Piotr Robert

Wili Ski

Jeremi Naumczyk

WILINSKI et

Keywords: dissolved air flotation (DAF), ozonation, water and wastewater treatment, industrial wastewater

The lack of fresh water is one of the major threats for people. The extremely sufficient and cost saving methods for water and wastewater treatment must be applied. The paper shows possibility of using traditional Dissolved Air Flotation method (DAF) with alternation of feeding gas by ozone (Dissolved Ozone Flotation -DOF) instead of air to obtain better treatment results and possibilities of decreasing the costs of water and wastewater treatment. Moreover the DOF method may come in effective in case of more and more restrictive recommendations regarding water quality and micro-pollutants removal. As the method is on early stage of the research many technical aspects and mechanisms must be taken into consideration and to be investigated. Presumably the DOF method could be applied in technical scale for pre-treatment of industrial wastewaters, fracturing fluids, water with algae or for final separation of effluent and excess sludge in municipal wastewater treatment plants.

INTRODUCTION

Nowadays, the lack of freshwater impels governments to create new, more restrictive law and private companies to create new, sufficient and cost-and energy-effective technologies and methods for purification of water and treatment of wastewater. The shortage of freshwater can be seen especially in Asia (fast growing population) and Africa (lack of freshwater reservoirs). Poland has problem with limited amount of freshwater. In many cases it is bad quality water. All in all, this issue has high importance, as water (clean freshwater) is at the bottom of human's life.

Flotation method is mainly used in two sectors: mining industry (for separation of metal ores) and in wastewater treatment process (both for municipal and industrial wastewaters) for separation of suspended solids, emulsions, chemical sludge or excess sludge. Conventional flotation relies on floating of solids (mainly suspended solids) on the top of the liquid by air bubbles (in conventional process they have and average diameter of 100 -300 µm). Better separation effect is obtained when air bubbles are very small (micro and nano). Special dispersing pumps are able to create air-water mixture of nanobubbles and process is named as micro-and nanoflotation. Coagulants and flocculants are used in the process for better agglomeration of small particles and colloids. Ferrous or aluminum sulfates are the most common coagulants and they are mixed with water or wastewater before entering flotation unit.

Nowadays, micro and nanoflotion with ozone (Dissolved Ozone Flotation, DOF) is in laboratory research scale. The research is conducted mainly in Asia: South Korea (Ulsan University), Japan (Kyoto) and China (Xian). However it is very early stage of the research. In this method ozone is used instead of atmospheric air. This substitution causes ability to obtain two processes in one unit: separation of solids and emulsions by gas bubbles (as in conventional flotation) and oxidation of soluble organic compounds using strong oxidizing agent -ozone. Synergy of those two processes (separation and oxidation) can lead to better treatment effects. It can cause positive results as: decreasing dosing coagulants and flocculants, pathogen removal, improvement of wastewater biodegradability, micro-pollutants removal (antibiotics, hormones, personal care products), decreasing the amount of excess biological sludge (in case that DOF unit is used for separation of effluent from excess activated sludge).

Previous research was focused on process efficiency, but only relationship between dose of ozone and treatment efficiency was measured. It must be mentioned that in the past research, the conventional flotation (coarse bubbles) was implemented (not micro -nanoflotation with bubbles size of 1-20 µm). Thus, in the research essential fact was omitted. The size of bubble has enormous influence on kinetics and efficiency of oxidation process. The main parameter which can limit the process kinetics is mass transfer of ozone into the solution (wastewater). The efficiency of the process depends on total area of ozone bubbles in the solution. The bigger area (the amount of bubbles generated) causes higher mass transfer kinetics of ozone and velocity of organic compounds oxidation is increasing. In conclusion, this problem can be solved using appropriate air dispersing pumps (micro-and nano-bubbles pumps).

Until now, the research on conventional flotation with ozone as feeding gas was made on municipal, livestock wastewater and as the method of tertiary treatment. During testing of municipal wastewaters, LEE et al. (2008) observed the higher efficiency of the process for DOF method comparing with conventional DAF in case of reducing: suspended solids, color, Biological Oxygen Demand (BOD), turbidity, total phosphorus. Additionally, the great effect of disinfection and removing coliform bacteria was noticed. LEE et al. (2006) made the research on livestock wastewater. The effects were as well good considering the reduction of suspended solids and Chemical Oxygen Demand (COD). JEAONG et al. (2011) claimed, for pigment wastewater, efficiency of DOF method combined with sequencing batch reactor (SBR). Separate SBR and DOF-PO 2 method did not fulfilled the discharge limits. After combining both methods required limits were obtained. The DOF method was tested by YA-LING et. al (2010) for checking the ability of algae removal from freshwater. Small amount of ozone in feeding gas gave positive effect of algae cells agglomeration and better flotation on the top of the solution afterwards.

As DOF method is new and innovative technology, many questions appear and must be answered. The aims of the research (first year of ongoing PhD study) are following:

• to examine the effectiveness of a combination of two processes: micro-and nanoflotation with ozonation, • to examine technical and operational factors affecting the process (bubbles size, pH conditions, coagulant and flocculant addition), • to examine treatment efficiency of the DOF process compare to DAF process in case of treatment fracturing fluids, industrial wastewater and water containing algae, • to choose trace micro-pollutant (i.e. biocide in used fracturing fluid) and check its removal efficiency by DOF with comparison with DAF method, • to examine the potential reduction of operating costs and treatment efficiency, • to research the influence of ozone on potential increase of wastewater biodegradability.

MATERIAL & METHODS

Testing method

Dissolved air flotation unit with the volume of 150 L (active volume) was used as testing unit. Air dispersing system was supported by micro-nano bubble pump Karyu Turbo Mixer15NPD (KTM Nikuni Pump). The pump has mixing tank for preparation of air-water feed. Ozone was generated by BNP Ozone-Generator S0Z-Y0B-10G (power 400W, ozone output 10g/h) and connected to KTM pump to generate air-ozone-water mixture. Flocculants and coagulants (Iron (III) sulfate) used in DAF process were dosed directly to the reactor.

Chemical analysis and process parameters analysis

Laboratory analysis was conducted to obtain the values of: COD, BOD 5 , Total Suspended Solids (TSS), pH.

In further analysis other parameters will be measured: Total Organic Carbon (TOC), biodegrability, toxicity, selected micro-pollutants concentration decrease (by HPLC). Also process parameters will be measured: bubbles size (ozone mass transfer), optimum ozone concentration, process kinetics, coagulant and polymer dosage.

Design of dimensions of biological treatment step ATV-DVWK method was used for dimensioning of biological step after DAF and DOF pretreatment and show how each method influence next treatment step. The calculation was made based on organic matter removal (without nitrification and denitrification processes).

RESULTS AND DISCUSSION

Fruit processing wastewater

The test was made at the fruits processing factory (apples). The factory produces apple's concentrate. The average daily wastewater flow is Q d = 1 400m 3 /d (wastewater from production). The plant has own mechanical-biological WWTP. However the owner wants to enhance the treatment efficiency, especially before biological step (by reduction of loadings on biology). Wastewater for analysis was taken from sewer with wastewater from production.

The experiment procedure and results

Flotation unit was fulfilled with 150L of wastewater and then flotation process was conducted for 20 minutes in each case (DAF and DOF). For DAF method iron (III) sulfate was used as a coagulant (0.3 mL of iron (III) sulfate)/1 L wastewater) and anionic polymer as a flocculant (2mL of polymer/1L wastewater). The kind of coagulant and flocculant and their quantity were chosen based on author's previous experiences in this kind of industry wastewater and jar tests.

In DOF method coagulant was not dosed. Instead of air-water mixture for flotation (in traditional DAF method) air-ozone-water mixture was used. Ozone was used in quantity app. 3,5g/run of DOF test. The amount of anionic polymer added was 1.5 mL/L of wastewater.

In table 1 The figure 2 shows colour difference between raw wastewater and wastewater after DAF treatment. The next figure (no 3) shows DAF and DOF pilot-test unit during the test in factory. The design procedure was conducted to compare influence of using ozone in flotation process on biological treatment step. It led to show merits of DOF process comparing with DAF as a pretreatment method before biological treatment. Biological step dimensions for DAF and DOF as pre-treatment step were calculated based on ATV-DVWK method. The design was made for 15°C and calculated basing on COD loading.

For the air distribution system, air grid with diffusers (fine bubbles) was designed. The reactor high was assumed as H=6.0m.

The results are shown in table 2. The results obtained from ATV procedure shown significant reduction of exploitation area, oxygen (air) demand, sludge production and energy demand by using DOF instead of DAF.

For the results from table 2 yearly exploitation savings were calculated. Working year was assumed as 250 days (24h/d operation) and for 1 400m 3 of wastewater flow. The following savings were calculated:

• 21 500 €/ year -by reducing usage of iron (III) sulfate, 3 500 €/ year -by lower sludge production, • 10 800 €/ year -by lower energy consumption by air blower, Obviously cost of the ozone generation must be subtracted from total savings. However the cost of ozone generation amount to only 17% of iron sulfate dosage. In total savings are calculated as ca. 32 000 €/ year. This value is approximated, however it gives positive and prospective sight of DOF technology and reasons for further research.

CONCLUSIONS

As previous results obtained by Lee (2006), Jin (2006), Cheng (2010) and others and first experiment made by author at fruit processing plant showed promising effects, consecutive experiments must be carried on. Further laboratory research will be focused on DOF process efficiency for treatment of: fracturing fluids from shell-gas exploitation process (concentration reduction of selected micro-pollutant i.e. biocide), selected industrial wastewater (i.e. cosmetics wastewater) and water containing algae. The most important questions regard process kinetics and mechanism, factors affecting process and merits and demerits of DOF method.

It cannot be omitted that there are threats which may discontinue research on DOF method. One of the major thread is organic micro-pollutants and chemical compounds transformation by ozonolysis process. There is no information about the research on this process regarding wastewater. On the beginning of nineties the similar problem appeared regarding ozonation of potable water in case of bromines. As those ions are considered to be cancerogenic, many researchers focused on the formation of bromines and reaction mechanisms. Bi et al. (1999) underlined the problem and showed the further difficulties which could appear i.e. in case of modelling of bromines formation and proper technology application and design. The similar objections should be considered during DOF research in this PhD thesis. In consecutive research toxicity tests would be applied to check how the DOF process can affect wastewater's influence on life forms. As DOF process may be used as a pre-treatment step before biological treatment, some concerns may rely the influence of residual ozone on microorganisms of activated sludge (bacteria). However the research made by LEEUWEN et al. (2009) showed curious and a bit surprising results. LEEUWEN examined ozone impact on bacteria presented in activated sludge. The research focused on ozonation as a pre-treatment method combined with biological stage and its influence on further biological treatment. From LEEUWEN research it can be seen than ozone had positive effect on microorganisms and treatment efficiency. The concentration of 16.7 mgO 3 /L caused proper biological treatment and increased biodegrability of onerous chemical compounds (methylene blue). Moreover the bacteria were not harmed by strong oxidant. Ozone caused selection of microorganims, but it had positive effect on the activated sludge population. Another threat or strong conviction is the price of ozone generation. It can be seen that over the years new ozone generators are manufactured. The new generators can produce up to 20% of ozone by weight (Primozone), whereas few years ago it was around 12 %. Other important factor is mentioned before micro-and nanobubble system which enables better ozone transfer into the surrounding medium (wastewater).

General efficacy of DOF process was checked. Consecutive research will be done in new laboratory flotation unit designed in purpose of this PhD thesis. Synthetic fracturing fluid will be produced and then treated in DAF/DOF unit. Further laboratory test would be focused on checking process efficiency in case of removal selected micropollutants i.e. biocide, wastewater toxicity and process parameters.

Figure 1 :

 1 Figure 1: Dissolved Air (DAF) and Dissolved Ozone Flotation unit scheme: 1 -Nikuni Pump, 2 -air-water mixture injection, 3 -main flotation unit tank, 4-sludge tank, 5 -clean water tank Collection of samples After pilot tests of DAF and methods, influent and effluent samples (1,0 dm 3 ) were collected for chemical analysis. At the moment only one test was made at the fruit processing factory. The test was conducted to check-up and compare pre-treatment efficiency of DAF and DOF method and to calculate possible reductions of the cost on the biological step of wastewater treatment. Further tests (i.e. on fracturing fluids for checking micro-pollutants removal efficiency) will be made during ongoing PhD research.

Figure 2 :

 2 Figure 2: DAF effluent and raw wastewater during tests

  are collected results from DAF and DOF tests and raw wastewater. Wastewater pretreatment efficiency was measured for each method (DAF and DOF) twice. The results in table 1 are average from two measurements. Higher treatment efficacy was observed for DOF process compare to DAF. The COD, COD soluble , BOD 5 concentrations are lower in the case of DOF unit effluent, 33.8%, 29.3% and 34.8% respectively compare to 20.1%, 6.6% and 20.3% in case of DAF unit. Those results were used for calculation of possible exploitation costs reduction in the next paragraph.

Table 1 : Parameters comparison for influent wastewater and effluent after DAF and DOF process for fruits processing industry (average from two measurements)

 1

	Parameter	Unit			Influent	After DAF [% removal]	After DOF [% removal]
	COD total	mgO 2 /dm	3	4 080	3 260 [20.1]	2 700 [33.8]
	COD soluble	mgO 2 /dm	3	3 310	3 090 [6.6]	2 340 [29.3]
	BOD 5	mgO 2 /dm	3	2 270	1 810 [20.3]	1 480 [34.8]
	TSS	mg/dm	3		930	310 [66.6]	510 [45.2]
	pH	-			9,0	8,0	8,8

Table 2 : Biological step dimensions for DAF and DOF as pre-treatment method (calculations for wastewater temperature T=15°C)

 2

	Parameter	Unit	After DAF	After DOF	% reduction for DOF compared to DAF
	Reactor size	m	3	3 807	3 587	5.8
	Oxygen demand	kgO 2 /h	105.2	129.0	18.5
	Air demand	Nm	3 /h	3 150	3 870	18.6
	Energy demand for aeration (air blower motor power)	kWh	110	130	15.4
	Excess sludge production	kg/d	1 816	1 648	9.3

12thWWW YES, Arcueil, France, 21 -25 May 2012

• GOTTSHALK, C.; Libra, J.A.; Saupe, A. (2009)


Cécile Da Silva

Olivier Proux
email: olivier.proux@grenoble.cnrs.fr

Jean-Louis Hazemann

Julianne James-Smith

Denis Testemale

Toshio Yamaguchi

X-ray Absorption Spectroscopy Study of Solvation and Ion-Pairing in Aqueous Gallium Bromide Solutions at Supercritical Conditions

Keywords: gallium bromide solution, ion solvation, ion pairing, supercritical fluids

X-Ray Absorption Spectroscopy measurements have been performed both at the Ga and Br Kedges on aqueous GaBr 3 solutions. The isobaric experiments have been recorded at 30 MPa from ambient temperature to 670 K for two GaBr 3 concentrations (0.017 and 0.17 mol/dm 3 ).

At room temperature, Ga 3+ and Br -ions are fully solvated, surrounded by water O atoms at 1.97 Å (Ga-O) and 3.37 Å (Br-O). When the temperature is elevated, Ga 3+ cations precipitate as gallium oxy-hydroxide colloids while Br -anions remain solvated. With a further increase in temperature, the gallium solid precipitates remarkably re-dissolved (25% and 50% for 0.017 and 0.17 mol/dm 3 respectively), due to the formation of   n n n   3 (aq) 4 2 O) (H GaBr (n=2, 3 or 4) tetrahedral complexes.

Introduction

Compared to water at ambient conditions, supercritical water (SCW) is unique in that it exhibits both gas-like and liquid-like properties. The high diffusivity and low viscosity of supercritical fluids enables them to penetrate and transport solutes from solid matrices. The smaller dielectric constant of SCW is responsible of the low solubility of inorganic salts.

Since the solvation capacity of supercritical fluids depend on pressure and temperature, one can achieve the optimum conditions for a particular separation process by adjusting the temperature and pressure of the fluid phase, in decontamination process [1] or metal extraction [2] for example. By characterizing the ion-water (hydration), ion-ion (ion-pairing) and water-water (hydrogen bonding) interactions, the unique properties of such system can be inspected. However, these features remain in some cases unexplored because of experimental difficulties in structural and/or spectroscopic measurements at high temperatures and high pressures. One of the most appropriate techniques for the structural study of the local order around the ions in solution is the X-ray Absorption Spectroscopy (XAS) including both the xray-absorption near-edge structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopic techniques. This spectroscopy allows characterization of the local atomic environment around the absorbing element (selected from its absorption edge) to extract structural information on ions of interest. This is one reason why these techniques can be applied to dilute systems (several mM). These advantages also make it an ideal technique to study supercritical aqueous electrolyte solutions of low density in which the solubility of salts can be much lowered. Thus a High Pressure and High Temperature (HP/HT) cell dedicated to simultaneous fluorescence and transmission XAS measurements was developed and is now used routinely [3].

The behaviour with P and T of the bromide anion associated to monovalent [4][5][6] or divalent cations [7][8][9][10][11] as counter ions in aqueous solutions is now well understood. The effect of ion-pairing in aqueous solutions, i.e. formation of pairs of oppositely charged ions with a common solvation shell, is a very rich topic. Ion-pair formations at high temperature and high pressure conditions, from an aqueous solution in which the ions are completely dissolved at ambient conditions, is mainly related to the strong decrease of the solvent permittivity with T [12]: it leads to the increase of the coulombic force between ions, a decrease of the solvation sphere and then ion pairing and formation of multi-ionic complexes. A limitation of the ionpairing occurs close to the supercritical temperature and along the critical isochore: the onset of density fluctuations promotes the development of dense dynamic clusters of water molecules around the ions, leading to a screening effect which possibly inhibits the ion pairing processes [13]. Previous studies of MBr 2 (M = Mn [11], Ni [7], Zn [8][9]) aqueous solutions have clearly described this effect. An increase of the number of M-Br pairs associated to a dehydration phenomenon (drop of the number of O neighbours) is observed when increasing the temperature at a constant high pressure. Then, when reaching the supercritical conditions, M-Br and M-O distances decrease, while Br-O distances are invariant or tend to increase slightly.

In the present study we focus our effort on the trivalent cation, Ga 3+ , with an ionic force superior than monovalent and divalent cations. Previous results from EXAFS, X-ray Diffraction and Raman experiments on the GaBr 3 system showed that the ion pairing effect occurred at ambient conditions in concentrated aqueous solutions ([GaBr 3 ] =2.4 mol/dm 3 ) [14] and is not observed for concentrations lower than 1 mol/dm 3 [15]. The main aim of this experiment was to determine the evolution of the structure of the ionic hydration and/or pairing at various P and T in aqueous GaBr 3 solutions. XAS measurements have been performed simultaneously in fluorescence and transmission modes with the HP/HT cell, both at the Ga and Br K-edges. The isobaric experiments have been recorded at 30 MPa from ambient temperature to 673 K for two GaBr 3 concentrations (0.017 and 0.17 mol/dm 3 ). The goal of this study is to probe the evolution of the local structure around Ga 3+ and Br -ions in solution, from ambient to supercritical state.

Experimental details

Sample preparation and the high pressure / high temperature device

Gallium bromide aqueous solutions were prepared by dissolving weighted amounts of GaBr 3 salts (GaBr 3 , 99.999%, Sigma-Aldrich) in deionised water. The GaBr 3 solution concentrations are 0.017 and 0.17 mol/dm 3 , with a measured pH equal to 2.7 and 1.9 respectively at ambient conditions. These concentrations are low enough in order to avoid any ion-pairing at ambient conditions [15].

The HP/HT cell used for these experiments has been described in details by Testemale et al. [3]. A schematic view of the set-up is shown in Fig. 1. The general principle consists of a helium-pressurized autoclave, and an internal sample container embedded in the heater. The main feature of the cell is then that the temperature and the pressure can be adjusted independently and are both stabilized by two independent pressure and temperature regulation devices [16]. For this particular study, the internal cell was in glassy carbon with a wall thickness machined down to 100 µm at the X-ray beam position, in order to limit the absorbance of the set-up as much as possible. The path length of the X-rays on the sample is 5 mm, the internal diameter of the carbon tube. Three apertures are present in the heater and vessel for the incident, transmitted and fluorescence beams. These apertures induce a small temperature difference between the value given by the thermocouple close to the furnace and the real sample temperature. A temperature calibration was then performed with pure water at done by precisely estimating the total X-ray absorption of all the constituents of the experimental system at 30 MPa: the two 0.8 mm beryllium windows of the vessel, the glassy carbon cell, the pressurized helium and the water at different furnace temperatures. The experimental estimation of the density of the water sample allows then to estimate the temperature of the sample area, by comparing to the theoretical density of water [START_REF] Lemmon | NIST Chemistry WebBook, NIST Standard Reference Database 69[END_REF] and then to establish a temperature calibration curve. In the following, all the mentioned temperatures are the sample real temperature. The precision on the furnace temperature measurement equals to 0.1 K. Due to the uncertainty of the calibration curve, one can estimate the error bar on the sample temperature to ±2 K.

The following procedure was followed to run an isobaric experiment: the pressure was progressively applied with a constant slope of 1 MPa/min; when the pressure inside the cell reached 30 MPa, the target temperature was reached (with a slope of 10°/min), acquisitions were done (for each temperature, 3 spectra were acquired); then the temperature was increased to the next target temperature, and so on.

X-ray absorption measurements

X-ray absorption spectroscopy experiments were performed on the CRG-FAME beamline (BM30B), located at the European Synchrotron Radiation Facility storage ring in Grenoble, operating in 2*1/3 filling mode at 6 GeV. Spectra were recorded both in fluorescence and transmission modes (~40 min/scan data collection time), at the Ga and Br K-edges, using a double-crystal Si(220) monochromator [START_REF] Proux | [END_REF]. The size, around 300x200 µm² (HxV, full width half maximum values), and the position of the X-ray spot on the sample were kept constant during the data acquisition. The full beam delivered by the bending magnet source was focused in the horizontal plane by the 2 nd crystal of the monochromator and by the 2 nd Rh-coated mirror in the vertical plane. Finally, a feedback system was used to maximize the output of the two-crystal X-ray monochromator [19]. Acquisitions of the XAS spectra   Fluorescence detection was achieved using a 30 element energy-resolved detector.

Fig. 1. Schematic view of the high pressure / high temperature vessel used for XAS measurements [3]. The gas pressure inside the vessel is stabilized with a special pressure regulation device [16]. Details of the internal heating system is shown in the left inset.

Extended X-ray Absorption Fine Structure analysis

A brief recall of the basic theory and fundamental analysis steps of EXAFS data treatment is present here. The spectra were reconstructed using the following formula [20], which describes the EXAFS oscillations within the framework of the cumulant expansion limited to the third order:

                 j 3 j 3 j j k 2 k R 2 2 j j j 2 0 k C 3 4 k R 2 k e e R k k f N S k 2 j 2 j , ) ( ) ( sin , ) (      (1)
The wavenumber k of the ejected photoelectron is given by

  2 edge e E E m 2 k   
, E edge being the absorption edge energy. 2 0 S accounts for the central atom inelastic losses. The sum is taken over the j scattering paths (single or multiple scattering paths). N j is the scattering path degeneracy (number of equivalent neighbors for single scattering). R j is the half path length (central atom-neighbor distance for single scattering).

   , k f j
is the scattering amplitude experienced by the photoelectron while scattering from the neighbors (    for backscattering). (k) is the energy-dependent electron mean free path.  j (k) is the phase shift due to the contributions both from the absorbing atom and the scattering atoms. The Debye-Waller factor, The XAS spectra at the Ga and Br K-edges were treated using the Horae package, comprising Athena and Artemis softwares [21]. XAS spectra were normalized to the absorption edge height (H), background-removed using the AUTOBK algorithm and weighted by k 2 . Fourier filtration was done over the k range from ~ 2.5 to 12 Å -1 (depending on signalto-noise ratio) using a Kaiser-Bessel apodization window to obtain the so-called radial distribution pseudo-function (RDF), which displays peaks roughly characteristic of each shell around the central atoms. Filtering of the RDF was done by inverse Fourier Transformation (FT) of the first peak(s) in the R-space.

   , k f j
, (k) and  j (k) were theoretically calculated using FEFF6.0 code [20] ) and if necessary the anharmonicity cumulant term C 3 . In addition to these structural parameters, a parameter, E, was varied to account for the difference between the experimental absorption-edge energy and its estimate made by FEFF.

The fitting procedure at the Ga K-edge was performed directly on the raw data. No anharmonicity cumulant term was used for the simulation, the total disorder being small enough to justify the description of the distribution function by a simple symmetric Gaussian function. It was also not necessary to take into account multiple scattering effects. The S 0 2 amplitude reduction factor was fitted to the EXAFS spectrum obtained at ambient temperature for the concentrated solution, with the number of O atoms on the first shell being known to be 6 [14][15].

Quantitative EXAFS analysis at the Br K-edge was performed on the filtered data at the Br K-edge, following the procedure described by Simonet et al. [8]. Complementary to the Br-O single-scattering paths, we added in the calculation the single-and multiple-scattering paths including the H atoms, i.e. Br-H, Br-H-O and Br-H-O-H paths to take into account the so-called focusing effect, which enhances the amplitude of the signals associated with linear configurations (Fig. 2b), [22]). The fact that the oxygen atoms are linked to the bromide via the hydrogen induces a disordered Br-O bond, and anharmonic treatments were then necessary to account for this disorder. Finally, the multi-electronic excitations were not taking into account, leading to tiny misfits between experiment and simulation around 5 and 7.5 Å -1 [23]. The S 0 2 amplitude reduction factor was kept constant equal to unity during the optimisation procedure at this edge.

Concentration of the species in solution

The concentration  T C of the dissolved species at a given temperature (T) can be directly calculated from the absorption edge height

  T H trans.
(see §2.3.) measured in the transmission mode [24]. This height is proportional to the density of the sample, the amount of dissolved absorbing species and the path length (l) of the X-ray beam inside the sample (constant, see right inset on Fig. 1):

  l T C T ρ T H trans.    ( 2 )
where (T) is the density of the sample and  

       ρ(T) ρ(300K) 300K H T H 300K C T C T C trans. trans. R    ( 3 )
For a simple calculation, we assume that the density of the sample is that of pure water, the influence of the concentration of the solvated species being rather small in the probed concentration range. Here we used the theoretical water density for (T) [START_REF] Lemmon | NIST Chemistry WebBook, NIST Standard Reference Database 69[END_REF]. At room temperature, and for these rather low concentrations, all the Ga 3+ and Br -ions are dissolved.

The relative concentration C R (T) is then directly the ratio of the dissolved quantity with respect to its total amount in the sample.

Errors on the C R (T) estimation are mainly due to the uncertainties on the height edge measurement and the temperature measurement for T>300 K. C R (T) can then be estimated simply from the differential form of equation 3:

        (T) T T (T) 300K H 300K ΔH T H T ΔH T C T ΔC trans. trans. R R        ( 4 )
 T H trans.

 is estimated to 0.001 and T to 2 K ( §2.1). From equation ( 4), it can be seen that the C R (T) error bar is maximum around the supercritical temperature where the decrease in the density is abrupt. C R (T) is around 0.6% at low temperature, around 3% in the supercritical region (the less favourable case). Moreover, these estimations are also slightly dependent on the initial assumption, i.e. the density of the sample is assumed to be that of pure water, and the uncertainty might be higher than the 3% calculated with eq. 4. This is especially true close to the supercritical point of water where the misestimation of the density is the larger. One can then considered that the values obtained with eq. 3 allow a very good quantitative or semi-qualitative estimation of the real C R (T) evolution.

Results

Qualitative analysis of the XAS spectra

The evolutions of the relative concentration C R (T) both for Ga and Br atoms are shown on (Ga K-edge) and Fig. 6 (Br K-edge). For comparison, the spectra of reference model compounds are also shown: the spectrum of solid -GaO(OH) obtained at the Ga K-edge by Pokrovski et al. [25] (Fig. 4 and Fig. 5) and that of the GaBr 3 salt ( §2.1) measured at the Br K-edge in the transmission mode (Fig. 6). The structure of these compounds is known. -

GaO

Concentration of ions in solution

The relative concentration of bromide in solution (Fig. 3) is stable around 1 for both sample solutions from 300 K to T C (~647 K at 30 MPa) and then decrease to reach, at 670 K, ~0.4 (0.017 mol/dm 3 ) and ~0.8 (0.17 mol/dm 3 ).

The evolution of the gallium concentration with temperature (Fig. 3) is completely different. A sharp decrease occurs at 370 K (0.017 mol/dm 3 ) and 465 K (0.17 mol/dm 3 ), C R (T) reaching a value close to zero. The amount of gallium in solution is then estimated around 10 - 3 mol/dm 3 for both initial sample solutions. Then C R (T) increases slightly from 560 K, reaches a maximum close to 650 K before finally decreasing. This re-solvation of gallium reaches 25% and 50% of the total amount of gallium for 0.017 mol/dm 3 and 0.17 mol/dm 3 respectively.

Fig. 4. Normalized XANES spectra obtained at the Ga K-edge for the 0.17 mol/dm 3 aqueous solution at 30 MPa and different temperatures. Comparison with the GaO(OH) spectra [25]. Spectra are shifted for clarity.

Ga cations solvation structure

Ga K-edge XANES spectra have been used as 'structural fingerprints' in order to determine the evolution of the gallium site geometry as a function of temperature. XANES spectra obtained for the concentrated solution at the Ga K-edge shows the presence of three different profiles (Fig. 4). At ambient conditions and at 370 K, the XANES displays an intense peak (the so-called white-line, labelled A) at 10379 eV and a large bump at higher energy (around 10394.5 eV). The intensity of the white line is related to the electronic transition probability 4p 1s  and its position is assigned to octahedral species [28]. On the first spectrum at 470 K (), a bump appears at 10399.5 eV, the width of the white line increases and its mean position shifts to higher energy. These features correspond to the characteristic features of the GaO(OH) spectrum, with a large white-line (B) at 10377.5 eV; they are still clearly noticeable for the second spectrum at this temperature () but not for the last one (). For this last spectrum, the XANES seems similar to that of the octahedral species at 300 K and 370 K. At higher temperatures (T≥560 K) the feature at 10401 eV disappears and a thin white-line at 10375 eV is now clearly visible: such features have already been assigned

to Ga tetrahedral environment [28]. Comparison with the GaO(OH) spectrum measured at ambient conditions in the transmission mode [25].

Complementary to this geometrical qualitative description of the gallium sites, the EXAFS spectra and their FT (Fig. 5) give quantitative information on the nature of the neighbours and structural parameters. Let us just recall that the backscattering amplitude of oxygen atoms, both for the Ga and Br K-edge, has a maximum in the low k-region (around 4-5 Å -1 ) whereas backscattering of heavier atoms such as gallium or bromide is maximum in the medium k-region, around 8 Å -1 , (Fig. 2). At T=300 K, the k 2 .(k) signal (Fig. 5a and5c) is dominated in the low k-region by the oxygen backscattering. This contribution is clearly visible in the FT (Fig. 5b and5d): a single peak centred around 1.4 Å constitutes the main part of the signal for both concentrations. At slightly higher temperatures (T≥370 K), another frequency appears in the oscillations, with beatings visible at 5 Å -1 (T=420 K, the previous valley is less pronounced), 7.5 Å -1 (clear appearance of a peak) and around 10 Å -1 (the previous single oscillation in this k-range is now double). This evolution is clearly identifiable by comparing the FTs where a peak at 2.55 Å is more and more visible. All these features are in agreement with the EXAFS oscillations and FT of -GaO(OH) solid reference, the second peak being associated to Ga-Ga bonds. For the diluted solution, this intermediate configuration seems to be stable from 370 K to 560 K (Fig. 5a and5b). The three spectra performed at each temperature are perfectly superimposable and the magnitude of the features is roughly constant. At 630 K, this contribution to the total signal seems to have completely disappeared. On the other hand, for the concentrated solution (Fig. 5c and5d), this structural feature is completely unstable. The first spectrum at 470 K () is rather similar to that of the diluted compound at the same temperature. The feature at 7.5 Å -1 becomes smaller for the second one () and almost disappears for the third one (), the signal being then almost identical to the 300 K spectrum. On the FT (Fig. 5d), the peak at 2.55 Å is well defined for the two first spectra at 470 K ( and ) and vanishes completely for the third one ().

When the temperature increases to 650 K, the maximum of the envelope of the EXAFS signal shifts to the high k-value and the contribution of the low k-region decreases (Fig. 5a and 5c). Such maximum of the amplitude of oscillations is compatible with the backscattering amplitudes of atoms heavier than oxygen, gallium or bromide (Fig. 2). This evolution is clearly seen on the FT (Fig. 5B and5d) with the appearance of a peak centred around 2 Å. In the previous temperature range and by comparison with the -GaO(OH) structure, the FT peak at 2.55 Å was attributed to Ga-Ga bonds. For these higher temperatures, the peak at 2 Å can then be attributed to Ga-Br ones. This evolution is progressive for [GaBr 3 ]=0.017 mol/dm 3 . For [GaBr 3 ]=0.17 mol/dm 3 the structural modifications seem to be abrupt, the EXAFS signal being almost similar from 560 to 650 K.

Br anions solvation structure

Br K-edge XANES spectra (data not shown) are less informative than those obtained at the Ga K-edge. The spectra display a single large white line at a constant energy whatever the temperature of analysis. Reversely the k 2 .(k) EXAFS spectra (Fig. 6a and6c) and the FT functions (Fig. 6b and6d) exhibit important changes with increasing temperature, for the two concentrations.

In the k-space, at ambient temperature, the signal is essentially dominated by the low kregion signal, characteristic of the Br-O backscattering (Fig. 2). No significant evolutions occur from 300 to 370 K. Between 370 and 560 K, a strong modification of the signal is clearly noticeable for the concentrated solution. The amplitude of the oscillations decreases in the low k-region until a contribution in the [6 -13.5 Å -1 ] k-range appears at 560 K which corresponds to the main oscillation of the GaBr 3 salt reference spectra, characteristic of Br-Ga bonds. This new contribution is also noticeable but with a smaller amplitude for the diluted solution. Moreover, concerning the GaBr 3 reference the k 2 .(k) signal is dominated by this Br-Ga contribution, but the relative importance of the low k-region signal due to Br-O bonds shows that this salt reference might be slightly hydrated.

Important structural changes around Br atoms with increasing temperature are observed from the k 2 .(k) spectra: these signatures are more subtle on the FT signal in the R-space (Fig. 6b and6d). In a first temperature range (T≤605 K for the diluted solution, Fig. 6b, T≤470 K for the concentrated solution, Fig. 6d), the signal is dominated by a broad peak (from 1.45 to 3.15 Å, centred at 2.45 Å). This peak is attributed from the k-space analysis to Br-O bonds. For both solution at higher temperatures, the interference between the Br-O and Br-Ga contributions leads to a decrease of the FT peak modulus around 2 Å, in the middle of the peak. This destructive interference is also present for the GaBr 3 FT signal. Such a feature has already been observed for the ZnBr 2 system [9].

Quantitative analysis

Simulations were performed on merged spectra obtained at a given temperature and constant pressure. Before merging, we carefully checked the superimposition of these spectra, characteristic of a stability of the local structure around the probed element during the total acquisition time (around 2 hours for 3 spectra). Such a merging was possible for most of temperatures, even in some particular cases where the relative amount of the probed element slightly decreases (Fig. 3). At 470 K for the concentrated solution at the Ga K-edge, the EXAFS spectra are different and characteristic of evolving structures in solution. The spectra cannot be merged and the simulation is performed only on the last acquisition (labelled )

where the amount of gallium is constant, at the experiment time scale, during all the acquisition.

Three different kinds of neighbours were necessary for the simulations: Ga-O and Br-O bonds characteristic of the hydration shell, Ga-Br and Br-Ga bonds characteristic of the ionpairing, and Ga-Ga bonds. All the details of the simulations are given in Table 1 for the Ga K- edge and Table 2 for the Br K-edge. The number and distance of the first coordination shell (hydration and ion-pairing) simulations are also shown in Fig. 7 (Ga K-edge) and Fig. 8 (Br K-edge) and those concerning the Ga-Ga 2 nd shell are gathered in Fig. 9 and Table 2. For comparison, the literature values obtained for the -GaO(OH) structure in the literature are given in Table 1 [25], the values obtained in our study for the GaBr 3 salt at the Br K-edge in Table 2. Concerning this reference, Br atoms are surrounded by 1.05±0.1 Ga atoms, instead of 4/3 Ga atoms, at 2.33 Å, bond length in complete accordance with the mean value deduced from the structure of the GaBr 3 anhydrous salt [27]. Br atoms are also surrounded by 0.35±0.05 O atoms at 3.55 Å. These results are then characteristic of a slightly hydrated structure of the GaBr 3 salt with respect to the anhydrous one [27].

O Ga / Br Conc. T N Ga-O R Ga-O  2 Ga-O 10 3 N Ga-X R Ga-X  2
Ga-X 10 Table 2: Br K-edge EXAFS analysis for the GaBr 3 solution at 30 MPa and increasing temperatures and for the GaBr 3 salt. Results for the first shell include Br-O and Br-Ga pairs. Columns are successively related to concentration (mol/dm 3 ), temperature (K), number and nature of neighbours, pair distance (Å),  2 (Å 2 , x10 3 ), anharmonic C 3 term of the O shell (x10 4 ), energy shift E (eV) and R-factor characteristic of the goodness of the fit. S 0 2 =1.

EXAFS simulations of the first coordination shells

At ambient conditions at both concentrations, we find ~6 oxygen neighbours (N Ga-O =6 by definition for the concentrated solution, §2.3) at 1.96 Å around Ga and ~8 at 3.36 Å around Br, in accordance with the literature [5,15,29]. For gallium (Fig. 7), the number of neighbours is also consistent with the octahedral site geometry found with the XANES analysis. When the temperature increases the number and bond length for Ga-O pairs are constant within uncertainty (T≤560 K) then decreases, to around N Ga-O =2 (0.017 mol/dm 3 ) and 0.5 (0.17 mol/dm 3 ) and R Ga-O =1.86-1.90 Å in the supercritical state (T≥605 K). Around Br (Fig. 8), the Br-O number continuously decreases to reach N Br-O =2.6 (0.017 mol/dm 3 ) and 3.6 (0.17 mol/dm 3 ) with a R Br-O bond length equal to 3.40 Å as it was already found in other Br systems [3,7]. However such apparent strong dehydration process around the Br -anions might be overestimated. Close to T C , simulations at the two K-edges give equivalent R Ga-Br and R Br-Ga bond lengths at 2.31-2.32 Å, a value slightly smaller than the value found in [GaBr 4 ] -measured in ambient conditions on concentrated solutions (R Ga-Br =2.33-2.34 Å, [14]). At T=650 K for the concentrated solution, the total number of neighbours around gallium atoms is close to 4. For this temperature the number of Br bonded to Ga atoms is around N=2.8 (0.017 mol/dm 3 ) and 3.8 (0.17 mol/dm 3 ), much smaller than the number of Ga bonded to Br atoms, around 0.3-0.4

for the two concentrations at the same temperature.

EXAFS simulations of the second coordination shell around Ga atoms

The results of the EXAFS simulations for the second Ga-Ga coordination shell (Fig.

characteristic of the formation of a -GaO(OH) like structure, are discussed only for the diluted solution due to the gallium precipitation occuring for the concentrated solution. The N Ga-Ga value, zero at 300 K, increases from 2.3 (370 K) to 4.9 (420 and 470 K). The value decreases then slightly in a first step (3.9 at 560 K), more strongly in a second one (2.3 at 605 K, 1.6 at 630 K). At 650 K no more Ga-Ga contribution is necessary for the simulation.

The R Ga-Ga bond length value equal 3.04 Å at 370 K and decreases continuously to reach 2.94 Å at 630 K (Table 1, Fig. 9 bottom). Comparison with the evolution of the relative concentration of Ga atoms in solution (top) and with the two first Ga-Ga bond lengths in GaO(OH) crystallized compound [25].

The presence of this Ga-Ga contribution can be directly correlated to the Ga concentration in solution (Fig. 9, top). The appearance of the Ga-Ga bonds at 370 K occurs simultaneously with the Ga precipitation. The N Ga-Ga increases from 370 to 470 K while the ratio of gallium in solution is decreasing. At 605 K the decrease of N Ga-Ga is associated with the increase of the amount of Ga in solution, which occurs simultaneously with the appearance of the Ga-Br bonds ( § 3.2.1).

Discussion

Gallium oxy-hydroxide formation

The solubility and formation of -GaOOH in aqueous solution has been extensively studied, both in basic and acid conditions [30,31]. In acid conditions, the following equilibrium occurs:

      ) aq ( ) s ( 2 3 ) aq ( H 3 ) OH ( GaO O H 2 Ga ( 5
)
The reaction is endothermic [32]. Thus, the increase of temperature constitutes the driving force for such structural formation. In this study we probed only the Ga atoms which remained in solution (Fig. 1). The -GaOOH solubility limit given in the literature [31] is low in these conditions, between 10 -6 and 10 -4 mol/dm 3 for pH ranging from 1.5 and 2.5 in the 423-523 K temperature range. These values are lower than the total amount of gallium estimated (10 -3 mol/dm 3 , §3.1.1). The structural state probed in our case is then far from equilibrium, the kinetic evolution being very low. Bénézeth et al. notice that the concentration limit is reached after typically one month, a time scale much more large than during our different sets of in situ experiment (the total counting time was around 40 minutes for each spectrum).

The mean Ga-Ga bond length is very close to the shorter distance of the crystallized -GaO(OH) (Fig. 9, bottom), especially at high temperature. The local order in these crystallites or colloids in suspension is then surprisingly limited to the first shells around the central Ga atoms. Moreover, the  2

Ga-Ga value associated to this bond is found really larger in the solution (11x10 -3 Å 2 , at T=630 K) than in the solid reference (4x10 3 Å 2 ). In our experiments, GaO(OH) (s) formation takes place in disorder colloids or nano-crystallites in suspension, followed by a precipitation.

Gallium-bromide ion pairing

At ambient conditions, Ga cations are entirely hydrated and octahedrally coordinated. At high temperature, Ga-Br association is clearly observed. The Ga-Br ion-pairing formation observed when the temperature increases is mainly driven by the evolution of Coulomb forces between ions. Indeed, the permittivity of water strongly decreases in high temperature conditions [12], and thus favours the attractive interaction between Ga cations and Br anions (the so-called ion pairing effect) by reducing the screening effect of the solvent. This effect has been detailed by Simonet et al. [9] for aqueous ZnBr 2 solution, for example. At T=650 K, Ga cations are surrounded by ~4 Br anions (3.8±0.2) in the 0.17 mol/dm 3 concentrated solution suggesting the presence of    4 GaBr complex. This EXAFS result is in accordance with the XANES spectrum obtained at this temperature for which the Ga cation was found in a tetrahedral site. Such a structure has been already determined by EXAFS and Raman spectroscopies on 1~2 mol/dm 3 GaBr 3 concentrated solutions at ambient conditions [14] but also with the trivalent analogous system InCl 3 in supercritical conditions where    4 InCl clusters are also formed [33]. If all the Ga atoms in solution formed    4 GaBr complex, the number of Ga-Br bonds, N Ga-Br , deduced from the EXAFS measurement, would be 4. One can thus estimate the fraction of Ga cations in solution involved in such a structure from the ratio between the number of Ga-Br bonds measured in the solution (gathered in Table 2) and the Ga-Br bonds in the complete    4 GaBr structure (i.e., 4):

  4 [Ga] ] [GaBr ] [GaBr 4 4 Br Ga Br Ga Br Ga N N N        ( 6 )
It results that in the concentrated solution, almost all the Ga cations (95%) in solution (which corresponds to ~50% of the total amount of Ga in the supercritical region, Fig. 3b ). The second hypothesis is the most reasonable since one would expect progressive replacement of water molecules by bromide ions in the solvation shell of Ga 3+ cations; the coexistence of the most brominated species along with the fully hydrated species seems doubtful. Literature results give ground to the existence of mixed species: in concentrated GaBr 3 solutions at ambient conditions

  n n n   3 (aq) 4 2 O) (H GaBr
( n=2 and 3) tetrahedral complexes are reported [14]. In high temperature hydrothermal InCl 3 solutions, binuclear indium chloride (    4 2 Cl(OH) In ) was also observed [33]: however such analogous polynuclear complexes are not present in the present case since no Ga-Ga bonds were measured in supercritical conditions.

Comparison with other systems

3 compares different systems probed by XAS where monovalent, divalent or trivalent cations are in aqueous solution with a halide anion (Br -or Cl -). We limit the comparison to the studies in which the initial concentration of salts in solution is low enough to avoid significant ion-pairing at ambient conditions. Ion pairing has not been observed for monovalent systems, even if molecular dynamic simulations predict a significant amount of such pairing in supercritical conditions [5,34] ( 7 ) with n=2, 3 or 4. From these equilibrium equations, the relative concentration of Br -anions with respect to the Ga 3+ cations appears to be the key point to determine the main

  n n n   3 (aq) 4 2 O) (H GaBr
species in solution. This does not seem to be completely the case in our experiment: the initial [Br]/[Ga] ratio is always equal to 3 in both cases but we find a n value equal to for the 0.17 mol/dm 3 solution and lower for 0.017 mol/dm 3 . Moreover for both experiments 1) most of the Br -anions are not involved in this association process, with the number of Br-O bonds being much higher than the Br-Ga ones at all the temperatures and 2) the main part of the Ga cations remain in the oxy-hydroxide form.

One possible explanation for this difference with other systems (see Table 3) may be found in the precipitation of GaO(OH) (s) that we observe in our experiments. Such oxyhydroxide precipitation, and then dissolution, modifies strongly the pH conditions in the solutions. In both concentrated and diluted solutions, Ga concentration after precipitation of GaO(OH) (s) is similar (see Fig. 3), although Ga concentration was ten times higher in the 0.17 mol/dm 3 solution: this indicates that more GaO(OH) (s) has been precipitated from the solution and the release of H + (see eq. 5), correlated to this precipitation, has been higher.

This difference would increase the pH difference between the two solutions (the initial concentrated solution pH was smaller than the diluted one). Further investigations are necessary to determine precisely this equilibrium process and the influence of the acidity.

Conclusion

The local environment around Ga and Br atoms of GaBr 3 aqueous solution from ambient to supercritical state has been measured using XAS spectroscopy. At room temperature, Ga 3+

and Br -ions are fully solvated, surrounded by water O atoms at 1.97 Å (Ga-O) and 3.37 Å (Br-O). When the temperature increases, Ga 3+ cations precipitate as GaO(OH) (s) in the temperature range over 370 -600 K, while Br -ions remain completely solvated. For higher temperatures, Ga 3+ cations are remarkably re-dissolved (25% and 50% for 0.017 and 0.17 mol/dm

  d is the thickness of the sample, I 0 , I t , I f are the intensities of the incident, transmitted and fluorescence beams, respectively (see Fig.1).

  mean-square variation of path length R j , a measure of both static and dynamic disorder of path j, the anharmonicity of the pair distribution being expressed by the third cumulant C 3,j .

Fig. 2 .

 2 Fig. 2. Theoretical backscattering amplitude used for the simulations at the Ga (a) and the Br (b) K-edges: single scattering processes involving O, Ga or Br neighbour atoms around Ga and Br central atoms, and multiple scattering processes involving O and H atoms around Br central atoms. Calculations are performed with the FEFF6.0 code, with N=1 and  2 =0.006Å -2 .

  values provides information about composition changes in the fluid induced by the temperature increase. Salt precipitation produces for example a reduction of the edge heights larger than that expected from the fluid density evolution, because the solid precipitate falls out of the beam path. To precisely monitor the amount of ions or complexes which remain dissolved as a function of T, independently of the fluid density evolution and of the initial concentration, we calculate the relative concentration C R (T):

Fig. 3 .

 3 Fig. 3. Relative concentrations C R (T) of dissolved Ga and Br ions in water at 30 MPa as a function of the temperature. Measurements from the height of the absorption edge measured in the transmission mode both at the Ga and Br K-edges during EXAFS acquisitions (40 min. for each spectra). (a) GaBr 3 concentration 0.017 mol/dm 3 . (b) GaBr 3 concentration 0.17 mol/dm 3 . Comparison with the theoretical density of water [17].

Fig. 3 .

 3 Fig. 3. Normalized XANES spectra obtained at the Ga K-edge for the set of experiments

Fig. 5 .

 5 Fig. 5. EXAFS oscillations (k 2 .(k), left figures, a and c) and modulus of their Fourier Transform (right figures, b and d) obtained for the GaBr 3 aqueous solution measured in the fluorescence mode at the Ga K-edge at 30 MPa at different temperatures for two concentrations, 0.017 mol/dm 3 (a and b) and 0.17 mol/dm 3 (c and d).

Fig. 6 .

 6 Fig. 6. EXAFS oscillations (k 2 .(k), left figures, a and c) and modulus of their Fourier Transform (right figures, b and d) obtained for the GaBr 3 aqueous solution measured in the fluorescence mode at the Br K-edge at 30 MPa at different temperatures for two concentrations, 0.017 mol/dm 3 (a and b) and 0.17 mol/dm 3 (c and d).

  Ferlat et al. have shown from EXAFS measurements associated withMolecular Dynamics simulations (MDEXAFS) a clear persistence of the Br -hydration shell from normal to supercritical conditions[6]. The authors interpret this difference between the classical EXAFS analysis and the MDEXAFS one by the strong increase of the local disorder around the Br -anion and not from a decrease of the number of neighbours. This strong disorder, due to dynamic local density fluctuations in addition to the classical bond length distribution, is well reproduced when one generates theoretical EXAFS spectra using snapshots of instantaneous configurations (MDEXAFS).

Fig. 7 .

 7 Fig. 7. Temperature evolution of the Ga-O and Ga-Br pair distances (bottom) and coordination numbers (top) at 30 MPa for the two studied concentrations, 0.017 mol/dm 3 (left) and 0.17 mol/dm 3 (right).

Fig. 8 .

 8 Fig. 8. Temperature evolution of the Br-O and Br-Ga pair distances (bottom) and coordination numbers (top) at 30 MPa for the two studied concentrations, 0.017 mol/dm 3 (left) and 0.17 mol/dm 3 (right).

Fig. 9 .

 9 Fig. 9. Temperature evolution of the Ga-Ga pair distance (bottom) and coordination number (top) at 30 MPa.

  (OH) crystallizes in orthorhombic structure (space group P n m a[26]): Ga atoms are surrounded by 6 O atoms in the first shells forming a distorted octahedron and 8 Ga in the second shell. GaBr 3 salt structure is monoclinic (space group P 2 1 /c[27]), built of Ga 2 Br 6

molecules consisting of two GaBr 4 tetrahedra with a common Br-Br edge: 4 Br atoms are surrounded by one Ga atom (Br-Ga bond length: 2.26 Å) and 2 Br atoms by 2 Ga atoms (2.46 Å), i.e. the mean Br-Ga bond number equals to 4/3 with a mean bond length around 2.33 Å.

Table 1 :

 1 Ga K-edge EXAFS analysis for the GaBr 3 solution at 30 MPa and increasing temperatures. Results for

	3	R

the first shell include Ga-O and Ga-Br pairs. Columns are successively related to concentration (mol/dm 3 ), temperature (K), number and nature of neighbours, pair distance (Å),  2 (Å 2 , x10 3 ), energy shift E (eV) and R factor characteristic of the goodness of the fit. S 0 2 =0.892.

  . Ion pairing occurs for all these divalent or trivalent systems. Except for the two rare earth elements (Gd and Yb), ion pairing occurs in a tetrahedral form, in a mixed environment (ZnCl 2 (H 2 O) 2 , ZnBr 2 (H 2 O) 2 , In 2 Cl(OH) 4+ ...) or pure

	form (ZnCl 4	2-, ZnBr 4	2-, InCl 4	-...). This structural form is consistent with the total number of
	neighbours around gallium cations found close to 4 supercritical state. Ab initio simulations
	of the X-ray-Absorption Near Edge Structure (XANES) spectra measured during the EXAFS
	acquisitions are under progress to validate this geometry.
	ions	reference		ion-pairing in supercritical conditions
	Li + , Cl -	[35]	no ion pairing up to supercritical conditions ( (LiCl]=3 and 9M)
	Ag + , Cl -K + , Br -Rb + , Br -Cs + , Br -	[36] [34] [4-6, 34] [34]	no ion pairing up to 300°C and saturated vapour pressure ([AgClO 4 ]=0.1M, [HClO 4 ]=3M) simulations show the formation of a significant amount of ion-pairs in SC conditions[3,28], but EXAFS experiments do not allowed a validation of this point
	Ca 2+ , Cl -	[37]	ion pairing for [CaCl 2 ]=1M
	Zn 2+ , Cl -Sr 2+ , Cl -	[38] [39]	ZnCl 2 (H 2 O) 2 compound ([ZnCl 2 ]=2M) ZnCl 4 2-compound ([ZnCl 2 ]=1M with an excess of Cl) no ion pairing up to 300°C and saturated vapour pressure ([SrCl 2 ]=0.1M, [HCl]=3M)
	Mn 2+ , Br -	[11]	MnBr 2 (H 2 O) 2 compound ([MnBr 2 ]<1M) MnBr 2+n (H 2 O) 2-n compound ([MnBr 2 ]<1M with an excess of Br)
	Ni 2+ , Br -	[7]	NiBr(H 2 O) 3 compound ([NiBr 2 ]=0.2M) NiBr 3 (H 2 O) compound ([NiBr 2 ]=0.2M+ [NaBr]=0.8M)
	Zn 2+ , Br -In 3+ , Cl -Gd 3+ , Cl -Yb 3+ , Cl -Ga 3+ , Br -	[8,9] [10] [31] [40] [41] this study	ZnBr 2 (H 2 O) 2 compound for [ZnBr 2 ]=1M ZnBr 4 2-compound for an excess of Br: [ZnBr 2 ]=1M + [NaBr]=6M InCl 4 -, In 2 Cl(OH) 4+ compounds GdCl n (H 2 O) 7-n +3-n compound ([GdCl 3 ]=6mM with an excess of Cl) YbCl n (H 2 O) 7-n +3-n compound ([YbCl 3 ]=6mM with an excess of Cl) GaBr 4 -([GaBr 3 ]=0.17M), Ga(H 2 O) 4-n Br n 3-n (n=2 or 3, [GaBr 3 ]=0.017M) compounds

Table 3 :

 3 Ion pairing in aqueous solutions at supercritical conditions, M=mol/dm 3 .The predominant species in the supercritical state progressively evolve from mixed to pure solvation shell with a progressive dehydration when the relative concentration of halide anion increases. From our results there is however particularities for the GaBr 3 aqueous solution at the supercritical state. The Ga-Br association occurs in supercritical domain starting not from a situation where both the cation and the anion are hydrated but with the cation involved in an oxy-hydroxyde structure:

	GaO(OH)	(s)		n	Br (aq) 		3H			 GaBr n	(H	2	O)	4		n	 3 (aq) n 		(4		n	)H	2	O

  3 respectively), ion-pairing occurs and pure or mixture tetrahedral specie 3 or 4) complexes are formed (R Ga-Br =R Br-Ga =~2.31 Å). In supercritical conditions, an equilibrium occurs between GaO(OH) (s) , Ga-Br-H 2 O complexes and Br -anions which remain hydrated. Further investigations are necessary to determine precisely this equilibrium process.

	 GaBr n	(H	2 O)	4		n	 n  3 (aq)	( n=2,

Acknowledgements

The authors thank G. S. Pokrovski for providing the -GaOOH reference spectrum and for fruitful discussions, E. Lahera, R. Bruyère and A. Prat for their great work on the HP/HT cell preparation and high pressure regulation system.