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Advances in the molecular-scale unde...

Hay, Michael Benjamin.

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Advances in the molecular-scale understanding of geochemical processes: Carboxyl structures in natural organic matter, organosulfur cycling in soils, and the coordination chemistry of aqueous aluminum.

紀錄類型:	書目-語言資料,印刷品 : Monograph/item
正題名/作者:	Advances in the molecular-scale understanding of geochemical processes: Carboxyl structures in natural organic matter, organosulfur cycling in soils, and the coordination chemistry of aqueous aluminum./
作者:	Hay, Michael Benjamin.
面頁冊數:	303 p.
附註:	Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4341.
Contained By:	Dissertation Abstracts International68-07B.
標題:	Chemistry, Analytical. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3271636
ISBN:	9780549110842

Advances in the molecular-scale understanding of geochemical processes: Carboxyl structures in natural organic matter, organosulfur cycling in soils, and the coordination chemistry of aqueous aluminum.
Hay, Michael Benjamin.

Advances in the molecular-scale understanding of geochemical processes: Carboxyl structures in natural organic matter, organosulfur cycling in soils, and the coordination chemistry of aqueous aluminum. - 303 p.

Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4341.

Thesis (Ph.D.)--Princeton University, 2007.

This dissertation examines the molecular structure and behavior of various soil components using spectroscopic techniques, focusing specifically on the following three topics: the structural environment of carboxyl groups in natural organic matter (NOM), the functional group chemistry and cycling of organosulfur in soil NOM, and the coordination chemistry of aqueous Al3+.

ISBN: 9780549110842Subjects--Topical Terms:

586156
Chemistry, Analytical.

Advances in the molecular-scale understanding of geochemical processes: Carboxyl structures in natural organic matter, organosulfur cycling in soils, and the coordination chemistry of aqueous aluminum.
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245 1 0 $a Advances in the molecular-scale understanding of geochemical processes: Carboxyl structures in natural organic matter, organosulfur cycling in soils, and the coordination chemistry of aqueous aluminum.
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500 $a Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4341.
502 $a Thesis (Ph.D.)--Princeton University, 2007.
520 $a This dissertation examines the molecular structure and behavior of various soil components using spectroscopic techniques, focusing specifically on the following three topics: the structural environment of carboxyl groups in natural organic matter (NOM), the functional group chemistry and cycling of organosulfur in soil NOM, and the coordination chemistry of aqueous Al3+.
520 $a The structural environment of carboxyl groups in dissolved NOM from numerous sources was studied using aqueous ATR-FTIR and 2D-NMR spectroscopy. The asymmetric stretching vibrational frequency of the carboxylate anion was measured for each NOM sample and compared with compiled values for model organic acids. The comparison suggests that the majority of carboxyl groups present in NOM likely occur in the close vicinity (alpha-position) of other O-containing functional groups, including hydroxyl, ether/ester, and neighboring carboxylates. The 2D-NMR results largely confirm this observation, which helps to explain the high acidity and metal-binding capacity of NOM.
520 $a X-ray absorption spectroscopy (XAS) at the S edge enables resolution of many chemical forms of S in complex macromolecules that cannot be identified using other techniques. Studies of forest floor leaf litter and dissolved NOM from leaf litter leachate collected at different decay stages have revealed speciation-dependent loss rates, including a fast-leaching sulfoxide fraction, a slower release of mono- and polysulfides, and a net enrichment of sulfonate and organosulfatetype structures in the solid fraction. The results indicate an active organosulfate role in the soil S cycle, beginning in the early stages of soil NOM formation.
520 $a XAS was also used to study the coordination geometry of aqueous Al 3+, in combination with Density Functional Theory structural optimization and XAS spectral prediction calculations. These results confirm the presence of 6-coordinate Al(H20)63+ and 4-coordinate Al(OH)4- complexes at low and high pH. Determination of the AlOH2+ coordination geometry is ongoing, but promising. Subtle differences in the X-ray spectra of aquo-Al and Al-organic complexes were attributed to differing orbital contributions from the O ligands, which suggest how Al-edge XAS may be used as a fingerprinting technique for determining Al speciation in complex solutions.
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