet months. Regarding the combined effects, future climate may reduce the low flows, which can be aggravated with eucalyptus/pine scenario. In turn, peak flows and soil erosion can be offset. Future climate may increase soil erosion and nitrate concentration, which can be aggravated with agriculture scenario. Results moreover emphasize the need to consider both climate and land‐cover impacts in adaptation and land management options at the watershed scale. Copyright © 2015 John Wiley & Sons, Ltd.     

Sensitivity of a hydraulic model to channel erosion uncertainty during extreme flooding

Recent research into flood modelling has primarily concentrated on the simulation of inundation flow without considering the influences of channel morphology. River channels are often represented by a simplified geometry that is implicitly assumed to remain unchanged during flood simulations. However, field evidence demonstrates that significant morphological changes can occur during floods to mobilize the boundary sediments. Despite this, the effect of channel morphology on model results has been largely unexplored. To address this issue, the impact of channel cross‐section geometry and channel long‐profile variability on flood dynamics is examined using an ensemble of a 1D–2D hydraulic model (LISFLOOD‐FP) of the ~1 : 2000 year recurrence interval floods in Cockermouth, UK, within an uncertainty framework. A series of simulated scenarios of channel erosional changes were constructed on the basis of a simple velocity‐based model of critical entrainment. A Monte‐Carlo simulation framework was used to quantify the effects of this channel morphology together with variations in the channel and floodplain roughness coefficients, grain size characteristics and critical shear stress on measures of flood inundation. The results showed that the bed elevation modifications generated by the simplistic equations reflected an approximation of the observed patterns of spatial erosion that enveloped observed erosion depths. The effect of uncertainty on channel long‐profile variability only affected the local flood dynamics and did not significantly affect the friction sensitivity and flood inundation mapping. The results imply that hydraulic models generally do not need to account for within event morphodynamic changes of the type and magnitude of event modelled, as these have a negligible impact that is smaller than other uncertainties, e.g. boundary conditions. Instead, morphodynamic change needs to happen over a series of events to become large enough to change the hydrodynamics of floods in supply limited gravel‐bed rivers such as the one used in this research. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrical resistivity imaging of hydrologic flow through surface coal mine valley fills with comparison to other landforms

Surface coal mining has altered land cover, near‐surface geologic structure, and hydrologic processes of large areas in central Appalachia, USA. These alterations are associated with changes in water quality such as elevated total‐dissolved solids, which is usually measured via its surrogate, specific conductance (SC). The SC of valley fill effluent streams is a function of fill construction methods, materials, and age; yet hydrologic studies that relate these variables to water quality are sparse due to the difficulty of conducting traditional hydrologic studies in mined landscapes. We used electrical resistivity imaging (ERI) to visualize the subsurface geologic structure and hydrologic flow paths within a valley fill. ERI is a noninvasive geophysical technique that maps spatiotemporal changes in resistivity of the subsurface. We paired ERI with artificial rainfall experiments to track infiltrated water as it moved through the valley fill. Results indicate that ERI can be used to identify subsurface geologic structure and track advancing wetting fronts or preferential flow paths. Our results suggest that the upper portion of the fill contains significant fines, whereas the deeper profile is primarily large rocks and void spaces. Water tended to pond on the surface of compacted areas until it reached preferential flow paths, where it appeared to infiltrate quickly down to >15 m depth in 75 min. ERI applications can improve understanding of how fill construction techniques influence subsurface water movement, and in turn may aid in the development of valley fill construction methods to reduce water quality effects.     

The Late Cretaceous Klepa basalts in Macedonia (FYROM)—Constraints on the final stage of Tethys closure in the Balkans

The waning stage(s) of the Tethyan ocean(s) in the Balkans are not well understood. Controversy centres on the origin and life‐span of the Cretaceous Sava Zone, which is allegedly a remnant of the last oceanic domain in the Balkan Peninsula, defining the youngest suture between Eurasia‐ and Adria‐derived plates. In order to investigate to what extent Late‐Cretaceous volcanism within the Sava Zone is consistent with this model we present new age data together with trace‐element and Sr–Nd–Pb isotope data for the Klepa basaltic lavas from the central Balkan Peninsula. Our new geochemical data show marked differences between the Cretaceous Klepa basalts (Sava Zone) and the rocks of other volcanic sequences from the Jurassic ophiolites of the Balkans. The Klepa basalts mostly have Sr–Nd–Pb isotopic and trace‐element signatures that resemble enriched within‐plate basalts substantially different from Jurassic ophiolite basalts with MORB, BAB and IAV affinities. Trace‐element modelling of the Klepa rocks indicates 2%–20% polybaric melting of a relatively homogeneously metasomatised mantle source that ranges in composition from garnet lherzolite to ilmenite+apatite bearing spinel–amphibole lherzolite. Thus, the residual mineralogy is characteristic of a continental rather than oceanic lithospheric mantle source, suggesting an intracontinental within‐plate origin for the Klepa basalts. Two alternative geodynamic models are internally consistent with our new findings: (1) if the Sava Zone represents remnants of the youngest Neotethyan Ocean, magmatism along this zone would be situated within the forearc region and triggered by ridge subduction; (2) if the Sava Zone delimits a diffuse tectonic boundary between Adria and Europe which had already collided in the Late Jurassic, the Klepa basalts together with a number of other magmatic centres represent volcanism related to transtensional tectonics.     

Intragrain oxygen isotope zoning in titanite by SIMS: Cooling rates and fluid infiltration along the Carthage‐Colton Mylonite Zone,Adirondack Mountains,NY, USA

Oxygen isotopes are an attractive target for zoning studies because of the ubiquity of oxygen‐bearing minerals and the dependence of mineral ¹⁸O/¹⁶O ratios on temperature and fluid composition. In this study, subtle intragrain oxygen isotope zoning in titanite is resolved at the 10‐μm scale by secondary ion mass spectrometry. The patterns of δ¹⁸O zoning differ depending on microstructural context of individual grains and reflect multiple processes, including diffusive oxygen exchange, partial recrystallization, grain‐size reduction, and grain growth. Using the chronological framework provided by structural relations, these processes can be related to specific events during the Grenville orogeny. Titanite was sampled from two outcrops within the Carthage‐Colton Mylonite Zone (CCMZ), a long‐lived shear zone that ultimately accommodated exhumation of the Adirondack Highlands from beneath the Adirondack Lowlands during the Ottawan phase (1090–1020 Ma) of the Grenville orogeny. Titanite is hosted in the Diana metasyenite complex, which preserves three sequentially developed fabrics: an early NW‐dipping protomylonitic fabric (S₁) is crosscut by near‐vertical ultramylonitic shear zones (S₂), which are locally reoriented by a NNW‐dipping mylonitic fabric (S₃). Texturally early titanite (pre‐S₂) shows diffusion‐dominated δ¹⁸O zoning that records cooling from peak Ottawan, granulite‐facies conditions. Numerical diffusion models in the program Fast Grain Boundary yield good fits to observed δ¹⁸O profiles for cooling rates of 50 ± 20 °C Ma^?1, which are considerably faster than the 1–5 °C Ma^?1 cooling rates previously inferred for the Adirondack Highlands from regional thermochronology. High cooling rates are consistent with an episode of rapid shearing and exhumation along the CCMZ during gravitational collapse of the Ottawan orogen at c. 1050 Ma. Texturally later titanite (syn‐S₂) has higher overall δ¹⁸O and shows a transition from diffusion‐dominated to recrystallization‐dominated δ¹⁸O zoning, indicating infiltration of elevated‐δ¹⁸O fluids along S₂ shear zones and continued shearing below the blocking temperature for oxygen (~≤500 °C for grain sizes at the study site). The texturally latest titanite (post‐S₃) has growth‐dominated δ¹⁸O zoning, consistent with porphyroblastic grain growth following cessation of shearing along the Harrisville segment of the CCMZ.