application of stable isotopes in environmental investigations

Application of Isotopes in Environmental Investigations

Application of Isotopes in Environmental Investigations

El Dorado Hills, CA Nevada City, CA Rocklin, CA San Andreas, CA Stockton, CA Reno, NV

Thomas Butler PG, CHG, CEGSenior Hydrogeologist/Geochemist

[email protected]

Thomas Butler PG, CHG, [email protected]

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Adapted from Training Handbook for Disposal of NonAdapted from Training Handbook for Disposal of Non--Designated Waste to Land Systems:Designated Waste to Land Systems:

Design, Operation, and Monitoring. Water Board Training Design, Operation, and Monitoring. Water Board Training Academy, July 2004 Academy, July 2004

Why Isotopes?

Potential Utility at Land Disposal FacilitiesSpatial Variability


3


Adapted from Training Handbook for Disposal of NonAdapted from Training Handbook for Disposal of Non--Designated Waste to Land Systems:Designated Waste to Land Systems:

Design, Operation, and Monitoring. Water Board Training Design, Operation, and Monitoring. Water Board Training Academy, July 2004 Academy, July 2004

WWTF WWTF NotNot Present When Present When GW Samples TakenGW Samples Taken

Why Isotopes?


4


Why Isotopes?


5

Why Isotopes?



6

Outline

What is an isotope?

Why is isotope geochemistry a useful tool in investigating environmental phenomena?

Practical examples….


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FundamentalsIsotope – One of two or more forms of an element that have the same number of protons (atomic number) however a different number of neutrons, and thus a different atomic mass. May be stable or radioactive


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FundamentalsIsotope Ratio:(R) = Heavy/Light

Stable Isotopes Expressed as:δR = (Rsample/Rref. – 1)*1000permil (‰)

From Kendall and McDonnnell, 1998


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Fundamentals

From Clark and Fritz, 1997


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Fundamentals

From Clark and Fritz, 1997

Why are stable isotope useful? – Fingerprinting (source) and Fractionation(changes in the isotopic values)

Fractionation Examples:

H2O –EvaporationNO3 –DenitrificationHydrocarbons –Degradation


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Fundamentals of Isotope Geochemistry

from Clark and Fritz, 1997


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Stable Isotopes of Water


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*from Kendall and McDonnell, 1998


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16



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18

Application

Water Rights Appropriation, Washoe County, Nevada

Application

Water Rights Appropriation, Washoe County, Nevada


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Water Rights AppropriationWashoe County, Nevada

-15.8/-122


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-130

-120

-110

-100

-90

-80

-70

-60

-18 -17 -16 -15 -14 -13 -12 -11 -10 -9 -8 -7 -6

δ18O (PERMIL, VSMOW)

δ2 H (P

ERM

IL, V

SMO

W)

WF-1W3BW-36W5CoyoteBiddleman WellBiddleman SpringWGWSUSGS Ave Truckee RiverUSGS 19USGS 20USGS 21USGS 22USGS 23USGS 24USGS 26USGS 29USGS 30USGS 38USGS 47USGS 51USGS 53Average Local RechargeTRCC-1TRCC-2TRCC-3

Typical of Groundwater Dominated by Precipitation Recharge

USGS Ave. Truckee River Water Recharge


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22



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Application

Salinity Impacts at a Land Disposal Facility, Solano County, California

Application

Salinity Impacts at a Land Disposal Facility, Solano County, California


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Application –Solano County

Sub-Regional


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Application – Solano County

Sub-Regional


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Sub-Regional


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Sub-RegionalButler, 2007


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Sub-Regional


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Local


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PP-3


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Combined Solute and Water Isotope Data Valuable for:

Identifying Regional Mixing Related to Agricultural Water SourcesFingerprinting Salinity Sources (wastewater vs. non-wastewater)Quantification of Regional Salinity trendsIdentification of processes/source influencing compliance wells


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Application

Salinity Impacts at a Land Disposal Facility, Yolo County, California

Application

Salinity Impacts at a Land Disposal Facility, Yolo County, California


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Application –Yolo County


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Application – Yolo County


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Combined Solute and Water Isotope Data Valuable for:

Fingerprinting Salinity Sources at Compliance Wells (percolated pond water vs. background source)Identification of Groundwater/Surface Water Mixing relationshipsQuantification of Chemical Changes in Effluent during Evaporation


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Application

Water Supply Investigation, San Joaquin County, California

Application

Water Supply Investigation, San Joaquin County, California


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Supply Well, San Joaquin County


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-69.2-8.932160ND-72M (Deep)

-77.6-10.6712ND-72M (Shallow)

-77.4-10.6236Park Supply Well

0019400Seawater

δ2H (permil, VSMOW)

δ18O (permil, VSMOW)Chloride (mg/l)Well/Water Source

Isotope data indicates that 89% of water at the ND-72M Deep is river water

This info was then used to model a theoretical Cl concentration = 2140 mg/l

(Very similar to the measured value)


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Application

Land Disposal Facility, Stanislaus County, California

Application

Land Disposal Facility, Stanislaus County, California


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Wastewater Treatment Plant – Conventional Aerated Pond Treatment, San Joaquin County, CA


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‐80

‐70

‐60

‐50

‐40

‐30

‐20

0 500 1000 1500 2000 2500 3000 3500 4000

Chloride (mg/L)

δ2 H (p

ermil, VSM

OW)

MW‐1 MW‐2 MW‐3 MW‐4 MW‐5 A‐Line Irrigation Ditch Effluent Reservoir Influent (composite) Water Supply


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‐80

‐70

‐60

‐50

‐40

‐30

‐20

0 500 1000 1500 2000 2500 3000 3500 4000

Chloride (mg/L)

δ2 H (p

ermil, VSM

OW)

MW‐1 MW‐2 MW‐3 MW‐4MW‐5 A‐Line Irrigation Ditch Effluent ReservoirInfluent (composite) Water Supply Evaporation Model (Closed)

Transpiration of Crops Irrigated with Local Groundwater

Transpiration of Crops Irrigated with Effluent Groundwater


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‐80

‐70

‐60

‐50

‐40

‐30

‐20

0 500 1000 1500 2000 2500 3000 3500 4000

Chloride (mg/L)

δ2 H (p

ermil, VSM

OW)

MW‐1 MW‐2 MW‐3 MW‐4MW‐5 A‐Line Irrigation Ditch Effluent ReservoirInfluent (composite) Water Supply Transpiration/Mixing Model Evaporation Model (Closed)

0%

20%

40%

60%

80%

100%

Transpiration of Crops Irrigated with Local Groundwater

Transpiration of Crops Irrigated with Effluent Groundwater


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Application

Water Supply Investigation, Mono County, California

Application

Water Supply Investigation, Mono County, California


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Hydraulic Connectivity of Well Supply and Surface Water – Mono County, California

Test Well 2Test Well 1

Reversed Creek - Upstream of Ski AreaGull Lake

Ski Area WellSpring Across from Ski Area


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Gull Lake hydraulically up gradient of supply wells and springs.

Are the springs and/or supply wells in hydraulic communication with the Lake?

Will production from the well likely have an impact on lake levels?

What are the sources (or other sources) of water to the supply wells?

Surface Water Monitoring

Potential Production Wells

Existing Production Well

Spring

Location GWE Well 1 7,556 feet Well 2 7,566 feet Gull Lake 7,602 feet


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Test Well 2Test Well 1

Reversed Creek - Upstream of Ski AreaGull Lake

Ski Area WellSpring Across from Ski Area


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-130

-125

-120

-115

-110

-105

-100

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

Chloride (mg/L)

δ2 H (p

erm

il, V

SMO

W)

Gull Lake

Reversed Creek - Upstream of Ski Area

Ski Area Well

Spring-Across from Ski Area

Test Well 1

Test Well 2


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7602 feet

7566 feet

7556 feet


Pumping Tests (Well 1 and Well 2)No response in observation well during pumping test of either Well 1 or Well 2

No response in Spring during Well 1 pumping test

There was a response in the Spring during Well 2 pumping test


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Isotopes and LandfillsSan Francisco Bay Area, California

Isotopes and LandfillsSan Francisco Bay Area, California


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Isotopes and Landfills


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Isotopes and MinesSan Francisco Bay Area, California

Isotopes and MinesSan Francisco Bay Area, California


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Processes Influencing Acid Generation and Metals Transport – Leona Heights Sulfur Mine, Oakland, California


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Exposed waste rock and acid minedrainage (Leona Heights SulfurMine, Oakland, Ca)


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-10

-8

-6

-4

-2

0

2

4

6

8

10

12

14

-16 -14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10

δ 18OWater (permil, VSMOW)

δ18

OSu

lfate

(per

mil,

VSM

OW

)

100%

75%

50%

25%

0%

LH

SM A

lameda C

ounty, Ca

PA C

oal Mines


Pyrite Oxidation:

1. FeS2(s) + 3.5O2 + H2O = Fe2+ + 2SO42- + 2H+ (pH>4)

Fe2+ + 0.25O2 + H+ = Fe3+ + 0.5H2O (Catalyzed by bacteria at pH <4)

3. FeS2(s) + 14Fe3+ + 8H2O = 15Fe2+ + 2SO42- +16H+

Stoichiometric Isotope-Balance Model:

4. δ18OSO4 = XH2O(δ18Ow + εw) + (1 – XH2O)[0.875(δ18Oa + εa) + 0.125(δ18Ow + εw)]

5. XH2O = (δ18OSO4 – 0.125*δ18Ow – 11.5375)/(0.875*δ18Ow – 7.4375)


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0.00

0.50

1.00

1.50

2.00

2.50

4/25/02 0:00 4/25/02 12:00 4/26/02 0:00 4/26/02 12:00 4/27/02 0:00 4/27/02 12:00 4/28/02 0:00

Date/Time Sampled (Pacific Standard Time)

Dis

solv

ed F

erro

us Ir

on M

ass

Flux

(mm

ol/m

in)

0

200

400

600

800

1000

1200

Inso

latio

n (W

/m2 )

Ferrous Iron

Insolation


63


7.10

7.30

7.50

7.70

7.90

8.10

7/3/2002 0:00 7/3/2002 12:00 7/4/2002 0:00 7/4/2002 12:00 7/5/2002 0:00 7/5/2002 12:00 7/6/2002 0:00

Date/Time

pH

0

200

400

600

800

1000

OR

P (m

V) a

nd

Inso

latio

n (W

/m2 )

pH Lake Aliso ORP Lake Aliso Insolation


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6.6 5.6 6.9 6.3 6.9 6.3

198

161

198

181191

161

72

49

6653

6653

0

50

100

150

200

250

7/3/2002 0:00 7/3/2002 12:00 7/4/2002 0:00 7/4/2002 12:00 7/5/2002 0:00 7/5/2002 12:00 7/6/2002 0:00

Date/Time

Mas

s Flu

x (m

g/m

in)

0

200

400

600

800

1000

1200

Inso

latio

n (W

/m2 )

Copper Manganese Zinc Insolation


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Solute Isotopes/Other Tools

http://www.kgs.ku.edu/Publications/pic14/pic14_1.htmlcommons.wikimedia.org/wiki/File:Boric-acid-2D.png

http://etharelkatatney.blogspot.com/2008/06/bitter-pill-to-swallow.html


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Source of Boron

from Hoefs, 2004

WastewaterNonmarine evaporitesBorax/NaBO4 (-1 to +7‰)


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Local


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PP-3


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Nitrate Source



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Pharmaceuticals and PCPs


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Rare Earth Elements

Anthropogenic Gadolinium

Lack of Anthropogenic Gadolinium


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Source of Recharge and Age Dating

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

0 10 20 30 40 50

Temperature (C)

Perc

ent R

elat

ive

Dec

reas

e in

Sol

ubili

ty He

Ne

NO

Ar

Kr

Xe

Typical USAGroundwaterTemperature


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Source of Recharge and Age Dating

Isotope/Compound Decay Product Half Life (yrs)

Issues/Deficiencies

Tritium (3H) Helium-3 (3He) 12.43 Accounting for excess air and crustal sources (6Li + n = 3H + α)

Sulfur Hexafluoride (SF6) NA NA Accounting for excess air and potential local sources

Chlorofluorocarbons (CFCs) NA NA Reduction of the CFCs has resulted in limited uses for recent GW Recharge

Krypton-85 (85Kr) Rubidum-85 (85Rb) 10.76 Large volume of water (~100 L)

Argon-39 (39Ar) Potassium-39 (39K) 256 Large volumes of water(~1000L); specialized analysis

Isotope/Compound Decay Product Half Life (yrs)

Issues/Deficiencies

Tritium (3H) Helium-3 (3He) 12.43 Accounting for excess air and crustal sources (6Li + n = 3H + α)

Sulfur Hexafluoride (SF6) NA NA Accounting for excess air and potential local sources

Chlorofluorocarbons (CFCs) NA NA Reduction of the CFCs has resulted in limited uses for recent GW Recharge

Krypton-85 (85Kr) Rubidum-85 (85Rb) 10.76 Large volume of water (~100 L)

Argon-39 (39Ar) Potassium-39 (39K) 256 Large volumes of water(~1000L); specialized analysis


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Fundamentals of Isotope Geochemistry

from U.S. Geological Fact Sheet 134-99from Clark and Fritz, 1997


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The End….The End….

http://www.youtube.com/watch?v=t5ZFoU0S5iE&NR=1

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