成都理工大学硕士论文答辩

1、Lectured by : Zeqin Li Department Environmental Science & EngineeringChengdu University of TechnologyChengdu, Sichuan Province, 610059P. R. China Phone: +86-28-84077542(O), 84078078(H) Fax: +86-28-84077066 E-mail: ; Principles of isotopic fractionation Hydrogen and oxygen isotope geochemistryCarbon

2、isotope geochemistrySulfur isotope geochemistry Isotope application ContentIsotopes can be divided into 2 kinds: radioactive (unstable) U-Pb, Rb-Sr, Th-Pb, K-Ar, Sm-Nb Nonradioactive(stable)H, O, C, S, N, He, Li, B Review1 Principles of isotopic fractionation Different isotopes of an elementDifferen

3、ces in mass result in Minor differences in physical-chemical behaviourTherefore, Stable Isotopic Fractionation due to differences in isotopic mass by 1) Physical processes2) Chemical reactions 3) Biological processes Isotopic FractionationExplain: Molecules with the lighter isotope react faster. why

4、 ? The molecules vibrational frequency is higher, bond strength of the element is weaker ), Reviewdifferences in bond strengths affect kinetics of reactions as the lighter isotope forms weaker bonds than heavier isotope. Molecules with the lighter isotope react faster, and are concentrated preferent

5、ially into reaction productsUnidirectional reactions (e.g. open systems where products escape) are effective at fractionating isotopes goes to 1 with increasing T because small differences in bond strengths at high T are not as effective in causing fractionation as at low T.Vibrational frequency dep

6、ends on the temperature of the system.ReviewFractionation factor - ab=Ra/Rb Ra is the ratio of heavy isotope and light isotope in A phase. Rb is the ratio of heavy isotope and light isotope in B phase. O isotopic fractionation between Liquid Water and Vapour Water R l = 18O/16OH2Ol R v = 18O/16OH2Ov

7、 lv R l /R v As it is difficult to calculate an equilibrium constant (K) for isotopic differentiation of complex moleculesExample:For water (l) in EQ with vapour (v), the fractionation of O isotopes in water molecules is: lv = Rl/Rv = 1.0092 at 25oCfor H in water: lv = Rl/Rv = 1.074 at 25oC General

8、Rules for ab T: is T dependent, eg. = f (T). Isotope fractionation factors are greater at lower temperatures (vibration frequency gos to up limit)Reduced- oxidised: Light isotopes are enriched in reduced species and heavy isotopes are enriched in oxidised species. S Biogenic: Light isotopes are enri

9、ched in biogenic compounds, S &CExample: spl = (Rspl - Rstd)/Rstd x 1000 e.g for O: 18Ospl = Rspl-Rstd/R std x 103 Isotope Valuethe isotope to express a samples isotope compositionThe data in Table 17.1 indicate that 18O/16O ratio of average terrestrial is 0.200/99.762 = 0.00200 and that D/H ration

10、is 0.00015. Because it is difficult to measure small differences in such small ratios, the isotope composition of H, O, C and S are expressed as the per mille difference of the isotope ratios of a sample(spl) and a standard(std). 18Ospl = (18O/16O)spl - (18O/16O)std/(18O/16O) std x 103 34Sspl = (34S

11、/32S)spl-(34S/32S)std/(34S/32S) std x 103 e.g for S: 34Sspl = Rspl-Rstd/R std x 103 Positive values indicate that the sample is enriched in heavy isotopes relative to standard or depleted in light. Negative values indicate that the sample is depleted in heavy isotopes relative to standard or enriche

12、d in light. values express the deviation of Rspl from Rstd in , 18Ospl = (18O/16O)spl - (18O/16O)std/(18O/16O) std x 103 Again: spl = (Rspl - Rstd)/Rstd x 1000 Stable Isotope StandardsH, O: Standard Mean Ocean Water (SMOW) by Craig (1961).SMOW: D/H=0.0001558; 18O/16O=0.0020052 C, O: Belemnite from t

13、he Peedee Formation (PDB) in South Carolina (Craig, 1957) PDB: 13C/12C=0.0112372 S: Troilite from the Canon Diablo meteorite (CDT) for sulfur isotopes (Jensen and Nakai, 1963). CDT: 34S/32S=0.0450045 Delta values for the standards? Table 2-15 and Table 2-16For we need the isotope standardsAt the Ear

14、ths surface, coexisting compounds of H, O, C, & S have different isotopic composition (value ).What is the relationship of to ? (also R)We use the isotopevalue to express a samples isotope compositionThe isotope standards are used for reporting isotopic compositions; The isotope compositions of the

15、standards are 0. Summary of Isotope ValueFor phases a and b coexisting in EQ in natural systems, The relationship between values and the isotopic fractionation factor () is given by: For C, N, O & SWhy? Ref. the text p304-305, in detaila - b =ab 103lnab (1) 103ln ab = (A x 106/T2) + B ( TK) (2) (A &

16、 B are Constants) 103lnab ab (A x 106/T2) + B y =A x+B (Let: y= ab ; x = 106/T2) linearityEquation (2) is usually determined experimentally or from natural systems in EQSuperscriptsubscriptab = a bFigure : Temperature dependence of sphalerite-galena sulphur isotope fractionation factor ab = 103lnab

17、Isotopic fractionation factor values Summary for Principles of isotopic fractionation 103lnab = (A x 106/T2) + B (A & B are Constants) 103lnab ab (A x 106/T2) + Ba - b =ab 103lnab Oxygen has 3 isotopes: 16O, 17O and 18O and their abundances are 99.756%, 0.039%, 0.205% respectively. Because 17O is le

18、ss abundant and closer in mass to the dominant oxygen isotope 16O, Most measurements of oxygen isotopes are concerned with the ratio 18O/16O. 2 Oxygen and hydrogen isotopes Hydrogen has 2 isotopes: 1H and D and their abundances are 99.985 % and 0.015%, respectively. Variations in isotopic compositio

19、n of O and H caused mainly by: 1) Evaporation and condensation 2) Water-mineral interaction 3) Mixing of different type of waterCharacters:1) 18O & D of seawater is 0 18O & D for meteoric waters vary because of fractionation during evaporation and condensation .Rayleigh fractionation: Evaporation: v

20、apour depleted in D & 18O Condensation: liquid enriched in D & 18OFigure 2 O and H isotopes in the hydrosphereFigure 17.2 Example of Rayleigh fractionation Figure 2Atmospheric vapour has values more negative than atmospheric precipitation values of atmospheric vapour and precipitation become more ne

21、gative from coast to inland because atmospheric vapour and precipitation are derived from the evaporation of continental water which is already depleted with respect to heavy isotope values is lower in polar regions than equatorial regions values of vapour & precipitation correlate with latitude bec

22、ause fractionation increases with decreasing T Figure D and 18O Since H and O occur together in water molecules and since both experience the same sequence of events during the migration of air masses, the D and 18O values of meteoric water are strongly correlated and satisfy an empirical equationkn

23、ow as the meteoric-water-line (MWL): D=8 18O + 10 (Craig, 1961) But, each local area has its own meteoric water line (LMWL), which differs from the global average.Figure 4 (MWL) Site (north and east of Yucca Mountain) has higher Figure 1 Plot of D vs 18O for ground waters of the Ash Meadows and Alka

24、li Flat/Furnace Creek (Alk./Furn.) flow systems. surface waters and the meteoric water line (“MWL) of Craig (1961). “LMWL is the local meteoric water line. Analytical uncertainty is 0.2 for 18O and 2.5 for D.See Figure (“MWL) Meteoric water: derived from rain, snow, rivers, lakes, sea, percolates th

25、rough pore spaces in rocks and displaces interstitial waterConnate water: deposited with sediments, and is out of contact with atmosphere from the time of deposition. Seawater trapped in pore spaces for marine sedimentsDiagenetic water: released from solid phases as a result of mineral reactions dur

26、ing diagenesis; e.g., gypsum to anhydrite, smectite to illite.Formation water exists in layers of sedimentary rock prior to drilling, regardless of originBrine: water with salinity exceeding that of seawaterFigure5Underground water typesIsotope reequilibration of wate/rock (minerals) interactionOxyg

27、en isotope composition of minerals (SMOW)MineralHydrogenOxygenMontmorillonite0.941.027Kaolinite0.971.027Glauconite0.931.026Illite-1.0236Gibbsite0.9841.018Table 17.2 Isotope fractionation Factors for H and O between Clay Minerals-Water at Eath-Surface Temperature Figure 17.3, 17.4Oxygen isotope compo

28、sition of mineralsFractionation factor (mw) of Mineral water is the function of TTable 2-15 and Table 2-16Magmatic waterMetamorphic waterWater derived from the meteoric-waterhydrothermal water (W/R interaction & waters mixing )Figure5, Figure 6Mixing with the water with different H & O isotope reser

29、voirCarbon has 3 isotopes: 12C 98.9%, 13C 1.1%, negligible 14CCarbon is the principal element in the biosphere, but it occurs also in the lithosphere, hydrosphere, and atmosphere of the Earth.Fractionated by : organic & inorganic reactionsMany of these are not equilibrium processes. Values of 13C/12

30、C range from +4 (freshwater limestone) to 31 (petroleum).Biogenic organic C is lighter than inorganic C, due to fractionation during photosynthesis and during other biological processes3 Carbon IsotopesTable 2-15 and Table 2-16Sources of C in groundwater:1) dissolution of carbonate rocks (introducti

31、on of heavy C relative to PDB)2) oxidation of organic matter (introduction of light C in CO2)3) CO2 from soil gas (introduction of light C)C may be lost from water by the precipitation of carbonate minerals or loss of CO2 gasSulfur has four stable isotopes 32S, 33S, 34S, 36S32S (95.0 %) and 34S (4.2

32、%) are the most abundant. Variations in isotopic composition of S caused by: 1) anaerobic bacteria: (a) reduction of SO42- to H2S, H2S is enriched in 32S/34S (b) oxidation of S2- to SO42-, SO42- enriched in 34S/32S 2) isotope exchange reactions: 34S concentrates in species with highest S oxidation s

33、tate (-2, 0, +4, +6) or greatest bond strength 3) Redox reactions can produce large fractionations. They may be inorganically or biologically mediated 4 Sulfur IsotopesFigure 20.1S isotope composition in geological materials: 1) It is generally assumed that primordial earth sulfur and the earths man

34、tle also have a 32S/34S value of 22.22 ( 34S/32S=0). 2) Sulfides from igneous rocks show a narrow range of values, with most slightly enriched in 34S. 3) Other types of material, particularly sedimentary sulfates and sulfides from hydrothermal ore deposits, show wide variations in isotopic compositi

35、on. Such variations probably reflect the variety of processes and geologic conditions involved in forming these sulfides. Table 2-19 General Range of 32S/34S Ratios and of 34S/32S is the fractionation factor for S partitioned between SO2 and melt. (Fig. 28.4)When 1, 34S is partitioned into SO2 and t

36、he melt becomes depleted, 34S is negative.When 1, the melt is enriched in 34S, 34S is positive The sign of depends on whether S in the melt is oxidized (SO42-) or reduced (S2-)Figure 28.4Example for S fractionation However, S-isotope variations are complex and large ranges in 34S are not necessarily

37、 well understood.Equilibrium fractionation is generally inorganic whereas kinetic fractionation is generally bacterial.Total S decreases with depth because SO4-2 is more soluble than S-2, 34S increases with depth for both SO4-2 and S-2Near surface: SO4-2 is bacterially reduced to S-2, sulphate is en

38、riched in 34S.With burial: more sulphate is reduced to sulphide but as source sulphate was enriched in 34S, S-2 is enriched in 34S relative to shallow sediments Figure 28.15 Isotope applicatoin ba 103lnba = (A x 106/T2) + B ( TK) for H, O & S If EQ has been reached, S, O, and H isotopes can be used

39、for geothermometry a - b =ab 103lnab Isotope geothermometryab = a bFigure : Temperature dependence of sphalerite-galena sulphur isotope fractionation factor ab 103lnab ba 103lnba = (A x 106/T2) + B ( TK) 34S values of pairs of coexisting sulphide minerals increase with decreasing T (Table 17.5)18O v

40、alues of pairs of coexisting quartz-other minerals increase with decreasing T (Fig. 2.19)- Global changes in w: During the last few million years, the earth has experienced dramatic changes in global climate between glacial and interglacial periods, resulting in the waxing and waning of the large ic

41、e caps on the North American and Eurasian continent. Since the light isotope 16O is preferentially vaporized, freshwater and ice are isotopically lighter than seawater . During ice ages, large amounts of freshwater were locked in the polar ice caps, resulting in a drop in sea level of about 130m. Be

42、cause the 130m of water that have been removed from the ocean were isotopically light, the seawater remaining in ocean basins duringglacial ages was isotopically heavy, i.e. enriched in 18O compared to the seawater present in the oceans during interglacial periods. This effect produced heavy w value

43、s during glacial periods reflected in the heavy 18O recorded by foraminifera during the “even-numbered isotopic (orglacial) stages, and light w values during interglacial periods recorded during the “oddnumbered isotopic stages (Fig. Global changes ).Global climate changesDuring ice ages, 130m of wa

44、ter that have been removed from the ocean to form the ice sheet which were isotopically light, and the ocean is enriched in heavy O and H isotopes. During interglacial periods. the ice is back to the ocean, which result in it enriched in light isotopes 16O and 1H . 谢 谢！畷愛扷椪閭更硽栘趖揣陯螴漌撵爮祌蟱敦靜鵝強笵僙龡厁濣潓挒潏显

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