Environmental Isotopes in Hydrology

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What is an Isotope?
An element is defined by the number of protons (Z) in the nucleus The number of neutrons (N) defines the isotope(s) of that element The sum of Z and N gives the atomic weight (A) For an element (E):

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Oxygen
Most oxygen has 8 protons and 8 neutrons, giving a nuclide with 16 atomic mass units: About 0.2% of oxygen has 10 N instead of 8, thus the isotope: Usually written just:
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Stable and Unstable Isotopes?

Variation in the number of N in the nucleus can only vary in a limited range Too few or too many will make the nucleus unstable (a radionuclide) A stable isotope does not decay (it wont spontaneously change Z, N or A) Unstable isotopes will decay and are called radioisotopes (they are radioactive)

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 Over 270 stable nuclides and over 1700 radionuclide's have been identified Only a few isotopes are of practical importance in hydrology

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Mass Spectroscopy

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Environmental Isotopes
Environmental Isotopes are
Naturally occurring Found in abundance Principal elements in hydrological, geological and biological systems Relatively light elements (mass ratio)

H, C, N, O, S,
(advancement and Research)

These isotopes serve as tracers for water, carbon, nutrient and solute cycling
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Advancements and Research

Environmental isotopes are new used to trace not only groundwater provenance, but also recharge processes, subsurface processes, geochemical reactions and reaction rates. Their importance in studies of biogeochemical cycles and soil-water-atmosphere processes is increasingly being recognized, and new applications in contaminant hydrogeology are being made.

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Isotopes in Hydrology
Stable isotopic composition of water is modified by meteoric processes Recharge waters in a particular environment will have a characteristic isotopic signature Signatures serve as a natural tracer for the provenance of groundwater Radioisotopes decay provide a measure of circulation time, and thus groundwater renewability
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Ratios, Deltas () and Permils ()

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Stable Environmental Isotopes

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Environmental Radioisotopes

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Mass Ratio
Hydrogen (H) 1H Deuterium (D) 2H 3H Tritium (T)

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What is fractionation?

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Different Fractionation

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Temperature Effect on Fractionation

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Rainout and Rayleigh Distilation

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Rainout effect on 2H and 18O values

(based on Hoefs 1997 and Coplen et al. 2000).

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Temperature Effect on Precipitation Isotopic Ratio

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The Global Meteoric Water Line (GMWL)

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Isotopic Data
Oxygen-18 Hydrogen-2 Hydrogen-2 vs Oxygen-18 compared to GMWL Carbon-14 dates corrected with Carbon-13

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Oxygen and Hydrogen Isotopes

Oxygen - most abundant element in the earth's crust Hydrogen - very common in biosphere. Oxygen and Hydrogen combine to form water

DUH!
9 isotopic configurations for water 3 isotopic combinations for most all water molecules Isotopic composition different:
sea water polar ice atmospheric water vapor meteoric water

Due to Fractionation

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Oxygen and Hydrogen Isotopes

Stable isotope ratios of (2H/1H) and 18O/16O of water are reported as delta values () expressed as a per mil () deviation from a standard
SMOW (Standard Mean Ocean Water) VSMOW (Vienna SMOW). In carbonates PDB, a standard based on the Peedee Formation, carbonate rock found in South Carolina

O & H are used for determining precipitation sources and evaporation effects. O isotope ratio of solid phases (e.g. carbonate minerals) can record paleo-climate and paleo-hydrologic information O and Hs isotopic composition are used as a hydrosphere tracer

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Average D of Meteoric Water in North America

(modified from Kharaka and Thordsen 1992, and Taylor and Margaritz 1978)

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Evaporation and Relative Humidity (h) Effect on Isotopic Ratio

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Deviation form the GMWL of Different Rivers

http://www.sahra.arizona.edu

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Deviation form the GMWL

http://www.sahra.arizona.edu

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Water Rock Interactions

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Carbon Isotopes
12C

& 13C

12C

& 13C

Help understand food webs and carbon cycling in ecosystems Living matter (i.e., bacteria and plants)
takes up carbon through CO2 in the atmosphere often isotopically selective, generally preferring to break the weaker, light-isotope bonds

13C values can be used to distinguish between C3 and C4 plants

C3 - hot, dry (95% species) C4 - tropical, subtropical (higher 13C content)

13C values are used to understand the biogeochemical reactions controlling alkalinity in watersheds

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Radioactive 14C Isotope

14C

Half life of 5715 years

Age dating of material containing carbon Tracing hydrologic processes, such as groundwater flow and ocean circulation Radiocarbon dating of groundwater Measured in Percent Modern Carbon (pmc)

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14C

Dating Corrections

In groundwater the initial carbon is diluted with calcium carbonate which is dissolved from the sediments

Assume:
Closed system Only DIC All dilution is from carbonate

14

t = 8267 ln

C pmc

q 100

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Carbon 13

13C) (

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13C

vs

18O

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34S

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15N

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15N

vs

18O

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15N

vs

18O

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