Characterization of Organic Contaminants in New York/New Jersey Harbor Sediments Using FTIR‐ATR and Synchrotron FTIR

Dredging and remediation of contaminated Harbor sediments requires characterization of organic pollutants. In this paper, we apply a combination of Fourier transform IR attenuated total reflectance (FTIR‐ATR) and synchrotron FTIR techniques to the investigation of sediments and related materials from New York/New Jersey Harbor and other locations. The FTIR techniques give information on the functional groups of the compounds found in the sediments and make possible measurements with a spatial resolution of about 0.015 mm. Comparisons of natural organic materials namely, river and groundwater humic substances, recent marine and lacustrine sediments, and ancient sedimentary kerogen show that contaminated NY/NJ Harbor sediments display a strong and distinct absorption in their IR spectra at 2850–2950 cm^?1 identified as a C? H stretching band, indicative of the presence of anthropogenic hydrocarbons. We suggest that the presence of this band could be used for rapid screening for the presence of contaminant organic compounds in sediments encountered in dredging operations and/or as an indicator for the efficacy of sediment decontamination technologies used for treatment of dredged material.     

Artificial intelligence for identifying hydrologically homogeneous regions: A state‐of‐the‐art regional flood frequency analysis

Due to the severity related to extreme flood events, recent efforts have focused on the development of reliable methods for design flood estimation. Historical streamflow series correspond to the most reliable information source for such estimation; however, they have temporal and spatial limitations that may be minimized by means of regional flood frequency analysis (RFFA). Several studies have emphasized that the identification of hydrologically homogeneous regions is the most important and challenging step in an RFFA. This study aims to identify state‐of‐the‐art clustering techniques (e.g., K ‐means, partition around medoids, fuzzy C‐means, K ‐harmonic means, and genetic K ‐means) with potential to form hydrologically homogeneous regions for flood regionalization in Southern Brazil. The applicability of some probability density function, such as generalized extreme value, generalized logistic, generalized normal, and Pearson type 3, was evaluated based on the regions formed. Among all the 15 possible combinations of the aforementioned clustering techniques and the Euclidian, Mahalanobis, and Manhattan distance measures, the five best were selected. Several watersheds' physiographic and climatological attributes were chosen to derive multiple regression equations for all the combinations. The accuracy of the equations was quantified with respect to adjusted coefficient of determination, root mean square error, and Nash–Sutcliffe coefficient, whereas, a cross‐validation procedure was applied to check their reliability. It was concluded that reliable results were obtained when using robust clustering techniques based on fuzzy logic (e.g., K ‐harmonic means), which have not been commonly used in RFFA. Furthermore, the probability density functions were capable of representing the regional annual maximum streamflows. Drainage area, main river length, and mean altitude of the watershed were the most recurrent attributes for modelling of mean annual maximum streamflow. Finally, an integration of all the five best combinations stands out as a robust, reliable, and simple tool for estimation of design floods.     

A novel predictor–corrector algorithm for sub‐structure pseudo‐dynamic testing

A new predictor–corrector (P–C) method for multi‐site sub‐structure pseudo‐dynamic (PSD) test is proposed. This method is a mixed time integration method in which computational components separable from experimental components are solved by implicit time integration method (Newmark β method). The experiments are performed quasi‐statically based on explicit prediction of displacement. The proposed P–C method has an important advantage as it does not require the determination of the initial stiffness values of experimental components and is thus suitable for representing elastic and inelastic systems. A parameter relating to quality of displacement prediction at boundaries nodes is introduced. This parameter is determined such that P–C method can be applicable to many practical problems. Error‐propagation characteristics of P–C method are also presented. A series of examples including linear and non‐linear soil–foundation–structure interaction problem demonstrate the performance of the proposed method. Copyright © 2005 John Wiley & Sons, Ltd.     

A multimethod approach to inform epikarst drip discharge modelling: Implications for palaeo‐climate reconstruction

Resolving the hydrological processes that form speleothems and the palaeo‐climate archives that they contain is difficult. Typical approaches to hydrological investigation are not suited to karst landscapes, geophysics are seldom applied, drip monitoring and modelling have limitations, and ignoring potential hydrological impacts can result in a proxy record that does not reflect the external environment. We aim to understand the processes and controls that have created a palaeo‐climate proxy record preserved in a speleothem (JC001) in the “Grotto of Oddities,” part of the Jersey Cave at the Yarrangobilly Caves, Australia, to infer the likely nature and resolution of this record. Electrical resistivity tomography (ERT), traditional surveying, and drip discharge monitoring (April 2013 to February 2015) were used to investigate the structure and hydrology of the epikarst overlying the Grotto of Oddities. Data collected through these methods were then used to construct a physically informed and parsimonious drip hydrology model. Geophysics showed that changes in hillslope above the Grotto of Oddities are collocated with a region of low resistivity, which forms an epikarstic reservoir acting to supply enhanced discharge to the speleothem. Drip monitoring showed hysteretic behaviour with a distinct threshold response, and a simple drip classification indicated that the speleothem associated with the drip has the potential to record palaeo‐seasonality or an annual–decadal signal. Discharge modelling indicated discharge was comprised of quick and slow flow, and that discharge is probably perennial. These multimethod results together indicate that the speleothem likely represents a palaeo‐climate record of a length and resolution unprecedented for nonglacial areas of the Southern Hemisphere and for Australia in particular and will significantly enhance current knowledge of the climate of southeast Australia. Although ERT methods have previously been applied in the karst landscape, to our knowledge, this represents the first application of these multiple methods in combination as an approach to assess the fidelity of a speleothem, based on an understanding of the hydrological processes for palaeo‐climate reconstruction.     

A microcontroller‐based data‐logger design for seasonal hydrochemical studies

Detailed studies of seasonal patterns of karst processes are rare in remote regions with limited winter access. An important aspect of erosional and environmental processes is how these change over time, and how they relate to annual cycles of temperature, precipitation and runoff. Such measurements have consistently proved difficult in remote alpine areas, resulting in a paucity of continuous data from these environments. An automated data‐logger installation designed to perform under difficult conditions, including limited sunlight for solar recharge, heavy snowfall and disturbance by bears, has provided four years of data at a 2‐hour sampling interval of electrical conductivity (used to predict solute concentration), water level (used to predict discharge) and temperature, at the Marble Mountains karst resurgence, California, USA. Copyright © 2001 John Wiley & Sons, Ltd.     

Bioassay‐directed fractionation for analyzing estrogens in surface waters of the German Baltic Sea

A reversed‐phase fractionation method with subsequent biological and chemical analysis has been developed to estimate the contributions of the most potent estrogens to observed estrogenic effect potentials. Surface water samples were taken in the German Baltic Sea (Inner Wismar Bay and Darss Peninsula, sampling campaign July 2003) and were separated into seven individual fractions. Three fractions showed significant estrogenic activities and clear dose‐dependant responses were obtained in the yeast estrogen screen (YES). In the 2nd fractions liquid chromatographic‐electrospray‐tandem mass spectrometric (LC‐ESI‐MS‐MS) analyses showed the presence of bisphenol A (Inner Wismar Bay: 4.8 ng L^–1 and 6 ng L^–1; Darss Peninsula: 0.91 ng L^–1 and 1.7 ng L^–1) and ethinylestradiol (Inner Wismar Bay: 2.0 ng L^–1 and 6.0 ng L^–1; Darss Peninsula: < MDL and 1.7 ng L^–1), whereas estrogenic activities in the YES were only around 10% of the positive control E2. Although not identified prior in the total extract the natural hormones estradiol (Inner Wismar Bay: 0.13 ng L^–1 and 0.19 ng L^–1; Darss Peninsula: 0.12 ng L^–1 and 0.16 ng L^–1) and estriol (Inner Wismar Bay: < MDL and 0.33 ng L^–1; Darss Peninsula: < MDL) could be detected in the 3rd fractions, where high estrogenic potentials could be observed. The 4th fractions showed high responses as well and estrone were herein quantified with concentrations of 0.16 ng L^–1 and 0.18 ng L^–1 (Darss Peninsula) up to 0.37 ng L^–1 (Inner Wismar Bay). Measured and calculated estradiol equivalents for individual fractions correlated very well (R² = 0.78), when disregarding results of the 2nd fraction, where high deviations occurred.     

An efficient algorithm for identifying pulse‐like ground motions based on significant velocity half‐cycles

Ground motions with strong velocity pulses are of particular interest to structural earthquake engineers because they have the potential to impose extreme seismic demands on structures. Accurate classification of records is essential in several earthquake engineering fields where pulse‐like ground motions should be distinguished from nonpulse‐like records, such as probabilistic seismic hazard analysis and seismic risk assessment of structures. This study proposes an effective method to identify pulse‐like ground motions having single, multiple, or irregular pulses. To effectively characterize the intrinsic pulse‐like features, the concept of an energy‐based significant velocity half‐cycle, which is visually identifiable, is first presented. Ground motions are classified into 6 categories according to the number of significant half‐cycles in the velocity time series. The pulse energy ratio is used as an indicator for quantitative identification, and then the energy threshold values for each type of ground motions are determined. Comprehensive comparisons of the proposed approach with 4 benchmark identification methods are conducted, and the results indicate that the methodology presented in this study can more accurately and efficiently distinguish pulse‐like and nonpulse‐like ground motions. Also presented are some insights into the reasons why many pulse‐like ground motions are not detected successfully by each of the benchmark methods.     

Non‐linear system identification of the versatile‐typed structures by a novel signal processing technique

Non‐linear structural identification problems have raised considerable research efforts since decades, in which the Bouc–Wen model is generally utilized to simulate non‐linear structural constitutive characteristic. Support vector regression (SVR), a promising data processing method, is studied for versatile‐typed structural identification. First, a model selection strategy is utilized to determine the unknown power parameter of the Bouc–Wen model. Meanwhile, optimum SVR parameters are selected automatically, instead of tuning manually. Consequently, the non‐linear structural equation is rewritten in linear form, and is solved by the SVR technique. A five‐floor versatile‐type structure is studied to show the effectiveness of the proposed method, in which both power parameter known and unknown cases are investigated. Copyright © 2007 John Wiley & Sons, Ltd.     

The influence of bedrock‐derived acidity in the development of surface and underground karst: evidence from the Precambrian carbonates of semi‐arid northeastern Brazil

Very extensive cave systems are developed in Precambrian Una Group carbonates in the Campo Formoso area, eastern Brazil. In contrast, the area is largely devoid of significant surface karst landforms, as would be expected given its semi‐arid climate. The caves in the area display many morphological features characteristic of deep‐seated hypogenic caves, such as lack of relationship with the surface, ramiform/network pattern, abrupt variations of passage cross‐sections and absence of fluvial sediments, but do not show evidence of vertical passages marking the ascending path of acidic water nor present extensive gypsum or acid clay mineral deposits. Hydrochemical analyses of present‐day ground water indicate that oxidation of bedrock sulphide is an active process, and sulphuric acid may be the main agent driving carbonate dissolution in the area. A shallow mode of speleogenesis is thus proposed, in which sulphuric acid produced through the oxidation of sulphide beds within the carbonates controls cave initiation and development. Moreover, the geological situation of the area in an ancient stable passive margin precludes the possibility of deep‐seated sources of acidity. Under dry climate, due to the absence of recharge, solutional landforms will be largely subdued in the surface. Hypogenic processes, if present, are likely to predominate, producing a landscape characterized by a marked disparity in the comparative degree of development between surface and underground landforms. Rates of karst landform development have traditionally been analysed through a climatic perspective, runoff being the main controlling factor in promoting karst development. This view needs to be reassessed in the light of the growing awareness of the importance of climate‐independent processes related to hypogenic sources of acidity. Copyright © 2003 John Wiley & Sons, Ltd.     

Groundwater—Surface waters interactions at slope and catchment scales: implications for landsliding in clay‐rich slopes

Understanding water infiltration and transfer in soft‐clay shales slopes is an important scientific issue, especially for landsliding. Geochemical investigations are carried out at the Super‐Sauze and Draix‐Laval landslides, both developed in the Callovo‐Oxfordian black marls, with the objective to define the origin of the groundwater. In situ investigations, soil leaching experiments and geochemical modeling are combined to identify the boundaries of the hydrological systems. At Super‐Sauze, the observations indicate that an external water flow occurs in the upper part of the landslide at the contact between the weathered black marls and the overlying formations, or at the landslide basement through a fault network. Such external origin of water is not observed at the local scale of the Draix‐Laval landslide but is detected at the catchment scale with the influence of deep waters in the streamwater quality of low river flows. Hydrogeological conceptual models are proposed emphasizing the role of the interactions between local (slope) and regional (catchment) flow systems. The observations suggest that this situation is a common case in the Alpine area. Expected consequences of the regional flows on slope stability are discussed in term of rise of pore water pressures and physicochemical weathering of the clay shales.     

Potential of time‐lapse photography for identifying saturation area dynamics on agricultural hillslopes

Mapping saturation areas during rainfall events is important for understanding the dynamics of overland flow. In this study, we evaluate the potential of high temporal resolution time‐lapse photography for mapping the dynamics of saturation areas (i.e., areas where water is visually ponding on the surface) on the hillslope scale during natural rainfall. We take 1 image per minute over a 100 × 15 m² depression area on an agricultural field in the Hydrological Open Air Laboratory, Austria. The images are georectified and classified by an automated procedure, using grey intensity as a threshold to identify saturation area. The optimum threshold T is obtained by comparing saturation areas from the automated analysis with the manual analysis of 149 images. T is found to be highly correlated with an image brightness characteristic defined as the greyscale image histogram mode M (Pearson correlation r = 0.91). We estimate T as T = M + C where C is a calibration parameter assumed to be constant during each event. The automated procedure estimates the total saturation area close to the manual analysis with mean normalized root mean square error of 9% and 21% if C is calibrated for each event and taken constant for all events, respectively. The spatial patterns of saturation are estimated with a geometric mean accuracy index of 94% as compared to the manual analysis of the same photos. The patterns are tested against field observations for one date as a preliminary demonstration, which yields a root mean square error of the shortest distance between the measured boundary points and the automatically classified boundary as 23 cm. The usefulness of the patterns is illustrated by exploring run‐off generation processes of an example event. Overall, the proposed classification method based on grey intensity is found to process images with highly varying brightnesses well. It is more efficient than the manual tracing for a large number of images, which allows the exploration of surface flow processes at high temporal resolution.     

A reduced‐order modeling technique for tall buildings with active tuned mass damper

It is impractical to install sensors on every floor of a tall building to measure the full state vector because of the large number of degrees of freedom. This makes it necessary to introduce reduced‐order control. A kind of system reduction scheme (dynamic condensation method) is proposed in this paper. This method is iterative and Guyan condensation is looked upon as an initial approximation of the iteration. Since the reduced‐order system is updated repeatedly until a desired one is obtained, the accuracy of the reduced‐order system resulting from the proposed method is much higher than that obtained from the Guyan condensation method. Another advantage of the method is that the reduced‐order system is defined in the subspace of the original physical space, which makes the state vectors have physical meaning. An eigenvalue shifting technique is applied to accelerate the convergence of iteration and to make the reduced system retain all the dynamic characteristics of the full system within a given frequency range. Two schemes to establish the reduced‐order system by using the proposed method are also presented and discussed in this paper. The results for a tall building with active tuned mass damper show that the proposed method is efficient for the reduced‐order modelling and the accuracy is very close to exact only after two iterations. Copyright © 2001 John Wiley & Sons, Ltd.     

Long‐term assessment of nutrient flow pathway dynamics and in‐stream fate in a temperate karst agroecosystem watershed

Nutrient dynamics in karst agroecosystems remain poorly understood, in part due to limited long‐term nested datasets that can discriminate upland and in‐stream processes. We present a 10‐year dataset from a karst watershed in the Inner‐Bluegrass Region of central Kentucky, consisting of nitrate (nitrate‐N [NO₃^?]), dissolved reactive phosphorus (DRP), total organic carbon (TOC), and total ammoniacal‐N (TAN) measurements at nested spring and stream sites as well as flowrate at the watershed outlet. Hydrograph separation techniques were coupled with multiple linear regression and Empirical Mode Decomposition time‐series analysis to determine significance of seasonal processes and to generate continuous estimates of nutrient pathway loadings. Further, we used model results of benthic algae growth and decomposition dynamics from a nearby watershed to assess if transient storage in algal biomass could explain differences in spring and downstream watershed nutrient loading. Results highlight statistically significant seasonality for all nutrients at stream sites, but only for NO₃^? at springs with longitudinal variability showing significant decreases occurring from spring to stream sites for NO₃^? and DRP, and significant increases for TOC and TAN. Pathway loading analysis highlighted the importance of slow flow pathways to source approximately 70% of DRP and 80% of NO₃^?. Results for in‐stream dynamics suggest that benthic autotroph dynamics can explain summer deviations for TOC, TAN, and DRP but not NO₃^?. Regarding upland dynamics, our findings agree well with existing perceptions in karst for N pathways and upland source seasonality but deviate from perceptions that karst conduits are retentive of P, reflecting the limited buffering capacity of the soil profile and conduit sediments in the Inner‐Bluegrass. Regarding in‐stream fate, our findings highlighted the significance of seasonally driven nutrient processing in the bedrock‐controlled streambed to influence nutrient fluxes at the watershed outlet. Contrary to existing perceptions, we found high N attenuation and an unexplained NO₃^? sink in the bedrock stream, leading us to postulate that floating macrophytes facilitate high rates of denitrification.     

A computational workflow for rupture‐to‐structural‐response simulation and its application to Istanbul

Scenario‐based earthquake simulations at regional scales hold the promise in advancing the state‐of‐the‐art in seismic risk assessment studies. In this study, a computational workflow is presented that combines (i) a broadband Green's function‐based fault‐rupture and ground motion simulation—herein carried out using the “UCSB (University of California at Santa Barbara) method”, (ii) a three‐dimensional physics‐based regional‐scale wave propagation simulation that is resolved at  Hz, and (iii) a local soil‐foundation‐structure finite element analysis model. These models are interfaced with each other using the domain reduction method. The innermost local model—implemented in ABAQUS—is additionally enveloped with perfectly matched layer boundaries that absorb outbound waves scattered by the structures contained within it. The intermediate wave propagation simulation is carried out using Hercules , which is an explicit time‐stepping finite element code that is developed and licensed by the CMU‐QUAKE group. The devised workflow is applied to a  km region on the European side of Istanbul, which was modeled using detailed soil stratigraphy data and realistic fault rupture properties, which are available from prior microzonation surveys and earthquake scenario studies. The innermost local model comprises a chevron‐braced steel frame building supported by a shallow foundation slab, which, in turn, rests atop a three‐dimensional soil domain. To demonstrate the utility of the workflow, results obtained using various simplified soil‐structure interaction analysis techniques are compared with those from the detailed direct model. While the aforementioned demonstration has a limited scope, the devised workflow can be used in a multitude of ways, for example, to examine the effects of shallow‐layer soil nonlinearities and surface topography, to devise site‐ and structure‐specific seismic fragilities, and for calibrating regional loss models, to name a few.     

Stalactite drip rate variations controlled by air pressure changes: an example of non‐linear infiltration processes in the ‘Cueva del Agua’ (Spain)

A study of drip water from a stalactite in the Cueva del Agua (Granada, southern Spain) over four hydrological years has enabled a detailed characterization of infiltration through the non‐saturated zone of this cave. The most significant aspects are: (1) The drip water regime is not seasonal, but is linked instead to slow infiltration. Sudden changes in the drip water regime are detected, due to infiltration along the preferential flow paths and the draining of water of supersaturated water reserves from the microfissure and pore system. (2) The accumulation of excess rain in the unsaturated zone dislodges the reserve of supersaturated water from the matrix of microfissures and pores, giving rise to an average increase in drip intensity of 2·2 ± 0·5 mm h^?1 and 37 ± 13 µS cm^?1 in the electrical conductivity of the water. (3) Time‐series analysis of the drip water demonstrates a lack of linearity over time of the drip rate, indicating a chaotic regime. (4) When the dripping is constant, barometric oscillation of the air is the principal factor that causes the lack of linearity in the drip flow. In this way, over an average of 2–3 days, a mean variation of the air pressure inside the cave of 10 ± 3·7 mbar causes a mean oscillation in the drip rate of 0·5 ± 0·2 mm h^?1. This increase in air pressure is translated as an increase in the relative thickness of the gaseous phase of the drip water at the cost of the aqueous phase, so reducing the drip intensity of the stalactite. Copyright © 2006 John Wiley & Sons, Ltd.