dataesr/scientific-paragraphs-categorization huggingface dataset:
Over the last ten years, several comprehensive reviews of iron thermodynamics data were published. This work aims to: (i) propose a consistent set of Gibbs free energies (Δ f G 0 ) of ferrous hydroxide, Fe(OH) 2,cr and of synthetic Green rusts I and II; (ii) check the consistency of the data of these isostructural compounds by means of a correlation obtained with electronegativities of the anions. Experimental data are concentrations in aqueous solutions and pH, and must be processed to obtain ionic activity products (IAP). The model of Specific Interaction Theory (SIT) was used here. Firstly, some complexes whose existences are doubtful were removed from the SIT database. The new modified database is given here. Secondly, experimental data were processed. Thirdly, the following relation of regression between Gibbs free energies of formation of Green rusts and normalized Allred-Rochow electronegativities of anions was obtained as: Δ f G 0 = -488.
The specific interaction theory relies on Brønsted-Scatchard-Guggenheim extension of Debye-Hückel theory  [4]. All three models are incorporated in the version 3. 0 of Phreeqc code  [7]. The selection of the model is implicit in the choice of the database used, respectively phreeqc. dat (default choice), pitzer. dat and sit. dat. Other choices are A Consistent Set of Thermodynamic Data for Iron and Reevaluation of Green Rusts and FougeriteSolubilities 384 variants of phreeqc. dat, differing by the number of elements, complexes or organic molecules taken into account. Pitzer's model has proved to be much better suited in concentrated solutions and brines than Debye-Hückel extended law  [6, 8]  but parameters are available for a limited number of elements, including Fe, and it appears now as overparameterized  [9].
A Consistent Set of Thermodynamic Data for Fe Several attempts have been made recently to critically evaluate thermodynamic data for Fe compounds, both in solution and solid state  [4, 13, 14]. This was promoted by the need to accurately assess the long-term stability of steel containers used to confine radioactive wastes in repositories (Nuclear Energy Agency of the OECD, Thermochemical Database Project, NEA-TDB). The most extensive review  [4]  critically evaluates all experimental data from 1857 to 2008. An initial assessment of data was performed by extrapolating them to zero ionic strength, then they were first re-examined to ensure consistency between values from different thermodynamic cycles, and they were ultimately optimized using a weighted least-squares procedure  [4]. This work includes data for Fe(0), aqueous species, inorganic complexes of Fe 2+ and Fe 3+ with OH -, halide, sulfur, carbonate and silicon.
Auxiliary data are taken from the publication of CODATA Key Values  [15]. One must note that for sulfate ion the recent value  [3]  is -742. 628 kJmol -1 , which differs significantly from CODATA set, (-744. 004 ± 0. 418) kJmol -1. The review by Lemire et al. [4]  includes too many data on Fe minerals: magnetite, goethite, lepidocrocite, feroxyhyte, hematite, maghemite, siderite, Fe sulfides etc. The main data were incorporated in the sit. dat database. The modified database sit_mod_2016. dat is given in this paper as supplementary material. We will restrict here to complexes with OH -, Cl -, SO These complexes are no more considered because their existence is doubtful and the rationale has been detailed by Lemire et al. [4]. For example, the existence of Fe(OH) 3 , aq and Fe(OH)  4  -is doubtful because of the dimerisation of Fe(OH) 2 +.
Accordingly, they are removed from the sit_mod_2016. dat database, simply by "commenting" the corresponding lines in the database. As the process of revision and optimisation included the two methods, namely stepwise revision and global optimisation, there are some differences between the values in the synthesis  [4]  and the detailed values retained in the following chapters V to XI  [4]. For sake of consistency, we chose the values from Table  3 , with the auxiliary data from Table 4  [4]. But some values lack, especially enthalpies of reactions necessary to compute at temperatures different from the reference temperature. In some cases, Lemire et al. [4]  provided data, not formally retained in the TDB project, but proposed for incorporating provisionally in the models to this end. We selected those values of enthalpies for Fe(OH) + , Fe(OH) 2,aq and Fe(OH) 3 -, as regards Fe(II) species  [4] ; in the same way, we selected the value of 26 kJmol -1 for the enthalpy of reaction of formation of FeSO 4 + ; there seems to occur a change of coordination at temperatures larger than 328.
15 K with a doubling of the enthalpy  [4]. We selected here the value suited for lower temperatures. , Na + ) = 0. 24 from Lemire et al. [4]. Data are given with 3 decimals only to avoid propagation of errors due to rounding. + H + + (Ox) 2-= Fe(HOx) 2+ 9. 3 Fe 3+ + (Ox) 2-= Fe(Ox) + 9. 53 Fe 3+ + 2(Ox) 2-= Fe(Ox) 2 - 15. 57 Fe 3+ + 3(Ox) 2-= Fe(Ox) 3 3- 20. 2 • Data of oxalate complexes are not reviewed by Lemire et al. [4] , the values in the sit. dat database are from Akram et al. [16]. In order to be consistent, the specific interaction theory must be used to compute non-ideality interactions between ions. Throughout their study, Lemire, et al. [4]  provides values for the specific interaction coefficients of several cations with Cl -and ClO 4 -, and one value for the interaction between the anion Fe(SO) 4 2-and Na + (Table  1 ).
These values were incorporated in the sit_mod_2016. dat database, with now 17 ε values for cations against only 3 previously: 4 for Fe(II) (none before) and 13 for Fe(III) (3 before). The coefficient ε Table  3  Standard thermodynamic properties at 29,815 K, 10 5 Pa of some Fe minerals. Mineral ∆ f G° (T°) (kJmol -1 ) ∆ f H° (T°) (kJmol -1 ) S° (T°) (Jmol -1 K -1 ) Cp°. m (Jmol - (Fe 3+ , ClO 4 -) is changed from 0. 5 kgmol -1 to 0. 73 kgmol -1. The previous value ε (FeOH 2+ , Cl -) = 0. 186 kgmol -1 was kept, as no new value was found but it is significantly different from the value ε (FeOH 2+ , ClO 4 -) = 0. 46 kgmol -1 , while all coefficients of interaction of a given cation with Cl -and ClO 4 -are quite similar. For minerals, the values selected by Lemire, et al. [4]  were incorporated too in sit_mod_2016.
Ferrous Hydroxide White Rust The chemical composition of the solution at equilibrium with Fe(OH) 2 before the beginning of formation of GR2-SO 4 is given in Table  4. This corresponds to point (a)  [22]. Using our modified database (sit_mod_2016. dat), the equilibrium constant obtained (log K = 13. 133) is slightly different from reported previously as log K = 13. 32 ± 0. 18. Reprocessing of data leads here to Δ f G 0 m = -490. 035 ± 1 kJmol -1 , instead of -489 ± 1. 0 kJmol -1  [22].
Discussion The present reexamination of previous results was divided in five broad parts, first on "white rust", then on GRs according to the nature of intercalated anion (SO 4 2-, Cl -, CO 3 2-and oxalate). The starting points are the experimental original data of previous studies, in which solutions are in equilibrium both with the specific Green rust and Fe(OH) 2,cr. New values of Δ f G 0 m and log K are then determined with PhreeqC and the new database sit_mod_2016. dat. The value used here for Fe(OH) 2,cr is quasi-identical to the values used in the previous studies.
This formula, applicable when x is larger than 1/3, was explained as the effect of the substitution of hydroxyl groups by O 2-  [32, 37]. Although measurements by Mössbauer spectrometry have well confirmed the GR-0. 5 (Fe II /Fe III = 0. 5)  [32] , the other levels of the Fe II /Fe III mole ratio are still doubtful. Indeed, assuming a ratio larger than 0. 5, this gives a mole ratio Fe III /S different from 2. Calorimetry demonstrated that there is no thermodynamic preference for any Fe II /Fe III mole ratio  [32]. In addition, there is no significant statistical difference for GR2-SO 4 whether Na + is considered in the interlayer or not  [29] , so the classical structural formula for GR2-SO 4 is used here. In addition, values obtained here are based upon the most recent critically evaluated database for Fe  [4] , incorporated in sit_mod_2016.
Conclusion The thermodynamic data carefully selected on Fe compounds  [4]  were used here for sake of consistency with the Specific Interaction Theory to compute activity coefficients in aqueous solutions. Doubtful aqueous species were discarded. Those data and the parameters for SIT theory relative to Fe compounds were incorporated in a new sit database associated with PhreeqC geochemical model: this is the sit_mod_2016. dat database. The free energies of formation of ferrous hydroxide and different synthetic green rusts were then recalculated from the original experimental data. The reevaluated data for this group of isostructural compounds are very well correlated with the electronegativity of the interlayered anion, taken on the Allred-Rochow scale, and following the partial charges model  [10] , which confirms the robustness of the model.
Acknowledgements The  Universitéd'Avignonet des Pays de Vaucluse (UAPV)  is gratefully acknowledged for a  Agricol Perdiguier grant  to  Mrs. Jihaine Ben Nacib. The support of  Inra  and of the  EcoleSupérieured'Ingénieurs de l'Equipement Rural at Medjez-el-Bab (Tunisia)  and of her  Director Pr. HassenKharroubi  is gratefully acknowledged too.
 The reactions of formation of Fe aqueous complexes, with the values of log K and enthalpies of reaction, used to modify the sit. dat database are given in Table2for Fe(II) and Fe(III). 4 2-and CO 3 2-, without By comparison with other databases, phreeqc. dat, it appears that some complexes are no more considered:  for Fe(II): Fe(OH) 4 2-, FeHSO 4 + , FeCO 3 OH -, FeHCO 3 + ;  for Fe(III): Fe(OH) 3 , aq , Fe(OH) 4 -and Fe 3 (OH) 4 5+. considering sulfides, but oxalate complexes are considered too, as this set of data is used to reevaluate thermodynamic properties of green rusts. Indeed, oxalate forms stable green rusts, as sulfate, carbonate and chloride do. The properties of Fe aqueous complexes in STP conditions are given in Table1.
226 -50. 056 -282. 404 -108. 000 0. 76 0. 73 Fe(OH) 2+ -241. 094 -299. 886 -132. 871 0. 46 Fe(OH) 2 + -463. 107 -550. 170 0. 37 Fe 2 (OH) 2 4+ -490. 635 -627. 773 -331. 321 1. 04 FeCl 2+ -156. 119 -194. 656 -121. 309 0. 64 0. 62 FeCl 2 + -291. 332 -352. 226 -19. 410 0. 52 FeCl 3 -415. 700 FeCl 4 - -535. 501 FeSO 4 + -784. 488 -933. 396 0. 4 Fe(SO4) 2 - -1,539. 738 -1,849. 488 1, 3 FeHSO 4 2+ -795. 800 0. 58 Fe(CO 3 ) 3 3- -1,736. 918 FeCO 3 (OH) -842. 342 10 Fe(HOx) 2+ -743. 577 Fe(Ox) + -744. 890 Fe(Ox) 2 - -1,454. 661 Fe(Ox) 3 3- -2,154. 328 *Ox = oxalate. 1. [4]; 2. Data for oxalate complexes are not reviewed by Lemire, et al. [4], the values in the sit-database are from Akram et al. [16]; 3.  (Fe(SO 4 ) 2 -.
In the case of the in vivo measurement (''Closing of reaction centers during fluorescence induction by saturating light in vivo'' section), cells were exposed to 1500 lmol of photons,m -2 s -1 of orange light during one second. In both the cases, the signals were collected (integration time) every 100 ms. In addition, a very low-intensity experiment was carried out with 1 lmol of photons,m -2 s -1 of orange light during one minute and integration time of 10 s. Fluorescence is collected via a lens that focuses them into a fiber connected to a CCD spectrometer (USB2000?, OceanOptics). Home-made protocols written in National Instruments LabView and Wolfram Mathematica were used to carry out the data acquisition and the data analysis, respectively.
) after a quenching experiment on isolated PB and pre-converted OCP r (added at t = 18 s). The data matrix was obtained after continuous illumination of isolated PB in 0. 8 M phosphate buffer with 590 nm light (300 lmol photons m -2 s -1 ). Fluorescence spectra were acquired every 100 ms. For selected timepoints, acquired spectra in the range 640-800 nm (b) and time courses (a) are shown. Key to a black 640 nm, gray 653 nm, maroon 666 nm, brown 678 nm, red 691 nm, orange 703 nm. Key to b black 0. 3 s, gray 7. 2 s, maroon 14. 1 s, brown 21. 0 s, red 27. 9 s, orange 34. 8 s. To this data matrix, we apply the SVD described by Eq. 1. The scree plot of the first 10 diagonal elements of S is shown in e. c and d display the first three lsv and rsv in black, red and gray, respectively For richer data featuring a matrix of rank 3 (or higher), additional criteria would be needed to determine eight (or more) coefficients a ij.
Results and discussion Our spectra-decomposing method and analysis protocol were applied to two well-defined systems under different conditions. The first system studied (''OCP-related PB fluorescence quenching in vitro'' section) is in vitro quenching of PB fluorescence by pre-converted OCP r , where only two states were expected (quenched and unquenched PB). The second system is the spectral transition during a single saturation pulse of white light with intact WT Synechocystis cells in vivo (''Closing of reaction centers during fluorescence induction by saturating light in vivo'' section). These two systems are discussed in the following two sections. Each section consists of (i) description of the light protocol, (ii) description of the results, and (iii) conclusions. Based on this, the method is applied to more complex datasets of intact living cells acquired during orange light irradiation (''In vivo fluorescence induction with orange light in wild-type and PSI-, and PSII-deficient mutants of Synechocystis'' section).
OCP-related PB fluorescence quenching in vitro The OCP-PB interaction has been reconstituted and characterized in vitro  (Gwizdala et al. 2011; Jallet et al. 2012; Wilson et al. 2012). In particular, the effects on the kinetics of fluorescence quenching as a function of OCP/PB ratio have been investigated using a PAM fluorometer and we present here one of the protocols with the aim of validating our method (see the ''Time-resolved fluorescence spectra at room temperature'' section). What we expect to see is: evidence for PB in either an unquenched (before OCP r is added) or a quenched state (once OCP r binds to the PB core)  (Gwizdala et al. 2011). First, a selected visualization of the acquired data matrix is depicted in Fig. 1. Time-dependent fluorescence levels at specific wavelengths (Fig.
The data matrices are of rank 2 (see Figures  S3-5 ). The analysis of the Synechocystis DPSII mutant yields the results as shown in Fig. 4. We associate SAS 1,DPSII with PB emission and SAS 2,DPSII with a quenched form of the PB. To resolve its origin, more datasets are necessary, however, given (i) the lack of fully assembled PSII RCs in this particular mutant and supported by (ii) the high amount of PSI complexes typically present in cyanobacterial thylakoids  (Melis 1989; Moal and Lagoutte 2012; Shevela et al. 2013 ), a direct transfer from PB to PSI could be the origin of the quenching. Moreover, there is no DCMUrelated effect on the dynamics (panel c of Figure  S6 ). This is a sensible observation: DCMU is expected to block transfer from Q A -(the primary quinone electron acceptor of PSII) to the plastoquinone pool (PQ) by binding to the Q B site of the D1 protein  (Krause and Weis 1991).
Acknowledgments AMA gratefully acknowledges  Michael Reus  for his valuable assistance in re-building the set-up in Amsterdam. Prof. dr. K. J. Hellingwerf  and dr. F. Branco dos Santos are thanked for critical reading of the text and helpful discussions. The anonymous reviewers are especially thanked for their helpful comments. Jaroslav Krafl  is thanked for carrying out spectrally resolved fluorescence measurements in Tr ˇebon ˇwith cyanobacteria mutants. These mutants were kindly provided by  Josef Komenda  and  Martin Tichy  from  Tr ˇebon ˇ's laboratory (DPSII, DPSI) ; the DPSI mutant was originally constructed by  Wim Vermaas  ( Arizona State University, Tempe, Arizona, U. S. ). This research was performed as part of the  BioSolar Cells research programme , sponsored by the  Dutch Ministry of Economic Affairs.
This work is part of the research programme of the  Foundation for Fundamental Research on Matter (FOM) , which is part of the  Netherlands Organisation for Scientific Research (NWO). MG, IHMvS, and RvG acknowledge financial support of the  European Research Council  ( Advanced Grant Proposal 267333  ( PHOT-PROT ) to RvG). RvG was further supported by the  NWO Council of Chemical Sciences (NWO-CW)  via a  TOP-Grant  ( 700. 58. 305 ), and by the  EU   FP7  Project  PAPETS  ( GA 323901 ). RvG gratefully acknowledges his  Academy Professor grant  from the  Netherlands Royal Academy of Sciences  (KNAW). MG acknowledges financing from  EMBO (LTF). BvO acknowledges financial support by the  NWO  through a  Veni grant. He further acknowledges  Roberta Croce  for financial support from her  NWO   Vici grant.
Results Structural transformations in Fe 2 O 3. In agreement with previous studies  4, 5, 7, 8, 12  , our cold compression experiments on hematite single crystals to 54(1) GPa result in a transition to the z-Fe 2 O 3 phase manifested by a B8. 4% volume discontinuity (Supplementary Fig. 1 ). Although in earlier work we indexed the diffraction pattern of z-Fe 2 O 3 in a monoclinic unit cell  12  , the new extended dataset acquired in the present work showed that the structure is in fact triclinic (see Supplementary Note 1 for details), similar to Mn 2 O 3 (ref. 14). An insufficient number of independent reflections prevented structural refinement of z-Fe 2 O 3 in triclinic symmetry, so we used a monoclinic model  12   further pressure increase from 54(1) to 67(1) GPa, we observed a reduction in the splitting of reflections, indicating an increase in symmetry.
5-1°scanning of the same o range. The crystallographic information is also available as Supplementary Data 1-7. Data analysis. Integration of the reflection intensities and absorption corrections were performed using CrysAlisPro software  36. The structures were solved by the direct method and refined in the isotropic approximation by full matrix leastsquares refinements using SHELXS and SHELXL software  37  , respectively. SMS spectroscopy. Energy-domain Mo ¨ssbauer measurements were carried out at the nuclear resonance beamline ID18 at ESRF (see ref. 38 for more details).
Acknowledgements We thank  K. Glazyrin  for synthesis of non-enriched Fe 2 O 3 and  V. Cerantola  for synthesis of FeCO 3 and for assistance with HPHT experiments at  ESRF  and  APS. We appreciate the technical assistance of  S. Linhardt  and  S. U ¨belhack. N. D. and L. D. thank the  German Research Foundation (Deutsche Forschungsgemeinschaft, DFG)  and the  Federal Ministry of Education and Research (BMBF, Germany)  for funding. N. D. thanks the  DFG  for financial support through the  Heisenberg Program  and project no. DU 954-8/1 , and  BMBF  for the grant no. 5K13WC3  (Verbundprojekt  O5K2013 , Teilprojekt 2, PT-DESY). We acknowledge the  European Synchrotron Radiation Facility  for provision of synchrotron radiation facilities. Portions of this work were performed at GeoSoilEnvir-oCARS (sector 13),  Advanced Photon Source (APS) ,  Argonne National Laboratory.
"But when energy costs to GDP ratio goes beyond the threshold, it eliminates the impact of factors contributing to the economic growth and slows it down, so the potential economic growth is not realized". King et al. (2015b)  estimate energy expenditures as a fraction of GDP for the period 1978-2010 for 44 countries representing 93-95% of the gross world product (GWP) and 73-79% of the IEA's listed world Total Primary Energy Supply (TPES) (>78% after 1994). The methodology used by these authors is set out in full in their article but it should be pointed out that they consider coal, oil, and natural gas for three sectors (industrial, residential, and electricity production), plus non-fossil (nuclear, renewable) electricity production for two sectors (industrial and residential). The quantities and prices of these different commodities were mostly retrieved from databases of the US Energy Information Administration (EIA).
Conclusions and policy implications In this article we estimated the level of energy expenditure from 1850 to 2012 for the US and the global economy, and from 1300 to 2008 for the UK. Our results indicate that periods of high or suddenly increasing energy expenditure levels are associated with low economic growth rates: for instance from 1850 to 1945 (very high energy expenditure levels), from  1975 to 1976 (surge), and from 1981 to 1983 (surge). On the contrary, periods of low and decreasing energy expenditure are associated with high and increasing economic growth rates: for instance from 1945 to 1973, and in the early 2000s. Over the more restricted period 1960-2010 for which we have continuous year-to-year data for the US, we performed several Granger causality tests that consistently show a one way temporal causality running from the level of energy expenditure (as a fraction of GDP) to economic growth.
Acknowledgements We thank  Roger Fouquet  and  Carey King  for providing us with their data in very easy-to-use forms. We thank  Pierre-André Jouvet ,  Nicolas Legrand , and  Benoit Chèze  for their helpful comments on an earlier version of this article. We have also greatly appreciated all the suggestions made by scholars at the RITM seminar, Climate Economics Chair seminar, Paris-Sorbonne seminar, LEO seminar, and the  Fourth International Symposium on Energy and Finance Issues. Three anonymous reviewers have added much to the quality of this article through their insightful comments.
Acknowledgements We thank financial support from  Generalitat Valenciana  ( ISIC/ 2012/008   Institute of Nanotechnologies for Clean Energies ). We acknowledge the financial support of the  European Community  through the  Future and Emerging Technologies (FET)  programme under the  FP7 , collaborative Project contract n8 309223 (PHOCS). Additionally, the  EU projects "Sunflower"  ( FP7-ICT-2011-7-contract num. 287594 ) and the  SFUMATO-FUI  Project  AAP12  are acknowledged. A. G. would like to thank the  Spanish Ministerio de Economía y Competitividad  for a  Ramón y Cajal Fellowship  ( RYC-2014-16809 ).
Thermochemical storage demonstration system for space heating and DHW; MERITS project, TNO MERITS is an R&D project supported by the European FP7 program with the aim to build a prototype of a compact rechargeable thermal battery. Such a product would offer a new solution for improved use of renewable sources for domestic heating, cooling and hot water appliances and thus greatly contribute to the European ambition of an energy-neutral built environment by 2050. The project is carried out by four research institutes (TNO, VITO, Tecnalia, Fraunhofer ISE), two universities (Ulster University, University of Lleida), two SME's (De Beijer RTB, Zonne-Energie Nederland BV), and two industries (Mostostal, Glen Dimplex). The team works with novel high energy density thermochemical materials that can supply required heating, cooling and domestic hot water for a dwelling with up to 100% renewable energy sources (e.
Acknowledgements The financial supports of the  European Commission  for subsidizing the  COMTES  project within the  7th framework program  for research is acknowledged. The University of Bayreuth sincerely thanks the  Federal Ministry of Economic Affairs and Energy (BMWi) ,  Germany  for the research funding and support. The work of  ZAE Bayern  was supported by the  German Federal Ministry for Economic Affairs and Energy (BMWi)  under the project code  0327383B , and by the  Federal Ministry for the Environment, Nature Conservation and Nuclear Safety (BMU)  under the project codes  0329605O  and  0325978A. The university of Zaragoza thanks the  Spanish Government  for the partial funding of this work within the framework of research projects  ENE2008-06687-C02-02 ,  ENE2011-28269-C03-01  and  ENE2014-57262-R.