Chemical forms of sulfur in geological and archeological asphaltenes from Middle East, France, and Spain determined by sulfur K- and L-edge X-ray absorption near-edge structure spectroscopy

Sarret, Géraldine; Connan, Jacques; Kasrai, M.; Bancroft, G.M.; Charrié-Duhaut, Armelle; Lemoine, Sylvie; Adam, Pierre; Albrecht, Pierre; Eybert-Bérard, Laurent

doi:10.1016/s0016-7037(99)00205-7

Cited by 119 publications

(102 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Table 1. Energy position of the sulphur K-edge white line for different sulphur compounds from literature data: coal [14], petroleum and asphaltenes [15], minerals [16], soils [19][20][21], residual oil fly ash [22,23]. After qualitative analysis, the relative proportions of the sulphur forms were estimated by means of a least-squares fitting procedure using Gaussian curves for the different sulphur forms peaks and an arctangent curve for the edge step at 2481 eV (oxidized S) [20].…”

Section: Resultsmentioning

confidence: 99%

“…An alternative approach can be provided by X-ray absorption near edge spectroscopy (XANES), that has already been used to distinguish and measure species of S in several matrices such as coal [14], petroleum and asphaltenes [15], minerals [16], biological samples [17][18][19], soils [13,20,21], as well as in matrices similar to PM 10 like residual oil fly ash particulate matter [22,23].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Sulphur speciation of PM10 samples by XANES spectroscopy

Cozzi

Pellegrini²,

Adami

et al. 2009

Open Chemistry

View full text Add to dashboard Cite

Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to identify sulphur compounds in PM10 samples collected simultaneously at two sites with different environmental situations in the province of Trieste (NE of Italy), during summer and winter seasons respectively. The first site is an industrial site located near a steel mill plant and the second is a coastal site. The sulphur speciation at the industrial site has shown the presence of the following sulphur compounds in both seasons: organic compounds (thiophenes or Polycyclic Aromatic Sulphur Heterocycles -PAHs) and sulphates while in the winter season sulphites were also present. In the coastal site organic compounds (thiophenes or PASHs) and sulphate were found during winter season, moreover bisulphates were found during summer season. Relative percentages of the different sulphur compounds have shown that sulphate is the most abundant form of sulphur in the industrial site samples during both seasons and in the coastal site sample collected during the winter season (> 98%); in the coastal site sample collected during the summer season the relative percentages of bisulphate and sulphate were around 40% and 60% respectively.. © Versita Warsaw and Springer-Verlag Berlin Heidelberg.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Sulphur speciation of PM10 samples by XANES spectroscopy

Cozzi

Pellegrini²,

Adami

et al. 2009

Open Chemistry

View full text Add to dashboard Cite

show abstract

“…Principal component analysis (17) of the spectra indicates at least six significant sulfur components, with mostly four types of reduced species contributing to the major peak at 2,473 eV (1 eV ϭ 1.602 ϫ 10 Ϫ19 J). Curve fitting with XANES spectra of standard compounds (15)(16)(17)(18) quantitatively reveals thiols (R-SH), disulfides (R-SS-RЈ with a characteristic doublepeak), and elemental sulfur (S 8 ) in all samples and in core 2 also pyrite (FeS 2 ) in sharply varying amount (Fig. 4 and Table 1).…”

Section: Sulfur and Iron Analysesmentioning

confidence: 96%

Sulfur accumulation in the timbers of King Henry VIII's warship Mary Rose : A pathway in the sulfur cycle of conservation concern

Sandström

Jalilehvand²,

Damian³

et al. 2005

Proc. Natl. Acad. Sci. U.S.A.

115

137

View full text Add to dashboard Cite

In marine-archaeological oak timbers of the Mary Rose large amounts of reduced sulfur compounds abound in lignin-rich parts such as the middle lamella between the cell walls, mostly as thiols and disulfides, whereas iron sulfides and elemental sulfur occur in separate particles. Synchrotron-based x-ray microspectroscopy was used to reveal this environmentally significant accumulation of organosulfur compounds in waterlogged wood. The total concentration of sulfur in reduced forms is Ϸ1 mass % throughout the timbers, whereas iron fluctuates up to several mass %. Conservation methods are being developed aiming to control acid-forming oxidation processes by removing the reactive iron sulfides and stabilizing the organosulfur compounds.organosulfur ͉ waterlogged wood ͉ iron sulfides ͉ conservation ͉ marine archaeology

show abstract

“…Differential reduction of organic S compounds to H 2 S does not identify the organic functional groups or the intermediate oxidation states of S. The pyrolysis -gas chromatography -mass spectrometry approach is used for coal, kerogens and aquatic humic substances, but is limited to speciation of thermally stable forms of S. Within this context, S K-and L-edge XANES spectroscopy are proving to be invaluable, non-destructive, and in some cases in situ, techniques for characterizing the S functional groups in natural organic matter. The method has been applied to coals (e.g., Hussain et al 1982, Spiro et al 1984, Huffman et al 1991, George et al 1991, Brown et al 1992, Kasrai et al 1990, 1996b, Olivella et al 2002, Huggins et al 1997, heavy petroleum asphalts (bitumens) and asphaltenes (George & Gorbaty 1989, Gorbaty et al 1991, Waldo et al 1991, Kasrai et al 1994, Vairavamurthy et al 1994, Sarret et al 1999, kerogens , Sarret et al 2002 and sediments, soils and humus (Vairavamurthy et al 1994, 1997, Morra et al 1997, Olivella et al 2002, Qian et al 2002, Beauchemin et al 2002, Solomon et al 2003, Jokic et al 2003. FIG.…”

Section: Organic Geochemistrymentioning

confidence: 99%

Xanes Spectroscopy of Sulfur in Earth Materials

Fleet¹

2005

The Canadian Mineralogist

153

134

View full text Add to dashboard Cite

X-ray absorption near-edge structure (XANES) spectroscopy is the ideal non-destructive technique for characterizing and quantifying S species in compositionally complex natural materials such as silicate glasses and minerals, coals, asphalts and asphaltenes, kerogens and humic substances. Sulfur absorption edges represent the transition of S 1s and 2p core electrons to unoccupied antibonding orbitals at the bottom of the conduction band. Shifts in the position of the absorption-edge feature of S K-and L-edge XANES spectra constitute a chemical ruler for oxidation state of both inorganic and organic species of S; the S K edge shifts from 2469.5 eV for chalcopyrite (2-oxidation state) to 2482 eV for gypsum (6+). However, chemical state of S in Earth materials is most readily assigned by comparing the overall XANES profi le with spectra for reference compounds. Sulfur XANES spectra are reviewed for pyrite, troilite, pyrrhotite and NiAs-type Co 0.923 S and Ni 0.923 S, niningerite (MgS), oldhamite (CaS), alabandite (MnS) and cubic FeS, and sphalerite and related phases, as well as for selected solid-solutions of the monosulfi des. Sulfur XANES spectra for FeS, CoS, NiS, MgS, CaS, MnS and ZnS have been simulated by multiple scattering calculations. The S K-edge XANES of transition-metal-bearing monosulfi des generally show anomalous absorption consistent with hybridization of the fi nal S 3p * antibonding states with empty 3d orbitals on the metal atoms. Various applications of S K-and L-edge XANES fi ngerprinting are discussed, including speciation of inorganic S in basaltic glasses, lazurite and haüyne, identifi cation of organic functional groups of S in coals, kerogens and humic substances extracted from subtropical soils and marine sediments, and the association of sulfated sugars with calcifi cation of coral aragonite skeletons.Keywords: XANES spectroscopy, chemical state of S, electronic structure and bonding, sulfi des, sulfates, magma, organic geochemistry. SOMMAIRELa spectroscopie d'absorption des rayons X dans la région pré-seuil (XANES) s'avère la technique non-destructive par excellence pour caractériser et quantifi er les espèces de soufre dans les matériaux naturels de composition complexe, par exemple les verres silicatés et minéraux, charbons, asphaltes et asphaltènes, kérogènes et substances humiques. Les seuils d'absorption du soufre résultent de la transition des électrons 1s et 2p du noyau à des orbites non occupés anti-liaisons à la base de la bande de conduction. Les décalages dans la position des seuils K et L du soufre des spectres XANES constituent un barème chimique important dans l'évaluation du niveau d'oxydation du soufre, à la fois pour les espèces inorganiques et organiques; le seuil K est déplacé de 2469.5 eV dans la chalcopyrite (valence 2-) à 2482 eV dans le gypse (6+). Toutefois, l'état du soufre des matériaux terrestres est plus facilement attribué en comparant le profi l XANES entier d'un échantillon aux spectres des composés de réfé-rence. Les spectres XANES du soufre so...

show abstract

Chemical forms of sulfur in geological and archeological asphaltenes from Middle East, France, and Spain determined by sulfur K- and L-edge X-ray absorption near-edge structure spectroscopy

Cited by 119 publications

References 22 publications

Sulphur speciation of PM10 samples by XANES spectroscopy

Sulphur speciation of PM10 samples by XANES spectroscopy

Sulfur accumulation in the timbers of King Henry VIII's warship Mary Rose : A pathway in the sulfur cycle of conservation concern

Xanes Spectroscopy of Sulfur in Earth Materials

Contact Info

Product

Resources

About