Assessment of alternative adsorption models and global sensitivity analysis to characterize hexavalent chromium loss from soil to surface runoff

We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AIC_C] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.     

Rift-related Jurassic basaltic phreatomagmatic volcanism in the central Transantarctic Mountains: precursory stage to flood-basalt effusion

 The Middle Jurassic Kirkpatrick flood basalts and comagmatic Ferrar intrusions in the Transantarctic Mountains represent a major pulse of tholeiitic magmatism related to early stages in the breakup of Gondwana. A record of the volcano-tectonic events leading to formation of this continental flood-basalt province is provided by strata underlying and only slightly predating the Kirkpatrick lavas. In the central Transantarctic Mountains, the lavas rest on widespread (≥7500 km²) tholeiitic pyroclastic deposits of the Prebble Formation. The Prebble Formation is dominated by lahar deposits and is an unusual example of a regionally developed basaltic lahar field. Related, partly fault-controlled pyroclastic intrusions cut underlying strata, and vents are represented by the preserved flanks of two small tephra cones associated with a volcanic neck. Lahar and air-fall deposits typically contain 50–60% accidental lithic fragments and sand grains derived from underlying Triassic – Lower Jurassic strata in the upper part of the Beacon Supergroup. Juvenile basaltic ash and fine lapilli consist of nonvesicular to scoriaceous tachylite, sideromelane, and palagonite, and have characteristics indicating derivation from hydrovolcanic eruptions. The abundance of accidental debris from underlying Beacon strata points to explosive phreatomagmatic interaction of basaltic magma with wet sediment and groundwater, which appears to have occurred in particular where rising magma intersected upper Beacon sand aquifers. Composite clasts in the lahar deposits exhibit complex peperitic textures formed during fine-scale intermixing of basaltic magma with wet sand and record steps in subsurface fuel-coolant interactions leading to explosive eruption. The widespread, sustained phreatomagmatic activity is inferred to have occurred in a groundwater-rich topographic basin linked to an evolving Jurassic rift zone in the Transantarctic Mountains. Coeval basaltic phreatomagmatic deposits of the Mawson and Exposure Hill Formations, which underlie exposures of the Kirkpatrick Basalt up to 1500 km to the north along strike in Victoria Land, appear to represent other parts of a regional, extension-related Middle Jurassic phreatomagmatic province which developed immediately prior to rapid outpouring of the flood basalts. This is consistent with models which assign an important role to lithospheric stretching in the generation of flood-basalt provinces. Received: 28 August 1995 / Accepted: 18 April 1996     

Fate and effects of a heavy fuel oil spill on a Georgia salt marsh

Addition of a heavy oil to a Spartina salt marsh in the autumn resulted in high concentrations of polycyclic aromatic hydrocarbons in sediment and benthic animals. The highest concentrations of phenanthrene, chrysene and fluoranthene in the sediment were 112, 105 and 75 ng/g sediment, respectively. These concentrations rapidly decreased during the 20 week period following the spill. The times for these hydrocarbons to decrease to 50% of their highest values, i.e. half-life, were approximately 100, 70 and 30 days in sediment, mussels and oysters, respectively. Benthic macrofauna species showed three responses to oil addition which included no change, an increase, or a decrease in the population. No changes were noted in populations of fiddler crabs (Uca pugnax), oysters (Crassostrea virginica), and mussels (Modiolus demissus). Mud snails (Nassarius obsoleta) increased in density after the spill due to immigration of adult snails from untreated areas to scavenge on animals killed by the oil. Many of the adult periwinkles (Littorina irrorata) were killed by the oil. In the spring, juvenile periwinkles recolonised to oiled areas as a result of larvae settling.     

砂泥岩裂隙岩体埋深和岩性对渗透性影响分析

采用表征岩体渗透性的单位吸水量ω为参数,有效地分析了砂泥岩裂隙岩体中相对埋深和岩性对渗透性空间分布规律的影响.研究区内,在不同深度单位吸水量的最大值和最小值相差3-4个数量级,渗透性表现出显著的随机特征.通过将压水试验数据离散化并在不同深度上取logω的平均值,凸现了渗透性的结构特征.ω均值在一定范围内随相对深度表现出负指数分布规律;剔除logω的线性趋势项后,logω残差表现出与地层内部岩性相对应的规律.此外,研究还发现,渗透性参数随相对深度呈负指数分布规律是由含裂隙的砂岩介质引起的.这些规律为裂隙岩体的渗流计算和模拟奠定了基础.文章所提出的对压水试验数据离散化并在不同深度取均值以找出渗透性和深度关系,以及去除线性趋势项研究渗透性和岩性之间关系等方法具有广泛的应用价值.     

Using Sequential Self-Calibration Method to Identify Conductivity Distribution: Conditioning on Tracer Test data

An iterative inverse method, the sequential self-calibration method, is developed for mapping spatial distribution of a hydraulic conductivity field by conditioning on nonreactive tracer breakthrough curves. A streamline-based, semi-analytical simulator is adopted to simulate solute transport in a heterogeneous aquifer. The simulation is used as the forward modeling step. In this study, the hydraulic conductivity is assumed to be a deterministic or random variable. Within the framework of the streamline-based simulator, the efficient semi-analytical method is used to calculate sensitivity coefficients of the solute concentration with respect to the hydraulic conductivity variation. The calculated sensitivities account for spatial correlations between the solute concentration and parameters. The performance of the inverse method is assessed by two synthetic tracer tests conducted in an aquifer with a distinct spatial pattern of heterogeneity. The study results indicate that the developed iterative inverse method is able to identify and reproduce the large-scale heterogeneity pattern of the aquifer given appropriate observation wells in these synthetic cases.     

Relations between climatic variability and hydrologic time series from four alluvial basins across the southwestern United States

Hydrologic time series of groundwater levels, streamflow, precipitation, and tree-ring indices from four alluvial basins in the southwestern United States were spectrally analyzed, and then frequency components were reconstructed to isolate variability due to climatic variations on four time scales. Reconstructed components (RCs), from each time series, were compared to climatic indices like the Pacific Decadal Oscillation (PDO), North American Monsoon (NAM), and El Niño-Southern Oscillation (ENSO), to reveal that as much as 80% of RC variation can be correlated with climate variations on corresponding time scales. In most cases, the hydrologic RCs lag behind the climate indices by 1–36 months. In all four basins, PDO-like components were the largest contributors to cyclic hydrologic variability. Generally, California time series have more variation associated with PDO and ENSO than the Arizona series, and Arizona basins have more variation associated with NAM. ENSO cycles were present in all four basins but were the largest relative contributors in southeastern Arizona. Groundwater levels show a wide range of climate responses that can be correlated from well to well in the various basins, with climate responses found in unconfined and confined aquifers from pumping centers to mountain fronts.     

Objective cyclone climatologies of the North Atlantic – a comparison between the ECMWF and NCEP Reanalyses

Simple and easily reproducible techniques have been used to construct two objective cyclone climatologies of the North Atlantic-European sector. The goal of this study is to increase understanding of cyclones with the potential to cause damage, in particular, those reaching Beaufort category 7 and above. The two climatologies constructed here span the period 1979–2000 and have been developed from reanalysis mean sea level pressure data from the ECMWF (European Centre for Medium Range Weather Forecasts) and NCEP (National Centres for Environmental Prediction). The ECMWF reanalysis data are only available for 15 years, and have been extended from 1994 using operational analyses. The major temporal and spatial characteristics of North Atlantic cyclones are examined and a comparison between the climatologies developed from the two data sets is carried out. The well-known cyclogenesis regions along the east coast of the United States and to the southeast of Greenland are replicated by both reanalyses, as is the characteristic southwest/northeast orientation of the dominant cyclone track across the Atlantic basin. However, only weak correlations are found between the time series of cyclone frequency produced from the two reanalyses, and this is particularly true for the lower intensity Beaufort Scale category 0–6 cyclones. This result, together with the large differences in the spatial distribution of cyclones over Greenland for Beaufort Scale 0–6 cyclones, indicates the NCEP reanalyses generates fewer systems than the ECMWF reanalyses. The overall conclusion is that the ECMWF mean sea level pressure data produce a more comprehensive climatology of North Atlantic cyclones at all scales.     

Assessing scleractinian corals as recorders for paleo-pH: Empirical calibration and vital effects

Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ¹¹B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ¹¹B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ¹¹B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.     

Evaluation and Monitoring of Service Quality: Discussing Ways to Meet INSPIRE Requirements

Service oriented architectures (SOA) are widely used nowadays. As the name implies such architectures rely on services. Germany developed a marine‐specific service oriented data infrastructure (MDI‐DE – Marine Dateninfrastruktur Deutschland) from 2010 to 2013. The services in MDI‐DE can contribute to fulfilling reporting commitments for various European and national legislation. The services of MDI‐DE (just like other services affected, for instance, by INSPIRE) have to meet specific requirements regarding performance, availability and conformity (quality of service, QoS). Although SOA is an important field in scientific research there are very few publications and studies available on QoS, especially regarding INSPIRE requirements. The services of MDI‐DE were analyzed using various existing tools. Their usefulness to reflect where either the aspect's performance, availability or conformity needs improvement was partly verified. Due to varying results and the neglect of some services for various reasons it can be stated that the more tools are used, the more conclusive the outcome. Furthermore, service quality was not coherent when measured with different tools. This means that measuring QoS in terms of INSPIRE will be very difficult to do in the future and there is the danger that people will choose the tools with which their services perform best.