Qualitative estimation of the contents of seeping water and estimation of the flow velocity in clay barriers by impedance spectroscopy

In this work, the flow of different kinds of liquids (differences in polarity, aromaticity, molecular size) through a layer of Friedland clay and the interaction of these liquids with the clay particles are investigated by means of electrical impedance measurements. The instationary flow can be described by data obtained from complex impedance plots. The gradient of the ohmic part of the impedance gives information about the strength of the driving force and the speed of flow/diffusion of the liquid through the clay. Different kinds of liquids lead to completely different impedance spectra. From time-dependent impedance measurements on a layer of defined thickness, information can be gained about the contents of the liquid flowing or diffusing through the clay. The impedance spectroscopy could be a powerful method for the development of an in situ monitoring system in waste disposal sites having clay barriers. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Core electron spectroscopy of water solutions

O1s spectra from water in glycol, dimethylformamide and LiCl solutions have been recorded. The liquid/vapour shift is found to differ between the three solutions and from that measured for the pure organic solvents. The correlation of the shifts with molecular size and polarizability is discussed. The O1s binding energy for H₂O in the LiCl solution is measured to be 538.0 eV. From the liquid/vapour shift in this solution an estimate is obtained of. the electronic polarization contribution to the solvation energy of the K⁺ ion in water.     

Continuous analysis of δ¹⁸O and δD values of water by diffusion sampling cavity ring-down spectrometry: a novel sampling device for unattended field monitoring of precipitation, ground and surface waters

A novel sampling device suitable for continuous, unattended field monitoring of rapid isotopic changes in environmental waters is described. The device utilises diffusion through porous PTFE tubing to deliver water vapour continuously from a liquid water source for analysis of δ1?O and δD values by Cavity Ring-Down Spectrometry (CRDS). Separation of the analysed water vapour from non-volatile dissolved and particulate contaminants in the liquid sample minimises spectral interferences associated with CRDS analyses of many aqueous samples. Comparison of isotopic data for a range of water samples analysed by Diffusion Sampling-CRDS (DS-CRDS) and Isotope Ratio Mass Spectrometry (IRMS) shows significant linear correlations between the two methods allowing for accurate standardisation of DS-CRDS data. The internal precision for an integration period of 3 min (standard deviation (SD) = 0.1‰ and 0.3‰ for δ1?O and δD values, respectively) is similar to analysis of water by CRDS using an autosampler to inject and evaporate discrete water samples. The isotopic effects of variable air temperature, water vapour concentration, water pumping rate and dissolved organic content were found to be either negligible or correctable by analysis of water standards. The DS-CRDS system was used to analyse the O and H isotope composition in short-lived rain events. Other applications where finely time resolved water isotope data may be of benefit include recharge/discharge in groundwater/river systems and infiltration-related changes in cave drip water.     

Comparative assessment of the ELBA coarse-grained model for water

The ELBA force field for water consists of a single spherical site embedded with a point dipole. This coarse-grained model is assessed here through the calculation of fundamental properties of bulk liquid water and the water–vapour interface. Accuracy and efficiency are evaluated and compared against simulations of standard three- and four-site atomistic models. For bulk liquid systems, ELBA reproduces accurately most of the investigated properties. However, the radial distribution function deviates from atomistic and experimental data, indicating a loss of local structure. The water–vapour interface, simulated over a range of temperatures from 300 to 600 K, is captured realistically in terms of its density distribution, and the accuracy in reproducing the experimental surface tension is as high as that of the best atomistic model. The critical temperature of ELBA is also found to be in excellent agreement with experiment. However, the interfacial electric field and surface potential are missing. The computational speed-up of ELBA compared to traditional atomistic models is estimated to be between one and two orders of magnitude.     

Electrochemical measurements on clay minerals for possible sensor applications

Natural clays were characterized by XRD, TGA and SEM/EDX, then pressed to pellets and analyzed by impedance measurements under various defined gas compositions and temperatures. From the Nyquist plot, conductivity values were calculated for the different clay samples. A strong dependence of the conductivity on the water vapour concentration at low temperatures was found for all investigated clay samples. Partial substitution of water by methanol led to a decrease in conductivity at low temperatures, confirming the essential role water plays in the conductivity mechanism at these temperatures. Increasing the temperature resulted in a decrease in conductivity, until a turn-over point was reached. Beyond this temperature an Arrhenius behaviour was observed, suggesting a change in the conductivity mechanism. Paper presented at the 5th Euroconference on Solid State Ionics, Benamádena, Spain, Sept. 13–20, 1998.     

How water and counterions diffuse into the hydrated montmorillonite

Molecular dynamics simulations have been performed to study the diffusive transport properties of water and counterions in 1-, 2- and 3-layer hydrated Wyoming-type montmorillonite (MMT). The considered counterions included in the clay are monovalent cations, such as Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, and divalent cations, such as Ca²⁺, Ni²⁺, Zn²⁺ and Pb²⁺. The diffusion simulation results of Li-, Na-, K-, Cs-MMT, based on NVE ensemble and SPC/E water model, compared well to available experimental quantities and previous simulations, which permit us to study the diffusion behaviour of heavy metal counterion including in the different hydrated montmorillonite. Our simulation results show that the diffusion coefficients of both water molecule and counterions increase versus the quantity of water content. At the same hydrated state, the diffusion of cations strongly depends on their size, weight and capacity of attracting water. Monovalent cations diffuse always much faster than divalent ones. Although the increasing of hydrate degree can raise the diffusion coefficient of divalent heavy cations, the activity of these heavy counterions is still very weak. The diffusion of cations in the interlayer space of clay is much weaker than that in bulk water. That means the presence of charged clay has great influence on the diffusion of cations, which change totally the diffusion behaviour of cations.     

Dynamics of water intercalation fronts in a nano-layered synthetic silicate: A synchrotron X-ray scattering study

We performed synchrotron X-ray scattering studies of the dynamics of the water intercalation front in a Na–Fluorohectorite clay. Like other smectite clays, fluorohectorite particles can swell due to intercalation of successive water layers. Monitoring the intensities of Bragg peaks of the known 1- and 2-water-layer hydration states at different positions in the sample enabled spatial and temporal measurement of the proportions of the different hydration states. From experiments with controlled temperature and an imposed humidity gradient on a quasi one-dimensional powder sample, we were able to localize the intercalation front and demonstrate that the width of this front was smaller than 2 mm after penetrating 9 mm into the sample. The speed at which the intercalation front advanced through the sample during the diffusion process was shown to decrease with time. The diffraction signature of random water intercalation in the vicinity of the intercalation front also provided information on the changes in the water content of the mesopores around clay particles.     

Evaluation of suitable spectral intervals for near-IR laboratory detection of water vapour continuum absorption

The water vapour continuum absorption is an important component of molecular absorption of radiation in atmosphere. However, uncertainty in knowledge of the value of the continuum absorption at present can achieve 100% in different spectral regions leading to an error in flux calculation up to 3-5 W/m² global mean. This work uses line-by-line calculations to reveal the best spectral intervals for experimental verification of the CKD water vapour continuum models in the currently least-studied near-infrared spectral region. Possible sources of errors in continuum retrieval taken into account in the simulation include the sensitivity of laboratory spectrometers and uncertainties in the spectral line parameters in HITRAN-2004 and Schwenke-Partridge database. It is shown that a number of micro-windows in near-IR can be used at present for laboratory detection of the water vapour continuum with estimated accuracy from 30% to 5%.     

Continuous wave MRI diffusion study of water in bentonite clay

Three-layered clay minerals such as montmorillonite (bentonite) exhibit very short transverse relaxation times. This is especially true for samples with relatively low water contents in the region of 20% to 30%, which is the water content typically used in environmental technology applications (e.g., as a mineral liner material for landfills). The diffusion of water in samples with such short transverse relaxation times can be measured with NMR by observing the moisture gradients or isotope tracer fronts propagating through appropriately prepared samples by means of continuous wave MRI. The first results from such studies on bentonite clays are presented in this paper.     

Temperature effects on the diffusion of water and monovalent counterions in the hydrated montmorillonite

We investigate here the effect of temperature on the diffusion of water and cations in the Wyoming-type montmorillonite clay. The considered cations are monovalent compensating ions, such as Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ in one-, two- and three-hydration states. For this purpose, molecular dynamics simulations have been performed to obtain the dynamic behaviour regarding the interlayer ions and water molecules under a temperature range between 260 and 400 K. The diffusion coefficient of water and cations in different hydrated clays increases with temperature. The influence of temperature on the diffusion of water is much greater than that of cations in one-, two- or three-hydrated clay. The degree of hydration plays an important role on the diffusion behaviour of water and counterions. We found that the effect of temperature is negligible in weakly hydrated clay, whereas it became significant in highly hydrated one. Besides, the size and mass of cations’ hydrate also affect the diffusion behaviour of water and cations in the interlayer space of hydrated clay.     

A continuous stream flash evaporator for the calibration of an IR cavity ring-down spectrometer for the isotopic analysis of water

A new technique for high-resolution simultaneous isotopic analysis of δ¹⁸O and δD in liquid water is presented. A continuous stream flash evaporator has been designed that is able to vapourise a stream of liquid water in a continuous mode and deliver a stable and finely controlled water vapour sample to a commercially available infrared cavity ring-down spectrometer. Injection of sub-microlitre amounts of the liquid water is achieved by pumping liquid water sample through a fused silica capillary and instantaneously vapourising it with 100% efficiency in a home-made oven at a temperature of 170?°C. The system's simplicity, low power consumption and low dead volume together with the possibility for automated unattended operation provides a solution for the calibration of laser instruments performing isotopic analysis of water vapour. Our work is mainly driven by the possibility to perform high-resolution online water isotopic analysis on continuous-flow analysis (CFA) systems typically used to analyse the chemical composition of ice cores drilled in polar regions. In the following, we describe the system's precision and stability and sensitivity to varying levels of sample size and we assess the observed memory effects. A test run with standard waters of different isotopic compositions is presented, demonstrating the ability to calibrate the spectrometer's measurements on a VSMOW scale with a relatively simple and fast procedure.     

Condensation of laser‐produced gold plasma during expansion and cooling in a water environment

Physical processes involved in laser ablation in liquid (LAL) are studied using a gold target irradiated through transparent water. During and after irradiation, the heated material from the surface of a target produces a plume that expands into liquid‐forming nanoparticles (NPs). The LAL method of NP production is ecologically much cleaner than others. A better understanding of the processes associated with complicated hydrodynamic phenomena leading to LAL is important for controlled manufacturing. We consider laser pulses with different durations τ_L covering fifth orders of magnitudes ranging from 0.1 ps to 0.5 ns and large absorbed fluences F_abs near optical breakdown of liquid. It is shown that the trajectory of the contact boundary with liquid at the middle and late stages after passing the maximum intensity of the longest pulse is rather similar for very different pulse durations if energies F_abs are comparable. We trace how hot (in a few eV range) dense gold plasma expands, cools down, intersects a saturation curve, and condenses into NPs appearing first inside the water‐gold diffusively mixed intermediate layer where gold vapour has the lowest temperature. Later, the pressure around the gold‐water contact drops down below the critical pressure for water. As a result, the nanoparticles find themselves in gaseous water bubble where density of water gradually decreases to 10^?4 ? 10^?5  g/cm³ at maximum bubble expansion.     

The application of electrical resistance measurements to water transport in lime–masonry systems

The paper describes an experimental determination of impedance spectroscopy derived resistance measurements to record water transport in lime–masonry systems. It strongly supports the use of Sharp Front theory and Boltzmann’s distribution law of statistical thermodynamics to corroborate the data obtained. A novel approach is presented for the application of impedance measurements to the water transport between freshly mixed mortars and clay brick substrates. Once placed, fresh mortar is dewatered by brick and during this time the volume fraction water content of the mortar is reduced. An equation is derived relating this change in water content to the bulk resistance of the mortar. Experimental measurements on hydraulic lime mortars placed in contact with brick prisms confirm the theoretical predictions. Further, the results indicate the time at which dewatering of a mortar bed of given depth is completed. The technique has then potential to be applied for in situ monitoring of dewatering as a means of giving insight into the associated changes in mechanical and chemical properties.     

Evidence for the contribution of water dimers to the near-IR water vapour self-continuum

The nature of the water vapour continuum absorption and the possible contribution of water dimers (WD) to this phenomenon have been a matter of debate for many years. The current work presents an overview and analysis of a number of experiments, both recent and old, where spectral signatures, similar to recent theoretical predictions for WD, have been observed in equilibrium laboratory conditions within near-infra-red (IR) water vapour absorption bands. These experiments, in contrast to those where water complexes are usually studied in non-equilibrium and low-temperature conditions, can give direct information about the possible WD amount in atmospheric conditions. Intercomparison of the results of these works and the recent ab initio prediction for WD band intensities and positions testifies in favour of a significant contribution of WD absorption to the water vapour self-continuum in the centre of the strongest near-IR water vapour absorption bands.     

Polydisperse spray diffusion flames in oscillating flow

The phenomenon of droplet clustering or grouping found when a spray of droplets is moving in an oscillating host flow field is investigated for the case of a polydisperse spray that fuels a laminar co-flow diffusion flame. A mathematical solution is developed for the liquid phase based on use of small Stokes numbers for size sections into which the polydisperse spray size distribution is divided. Droplet clustering in the oscillatory flow field is accounted for by constructing a special model for the sectional vaporization Damkohler numbers in accordance with droplet size. Combining this with a formal solution for a gas phase Schvab-Zel'dovich variable yields the means whereby flame dynamics can be described. Results calculated from this solution demonstrate that preferential droplet size behaviour (with smaller droplets tending to cluster to a greater extent and reduce the vaporization Damkohler number more than larger ones) can have a major impact on the flame dynamics through local droplet enrichment with attendant consequences on the production of fuel vapour. The dynamics of the sort of flame (over- or under-ventilated) and the occurrence of flame pinching leading to multiple flame sheets are altered under these circumstances. However, potential control of the actual initial spray polydispersity may reduce the intensity of such effects.     

A continuous stream flash evaporator for the calibration of an IR cavity ring-down spectrometer for the isotopic analysis of water

A new technique for high-resolution simultaneous isotopic analysis of δ1?O and δD in liquid water is presented. A continuous stream flash evaporator has been designed that is able to vapourise a stream of liquid water in a continuous mode and deliver a stable and finely controlled water vapour sample to a commercially available infrared cavity ring-down spectrometer. Injection of sub-microlitre amounts of the liquid water is achieved by pumping liquid water sample through a fused silica capillary and instantaneously vapourising it with 100% efficiency in a home-made oven at a temperature of 170 °C. The system's simplicity, low power consumption and low dead volume together with the possibility for automated unattended operation provides a solution for the calibration of laser instruments performing isotopic analysis of water vapour. Our work is mainly driven by the possibility to perform high-resolution online water isotopic analysis on continuous-flow analysis (CFA) systems typically used to analyse the chemical composition of ice cores drilled in polar regions. In the following, we describe the system's precision and stability and sensitivity to varying levels of sample size and we assess the observed memory effects. A test run with standard waters of different isotopic compositions is presented, demonstrating the ability to calibrate the spectrometer's measurements on a VSMOW scale with a relatively simple and fast procedure.     

Experimental studies on natural convection boiling of water in a vertical annulus of a closed-loop thermo-siphon

Experimental studies on natural convection boiling of water in an internally heated narrow vertical annulus, with the liquid circulating through a cold leg forming a closed-loop thermo-siphon, have been carried out. The radius and aspect ratios of the annulus are 1.184 and 352, respectively. The experimental data, which consist of wall and liquid temperatures, liquid and vapor flow rates, and differential pressure across the test section, are recorded on a data logging system. The experiments have been performed for a constant heat flux of 15–35 kW/m² from the startup period until the steady state to study the transient behavior of the system. The boiling and non-boiling zones in the annulus have been identified and presented graphically through the liquid and wall temperatures for the steady state. They have been also verified through the visual photographs of the flow patterns in the annulus. The flow is found to be oscillatory in nature with no particular trend. Although the experimental data seems to be scattered, but when analyzed for a short duration, they are found well within the ±3σ (three sigma). This confirms the quasi-steady-state condition of the system. The steady-state values of Reynolds number and liquid circulation rate come out to be 133.1–453.5 and 7.0–23.87 g/s, respectively, while the Nusselt number and heat transfer coefficient are 7.98–13.57 and 1433.57–2435.35 W/m²K, respectively. Mathematical correlations for liquid mass flow rates, heat transfer coefficient, Reynolds number, and Nusselt number have been developed and compared with the existing correlations, which are in good agreement.     

The dipole moment distribution on water is improved by using large flexibility and large bending angle

A highly flexible model of water with fixed charges is used to study properties of water. The bending angle of an isolated molecule is 125^○ that was chosen to match the experimental dipole moment. The geometry of water in the liquid phase is made closer to that of the rigid SPC/E model by decreasing the bending angle spring constant, k _Θ. The new model, called SPCE-FHΘ, is a modified version of the recently proposed SPCE-FH [J. Alejandre, G.A. Chapela, F. Bresme and J.-P. Hansen, J. Chem. Phys. 130, 174505 (2009)] to simulate ionic solutions which includes short ranged interactions on the hydrogen atoms. By increasing angle flexibility it is possible to obtain, in the liquid phase at ambient conditions, bending angles ?Θ(HOH)? ～ 109^○, dipole moment ?μ? ～ 2.5 D and dielectric constant ?ε? ～ 80. The dipole moment distribution at room temperature goes from 1.5 to 3.5 D due to large fluctuations in bending angle and has the same trend found in ab initio simulations of liquid water. The dipole moment profile at the interface of water varies from 1.9 D in the vapour phase to 2.5 D in the liquid region at 400 K. The SPCE-FHΘ gives dipole moment, dielectric constant, coexisting densities and surface tension along the liquid–vapour coexistence line closer to the experimental values than those obtained for the SPC/E force field.     

Extinguishment of propane/air co-flowing diffusion flames by fine water droplets

In the present study, extinguishment of propane/air co-flowing diffusion flame by fine water droplets was investigated experimentally. Water droplets are generated by piezoelectric atomizers with the maximum droplets flow rate of 1500 ml/h. When the fuel injection velocity U_f is low, an attached laminar diffusion flame with a premixed flame at the base is stabilized. At some distance from the burner rim, a transition from laminar to turbulent diffusion flame occurs, and a turbulent diffusion flame is formed in the downstream region. When the fuel injector rim is thin (δ = 0.5 mm), the flame stability deteriorates with increase of the co-flowing air stream velocity U_a and the water droplets flow rate Q_m. The stability mechanism can be explained by the balance of the gas velocity and the burning velocity of premixed flame formed at the base. However, when the injector rim is thick (δ = 5 mm), a recirculation zone is produced downstream of the injector rim. The dependence of the quenching distance H_q on U_f and Q_m is relatively weak, and the stability diagram shows curious features. It was shown that U_a is crucially important since it determines flow residence time; if U_a < 0.4 m/s, water droplets can evaporate when they go by the recirculation zone, and the water vapor can diffuse into the recirculation zone. However, if U_a > 0.4 m/s, the water droplets should pass by the recirculation zone without sufficiently evaporated and are not so effective to extinguish the flame. The supply velocity of droplet-laden air should be low enough so that water droplets can evaporate and water vapor can diffuse into the premixed region at the base to obtain sufficient effectiveness of water droplets for fire suppression.