Tables for
Volume I
X-ray absorption spectroscopy and related techniques
Edited by C. T. Chantler, F. Boscherini and B. Bunker

International Tables for Crystallography (2023). Vol. I. Early view chapter

Cells for spectroscopy of fluids at elevated pressure and temperature

Denis Testemalea and Joel Bruggerb*

aCNRS, Université Grenoble Alpes, Institut Néel, 38000 Grenoble, France, and bSchool of Earth, Atmosphere and the Environment, Monash University, Clayton, Victoria 3800, Australia
Correspondence e-mail:

The study of reactions involving liquids at elevated temperatures and/or pressures is important in a wide range of disciplines, including earth and planetary sciences, corrosion, materials, geo-engineering and biological/environmental studies. In situ X-ray absorption spectroscopy (XAS) measurements have had a profound impact on the field by providing direct insights into molecular-level reaction mechanisms at elevated pressure and temperature. This chapter summarizes the various approaches underpinning the design of reaction cells suitable for the study of these reactions under extreme conditions via XAS methods.

Keywords: high pressure; high temperature; hydrothermal solutions; melts; in situ; reaction cells.

1. XAS and in situ studies of liquids at high pressure and temperature

Liquids (for example supercritical aqueous fluids and melts) under extreme conditions (of temperature, pressure or composition) play an important role in both natural and manmade systems, for example in planetary sciences, economic geology and hydrometallurgy, corrosion in power plants, catalysis, geo-engineering (for example geothermal energy and CO2 sequestration) and material sciences (Brugger et al., 2010[link]; Darr & Poliakoff, 1999[link]). These applications rely on our understanding of the structure of liquids, of the nature and thermodynamic stability of relevant inorganic and organometallic complexes, and of the mechanisms and kinetics of reactions over a wide range of pressures and temperatures.

The increased availability of XAS combined with developments in spectroscopic cell design have had a profound impact on the study of melts and aqueous fluids at high pressure and temperature (Filipponi, 2001[link]; Brugger et al., 2016[link]), similar to its impact on catalysis (Agistini et al., 2023[link]) and high-pressure research (Aquilanti, 2023[link]). X-rays make it possible to probe the electronic structure of atoms in fluids in situ under extreme conditions. XAS is sensitive to the short-range structure around a specific atom and hence is ideally suited for the study of complex, multi-component liquids, such as those encountered in nature. The capacity of extended X-ray absorption fine structure (EXAFS) to provide direct quantitative information about the hydration and structure of metal complexes (including metal–ligand distances) in dilute solutions motivated much of the early work on hydrothermal solutions (see, for example, Pfund et al., 1994[link]; Seward et al., 1993[link], 1995[link], 1996[link]; Wallen et al., 1996[link]). The quantitative nature of EXAFS and X-ray absorption near-edge structure (XANES) (see, for example, Benfatto et al., 2002[link]; Liu et al., 2007[link]) remains one of the main strengths of the technique. A recurrent theme in the field is the drive to fully exploit the unique features offered by X-ray beams at synchrotrons. For example, XAS studies have been combined with quantitative measurements of mineral solubility via measurements of X-ray fluorescence or step height (Fig. 1[link]; see, for example, Daval et al., 2010[link]; Liu et al., 2008[link]; Pokrovski et al., 2005[link]; Sanchez-Valle et al., 2004[link]; Wilke et al., 2012[link]) and with measurements of absolute absorbance used to measure the density of the fluid (see, for example, Etschmann et al., 2010[link]; Pokrovski et al., 2008[link]); such measurements also offer a convenient way to calibrate the temperature and pressure at the beam position by comparison with the known equation of state of a sample (Fig. 1[link]). Time-resolved measurements have been used to investigate the kinetics of redox reactions (Cochain et al., 2013[link]), either beam-induced or biologically induced (Mayanovic et al., 2012[link]; Picard et al., 2012[link]), and the kinetics of mineral dissolution (Daval et al., 2010[link]; Testemale, Dufaud et al., 2009[link]). The spatial resolution offered by focused X-ray beams has been used to probe separated phases such as fluid/melt (Louvel et al., 2013[link]) and liquid/vapour (`boiling'; Pokrovski et al., 2008[link]) or to limit the effects of beam-induced photoreduction (see, for example, Tooth et al., 2013[link]).

[Figure 1]

Figure 1

XAS data for metals in hydrothermal fluids. In this example, aqueous solutions containing 0.045 M Fe2+, 0.35 M NaCl and 0.1 M HCl were measured in an autoclave at 500 bar from 100 to 450°C (Testemale, Brugger et al., 2009[link]). Both transmission (left) and fluorescence (right) spectra were measured concurrently thanks to the geometry of the autoclave (a cross section is shown at the top). This is a typical example of low-concentration measurements where the fluorescence spectra are essential for good spectral data quality (XANES and EXAFS analysis), but the absorbance spectra (transmission) are useful for the quantitative determination of fluid density (the absolute absorbance levels are directly proportional to the fluid density) and of the dissolved metal concentration (which is derived from the variation of absorbance over the absorption edge).

The three main challenges that need to be addressed to measure high-quality XAS data on liquids at elevated temperature and/or pressure are the following. (i) The choice of materials, which need to be X-ray transparent and yet resistant to extremes in pressure and temperature, inert relative to samples that are commonly highly corrosive (for example acidic or strongly oxidizing or reducing), able to contain the liquid and sufficiently pure not to spoil the data with an unwanted contribution to the signal. (ii) A reliable control of reaction parameters, in particular pressure, temperature and sample composition, for long periods of time and with suitable precision. Collection of EXAFS data from dilute samples can take up to >10 h (see, for example, Pokrovski et al., 2009[link]), and for low-density (<0.8 g cm−3) aqueous fluids small fluctuations in pressure will cause density fluctuations that are sufficient to affect the quality of the EXAFS data. (iii) Safety in the beamline environment.

Many types of experimental devices have been used for in situ XAS measurements of liquids at high temperature and/or pressure (see the exhaustive review by Filipponi, 2001[link]) and some of them are succinctly presented below to illustrate the various approaches used and to highlight their advantages and limitations.

2. Cells for in situ high-temperature XAS measurements of melts

Cells operating at ambient or low pressure, under a controlled atmosphere or under vacuum have extensively been used to study solids at high temperatures and their temperature-driven structural and redox modifications (phase transitions, melting mechanisms, kinetics of oxidation–reduction reactions etc.). The same cell designs can be adapted for the study of melts and most are based on resistive heating. The graphite crucible-based `L'Aquila–Camerino oven' (Filipponi & Di Cicco, 1994[link]) allows measurements up to 2250°C. The `heating-wire' design (Mysen & Frantz, 1992[link]) has been replicated and optimized (Richet et al., 1993[link]; Farges et al., 1995[link]) and makes EXAFS measurements of melts possible up to 3500°C (under vacuum). These designs benefit from very short heating and cooling times (>100°C s−1). High photon fluxes allow the collection of time-resolved XAS measurements at very high temperatures (Cochain et al., 2013[link]).

The levitation technique is a notable alternative method for high-temperature measurements at low pressures; coupled with laser heating, it offers an efficient, simple and compact containerless method to place a sample in an X-ray or neutron beam (Hennet et al., 2011[link]) and is suitable for XAS fluorescence measurements (Landron et al., 1997[link]).

3. Cells for in situ XAS measurements of liquids

Fig. 2[link] shows the different families of cells that are frequently used for XAS measurements at high temperature and moderate to very high pressures.

[Figure 2]

Figure 2

Summary of the pressure range versus volume of the various families of high-pressure cells used for XAS in situ measurements of liquids. The temperature domains are imposed by the heating technology: <800°C, heating stage for fluid inclusions and capillaries; <1200°C, resistive heating for autoclaves and Paris–Edinburgh cells; <3000°C, laser heating for DAC. The grey band along the volume axis depicts the range of volumes probed with synchrotron beams.

3.1. Very high pressures

Very high pressure cells include the hydrothermal diamond anvil cell (DAC) and the Paris–Edinburgh (PE) cell, which are described in detail in Aquilanti (2023[link]). In the context of hydrothermal fluids, they are capable of much higher pressures than other current XAS cells: PE cells have occasionally been successfully adapted to aqueous fluids at up to ∼6.4 GPa and 275°C (Filipponi et al., 2003[link]; Migliorati et al., 2013[link]). The minuscule to very small volumes (<100 nl in the DAC), the high density of the materials crossed by the X-rays and the difficulty in accurately controlling pressure are their limitations for hydrothermal fluids.

3.2. Fluid inclusions

Fluid inclusions are mentioned here even if they are not experimental cells per se, as they allow the investigation of high-pressure/high-temperature fluids (Roedder, 1984[link]) and are sometimes considered as microbatch reactors for the in situ investigation of hydrothermal fluids by XAS (Frantz et al., 1988[link]). They consist of small quantities of fluids that are trapped in a host mineral during its crystallization. They can be either natural (recording the fluids from which hydrothermal minerals form) or synthetic inclusions prepared under controlled conditions. At room temperature and pressure, fluid inclusions may contain several phases (fluid, gas bubble, precipitated mineral), but they still retain the original bulk composition, and upon heating the original speciation can be analysed, for example by XAS (see, for example, Cauzid et al., 2007[link]; Sanchez-Valle et al., 2004[link]). Disadvantages include the impossibility of controlling the pressure (the volume is constant) and the very small volume (<1 nl), which can lead to significant issues with beam damage (see below and, for example, James-Smith et al., 2010[link]).

3.3. Moderate pressure

A simple and safe cell design is based on the use of fused silica glass capillary capsules (FSCCs; Chou, 2012[link]). This design has been used in many optical spectroscopy studies (for example, Raman) and has successfully been adapted to XAS measurements (Wallen et al., 1996[link]; Hoffmann et al., 2000[link]). The small beam size and high flux offered by synchrotron sources are essential given the small internal diameter (a few hundred micrometres) of the capillaries. FSCCs are inherently safe, have a large opening for fluorescence measurements and allow optical observation of the sample during the collection of XAS data. One obvious handicap is the reactivity of silica at temperatures of ∼400°C or above (Hoffmann et al., 2000[link]), which hinders the study of hydrothermal fluids under these conditions.

The main group of cells for in situ XAS measurements of hydrothermal fluids includes various autoclave-type designs, which offer easy sample loading, flexible geometrical design (in particular to measure the transmitted and/or fluorescence photons; see Fig. 1[link]) and accurate control over temperature and pressure. Pressure is typically limited to less than ∼2 kbar (Fig. 2[link]).

In a pioneering study, Seward et al. (1996[link]) used an externally heated autoclave fitted with 2 mm silica windows to explore the evolution of Ag+ coordination from ambient to 350°C via EXAFS. Such a design is limited to high X-ray energies (the Ag K edge is 25.514 keV) due to the strong absorption of the thick silica windows and does not allow pressure control (the cell operates at the equilibrium vapour pressure). Similar cells with a simple design in which the container is sealed and the pressure is not regulated were also developed during the same period (for example thick silica tubes or an alloy body closed by Kapton windows; Mosselmans et al., 1996[link]).

At the Pacific Northwest National Laboratories, a number of flowthrough cells were built based on a design featuring an externally heated body fitted with diamond windows and two ports for incoming and outgoing solution flow (Pfund et al., 1994[link]; Fulton et al., 2000[link], 2004[link]; Hoffmann et al., 2000[link]). Compared with closed-system designs, flowthrough reaction cells have the advantage of reduced beam damage and offer flexibility for changing or controlling the fluid composition over time, such as keeping the pH of the solution constant. By reducing the diamond thickness and the length of the beam path, EXAFS spectra could even be measured at very low X-ray energies for hydrothermal solutions up to supercritical conditions (the Ca K edge at 4038 eV; Fulton et al., 2004[link]). Diamond is one of the few materials that is able to withstand the chemically aggressive character of hydrothermal solutions, but its use comes at the price of the presence of diffraction peaks in the XAS signal, such as in the case of DAC cells (Aquilanti, 2023[link]), and the small unsupported diameter of the windows.

An internally heated autoclave was developed at the Institut Néel, CNRS, France and was installed on the FAME and FAME-UHD XAS beamlines at the ESRF (Testemale et al., 2005[link], 2016[link]). Derivatives of this design have also been installed at the Australian Synchrotron and at DESY, Germany (Klemme et al., 2021[link]; Tian et al., 2012[link]). The autoclave is based on the design of Tamura et al. (1995[link]), which introduced the separation of the requirements for heat and chemical resistance from the requirements for physical strength (containment pressure). An internal cell of varying volume (i.e. the pressure is equal to the externally imposed pressure) was placed in a helium-pressurized (HP) autoclave, enabling, for example, EXAFS measurements of liquid selenium up to 1600°C and 600 bar (Tamura et al., 1995[link]; Soldo et al., 1998[link]). The design is flexible in that both transmission and fluorescence (with high solid angle) signals can be measured concurrently (Fig. 1[link]), and the materials and thickness of the internal cell and autoclave windows can be easily customized for specific applications, for example to minimize the beam absorbance to access low-energy edges of down to ∼6 keV (Mn Kα fluorescence at 5.9 keV; Tian et al., 2014[link]) or maximize the mechanical strength to reach higher pressures of up to 150 MPa and 500°C (Ranieri et al., 2012[link]). The key materials in this design are beryllium and glassy carbon. The former has low Z, low density and good mechanical strength and thus is used to build the autoclave windows. The latter is extremely chemically resistant (for example, to HCl, H2S etc.) to high temperatures (>1000°C), contains few impurities, has a low density and can be machined; it is used for the internal cell and for HP autoclave windows (Testemale et al., 2016[link]). Pressure and temperature are controlled independently and precisely (Bruyère et al., 2008[link]), which allows the study of phase separation and low-density fluids of importance, for example in economic geology, down to fluid densities of ∼0.1 g cm−3 (Liu et al., 2008[link]). A sample area of about 5 mm in diameter is accessible to the X-ray beam; this allows sample homogeneity to be checked, measurements in multiphase systems or minimization of beam damage. This autoclave to date has achieved temperatures of ∼1000°C and pressures of ∼200 MPa.

All of these autoclave-type designs offer relatively large sample volumes (∼1–1000 µl; see Fig. 2[link]). This situation provides a number of benefits for in situ spectroscopy: it reduces the risk of beam damage (see below), it removes the need for microfocused beams, it allows direct measurements of temperature and pressure without the use of a calibrant and it allows sample recovery for further measurements, such as cell counting in bacterial cultures (Picard et al., 2012[link]).

4. Beam damage in reaction cells

Ionizing radiation induces the radiolysis of water, thus producing radiolytic species such as [{\rm HO}^{\bullet}], H3O+, [{\rm H}^{\bullet}], [{\rm O}_{2}^{\bullet -}], [{\rm O}^{\bullet}] and the hydrated electron, [{\rm e}_{\rm aq}^{-}], which upon reaction with one another produce redox-active species such as hydrogen peroxide and dissolved hydrogen [H2(aq)] and oxygen [O2(aq)] (Jayanetti et al., 2001[link]; Saffré et al., 2011[link]). As reviewed by Brugger et al. (2016[link]), the effects of radiolytic species on the oxidation states of metal ions in solutions within a spectroscopic cell under X-ray illumination are well established, yet are difficult to predict. The nature of the effect (for example reduction versus oxidation) and the rate of the photoreaction depend upon the solution composition, temperature and the volume of the fluid compared with the volume affected by the beam (Fig. 2[link]). The effects of beam damage need to be carefully considered when interpreting XAS data on hydrothermal reactions. These effects are particularly extreme in the case of small sample volumes, such as fluid inclusions and DAC microbeam experiments (see, for example, Mayanovic et al., 2012[link]), where the sample volume is a few nanolitres and the beam flux is very high, at insertion-device beamlines. In the case of larger sample volumes (relative to the volume of fluid within the beam) and/or lower flux bending-magnet beamlines, beam damage can have beneficial effects, for example by promoting the rate of conversion of the ion in solution to the thermodynamically stable species (see, for example, Fulton et al., 2000[link]) or the rate of mineral dissolution in the case of in situ solubility experiments.

5. Future developments

The study of fluids under extreme conditions is a rapidly evolving field. Current trends include (i) co-measurements of EXAFS and other spectroscopies (for example optical and vibrational spectroscopy, small-angle scattering), as well as better control of solution chemistry parameters, in particular pH and redox, (ii) accessing higher pressures with autoclave designs, since deep-earth processes are a hot topic in hydrothermal geochemistry (see, for example, Sverjensky et al., 2014[link]), (iii) lower energy (lower Z elements) spectroscopy enabled by new materials and (iv) adaptation to new detection methods on XAS beamlines, in particular high spectral resolution spectroscopy (Hazemann et al., 2009[link]).


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