Progress and new directions in high temperature calorimetry revisited

 High temperature reaction calorimetry has seen considerable advances over the past twenty years. New and more sensitive calorimeters, improved sample handling techniques, and better control of the final dissolved state has made solution calorimetry and drop solution calorimetry, using molten lead borate and other solvents, very versatile and reliable techniques. This paper summarizes these advances and presents examples of specific applications to problems of transition metal oxide chemistry, high pressure geophysics, melt and glass energetics, and metastable materials relevant to the earth sciences. Received June 3, 1996 / Revised, accepted Spetember 23, 1996     

Pedogenic factors affecting magnetic susceptibility of the last interglacial palaeosol S1 in the Chinese Loess Plateau

The magnetic susceptibility has been used as a quantitative or semi‐quantitative proxy for reconstructing the summer monsoon intensity in the Chinese Loess Plateau based on extensive studies on climatic or/and environmental mechanisms producing the magnetic susceptibility signatures. However, the precise nature of the link between past climates and the susceptibility signatures has remained uncertain primarily due to lack of our understanding in the ?nalizing and preserving processes of the signatures. This paper attempts to examine the reliability or acceptability of this summer monsoon proxy from non‐magnetic perspectives of soil‐forming processes. We chose nine sections along two transects: one across the western part of the Chinese Loess Plateau and another across the eastern part. Several conclusions can be drawn from our analytical data. First, clay translocation within the S1 palaeosol pro?les, as indicated by ?eld‐observed clay coatings on ped faces in Bt and Bk horizons and demonstrated by laboratory‐analysed clay contents, must have moved some of the magnetic minerals downward so that the susceptibility re?ects only the post‐translocation distribution of the magnetic‐susceptibility‐producing minerals. Second, the best‐developed palaeosol S1S3 at most of the sections studied is not expressed by the magnetic susceptibility because this palaeosol developed in underlying coarse loess (L2) and coarse textures tend to lower the susceptibility. Third, carbonate concentration is normally negatively correlated with the magnetic susceptibility or simply suppresses the magnetic susceptibility peak when the susceptibility enhancement exceeds the carbonate dilution effect. To conclude, extreme caution must be observed when using magnetic susceptibility signatures to retrieve high‐resolution records of the last interglacial palaeoclimate in the Chinese Loess Plateau. Copyright © 2004 John Wiley & Sons, Ltd.     

Optimal design of viscoelastic dampers using eigenvalue assignment

In this study a procedure for determining the optimum size and location of viscoelastic dampers is proposed using the eigenvalue assignment technique. Natural frequencies and modal damping ratios, required to realize a given target response, are determined first by the convex model. Then the desired dynamic structural properties are realized by optimally distributing the damping and stiffness coefficients of viscoelastic dampers using non‐linear programming based on the gradient of eigenvalues. This optimization method provides information on the optimal location as well as the magnitude of the damper parameters. The proposed procedure is applied to the retrofit of a 10‐story shear frame, and to a three‐dimensional structure with an asymmetric plan. The analysis results confirm that the responses of model structures retrofitted by the proposed method correspond well with the given target response. Copyright © 2003 John Wiley & Sons, Ltd.     

Seismic structural control using an electric servomotor active mass driver system

This study investigates an electric‐type active mass driver (AMD) system for structural vibration control. Composed primarily of an electric servomotor and a ball screw, the electrical AMD system is free from noise problems, oil leakage, and labor‐intensive maintenance that commonly are associated with hydraulic AMD systems. The desired stroke amplification of the mass and the power demand of the servomotor can be adjusted via the ball screw pitch, which in turn affects the effectiveness and efficiency of the system. Meanwhile, an instantaneous optimal direct output feedback control algorithm is adopted. Numerical simulation is performed using a five‐story steel frame as the object structure under the conditions of the 1940 El Centro earthquake. The AMD system proves to be effective and efficient within a certain range of the ball screw pitch. The reductions of the peak responses can reach as high as 70% if properly designed. Requiring only the velocity measurement of the top floor for on‐line feedback control, the proposed control algorithm is recommended for practical implementation. Copyright © 2004 John Wiley & Sons, Ltd.     

Rhenium and chalcophile elements in basaltic glasses from Ko’olau and Moloka’i volcanoes: Magmatic outgassing and composition of the Hawaiian plume

The behavior of chalcophile metals in volcanic environments is important for a variety of economic and environmental applications, and for understanding large-scale processes such as crustal recycling into the mantle. In order to better define the behavior of chalcophile metals in ocean island volcanoes, we measured the concentrations of Re, Cd, Bi, Cu, Pb, Zn, Pt, S, and a suite of major elements and lithophile trace elements in moderately evolved (6-7% MgO) tholeiitic glasses from Ko’olau and Moloka’i volcanoes. Correlated variations in the Re, Cd, and S contents of these glasses are consistent with loss of these elements as volatile species during magmatic outgassing. Bismuth also shows a good correlation with S in the Ko’olau glasses, but undegassed glasses from Moloka’i have unexpectedly low Bi contents. Rhenium appears to have been more volatile than either Cd or Bi in these magmas.Undegassed glasses with 880-1400 ppm S have 1.2-1.5 ppb Re and 130-145 ppb Cd. In contrast, outgassed melts with low S (<200 ppm) are depleted in these elements by factors of 2-5. Key ratios such as Re/Yb and Cu/Re are fractionated significantly from mantle values. Copper, Pb, and Pt contents of these glasses show no correlation with S, ruling out segregation of an immiscible magmatic sulfide phase as the cause of these variations. Undegassed Hawaiian tholeiites have Re/Yb ratios significantly higher than those of MORB, and extend to values greater than that of the primitive mantle. Loss of Re during outgassing of ocean island volcanoes, may help resolve the apparent paradox of low Re/Os ratios in ocean island basalts with radiogenic Os isotopic compositions. Plume source regions with Re/Yb ratios greater than that of the primitive mantle may provide at least a partial solution to the “missing Re” problem in which one or more reservoirs with high Re/Yb are required to balance the low Re/Yb of MORB.Lithophile trace element compositions of most Ko’olau and Moloka’i tholeiites are consistent with variable degrees of melting of fertile mantle peridotite. However, light rare earth element (LREE)-enriched glasses have trace element compositions more consistent with a garnet-rich source having a distinctive trace element composition. This provides additional evidence for a unique source component possibly related to recycled oceanic crust contributing to Ko’olau tholeiites.     

U-Th dating of Lake Lisan (late Pleistocene dead sea) aragonite and implications for glacial east Mediterranean climate change

U-series dating can be an effective means to obtain accurate and precise ages on Quaternary carbonates. However, most samples require a correction for U and Th in admixed detritus. This complication is often addressed through generation of U-Th isochrons, requiring analyses of several coeval samples. In addition, presence of water-derived (hydrogenous) Th in the carbonate can cause inaccuracies in isochron ages.This study reports a high-resolution U-series chronology of sediments deposited by Lake Lisan, the last glacial precursor of the Dead Sea. The strategy employed combines multiple measurements from a few stratigraphic heights and fewer analyses from many heights in a single described and measured section. The resulting chronology is based on ages at 22 heights in a ∼40-m-thick section covering the interval of ∼70-14 calendar ka BP. The effects of admixed detritus are evaluated using trace elements. Nearly pure aragonite samples, indicated by very low abundances of insoluble elements such as Nb and Zr, were found to contain hydrogenous Th, which causes the uncorrected U-²³⁰Th age of a modern sample to be ∼2.5 ka. Nevertheless, accurate ages have been obtained by correcting for the detrital and aqueous interferences. The resulting ages are in stratigraphic order, and their accuracy is evidenced by consistency of Lisan Formation U-series and ¹⁴C ages with the coral-based calendar-radiocarbon age calibration.The U-Th ages provide a context to unravel the limnological history of Lake Lisan. Boundaries between the Lower, Middle, and Upper stratigraphic units correspond to the MIS 4/3 and 3/2 transitions, respectively. During MIS 2 and 4 the lake generally showed a stable two-layer configuration and a positive fresh-water balance, reflected by deposition of laminated aragonite-detritus. Dry intervals during MIS 2 and 4 are indicated by thick gypsum layers and an inferred depositional hiatus, which are temporally associated with Heinrich events H1 at ∼17 ka and H6 at ∼65 ka, respectively. During MIS 3 the lake level was unstable with intermittent dry periods indicated by abundant clastic layers and a significant hiatus between ∼43-49 ka. Clastic layers are associated with Dansgaard-Oeschger events during MIS 3, and indicate lake level declines during abrupt Northern Hemisphere warmings. Overall, the climate of the Eastern Mediterranean region shows a strong linkage to the Northern Hemisphere climate, with increasing lake size and stability during cold periods, and fluctuations and dessication during warmings and Heinrich events.     

The Elusive AD 1826 Tsunami, South Westland, New Zealand

In AD 1826 sealers reported earthquake and tsunami activity in Fiordland, although, contemporary or near‐contemporary accounts of tsunami inundation at the time are elusive. A detailed analysis of recent sediments from Okarito Lagoon builds on contextual evidence provided by earlier research concerning past tsunami inundation. Sedimentological, geochemical, micropalaeontological and geochronological data are used to determine palaeoenvironments before, during and after what was most probably tsunami inundation in AD 1826. The most compelling chronological control is provided fry a young cohort of trees growing on a raised shoreline bench stranded fry a drop in the lagoon water level following tsunami inundation.     

MTBE in Drinking Water Production – Occurrence and Efficiency of Treatment Technologies

In Germany, the gasoline additive methyl tert‐butyl ether (MTBE) is almost constantly detected in measurable concentrations in surface waters and is not significantly removed during riverbank filtration. The removal of MTBE from water has been the focus of many studies that mostly were performed at high concentration levels and centred in understanding the mechanisms of elimination. In order to assess the performance of conventional and advanced water treatment technologies for MTBE removal in the low concentration range further studies were undertaken. Laboratory experiments included aeration, granulated activated carbon (GAC) adsorption, ozonation and advanced oxidation processes (AOP). The results show that the removal of MTBE by conventional technologies is not easily achieved. MTBE is only removed by aeration at high expense. Ozonation at neutral pH values did not prove to be effective in eliminating MTBE at all. The use of ozone/H₂O₂ (AOP) may lead to a partly elimination of MTBE. However, the ozone/H₂O₂ concentrations required for a complete removal of MTBE from natural waters is much higher than the ozone levels applied nowadays in waterworks. MTBE is only poorly adsorbed on activated carbon, thus GAC filtration is not efficient in eliminating MTBE. A comparison with real‐life data from German waterworks reveals that if MTBE is detected in the raw water it is most often found in the corresponding drinking water as well due to the poor removal efficiency of conventional treatment steps.     

Short‐term intertidal bar mobility on a ridge‐and‐runnel beach,Merlimont, northern France

Digital elevation models and topographic pro?les of a beach with intertidal bar and trough (ridge‐and‐runnel) morphology in Merlimont, northern France, were analysed in order to assess patterns of cross‐shore and longshore intertidal bar mobility. The beach exhibited a pronounced dual bar–trough system that showed cross‐shore stationarity. The bars and troughs were, however, characterized by signi?cant longshore advection of sand under the in?uence of suspension by waves and transport by strong tide‐ and wind‐driven longshore currents. Pro?le changes were due in part to the longshore migration of medium‐sized bedforms. The potential for cross‐shore bar migration appears to be mitigated by the large size of the two bars relative to incident wave energy, which is modulated by high vertical tidal excursion rates on this beach due to the large tidal range (mean spring tidal range = 8·3 m). Cross‐shore bar migration is also probably hindered by the well‐entrenched troughs which are maintained by channelled high‐energy intertidal ?ows generated by swash bores and by tidal discharge and drainage. The longshore migration of intertidal bars affecting Merlimont beach is embedded in a regional coastal sand transport pathway involving tidal and wind‐forced northward residual ?ows affecting the rectilinear northern French coast in the eastern English Channel. Copyright © 2004 John Wiley & Sons, Ltd.     

An automated salt‐tracing gauge for flow‐velocity measurement

This article introduces the SVG (salt‐velocity gauge), a novel automated technique for measuring flow velocity by means of salt tracing. SVG allows a high measuring rate (up to one every 2 seconds), short control section length (down to 10 cm), high accuracy (+[sol ]?1·5 cm s^?1), and unbiased calculation of the mean velocity in experimental conditions with turbulent, supercritical flow. A few cubic centimetres of saturated salt solution (NaCl) are injected into the flow at regular time intervals using a programmable solenoid valve. The tracer successively passes two conductivity probes placed a short distance downstream. The transformation of the signal between the two probes is modelled as a one‐dimensional diffusion wave equation. Model calibration gives an estimation of the mean velocity and the diffusion for each salt plume. Two implementations of the SVG technique are described. The first was an outdoors simulated rainfall experiment in Senegal (conductivity probes at 40 cm apart, 8 Hz measurement rate, salt injections at 10 second intervals). Mean velocity was estimated to range between 0·1 and 0·3 m s^?1. The second was a laboratory‐based flume experiment (conductivity probes at 10 cm apart, 32 Hz, salt injections at 2 second intervals). Another SVG with probes at 34 cm apart was used for comparison. An acoustic Doppler velocimeter (ADV) was also used to give an independent assessment of velocity. Using the 10 cm salt gauge, estimated mean velocity ranged from 0·6 to 0·9 m s^?1 with a standard deviation of 1·5 cm s^?1. Comparisons between ADV, 10 cm SVG and 34 cm SVG were consistent and demonstrated that the salt‐tracing results were unbiased and independent of distance between probes. Most peaks were modelled with r² > 90 per cent. The SVG technology offers an alternative to the dye‐tracing technique, which has been severely criticized in the literature because of the wide interval of recommended values for the correction factor α to be applied to the timings. This article demonstrates that a fixed value of α is inappropriate, since the correction factor varies with velocity, diffusion and the length of the control section. Copyright © 2005 John Wiley & Sons, Ltd.