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FE 537
Oregon State University
CatchmentCatchment ScaleScale(Isotope Hydrology (Isotope Hydrology
PrimerPrimer Aside)Aside)
FE 537
Oregon State University
Primer HistoryPrimer History
Last 5 years:For IAEA in South Africa and China
CSIRO Catchment Modeling School, MelbourneDept. of Civil Engineering, U. Western Australia
Dept,. of Physical Geography and Quaternary Studies, Stockholm UniversityDept. of Civil and Env. Engineering, Stuttgart University
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AcknowledgementsAcknowledgements
Carol Kendall, USGS Menlo Carol Kendall, USGS Menlo ParkParkDon Siegel, Syracuse Don Siegel, Syracuse
UniversityUniversityIAEA Isotope Hydrology IAEA Isotope Hydrology
SectionSection
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Tracing the hydrologic cycleTracing the hydrologic cycle
Rainfall and where it goesRainfall and where it goesLake water and its evaporation, inflows and Lake water and its evaporation, inflows and
outflowsoutflowsWater residence time, transit time, water ageWater residence time, transit time, water ageComposition of Composition of streamflowstreamflowNew ways to calibrate and test hydrologic New ways to calibrate and test hydrologic
modelsmodelsA very different data source to help structure, test and A very different data source to help structure, test and
calibrate modelscalibrate modelsA way to figure out where trees (and other A way to figure out where trees (and other
vegetation) get their watervegetation) get their water
Hooper (2001)
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Potential usefulness to local problemsPotential usefulness to local problems
Determining components of flowto the Swedish Rivers
Quantifying “success” inLand rehabilitation
Lake/reservoir evaporation
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Oregon State University
A Useful Quote...A Useful Quote...
““The role of isotopes is like the role of the The role of isotopes is like the role of the aliens in the famous scialiens in the famous sci--fi movie fi movie ““The The Invasion of the Body SnatchersInvasion of the Body Snatchers””. Isotopes . Isotopes and trace elements have pervaded the and trace elements have pervaded the entire discipline (geochemistry) and they entire discipline (geochemistry) and they are us now!are us now!””
K. K. TurekianTurekian, Editor, EditorGeochimicaGeochimica et et CosmochimicaCosmochimica ActaActa…….the same could now be said .the same could now be said for Hydrology!for Hydrology!
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A recent GEOREF Search A recent GEOREF Search by by AgarwaalAgarwaal (2002 HP) (2002 HP)
19651965--19701970: 650 papers : 650 papers using isotope tracers using isotope tracers 19951995--20002000 over 6500 over 6500
papers using isotope tracers papers using isotope tracers in groundwater studies in groundwater studies alonealone
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References References -- TextbooksTextbooks
Clark, I. and Fritz, P. 1998. Environmental Clark, I. and Fritz, P. 1998. Environmental Isotopes in Hydrogeology. Lewis Publisher Isotopes in Hydrogeology. Lewis Publisher (w/ web(w/ web--link)link)Kendall, C. and McDonnell, J.J. (eds.), Kendall, C. and McDonnell, J.J. (eds.), 1998. Isotope Tracers in Catchment 1998. Isotope Tracers in Catchment Hydrology. Elsevier (w/ webHydrology. Elsevier (w/ web--link)link)FerronskyFerronsky, V. I. And , V. I. And PolyakovPolyakov, V. A., 1982 , V. A., 1982 . Environmental Isotopes in the . Environmental Isotopes in the Hydrosphere. Wiley & Sons.Hydrosphere. Wiley & Sons.MazorMazor, E., 1991. Applied Chemical and , E., 1991. Applied Chemical and Isotopic Groundwater Hydrology. Open Isotopic Groundwater Hydrology. Open University PressUniversity Press
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The classicThe classic
Rodhe, A., 1987. The origin of streamwatertraced by oxygen-18. Ph.D. thesis, Uppsala Univ., Dept Phys. Geogr., Div. Hydrol., Report Series A 41, 290 p. + Appendix 73 p.
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Isotope Tracers in Isotope Tracers in CatchmentCatchmentHydrologyHydrology
“…“…Isotope tracers have been Isotope tracers have been among the most useful tools for among the most useful tools for understanding:understanding:
--GroundwaterGroundwater--surface water surface water interactionsinteractions--StreamflowStreamflow generationgeneration--FlowpathFlowpath dynamicsdynamics””
Kendall, C. and J. McDonnell Kendall, C. and J. McDonnell edseds (1998). (1998). Isotope Tracers in Isotope Tracers in
CatchmentCatchment HydrologyHydrology, , Elsevier Science Publishers, Elsevier Science Publishers,
817p 817p
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Oregon State University
References References -- InternetInternet
USGS Isotope Interest Group Home Page USGS Isotope Interest Group Home Page (http://(http://wwwcamnl.wr.usgs.gov/isoigwwwcamnl.wr.usgs.gov/isoig/)/)ISOGEOCHEM Web Page with an EISOGEOCHEM Web Page with an E--mail mail Discussion List in Stable Isotope Discussion List in Stable Isotope Geochemistry Geochemistry ((http://geology.uvm.edu/geowww/isogehttp://geology.uvm.edu/geowww/isogeochem.htmlochem.html))IAEA web page and online teaching IAEA web page and online teaching materialsmaterials
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Head of IAEA Isotope HydrologyHead of IAEA Isotope Hydrology
See Summer 2005 Science Times article in NYT by Pradeep and his IAEA group
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Isotopes in HydrologyIsotopes in Hydrology
Environmental IsotopesEnvironmental Isotopes
STABLESTABLE
22H/HH/H
RADIOACTIVERADIOACTIVE
CosmogenicCosmogenic PrimordialPrimordial Fallout ProductsFallout Products
Daughter ProductsDaughter Products
1818O/O/1616OO 1313C/C/1212CC
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The Isotopes of General Hydrologic The Isotopes of General Hydrologic Interest in HydrologyInterest in Hydrology
OxygenOxygen--18 and 18 and OxygenOxygen--1616HydrogenHydrogen--2 2
(Deuterium) and H(Deuterium) and H--11Tritium (HTritium (H--3)3)
(From Don Siegel, SU)
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Isotope hydrologyIsotope hydrology
T
Kendall (2001)
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Isotope biogeochemistryIsotope biogeochemistry
T
Kendall (2001)
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Applications of Isotopes as Tracers:Applications of Isotopes as Tracers:
1.1. Tracers of the water itself (D, O, T)Tracers of the water itself (D, O, T)= Isotope Hydrology= Isotope Hydrology
2.2. Tracers of solutes or reactions (C, N, S)Tracers of solutes or reactions (C, N, S)= Isotope Biogeochemistry= Isotope Biogeochemistry
This usage is This usage is NOTNOT universal, but is very universal, but is very useful (conceptually)useful (conceptually)
Kendall (2001)
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Isotopes of water = history of waterIsotopes of water = history of water
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FundamentalsFundamentals
Isotopes are atoms of the same element Isotopes are atoms of the same element that have different numbers of neutrons.that have different numbers of neutrons.1818O and O and 22H are constituent part of natural H are constituent part of natural water moleculeswater molecules——they they areare the water the water molecule molecule Applied naturally during precipitation Applied naturally during precipitation
eventseventsConservative at ambient temperaturesConservative at ambient temperaturesOnly mixing can alter concentrationOnly mixing can alter concentration
Kendall (2001)
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n
3He
1H
15N
10B
17O
6Li
14C
14N
16O
12C
9Be
2H
7Li
4He
10Be
13C
number of neutrons N
number of protons Z
3H
11B
18O
Isotopes are atoms of the same element that have
different numbers of neutrons.
C. Kendall, USGS
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Stable Isotopes Stable Isotopes 22H and H and 1818OO
Relative amounts in earthRelative amounts in earth’’s hydrosphere: s hydrosphere: 1818O = 0.2%, O = 0.2%, 22H H = 0.015%= 0.015%1818O and O and 22H content of water changes only through H content of water changes only through fractionation associated with phase exchange processes fractionation associated with phase exchange processes (except for saline waters)(except for saline waters)Conservative behavior Conservative behavior -- once isotopes become part of once isotopes become part of water molecule, they change only through mixingwater molecule, they change only through mixing
0.20%0.20%101088881818OO99.76%99.76%8888881616OO
AbundanceAbundanceNeutronsNeutronsProtonsProtonsElectronsElectronsNameName
C. Kendall, USGS
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Delta Isotope =(i.e. δ in o/oo )
Ratio sample Ratio standard
Ratio standard
x 1000
A DELTA O-18 = -10 o/oo means there is 10 parts per thousand less O-18 in the sample than in the standard, standard "mean" oceanic water (SMOW)
Note ratio is 18O/16O (or 2H/1H for deuterium)
Parts Per Mil Nomenclature
-
(From Don Siegel, SU)
…in other words……
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Fractionation
Some atoms of elements can have different weights. light
heavy
Fractionation—sorting the “light” from the "heavy" versions of the elements.
Fractionation
(From Don Siegel, SU)
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Fractionation Effects Associated with Phase Fractionation Effects Associated with Phase Changes of HChanges of H22OO
EvaporationEvaporation –– vapor that forms is lighter vapor that forms is lighter than surrounding waterthan surrounding waterCondensation Condensation –– liquid that forms is heavier liquid that forms is heavier than surrounding vaporthan surrounding vaporSo, precipitation selectively removes So, precipitation selectively removes 1818O O and and 22H from the vapor phaseH from the vapor phase
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In other wordsIn other words……
University of Arizona
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Fractionation in Fractionation in δδ1818O and O and δδDDduring the hydrologic cycleduring the hydrologic cycle
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Commonly Used Terms:Commonly Used Terms:
heavy vs. light isotopesheavy vs. light isotopesthe the ““heavyheavy”” isotope is the one with more neutrons; it is isotope is the one with more neutrons; it is also generally the less abundant isotope.also generally the less abundant isotope.
enriched vs. depletedenriched vs. depletedremember to state remember to state whatwhat isotope is in short supply:isotope is in short supply:
does does ““enriched sulfateenriched sulfate”” mean that:mean that:the sulfate is enriched in heavy sulfur the sulfate is enriched in heavy sulfur ORORthe sulfate is enriched in light sulfur?the sulfate is enriched in light sulfur?
positive vs. negativepositive vs. negative--10 10 00//0000 is more positive than is more positive than ––20 20 00//0000
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Oregon State University
Fractionation Effects on Fractionation Effects on 1818O and O and 22HH
Equilibrium fractionationEquilibrium fractionation –– vapor pressure of water vapor pressure of water containing light isotopes > water containing heavy containing light isotopes > water containing heavy isotopes, therefore vapor is enriched in light isotopesisotopes, therefore vapor is enriched in light isotopes
E.g. at 100% humidity when the air is still and the E.g. at 100% humidity when the air is still and the system is almost chemically closedsystem is almost chemically closed
Kinetic fractionationKinetic fractionation –– rapid phase changes increase rapid phase changes increase fractionation because light isotopes diffuse more rapidly fractionation because light isotopes diffuse more rapidly than heavy onesthan heavy ones
E.g. this is more typical in hydrological systems where E.g. this is more typical in hydrological systems where the system is out of chemical equilibrium (<100% the system is out of chemical equilibrium (<100% humidity) or the products become slightly separated humidity) or the products become slightly separated from the reactants (i.e. from the reactants (i.e. thth resultant vapor is blown resultant vapor is blown downwind).downwind).
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http://ww
wrcam
nl.wr.usgs.gov/isoig/isopubs/itchfig2-3.htm
l
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Example of a Rainfall Event:Example of a Rainfall Event:Fractionation in Fractionation in δδ1818O during the hydrologic cycleO during the hydrologic cycle
Kendall (2001)
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Fractionation Effects Associated with Phase Fractionation Effects Associated with Phase Changes of HChanges of H22O O ---- summarysummary
EvaporationEvaporation –– vapor that forms is lighter vapor that forms is lighter than surrounding waterthan surrounding waterCondensation Condensation –– liquid that forms is heavier liquid that forms is heavier than surrounding vaporthan surrounding vaporSo, precipitation selectively removes So, precipitation selectively removes 1818O O and and 22H from the vapor phaseH from the vapor phase
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Fractionation in the hydrological
cycle
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Some Some ““EffectsEffects””
Amount Effect:Amount Effect:The more rainfall, the The more rainfall, the
more depleted the rainmore depleted the rainApparent Temperature Apparent Temperature Effect:Effect:
Approximately 0.5Approximately 0.5%%0 0 for every for every °°C for oxygenC for oxygenEvaporation:Evaporation:
As rain falls through As rain falls through dry air, it may evaporate, dry air, it may evaporate, resulting in heavier rainresulting in heavier rain
Kendall (2001)
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Some Some ““EffectsEffects””
Altitude effect:Altitude effect:On the windward (not On the windward (not
lee) side of a lee) side of a mountain mountain the rain gets lighter with the rain gets lighter with
increasing altitudeincreasing altitudeGRADIENTSGRADIENTS
1818O: O: --0.15 to 0.15 to ––0.5%0/100 0.5%0/100 metersmeters
D: D: --1.5 to 4%0/100 meters1.5 to 4%0/100 meters
Continental Effect:Continental Effect:Delta values decrease Delta values decrease
inlandinlandKendall (2001)
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Geography and Seasonality of Geography and Seasonality of 1818O and O and 22H H Content of PrecipitationContent of Precipitation
Precipitation becomes lighter as air mass Precipitation becomes lighter as air mass moves inlandmoves inlandPrecipitation becomes lighter with Precipitation becomes lighter with increasing elevation increasing elevation –– orographicorographic effecteffectPrecipitation becomes lighter towards the Precipitation becomes lighter towards the poles and is lighter in winter than summerpoles and is lighter in winter than summer
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Altitude EffectAltitude Effect
Source: IAEA
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Amount effectAmount effect
Source: IAEA
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Temperature EffectTemperature Effect
Source: IAEA
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Continental effectContinental effect
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Continental EffectContinental Effect
Mean δO18 of the Columbia Watershed vs distanz from the West Coast
-18
-17
-16
-15
-14
-13
-12
-11
-10
-9
-8
0 100 200 300 400 500 600 700 800 900 1000 1100Distanz from the West Coast [km]
Mea
n δ
O18
Errorbars = 2x Stdev O18
Starke, McDonnell and Kendall, in prep
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Elevation EffectElevation Effect
Mean δO18 of Columbia Watershed vs elevation
-20
-18
-16
-14
-12
-10
-8
-6
0 200 400 600 800 1000 1200 1400 1600 1800
elevation [m]
mea
n δ
O18
Errorbars = 2x Stdev
Starke, McDonnell and Kendall, in prep
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Air Temperature “Effect”
0- 10- 20- 30- 40
20
- 20
- 40
Delta O-18
0
Northern Sweden
AirTemp.(C)
Vienna
(after Don Siegel, SU)
Athens
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Latitudinal Latitudinal ControlsControls
NorthernNorthernHemisphereHemisphere
IAEA
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Latitudinal Controls Southern Latitudinal Controls Southern HemisphereHemisphere
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Temperature EffectsTemperature Effects
IAEA
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-40.00
-30.00
-20.00
-10.00
0.00
J F M A M J J A S O N D
Spring SummerWinter Fall
Waco, Texas
Chicago, Illinois
Barrow, Alaska
Lower Warmer Latitude
Higher, Colder Latitude
δ18
O (o
/ oo)
Months
Latitudinal Effect
(From Don Siegel, SU)
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Some spatial data
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summary
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Why are 18-O and D so similar?
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Global Meteoric Water Line
0- 10- 20- 30- 40
0
- 100
- 200
- 300
δ D = 8 δ18 O + 10
δ18 O
δD
(From Don Siegel, SU)
…because they are related
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dDdD = 8 d18O + 10 (= 8 d18O + 10 (Factoids)Factoids)The slope is 8 (actually, different data sets give slightly diffThe slope is 8 (actually, different data sets give slightly different values) erent values) because this is approximately the value produced by equilibrium because this is approximately the value produced by equilibrium RayleighRayleigh condensation of rain at about 100% humidity. condensation of rain at about 100% humidity. The value of 8 is also close to the ratio of the equilibrium fraThe value of 8 is also close to the ratio of the equilibrium fractionation ctionation factors for H and O isotopes at 25factors for H and O isotopes at 25--3030ººC. At equilibrium, the d values of C. At equilibrium, the d values of the rain and the vapor both plot along the MWL, but separated bythe rain and the vapor both plot along the MWL, but separated by the the 18O and 2H enrichment values corresponding to the temperature of18O and 2H enrichment values corresponding to the temperature of the the cloud base where rainout occurred. cloud base where rainout occurred. The yThe y--intercept value of 10 in the GMWL equation is called the intercept value of 10 in the GMWL equation is called the deuterium excessdeuterium excess (or d(or d--excess, or d parameter) value for this equation. excess, or d parameter) value for this equation. The term only applies to the calculated yThe term only applies to the calculated y--intercept for sets of meteoric intercept for sets of meteoric data "fitted" to a slope of 8; typical ddata "fitted" to a slope of 8; typical d--excess values range from 0 to 20excess values range from 0 to 20The fact that the intercept of the GMWL is 10 instead of 0 meansThe fact that the intercept of the GMWL is 10 instead of 0 means that that the GMWL does not intersect d18O = the GMWL does not intersect d18O = dDdD = 0, which is the composition = 0, which is the composition of average ocean water (VSMOW). of average ocean water (VSMOW). The GMWL does not intersect the composition of the ocean, the soThe GMWL does not intersect the composition of the ocean, the source urce of most of the water vapor that produces rain, because of the 10of most of the water vapor that produces rain, because of the 10‰‰kinetic enrichment in D of vapor evaporating from the ocean at akinetic enrichment in D of vapor evaporating from the ocean at an n average humidity of 85%. average humidity of 85%.
http://wwwrcamnl.wr.usgs.gov/isoig/isopubs/itchch2.html#2.3
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IAEA Stations in GNIPIAEA Stations in GNIP
IAEA
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IAEA (2001). GNIP Maps and Animations, International Atomic Energy Agency, Vienna.Accessible at http://isohis.iaea.org
GloballyGlobally
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Global Atmospheric Circulation System Distills Water Isotopes
equator“Heavier”WaterRemains
”Light“water vapor
HeavierRain Falls
Even lighterwater vapor
CondensationEvaporation
Cold
HotHot
Raleigh Distillation
Solar Heat
(From Don Siegel, SU)
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IAEA (2001). GNIP Maps and Animations, International Atomic Energy Agency, Vienna.Accessible at http://isohis.iaea.org
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IAEA (2001). GNIP Maps and Animations, International Atomic Energy Agency, Vienna.
Accessible at http://isohis.iaea.org
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Precipitation in midPrecipitation in mid--latitude regionslatitude regions
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The The δδDD and and δδ18180 0 taken from the GNIP taken from the GNIP database were amountdatabase were amount--weighted weighted
according to:according to:
where Pi and where Pi and δδDDii are the monthly are the monthly precipitation amount (mm) and the precipitation amount (mm) and the
isotopic composition (isotopic composition (‰‰), respectively, ), respectively, and n is the number of months.and n is the number of months.
iiiw PPxn
i
n
i 11 ==ΣΣ= δδ
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Characteristics of Characteristics of δδDD and and δδ18180 of 0 of Precipitation:Precipitation:
Consistent Consistent averageaverage compositions over time and compositions over time and space.space.Annual cycle of compositional changesAnnual cycle of compositional changes——heavy heavy in summer and light in winter.in summer and light in winter.Large variations Large variations amongamong storms.storms.Often considerable variability within storms.Often considerable variability within storms.Snow often plots along lines of higher Snow often plots along lines of higher dd--exessexessthan rain.than rain.Storms derived from different storms tracks Storms derived from different storms tracks may have consistently different meteoric water may have consistently different meteoric water lines.lines.
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Database of HDatabase of H-- and Oand O--IsotopesIsotopes
•• Global Network for Isotopes Global Network for Isotopes in Precipitationin Precipitation
http://www.iaea.or.at/prograhttp://www.iaea.or.at/programs/ri/gnip/gnipmain.htmms/ri/gnip/gnipmain.htm
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Now, back to the MWLNow, back to the MWL
IAEA
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This knowledge can be very powerfulThis knowledge can be very powerfule.g. Lake e.g. Lake ChalaChala in Kenyain Kenya
People wanted to use the Lake water for People wanted to use the Lake water for irrigation, but wanted to make sure that irrigation, but wanted to make sure that using lake water would have no adverse using lake water would have no adverse effect on the discharge of nearby springs effect on the discharge of nearby springs whose waters were already being utilized.whose waters were already being utilized.
(i.e., they didn(i.e., they didn’’t want to t want to ““rob Peter to pay rob Peter to pay PaulPaul””))
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Can they tap lake water without Can they tap lake water without affecting spring flow?affecting spring flow?
Carol Kendall, USGS
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MWL at a single site MWL at a single site –– Woods Lake USAWoods Lake USA
Doug Burns, USGS
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Groundwater Isotopes Same as thatfor Average Precipitation
0- 10- 20- 30- 40
0
- 100
- 200
- 300
Groundwater Sample
Well Mixed System--HighDispersion
Average Precipitation
δ18 O
δD
(From Don Siegel, SU)
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0- 10- 20- 30- 40
0
- 100
- 200
- 300
Groundwater SampleAverage Precipitation
SummerRecharge
WinterRecharge
Pleistocene GlacialMeltwater!!
"Plug Flow" -Low Dispersion
Groundwater Isotopes Different thanthat for Average Precipitation
δ18 O
δD
(From Don Siegel, SU)
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-20
-15
-10
-5
0
δ 18
O (p
er m
il SM
OW
)
Jan-93 Jan-94 Jan-95 Jan-96-10
0
10
20
air t
empe
ratu
re (°
C)
Neversink watershed, 1993 - 1996
Vitvar, 2000
Seasonal Variation in Seasonal Variation in 1818O of PrecipitationO of Precipitation
Vitvar, SUNY-ESF
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What you might see in the SpringWhat you might see in the Spring
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Kendall (2001)
Individual Rainfall Events