Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

Saprolite Remnants as Indicators of Pre-Glacial Landform Genesis in Southeast Sweden

Twenty‐six sites with remnants of gravelly saprolites (grus) have been located in southeast Sweden. Joint block hills (castle kopjes) and steep rock walls with weathered joints as well as rounded boulders are documented to have an origin in deep weathering and subsequent stripping of saprolites. The saprolite remnants and landforms result from the fragmentation of the re‐exposed sub‐Cambrian peneplain along fracture systems. Only shallow saprolites occur on the elevated intact parts of the sub‐Cambrian peneplain, while saprolites up to 20 m thick are encountered in areas where the sub‐Cambrian peneplain is fractured and dissected. Neogene uplift with reactivation of the weathering system is thought to be the main cause of saprolite formation. Deep weathering is thus judged to have been the major agent of landform formation in the study area, while glacial and glaciofluvial erosion has contributed mainly by stripping saprolites, detaching corestones, and plucking joint blocks along weathered joints.     

Is there a superior conceptual groundwater model structure for baseflow simulation?

Previous work has shown that streamflow response during baseflow conditions is a function of storage, but also that this functional relationship varies among seasons and catchments. Traditionally, hydrological models incorporate conceptual groundwater models consisting of linear or non‐linear storage–outflow functions. Identification of the right model structure and model parameterization however is challenging. The aim of this paper is to systematically test different model structures in a set of catchments where different aquifer types govern baseflow generation processes. Nine different two‐parameter conceptual groundwater models are applied with multi‐objective calibration to transform two different groundwater recharge series derived from a soil‐atmosphere‐vegetation transfer model into baseflow separated from streamflow data. The relative performance differences of the model structures allow to systematically improve the understanding of baseflow generation processes and to identify most appropriate model structures for different aquifer types. We found more versatile and more aquifer‐specific optimal model structures and elucidate the role of interflow, flow paths, recharge regimes and partially contributing storages. Aquifer‐specific recommendations of storage models were found for fractured and karstic aquifers, whereas large storage capacities blur the identification of superior model structures for complex and porous aquifers. A model performance matrix is presented, which highlights the joint effects of different recharge inputs, calibration criteria, model structures and aquifer types. The matrix is a guidance to improve groundwater model structures towards their representation of the dominant baseflow generation processes of specific aquifer types. Copyright © 2014 John Wiley & Sons, Ltd.     

Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Gradients in coral reef communities exposed to muddy river discharge in Pohnpei,Micronesia

This study analyzed how coral communities change along a gradient of increasing exposure to a mud-discharging river in the Enipein Catchment, Pohnpei, Micronesia. Using video transects, we quantified benthic communities at five sites along a gradient moving away from the river mouth towards the barrier reef. The most river-impacted site was characterized by a high accumulation of mud, low coral cover and low coral diversity. Although coral cover leveled off at ∼400 m from the river mouth to values found at the outer-most sites, coral diversity continued to increase with increasing distance, suggesting that the most distant site was still impacted by the river discharges. Fungiidae, Pavona, Acropora, Pachyseris and Porites rus all significantly increased in cover with distance from the river, while Turbinaria decreased. The combined presence and abundance of these six species groups, together with coral species richness, may help to indicate the effects of terrestrial runoff in similar runoff-exposed settings around Micronesia, whereas coral cover is not a sensitive indicator for river impact. Coral reefs are important resources for the people of Pohnpei. To prevent further degradation of this important resource, an integrated watershed approach is needed to control terrestrial activities.     

Multi-angle backscatter classification and sub-bottom profiling for improved seafloor characterization

This study applies three classification methods exploiting the angular dependence of acoustic seafloor backscatter along with high resolution sub-bottom profiling for seafloor sediment characterization in the Eckernförde Bay, Baltic Sea Germany. This area is well suited for acoustic backscatter studies due to its shallowness, its smooth bathymetry and the presence of a wide range of sediment types. Backscatter data were acquired using a Seabeam1180 (180 kHz) multibeam echosounder and sub-bottom profiler data were recorded using a SES-2000 parametric sonar transmitting 6 and 12 kHz. The high density of seafloor soundings allowed extracting backscatter layers for five beam angles over a large part of the surveyed area. A Bayesian probability method was employed for sediment classification based on the backscatter variability at a single incidence angle, whereas Maximum Likelihood Classification (MLC) and Principal Components Analysis (PCA) were applied to the multi-angle layers. The Bayesian approach was used for identifying the optimum number of acoustic classes because cluster validation is carried out prior to class assignment and class outputs are ordinal categorical values. The method is based on the principle that backscatter values from a single incidence angle express a normal distribution for a particular sediment type. The resulting Bayesian classes were well correlated to median grain sizes and the percentage of coarse material. The MLC method uses angular response information from five layers of training areas extracted from the Bayesian classification map. The subsequent PCA analysis is based on the transformation of these five layers into two principal components that comprise most of the data variability. These principal components were clustered in five classes after running an external cluster validation test. In general both methods MLC and PCA, separated the various sediment types effectively, showing good agreement (kappa >0.7) with the Bayesian approach which also correlates well with ground truth data (r²?>?0.7). In addition, sub-bottom data were used in conjunction with the Bayesian classification results to characterize acoustic classes with respect to their geological and stratigraphic interpretation. The joined interpretation of seafloor and sub-seafloor data sets proved to be an efficient approach for a better understanding of seafloor backscatter patchiness and to discriminate acoustically similar classes in different geological/bathymetric settings.     

Constructing the Klamath: Nature,Culture, and the Management of a Western River

Despite decades of scientific research, stakeholder negotiations, and policy proposals, management of the Klamath River in southern Oregon and northern California remains hotly contested. This research examines the sociocultural dimensions of proposed removal of four Klamath River dams. Using a social constructivist approach to analyze the discourse of public comments regarding dam removal, I find commenters rely on diverse ideas of nature and divergent problem framings, contest the role of science, and draw on embedded and meaningful sociocultural narratives to legitimize their management preferences. These discourses shape the terrain upon which management actions are perceived, valued, and contested, and make management actions meaningful beyond their immediate spatial and temporal context. Dam removal on the Klamath River is far more than an ecological problem amenable to a scientific or technical approach; instead, it is a complex project shot through with the sociocultural identities, visions, and narratives of all involved.     

Intercomparison of stratospheric water vapor profiles obtained during the Balloon Intercomparison Campaign

The Balloon Intercomparison Campaign (BIC) was set up to intercompare remote sensing measurements of a number of compounds other than water vapor; however, water vapor has strong absorption features throughout the infrared and mm wave regions of the spectrum. Therefore many of the investigators involved in BIC have absorption or emission features due to water vapor in the data they obtained during the balloon flights made under the campaign. These features have been used by the investigators to determine the stratospheric water vapor profiles which are compared in this paper. The profiles allow comparison of a wide range of remote sensing techniques involving both emission and absorption in the mid-infrared and emission techniques in the far infrared.     

Age,origin and climatic controls on vegetated linear dunes in the northwestern Negev Desert (Israel)

The stabilized northwestern (NW) Negev vegetated linear dunes (VLD) of Israel extend over 1300 km² and form the eastern end of the Northern Sinai – NW Negev Erg. This study aimed at identifying primary and subsequent dune incursions and episodes of dune elongation by investigating dune geomorphology, stratigraphy and optically stimulated luminescence (OSL) dating. Thirty-five dune and interdune exposed and drilled section were studied and sampled for sedimentological analyses and OSL dating, enabling spatial and temporal elucidation of the NW Negev dunefield evolution.In a global perspective the NW Negev dunefield is relatively young. Though sporadic sand deposition has occurred during the past 100 ka, dunes began to accumulate over large portions of the dunefield area only at ～23 ka. Three main chronostratigraphic units, corresponding to three (OSL) age clusters, were found throughout most of the dunefield, indicating three main dune mobilizations: late to post last glacial maximum (LGM) at 18–11.5 ka, late Holocene (2–0.8 ka), and modern (150–8 years). The post-LGM phase is the most extensive and it defined the current dunefield boundaries. It involved several episodes of dune incursions and damming of drainage systems. Dune advancement often occurred in rapid pulses and the orientation of VLD long axes indicates similar long-term wind directions. The late Holocene episode included partial incursion of new sand, reworking of Late Pleistocene dunes as well as limited redeposition. The modern sand movement only reactivated older dunes and did not lengthen VLDs.This aeolian record fits well with other regional aeolian sections. We suggest that sand supply and storage in Sinai was initiated by the Late Pleistocene exposure of the Nile Delta sands. Late Pleistocene winds, substantially stronger than those usually prevailing since the onset of the Holocene, are suggested to have transported the dune sands across Sinai and into the northwestern Negev.Our results demonstrate the sensitivity of vegetated linear dunes located along the (northern) fringe of the sub-tropical desert belt to climate change (i.e. wind) and sediment supply.     

Seasonality change and the third millennium BP rainforest crisis in southern Cameroon (Central Africa)

The third millennium BP crisis of the central African rainforest is not sufficiently understood. The low resolution of most pollen profiles and a large plateau of the calibration curve aggravate the exact dating of the event, and its causal climatic parameters are debated. We present a high-resolution pollen profile from the swamp site Nyabessan in the southern Cameroonian rainforest, covering the period 3100-2300 cal yr BP. Between 3100 and 2500 cal yr BP, the climate was favourable for a regional evergreen forest with Caesalpiniaceae and Lophira and a local Raphia swamp forest. Around 2500/2400 cal yr BP, a significant decrease of mature forest and swamp forest taxa and an increase of pioneers indicate that the rain forest was seriously disturbed and replaced by secondary formations. The dominance of Trema orientalis, a pioneer well adapted to seasonal desiccation, points to a much more accentuated seasonality after 2500 cal yr BP, which seems to be linked to a southwards shift of the ITCZ during the northern hemisphere winter months. We propose that the rain forest crisis between 2500 and 2200 cal BP created favourable conditions for farming and paved the way for a major expansion of Bantu speaking populations.