NATURAL WATERS xygen & ydrogen: Ideal, double isotopic tracer system 18, D, T Conservative tracers Intrinsic to the molecule δd vs. δ 18 plot Utility to ydrology: rigin and Age of Water Tracing of Water, Ions and Contaminants Paleotemperatures Elucidate Physical Processes
YDRGEN ISTPES 1.0079 Protium 1 1.0078503 99.985 at. % Deuterium.01410178 0.015 at. % Tritium 3 3.01605 1:10 18 alf life 1.3 yr
XYGEN ISTPES 15.9994 8p+8n 8p+9n 8p+10n xygen-16 16 15.9949146 99.76 at. % xygen-17 17 16.9991314 0.04 at. % xygen-18 18 17.999160 0.00 at. %
ELEMENT ISTPE ATMIC WEIGT amu ABUNDANCE atom % YDRGEN z = 1 1.0079 1 Protium 1.00785 99.985 Deuterium.01410 0.015 3 Tritium 3.0160493 ~10-16 (T 1/ =1.6 a) CARBN z = 6 1.011 1 C 1.00000 98.90 13 C 13.00335 1.10 14 C 14.0034 ~10-10 (T 1/ = 5730 a) XYGEN z = 8 15.9994 16 15.994915 99.76 17 16.999131 0.04 18 17.999160 0.0
Isotopic Molecules & Material Balance What causes isotopes to vary in abundance, or "fractionate"? is a mixture of 9 isotopic species = isotopologues 16 D 16 DD 16 17 D 17 DD 17 18 D 18 DD 18 Properties of these molecules are not identical. Thermodynamic differences exist between species.
STABLE ISTPLGUES F WATER 16 17 18 1 16 1 17 1 18 18.0106 amu Ab= 997,300 ppm P =3.756 torr 19.0148 amu Ab=400 ppm P =3.645 torr 0.0148 amu Ab=,000 ppm P =3.535 torr 16 17 18 1 16 19.0168 amu Ab=300 ppm P =.01 torr 1 17 0.011 amu Ab=.1 ppm 1 18 1.011 amu Ab= 0.6 ppm 16 17 18 16 17 18 0.031 amu Ab= 0.0 ppm P =0.54 torr 1.074 amu Ab=10-5 ppm.074 amu Ab.=5*10-5 ppm Criss & Farquharr 008
PRPERTIES F RDINARY AND EAVY WATER PRPERTY D Molar Mass 18.0158 0.0748 g!v @ 5 C 10.519 10.851 kcal/mole Vapor Pressure @ 5 C 3.756 0.544 torr Melting Point 0.00 3.8 C Boiling Point 100.00 101.4 C Critical Temperature 373.99 370.74 C Density @ 5 C 0.9970 1.01044 Viscosity @ 5 C 8.93 11.0 millipoise Disassociation Const. 1.0 x 10-14 1.95 x 10-15 Latent eat of Fusion 1436.3 ±1 @ 0 C 1515±10 cal/mole @ 3.8 C Toxicity None Poisonous
Isotopic Ratio: R = D/ 13 C/ 1 C 18 / 16 etc. Delta Values:! =1000 R x! R std R std "D = 1000 ( D/ ) x # ( D/ ) std ( D/ ) std " 18 = 1000 ( 18 / 16 ) # 18 / 16 x ( 18 / 16 ) std ( ) std Isotopic Fractionation Factor " A#B = R A /R B = 1000 + $A 1000 + $B
Table.3: Selected Isotopic Fractionation Factors Form: eq 1000 ln! A B = c 1 +10 3 c /T + 10 6 c 3 /T Type Phase A Phase B C1 C C3 T K range D/ Water Water vapor 5.61-76.48 4.844 73 to 373 K 1 13 C/ 1 C C3 - C(g) -4.10 9.5 0 78 to 398 13 C/ 1 C Calcite C(g).461-7.6663.988 73 to 773 3 18 / 16 C(g) Water -15.3 16.60 0 73 to 373 4 18 / 16 Calcite Water -.89 0.78 73 to 773 5 18 / 16 Quartz Magnetite 0 0 6.9 873 to 1573 6 34 S/ 3 S Sphalerite Galena 0 0 0.80 53 to 873 7 Ref References: 1) Majoube, 1971; ) Merlivat and Nief, 1967; 3) Majoube, 1970
Table.3: Selected Isotopic Fractionation Factors Form: eq 1000 ln! A B = c 1 +10 3 c /T + 10 6 c 3 /T Type Phase A Phase B C1 C C3 T K range D/ Water Water vapor 5.61-76.48 4.844 73 to 373 K 1 D/ Water Water vapor -100.0 15.013 58 to 73 K 18 / 16 Water Water vapor -.0667-0.4156 1.137 73 to 373 K 1 D/ Ice Water vapor -94.5 16.89 33 to 73 K 18 / 16 Ice Water vapor -8.4 11.839 40 to 73 K 3 Ref References: 1) Majoube, 1971; ) Merlivat & Nief, 1967; 3) Majoube, 1970
1.1 1.1 Water-Water Vapor 1.01 1.01 1.08 Majoube 1.008! D 1.06 1.04! D! 18 extrapolated 1.006 1.004! 18 1.0 1.00 Merlivat 1 C.. C.P. 1 0.98 0.998 0 50 100 150 00 50 300 350 400 T C
Material Balance Relationships Bulk isotope ratio of a multi-component system: R system = n! N j * j = 1 n! N j j= 1
R system = n! N j * j = 1 n = N 1 * + N * * +... + N n n N j! N j j = 1! j= 1 R system = N 1 n! N j j = 1 N 1 * N + N n 1!j= 1 N j N * N +... n R =! X system j R j j = 1 where the Xj are the mole fractions of the reference nuclide of interest, such that: n! j= 1 X j = 1
Simple Binary Mixing R 100:1 R 10:1 5:1 :1 (R 1 +R )/ 1:1 1: 1:5 1:10 R 1 0 0. 0.4 0.6 0.8 1 X 1:100
YDRSPERE 1.36 x 10 9 km 3 = 1.36 x 10 1 liters Seawater 97. % 3.5 wt % salt; very homogeneous covers 70% of the surface, mean depth 3.8 km Icecaps & Glaciers.15 % >75% of fresh water Pleistocene oscillations ± 100 m Groundwater 0.6 % % of all fresh water Lakes, inland seas 0.017% Atmosphere 0.001%! Stream Channels 0.0001%
YDRSPERE 1.36 x 10 9 km 3 = 1.36 x 10 1 liters Seawater 97. % 3.5 wt % salt; very homogeneous covers 70% of the surface, mean depth 3.8 km Icecaps & Glaciers.15 % >75% of fresh water Pleistocene oscillations ± 100 m Groundwater 0.6 % % of all fresh water Lakes, inland seas 0.017% Atmosphere 0.001%! Stream Channels 0.0001% USGS
Typical Values RESERVIR VLUME %!D! 18 cean 97. 0 ± 5 0 ± 1 Icecaps & Glaciers.15-30 ± 10-30 ±15 Groundwater 0.6 Vadose Water -40 ± 70-5 ±15 Dilute Groundwater -50 ± 60-8 ±7 Brines -75 ± 50 0 ±4 Surface Waters 0.017 Freshwater Lakes -50 ± 60-8 ±7 Saline Lakes & Inland Seas -40 ± 60 -± 5 River & Stream Channels -50 ± 60-8 ±7 Atmospheric Water 0.001-150 ± 80-0 ±10 Criss 1999
CEAN: 97. % of hydrosphere Mean depth ~ 3.8 km Volume = 1.37 x 10 9 km 3 SEAWATER: Very uniform, buffered Salinity 35 δ 18 = 0 ± 1 δd = 0 ± 5 Isotopic variations coupled with salinity variations E/P, sea ice Melt icecaps: δ 18 ~ -1 Sr, S Temporal Variations
E-W transect @ ~0 N Craig & Gordon 1965
Craig & Gordon 1965
! 18 0 - -4 ATLANTIC SURFACE WATERS Craig & Gordon 1965 Epstein & MAyeda a 1953 NADW ff Maine Greenland, E. Coast -6-8 -10 North Atlantic ff Bermuda NADW ff Greenland -1 15 0 5 30 35 40 Salinity
METERIC WATER Water that originates as precipitation in the hydrologic cycle Large isotopic variations: Values lowest in cold, high latitude, interior regions Approx Range: δ 18 = +4 to -6 δd = +40 to -500 e.g., SLAP (-55.5, -48)
δ 18 values of Meteoric Waters modified after Taylor 1974
Water Types: METERIC WATER: riginates as precipitation w/i hydrologic cycle Large variations: δ 18 = +4 to -6 δd = +40 to -500 Meteoric Water Line (MWL) δd = 8 δ 18 + 10 Slope: equilibrium effect y-intercept: kinetic effect Deuterium excess = δd - 8 δ 18 Some Local Variation Different water lines Intercept can be higher in low humidity regions, e.g., + for Mediterranean
SMW δd δd = 8 δ 18 + 10 δ 18 Craig 1961
0-100!D = 8! 18 + 10 SMW!D -00-300 -400 SLAP -500-56 -48-40 -3-4 -16-8 0! 18
-30 May 0-3 -40-50 MERAMEC!D -60-70 MISSISSIPPI -80-90 MISSURI -100-1 -11-10 -9-8 -7-6 -5! 18 Criss (1999)
0 Ladue, Missouri -5! 18-10 10-15 -0-5 1995 1996 1997 1998 1999 000 001 00 003 004 005 YEAR 5 0 Seimonthly Precipitation, Inches Criss
SMW δd => Evolved Waters δ 18 Craig 1961