Gravimetric Signal Research Articles

Kinetics of Charge Reversal in the Double Layer Studied with an Electrochemical Quartz Crystal Microbalance (EQCM-D)

Normal pulse voltammetry on inert electrolytes was combined with a new electrochemical quartz crystal microbalance (EQCM) with millisecond time resolution, which allows to probe the kinetics of charge reversal in the diffuse double layer (DL) after a step in electrode potential. The QCM responds to the charge reversal because the local viscosity-density product depends on the type and the concentration of the ions. The time resolution was improved to 1 ms using multifrequency lockin amplification, which allows to study kinetic effects in dynamic electrochemistry, which were previously not accessible with gravimetry. The noise was lowered to less than 10 mHz by modulating the electrode potential and averaging Δf and ΔΓ over many modulation cycles.The overtone scaling was found to be the same as in gravimetry (-Δf/n » const. and ΔΓ/n < -Δf/n with n the overtone order), which, however, is not caused by a deposition of a rigid film in the Sauerbrey sense. A Sauerbrey-type QCM response is also caused by changes in Newtonian viscosity inside a layer with a thickness far below the penetration depth of the shear wave (such as the double layer).The frequency response in the electrolytes studied correlated well with the viscosity B-coefficients of the respective ions as employed in the Dole-Jones equation. The time constants inferred from gravimetry were similar to the time constants (the RC-times) from electrochemical impedance spectroscopy (EIS). There were small differences, which presumably go back to slow rearrangements inside the Helmholtz layer, which are not seen in EIS.The QCM response to double layer recharging in inert electrolytes is of great importance for the interpretation of QCM results on processes involving Faradayic charge transfer. Such a response is omnipresent as a background and might be misinterpreted as a gravimetric signal.[1] References[1] Leppin, C.; Peschel, A.; Meyer, F. S.; Langhoff, A.; Johannsmann, D. Kinetics of Viscoelasticity in the Electric Double Layer Following Steps in the Electrode Potential Studied by a Fast Electrochemical Quartz Crystal Microbalance (EQCM). Analyst 2021, 146 (7), 2160–2171. Caption: Shifts in frequency and bandwidth in response to potential steps (left). The gravimetric signal followed the steps with a delay of a few milliseconds. The amplitude and the response time depend on cation type (right). The counter ion was NO3 -. Both the amplitude and the response time correlate well with the viscosity B-coefficient. Figure 1

An electrochemical quartz crystal microbalance (EQCM) based on microelectrode arrays allows to distinguish between adsorption and electrodeposition.

Using a precise electrochemical quartz crystal microbalance (EQCM), it was shown that electrogravimetry can be carried out with microelectrode arrays (MEAs). MEAs were prepared on the resonator surface by coating it with a thin polymer layer containing holes, where the holes constitute the microelectrodes. The preparation procedures, their benefits, and their limitations are discussed. Microelectrode-based electrogravimetry is challenging because the reduced active area reduces the QCM signal. It is still feasible. This work is limited to linear voltage ramps (as opposed to steps). The processes chosen for demonstration were the electrodeposition/stripping of copper and the redox cycling of methyl viologen dichloride (MVC). The current trace often showed microelectrodic behavior, depending on the sweep rate. For the case of copper deposition, the mass transfer rate was proportional to the electric current. For the case of MVC, the electric current showed a plateau at the ends of the current-voltage diagram, but the mass transfer rate did not change. The difference can be explained by adsorption and desorption going into saturation at the two ends of the voltage range. Based on whether or not a microelectrodic gravimetric signal is seen, it can be stated whether the mass transfer is closely linked to the current. Further advantages of the microelectrode-based EQCM are an improved access to fast processes, reduced effects of double layer recharging, and the possibility to work at a low electrolyte support.

Months of Gravity Changes Preceded the Tōhoku Earthquake

Using GRACE satellite data, researchers discovered anomalous gravimetric signals that occurred before a seismic event that started deep within Earth.

Petrophysical Characterization of Non-Magnetic Granites; Density and Magnetic Susceptibility Relationships

In this work we establish reliable correlations between density and magnetic susceptibility in three paramagnetic granites from the Pyrenees. In total, 128 sites (310 density measurements and &gt;2600 susceptibility ones) were studied in the Mont Louis-Andorra, Maladeta and Marimanha granitic plutons covering the main range of variability of magnetic susceptibility. Regressions were calculated for every granitic body and an integrated linear function was obtained for the entire dataset: ρ (kg/m3) = 2566 (kg/m3) + 0.541κ (10−6 S.I.) (R:0.97). This relationship is only valid in the paramagnetic domain, where iron is mostly fractioned in iron-bearing phyllosilicates and the occurrence of magnetite is negligible (or at least its contribution to the bulk susceptibility). This relationship, likely different in other bodies, allows for transforming magnetic susceptibility data into density data, helping to constrain gravity modelling when density data from rock samples are scarce. Given the large amount of AMS studies worldwide, together with the quickness and cost-effectiveness of susceptibility measurements with portable devices, this methodology allows for densifying and homogenizing the petrophysical data when modelling granite rock volumes based on both magnetic and gravimetric signals.

Development of a Lightweight Inertial Gravimeter for Use on Board an Autonomous Underwater Vehicle: Measurement Principle, System Design and Sea Trial Mission

The purpose of this paper is to present the design, development and testing of an innovative instrument called GraviMob, which allows performing dynamic measurements of underwater gravity anomalies. After recalling the interest in underwater gravimetry, we describe the system, the core of which consists of triads of accelerometers rigidly attached to an Autonomous Underwater Vehicle (AUV). The article also presents the mathematical methods for estimating the east, north and vertical components of the local gravity vector. An unscented Kalman filter, integrating AUV position and orientation data, performs estimation of gravity in a frame adapted to its interpretation. To assess its performance, GraviMob was tested in the Mediterranean Sea during the year 2016. A comparison of the surface gravimetric signal previously acquired by the French Navy indicates that the maximum discrepancy between the vertical gravity component and its reference is below 4 mGal. Components of the vertical deflection calculated from GraviMob’s measurements were compared with those calculated from recent gravity field models. While a remarkable agreement was found on the north component, there remains a discrepancy (7 arcsec) on the east component which can be largely reduced by refining the estimation of the orientation of GraviMob’s sensitive axes in the AUV.

Modeling gravimetric signatures of third-degree ocean tides and their detection in superconducting gravimeter records

We employ the barotropic, data-unconstrained ocean tide model TiME to derive an atlas for degree-3 tidal constituents including monthly to terdiurnal tidal species. The model is optimized with respect to the tide gauge data set TICON-td that is extended to include the respective tidal constituents of diurnal and higher frequencies. The tide gauge validation shows a root-mean-square (RMS) deviation of 0.9–1.3 mm for the individual species. We further model the load tide-induced gravimetric signals by two means (1) a global load Love number approach and (2) evaluating Greens-integrals at 16 selected locations of superconducting gravimeters. The RMS deviation between the amplitudes derived using both methods is below 0.5 nGal (1 nGal = 0.01 frac{text {nm}}{text {s}^2}) when excluding near-coastal gravimeters. Utilizing ETERNA-x, a recently upgraded and reworked tidal analysis software, we additionally derive degree-3 gravimetric tidal constituents for these stations, based on a hypothesis-free wave grouping approach. We demonstrate that this analysis is feasible, yielding amplitude predictions of only a few 10 nGal, and that it agrees with the modeled constituents on a level of 63–80% of the mean signal amplitude. Larger deviations are only found for lowest amplitude signals, near-coastal stations, or shorter and noisier data sets.

Analysis of earthquakes recordings of tidal gravimeters in the period range of 10-1000 s

The physical properties of tidal gravimetric instruments allow recording, not only tidal effects, but also waves generated by earthquakes. Three gravimetric stations with determined transfer functions and co-located seismic stations from the observatories in Western and Central Europe were selected for analysis. The observatories are equipped with almost all types of sensors available on the market, which allow for thorough analysis of earthquake recordings in the period range of 10–1000 s. In total, over 10,000 traces of worldwide earthquakes were investigated. The saturation levels of gravimeters as well as a correlation between the gravimetric and seismometric signals of an earthquake were carefully analysed. A simple processing scheme of gravimetric signal of earthquakes was adopted thanks to the probabilistic power spectral density analysis of continuous recordings. The detail analysis of transfer function of gravimeters allowed to define a period range when a sensitivity coefficient (calibration factor) and a time lag value only can be used to properly describe the properties of instruments. What’s more, it has been shown based on the calculated group-velocity dispersion curves of fundamental mode of Rayleigh waves, that the Earth’s mantle structure can be determined for greater depths from the recording of tidal gravimeters than from typical broad-band seismometers.

Refinement of Bouguer anomalies derived from the EGM2008 model, impact on gravimetric signatures in mountainous region: Case of Cameroon Volcanic Line, Central Africa

Global geopotential models have not included the very high frequencies of the Earth’s external gravity field. This is called omission error. This omission error becomes more important in mountainous areas (areas with highly variable topography). The work reported here consists in reducing the omission error in measurements of Bouguer gravity anomalies, by refining the global geopotential model EGM2008 using the spectral enhancement method. This method consists in computing the residual terrain effects and then coupling them to the gravimetric signal of the global geopotential model. To compute the residual terrain effects, we used the Residual Terrain Model (RTM) technique. To refine it required a reference surface (ETOPO1) developed up to degree 2190 (the maximum degree of the EGM2008 model) and a detailed elevation model (AW3D30). Computation was performed with the TC program of the GRAVSOFT package. The topography of the study area was assumed to have a constant density of 2670 kg/m3. For the inner and outer zones, the respective integration radii of 10 km and 200 km have been chosen. We obtained very important RTM values ranging from −53.59 to 34.79 mGal. These values were added to the gravity anomalies grid of the EGM2008 model to improve accuracy at high frequencies. On a part of the Cameroon Volcanic Line and its surroundings (mountainous area), we made a comparison between the residual Bouguer anomalies before and after refinement. We report differences ranging from −37.40 to 26.40 mGal. We conclude that the impact of omission error on gravimetric signatures is observed especially in areas with high variable topography, such as on the Cameroon Volcanic Line and around the localities of Takamanda, Essu, Dumbo, and Ngambe. This finding illustrates the great influence that topography has on accurate measurement of these gravity anomalies, and thus why topography must be taken into account. We can conclude that in preparing a global geopotential model, a high resolution DTM must be used to decrease the omission error: the degree of expansion has to increase in order to take the higher frequencies into account. The refined Bouguer anomalies grid presented here can be used in addition to terrestrial gravity anomalies in the study area, especially in mountainous areas where gravimetric data are very sparse or non-existent.

The Catalan magnetic anomaly: Its significance for the crustal structure of the Gulf of Lion passive margin and relationship to the Catalan transfer zone

Abstract The western part of the Gulf of Lion (GoL) passive margin, at the foot of the Pyrenees mountain chain, hosts the Catalan magnetic anomaly (CMA), a significant NW-SE-trending linear magnetic anomaly 50 km long with no associated gravimetric signal. The CMA is located on the continental slope near the NW-SE-trending Catalan transfer zone (CTZ), and it extends from the shelfbreak to the abyssal plain across thinned to hyper-thinned continental domain. This study interprets an updated geophysical dataset to better understand the Pyrenees–GoL transition and proposes a new interpretation of the CMA's source. Gravimetric and magnetic modelling of the lithosphere along two perpendicular cross-sections indicates that the CMA is generated by a magnetic body (80 × 20 × 12 km), called here the Catalan body, within the thinned continental domain. We interpret it as a mass of mafic material underplating and intruding the continental crust along a crustal fault belonging to the CTZ system. From the new map of Moho depths, a wide NW-SE-trending zone is highlighted on the western extremity of the GoL margin at the foot of the eastern Pyrenees Chain. It is characterized by (i) a heterogeneous crustal structure and mantle rise underneath the Tertiary Catalan sedimentary basin in the continental shelf area, (ii) a necking zone in a more proximal location compared to the eastern GoL margin, and (iii) the presence of magmatism (Catalan body) under and in the thinned continental crust, in the necking zone domain. These characteristics may be induced by the transtensional motion along the CTZ during the Tertiary opening of the Liguro-Provencal Basin, contemporary with the extension of the GoL margin. However, the role of inherited structures from the Hercynian orogeny, Mesozoic rifting and Pyrenean orogeny cannot be excluded when explaining the crustal heterogeneity, transfer zones and Moho morphology in this region.

Limits of Detection of Gravimetric Signals on Earth

Gravimetry is a well-established tool to probe the deep Earth’s processes. Geophysical signals coming from the deep Earth, like the inner core free oscillations, have however never been detected. Challenging quests raise the question of the limits of detection of elusive signals at the Earth’s surface. Knowledge of the instrumental limits and of the environmental noise level at a site is fundamental to judge the true sensitivity of an instrument. We perform a noise level comparison of various gravimeters and a long-period seismometer at the J9 gravimetric observatory of Strasbourg (France) to provide a reference of instrumental performances. We then apply a three-channel correlation analysis of time-varying surface gravity from superconducting gravimeter records to isolate the instrumental self-noise from the environmental noise. The self-noise coherence analysis shows that the instrumental noise level remains flat towards lower frequencies till 10−4 Hz. At seismic frequencies, the self-noise is well explained by a Brownian thermal noise model. At daily and sub-daily time-scales, self-noise is increasing with the period but to a much lesser extent than observed noise level. Observed Earth’s ambient noise level at sub-seismic frequencies is hence mostly due to unmodeled geophysical processes. At hourly time-scales, our ability to detect elusive signals coming from the deep Earth’s interior is not limited by the instrument capability but is mostly due to the environmental effects.

A New Tool for Airborne Gravimetry Survey Simulation

Airborne gravimetry represents nowadays probably the most efficient technique to collect gravity observations close to the Earth’s surface. In the 1990s, thanks to the development of the Global Navigation Satellite Systems (GNSS), which has made accurate navigational data available, this technique started to spread worldwide because of its capability to provide measurements in a fast and cost-effective way. Differently from other techniques such as shipborne gravimetry, it has the advantage to provide gravity measurements also in challenging environments which can be difficult to access otherwise, like mountainous areas, rain forests and polar regions. For such reasons, airborne gravimetry is used for various applications related to the regional gravity field modelling: from the computation of high accurate local geoid for geodetic applications to geophysical ones, specifically related to oil and gas exploration activities or more in general for regional geological studies. Depending on the different kinds of application and the final required accuracy, the definition of the main characteristics of the airborne survey, e.g., the planar distance between consecutive flight tracks, the aircraft velocity, etc., can be a difficult task. In this work, we present a new software package, which would help in properly accomplishing the survey design task. Basically, the developed software solution allows for generating a realistic (from the observation noise point of view) gravimetric signal, and, after that, to predict the accuracy and spatial resolution of the final retrievable gravimetric field, in terms of gravity disturbances, given the flight main characteristics. The proposed procedure is suited for airborne survey planning in order to be able to optimize the design of the survey according to the required final accuracy. With the aim to evaluate the influence of the various survey parameters on the expected accuracy of the airborne survey, different numerical tests have been performed on simulated and real datasets. For instance, it has been shown that if the observation noise is not properly modeled in the data filtering step, the survey results degrade about 25%, while not acquiring control lines during the survey will basically reduce the final accuracy by a factor of two.

Sample‐Controlled analysis under high pressure for accelerated process studies

AbstractThe potential of controlled rate thermal analysis (CRTA) for studying high‐pressure gas‐solid processes has been evaluated. CRTA is a type of smart temperature program based on a feedback system that uses any experimental signal related to the process evolution for commanding the temperature evolution. In this work, an instrument that uses the gravimetric signal for CRTA control has been designed and used for the study of two high‐pressure gas‐solid reactions: the highly exothermic thermal oxidation of TiC under high pressure of oxygen and the reduction in Fe2O3 under high pressure of hydrogen. Advantages of CRTA for discriminating overlapping processes and appraising kinetic reaction mechanisms are shown.

Analysis of the Illapel Mw = 8.3 Thrust Earthquake Rupture Zone Using GOCE-Derived Gradients

Satellite gravimetry has proven to be a useful tool to identify mass anomalies along a subduction interface, interpreted as heterogeneities related to the rupture process during megathrust earthquakes. In the last years, different works, reinforced with data derived from satellite gravity missions as GRACE and now GOCE, have analyzed not only the static component of the Earth gravity field, but also its temporal variations and relation to the seismic cycle.In particular, during the last decade, the Chilean margin has been affected by three megathrust earthquakes (withMw>8): Maule 2010 Mw = 8.8, Pisagua 2014 Mw = 8.2 and recently the Mw = 8.3 Illapel event. Then, the recently completed GOCE mission (November 2009 to November 2013) offered a unique opportunity to study the Maule February 2010 and Pisagua April 2014 events by means of gravity gradients, directly measured at satellite height altitudes, which allowed mapping density heterogeneities with greater detail than the gravity anomaly which has been used in most studies up to now. In the present work, we use the last GOCE model (GO_CONS_GCF_2_DIR_R5), the one of higher spatial resolution (N = 300, λ/2 ≈ 66 km) derived from satellite-only data. The methodology used is the same as that to study the previous events, with the addition that now we derived a relation between the associated depths of a causative mass with a determined degree of the spherical harmonic expansion. This allowed to ‘‘decompose’’ the gravimetric signal, by cutting off the degree/order of the harmonic expansion, as depth increases. From this analysis, we found that prominent oceanic features such as the Challenger fracture zone and the Juan Fernandez ridge played a key role in latitudinal seismic segmentation for the Illapel earthquake rupture zone, acting as barriers/attenuators to the seismic energy release. We compared the slip model from Tilmann et al. (Geophysical Research Letters 43: 574–583. doi: 10.1002/2015GL066963, 2016) for the Illapel earthquake with vertical gravity gradient with and without sediment correction, and at different degree/order of the harmonic expansion. From this analysis, we inferred that prominent oceanic features over the subducting Nazca plate play a key role in seismic segmentation not only at heavily sedimented trenches, but also at sediment-starved segments.

Detecting geophysical signals in gravity satellite missions

SUMMARY Geophysical events implying a large mass displacement especially in the vertical direction can produce a localized change of the Earth gravity field. The Sumatra earthquake of 2004 December is an example of this kind of geophysical phenomena. The aim of this work is to investigate the possibility of detecting such gravimetric changes by exploiting the information coming from gravity space missions. Proper testing procedures to be directly applied into the observation space have been set up. They require to propagate the effect of the geophysical event to the satellite observables and then to compare their track-wise spectra with the instrument noise level. These testing procedures have been applied to a realistic simulation of the gravimetric signal generated by the Sumatra earthquake, considering three different geodetic missions: the forthcoming GOCE mission, recovering a full gravity-gradient tensor, the presently flying GRACE mission, collecting low-low satellite-to-satellite tracking (SST) observations and a possible future gravimetric mission based on the same principle of GRACE, but with an improved accuracy thanks to the use of laser doppler interferometry. The results of the simulations confirm the higher capability of the SST missions of detecting gravity variations due to geophysical phenomena like the Sumatra earthquake. However, this signal could be seen also by a gradiometric mission like GOCE on condition that a considerable amount of observations is collected over the study area after the event.

Oscillations in hydrothermal systems as a source of periodic unrest at caldera volcanoes: Multiparameter insights from Nisyros, Greece

Unrest at collapse calderas is generally thought to be triggered by the arrival of new magma at shallow depth. But few unrest periods at calderas over the past decades have culminated in volcanic eruptions and the role of hydrothermal processes during unrest is drawing more and more attention. Here we report joint and simultaneous continuous multi‐parameter observations made at the restless Nisyros caldera (Greece), which reveal non‐steady short‐term oscillatory signals. The combined geodetic, gravimetric, seismic and electromagnetic records indicate that the oscillations are associated with thermohydromechanical disturbances of the hydrothermal system. The dominant period of oscillation (40–60 min) indicates short‐term processes most likely associated with instabilities in the degassing process. Amplitudes of recorded geodetic and gravimetric signals are comparable to amplitudes observed at other periodically restless calderas. We conclude that shallow aqueous fluid migration can contribute significantly to periodic unrest, explaining the lack of eruptions in many cases of unrest.

Electrochemical quartz crystal microbalance determination of nickel formal partial charge number during nickel-underpotential deposition on platinum in sulphate media

We studied nickel-underpotential deposition (UPD) on polycrystalline platinum in sodium sulphate media using Electrochemical Quartz Crystal Microbalance (EQCM). EQCM enables to separate hydrogen and nickel adsorption/desorption contributions, which was impossible solely with electrochemistry. Thus, nickel coverage can be determined: nearly 0.8 Ni UPD monolayer over platinum is deposited above nickel Nernst potential for pH 5.5. Coupling the gravimetric signal with nickel stripping peak coulometry yields the nickel formal partial charge number: ι Ni,EQCM = 1.3 ± 0.13. Electrochemical measurements using Swathirajan and Bruckenstein’s method give: ι Ni = 1.5 ± 0.17. Within the errors bars, both methods give similar results and ι Ni lower than z Ni 2 + : nickel adatoms apparently remain partially charged upon UPD on platinum following anion and nickel co-adsorption.

Quantized spectroelectrochemical behaviour of monolayer-protected gold cluster films assessed by reflectance spectroelectrochemical quartz crystal microbalance

The spectral changes occurring in multilayer films of hexanethiolate monolayer-protected Au 147 clusters (C6–Au 147 MPCs) as a consequence of quantized MPC core charging have been investigated in aqueous solutions using a multiresponse technique, UV–vis reflectance spectroelectrochemical quartz crystal microbalance (SEQCM). The joint technique, a combination of UV–vis near-normal incidence reflectance spectroelectrochemistry and electrochemical quartz crystal microbalance, has enabled us to follow both reflectance and gravimetric changes taking place in the MPC film concurrently with each single electron transfer event. Reversible film reflectance drops were observed upon anodic MPC charging, which were linearly dependent on the MPC charge state. The values of the formal potential and number of electrons transferred in each charging step, determined from the potential dependence of the reflectance changes, proved that the spectral features were induced by the discrete charging of the MPCs. Simultaneously, the gravimetric signal monitored with EQCM yielded values of the number of MPC-bound electrolyte ions as a function of the MPC redox state, both during voltammetric and potential step charging of the MPC films. Additionally, the dynamics of electron transfers in these multilayer MPC films has been investigated by electrochemical impedance spectroscopy (EIS). Thus, the film capacitance, the resistance to charge transfer, and the electron-transfer rate constant for MPC oxidation have been estimated.

Simultaneous heat-flow differential calorimetry and thermogravimetry for fast determination of sorption isotherms and heat of sorption in environmental or food engineering

A new experimental technique is described for the determination of desorption characteristics for engineering purposes. A TGA-DSC set-up is used in isothermal mode to achieve the thermal desorption of deformable standard materials like microcrystalline cellulose and kaolin in dry air. Assumptions on heat and mass transfer are made and discussed in order to derive desorption isotherms and heat of sorptions from the calorimetric and gravimetric signals. The method is rapid and accurate for high-temperature desorption processes T⩾40 ∘C. It is particularly reliable for small water activity values 0⩽ a w ⩽0.4 where a good agreement with standard methods is observed in spite of small apparent diffusion coefficients D≅10 −10 m 2 s −1 for the two products tested. The method is suitable for heat sensitive biological products because of the small residence time in the furnace (1 or 2 h ).

Combined electrochemical quartz crystal microbalance (EQCM) and probe beam deflection (PBD): validation of the technique by a study of silver ion mass transport

Abstract A quantitative combined electrochemical quartz crystal microbalance (EQCM) and probe beam deflection (PBD) analysis of the Ag+/Ago deposition/dissolution redox process in aqueous perchloric acid solution was achieved by comparing the cyclic -voltammetric, -gravimetric and -beam deflection responses. The recorded current and mass variation signals were superimposed upon the beam deflection profile by using the mathematical tool of quantitative convolution. The good correlation between the coulometric, gravimetric and optical signals, displayed in either differential or integral form, highlights the complementary nature of the responses from the combined instrument and demonstrates how current, mass and beam deflection represent a single electrochemical process.

Thermogravimetry in the analysis of results of a calorimetric experiment

A method based on a refined measurement equation is proposed for enhancing the accuracy of measurements of the specific heat of solids. The equation uses calorimetric and gravimetric output signals along with analytical representation of the output and baseline signals.