dating of young ground water with cfcs, sf6 h, and h/ he: … · 2004-12-22 · dating of young...
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Dating of young ground waterwith CFCs, SF6, 3H, and 3H/3He:Principles and Examples
L.N. Plummer, USGS, Reston, VA
U.S. Geological Survey, Office of Water QualityForensic Hydrology Workshop, Annapolis, MDSeptember 1, 2004
Selected Environmental TracersSelected Environmental Tracers00--50 Year Timescale50 Year Timescale
• 3H , 3H/3He• 85Kr• CFC-11, CFC-12,
CFC-113• SF6
• Event Markers: 3H, 36Cl, 14C
• Age: time elapsed since recharge
tracer1b.grf (JK Böhlke) 4/22/03
CFC-12
3H°
14C
36Cl
85Kr
1940 1950 1960 1970 1980 1990 2000Year
0
50
100
150
200
250
300
350
400
14C
(pm
c) a
nd 3
6 Cl (
atom
s m
-2 y
r-1
x10-
9 )
0
200
400
600
800
1000
1200
1400
3 H (
TU
) a
nd 8
5 Kr
(mB
q m
-3)
and
CFC
's (p
ptv)
and
SF
6 (1
0-2
ppt
v)
-11
-113
3He*
3H(1995)
SF6
Cook and Bohlke, 2000
Why measure environmental tracers in Why measure environmental tracers in ground water?ground water?
• Estimate fractions of young water and the mean age of the young fraction in mixtures.
• Evaluate vulnerability to contamination.
• Estimate recharge rates.• Calibrate models of groundwater
flow.• Estimate rates of geochemical
and microbiological processes. • Date historical records of
contaminant loading to aquifers.• Estimate remediation times.
Approach to “Dating” Young GW
• Collect water samples without contacting air.
• Minimize mixing effects by sampling monitoring wells with narrow screens.
• Analyze with high precision for CFCs, SF6, 3H, 3H/3He, and others (multi-tracer approach).
• Age interpretation. Evaluate multiple tracer data in context of models of groundwater flow.
• Age is model dependent.
Age InterpretationAge Interpretation
• Comparison of simulated and observed tracer concentrations. Lumped-parameter models. (1) multiple tracers from the source, (2) a time series from the source, or (3) multiple tracers from multiple sources in the system. Choose a model based on hydrogeology.
• Tracer plots. Method of comparing simulated and observed multiple tracer data; recognizing cases of possible piston flow and binary mixing (dilution); elimination of some mixing models.
• Flow-model calibration and simulation of age. Use of age information to calibrate the model. (Reilly et al., 1994; Inverse modeling; UCODE)
• All “ages”, regardless of method, are model dependent.• Contradictions? What’s wrong with the tracers? What’s wrong
with the model?
IAEA Guidebook on the Use of Chlorofluorocarbons in Hydrology
2004 Edition
INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA, 2004
0 200 400 600CFC-12 Concentration, pptv
0
20
40
60
80
100
CF
C-1
13 C
onc
entr
atio
n, p
ptv Piston Flow
Recharge DateBinary Mixing
20021990
1980
1960
1995
19751970
1985
BC
DA
QCFChttp://www.iaea.org/programmes/rial/pci/isotopehydrology/
USGS-CFC2004http://water.usgs.gov/lab/cfc
TRACERMODEL1J.K. Böhlke, is a Microsoft Excel spreadsheet program.
CFCIAEA Isotope Hydrology Laboratory Excel based program.
FLOW (FLOWPC)Lumped-parameter models, FORTRAN, Maloszewski and Zuber (1996).
TRACEREXCEL workbook (Bayari, 2002) http://www.iamg.org/CGEditor/index.htm
LUMPEDVisual Basic (Ozyurt and Bayari, 2003) http://www.iamg.org/CGEditor/index.htmhttp://www.sukimyasilab.hacettepe.edu.tr/english/software.shtml
BOXMODELEXCEL workbook (Zoellmann, Kinzelbach & Aeschbach-Hertig)http://www.baum.ethz.ch/ihw/boxmodel_en,html
Lumped Parameter Models
http://water.usgs.gov/lab/cfc
See extensive bibliography
Tritium/HeliumTritium/Helium--33
• Half-life 12.3 years; decays to 3He.
• Atmospheric thermonuclear weapons testing from the 1950’s, and especially in the period 1962-1963
• Initial 3H measured• Terrigenic He sources• Dispersion around bomb peak
• Confinement of 3He
Dating with 3H/3He
4Hem = 4Heeq + 4Heatm + 4Heter
3Hem = 3Heeq + 3Heatm + 3Heter + 3Hetri
Nem = Neeq + Neatm
δ 3He =R
Ra−1
⋅100
Measured
3Hm
Natm = (He/Ne)atm = 0.288 for air excessRatm = (3He/4He)atm = 1.384x10-6 for air excess (Ra)Rter = (3He/4He)ter = 2x10-8 for radiogenic helium (Rrad)
= 1x10-5 for mantle helium (Rman)
Some Definitions
Nem = Neeq + Neatm
4Hem = 4Heeq + Natm ⋅ Neatm + 4Heter3Hem = Req⋅4Heeq + Ratm ⋅ Natm ⋅ Neatm + Rter⋅4Heter + 3Hetri
3Hetri = 4Hem ⋅ Rm − Rter( )−4Heeq ⋅ Req − Rter( )− Natm ⋅ Nem − Neeq( )⋅ Ratm − Rter( )
τ =1λ
⋅ ln 1+3Hetri3Hm
ChlorofluorocarbonsChlorofluorocarbons
• CFC-12 (CF2Cl2), 1930• CFC-11 (CFCl3), 1936• CFC-113 (C2F3Cl3), 1944• Input smooth, increasing until
1990s (dating range ~1950 to early 1990s).
• Stable in aerobic environments.• In modern cases: dual ages.• Use of ratios.• Can detect post 1940’s water.• Collection/analysis not overly
labor intensive.• Problems with contamination,
degradation (anoxic), sorption?
New bottle method of collection.See http://water.usgs.gov/lab/cfc
Sulfur HexafluorideSulfur Hexafluoride
• Electrical insulator in high voltage switches
• First produced 1953• Very low solubility in water.• Does not degrade• Terrigenic source• Dating range: 1970-modern.• Smooth input, increasing in
air at 6%/yr; 5 pptv today.
1950 1960 1970 1980 1990 2000Year
0
200
400
600
CFC
, SF
6 C
onc
entr
atio
n (p
ptv)
1
10
100
1000
10000
Triti
um (
TU)
CFC-1
1
CFC
-12
CFC-113SF
6X10
0
3H
Dating with CFCs and SF6
• Henry’s law solubility Ci = KH x pi
• Requirements:
ØGas-water equilibrium at rechargeØRecharge temperatureØBarometric pressure at rechargeØKnowledge of atmospheric history of the gas
1950 1960 1970 1980 1990 2000Year
0
200
400
600
CFC
, SF 6
Con
cen
trat
ion
(ppt
v)
CFC-1
1
CFC
-12
CFC-113
SF6X
100
1940 1960 1980 2000Recharge Year
0
200
400
600
CF
C P
artia
l Pre
ssu
re (i
n p
ptv)
CFC-12
CFC-11
CFC-113
CFC
-12
CFC-11
CFC-113
5
5
5
Analyzedpg/kg CFC200.6 CFC-12486.5 CFC-1127.8 CFC-113
10 oC, 1 atm total pressure
306.2 pptv
169.7 pptv
23.0 pptv
KryptonKrypton--8585
• Radioactive noble gas with a half-life of 10.76 years.
• 85Kr in the atmosphere has steadily increased since the mid-1950s.
• Interpreted age insensitive to recharge temperature, altitude, etc.
• Does not degrade.• Atmosphere is only significant
source.• Although difficult to collect and
analyze, even a few 85Kr can often help resolve questions. 1950 1960 1970 1980 1990 2000
YEAR
0.01
0.1
1
10
100
85K
r (d
pm
/cc)
1955
1960
19701980
1990
1995
Piston flow line
DATE OF COLLECTIONExample: sample collected in 1990 had a SpecificActivity of Kr-85 of 10 dpm/cc. This would have aPiston flow recharge date of about 1975.
Tracer method of dating the young fraction in binary mixtures of young and old
• CFC pptv ratio defines age of young fraction.• % young water (pptv(measured) /pptv(ratio year)) x 100
• Cannot date outside range for ratio.• Cannot use if one of the CFCs in the selected ratio is “contaminated”, even
if ratio is “in range”.• Ratio-based age must be less than (younger than) apparent (piston flow)
model ages for both CFCs in the ratio.
1950 1960 1970 1980 1990 2000Year
0
0.2
0.4
0.6
0.8
1
Atm
osp
her
ic R
atio
(p
ptv
/pp
tv)
CFC-11/CFC-12
CFC-113/CFC-12
SF6X100/CFC-12
3H/3He Age Applies to that of the Young Fraction in Simple Binary Mixtures
τ =1λ
⋅ ln 1+3Hetri3Hm
λ = decay constant = ln 2/t1/2 = 0.05635 year-1
t1/2 = 12.3 years
3H/3He Age is based on an isotope ratio:(3Ho/3Hm)
Limitations
• Cost• Terrigenic He• Bubbles, Gas-stripping,
confinement• Mixing
• Contamination• Degradation • Mixing
3H/3He
SF6
•Terrigenic SF6
•Mixing
CFCs
85Kr
•Very difficult collectionand analysis
•No labs available to us
Delmarva PeninsulaAtlantic Coastal Plain
Locust Grove
Mod
elA
gein
Yea
rs
CFC-12
CFC-11
SF6
CFC-113
3 3H/ He
Numeric Simulation
85Kr
Böhlke and Denver (1995)
•CFC ages and NO3: 40-yr record of NO3 recharge rate.•Records increase in fertilizer application from the 1970’s.•20-35 % of applied fertilizer reached the aquifer.•Mean residence time of 20 yrs for gw discharge to local streams.
Blue Ridge Mountains of Virginia
Plummer, L.N., Busenberg, E., Böhlke, J.K., Nelms, D.L., Michel, R.L.,and Schlosser, P., 2001, Groundwater residence times in Shenandoah National Park, Blue Ridge Mountains, Virginia, USA: A multi-tracerapproach. Chemical Geology, v. 179/1-4, p. 93-111.
• 800 km2;elev. 170-1230 m• Annual precipitation averaged
114 cm; mean annual temperature,7.8 oC in high altitude, central part.
• Precambrian to Cambrian fracturedcrystalline rocks, metabasalts withthin cover of colluvium and residuum.
• Two largest springs have maximumdischarges of 20 and 11 l/sec. Mostwith max. discharge of < 2 l/sec.
• In drought, sprs. about 10% of max.• wells produce < 6 l/sec, and
typically < 1 l/sec.• 34 springs, 15 wells: 1996 (wet season),
1997 (dry season).• Shallow recharge through residuum
and colluvium recharge fracturesystem which has low storage.
•CFCs, 3H/3He, SF6, 35S, stable isotopes, dissolved N2, Ar.
Background
Well14
LewisSpring
SHENANDOAH NATIONAL PARKBIG MEADOWS AREA
Ground-Water-Flow System
EL=2800 EL=2800
EL=3520
NWSE
Lewis Mountain Spring
Sampling from a TypicalSpring Box and Weir
0 200 400 600CFC-12 (pptv)
0
100
200
300
CF
C-1
1 (p
ptv
)
Sample 1997.0Piston FlowExponential MixingBinary MixtureSprings, '96Springs, '97Wells, '96Wells, '97
300
100
50
3040
20
10
5
5
10
20
30
40
Hudson Spring
0 200 400 600CFC-12 (pptv)
0
20
40
60
80
100
CF
C-1
13 (p
ptv
)
Sample 1997.0Piston FlowExponential MixingBinary MixingSprings in 1996Springs in 1997Wells in 1996Wells in 1997
5
10
20
3040
10
20
30
40
50
100
300
52
2
Hudson Spring
0 200 400 600 800CFC-12 (pptv)
0
2
4
6
SF 6
(pp
tv)
Sample 1997.0Piston FlowExponential MixingBinary MixtureSprings, '96Springs, '97Wells, '96Wells, '97
5
10
20
3040
50100
300
5
10
20
3040
2
L
L
F
F
F
F
L
0 2 4 6SF6 (pptv)
0
4
8
12
16
203 H
(T
U)
Sample 1997.0Piston FlowExponential MixingBinary MixtureSprings, '96Springs, '97Wells, '96Wells, '97Wash. D.C. , Exp. Model
Two 3H inputfunctions:
• Wash. DC(upper)
• Wash. DCscaled to SNP(lower)
Also 0-2 cc/Lof excess air
Precipitation
Ground-Water Reservoir Spring
Discharge
Average -8.2 per milAmplitude 9.6 per milStd. Dev. 2.8 per mil
Average -8.2 per milAmplitude1.1 per milStd. Dev. 0.3 per mil
ResidenceTime2 Years
-16
-12
-8
-4
δO
perm
il
-16
-12
-8
-4
-16 -12 -8 -4
δ18O per mil
-120
-100
-80
-60
-40
-20
0δD
per
mil Precipitation
d Excess 16.1 per mil
Springs and Wellsd Excess 16.4 per mil
1999.0 1999.2 1999.4 1999.6 1999.8Date
-12
-10
-8
-6
-4
δ18 O
(per
mil)
SpringBrowntown ValleyByrd's Nest 3Furnace HudsonLewisPrecipitation
1 Std. Dev. Model Max. - M
in. Model
0.00 0.01 0.10 1.00 10.00 100.00Residence Time, years
0.1
1.0
10.0
δ18 O
Sea
son
al V
aria
tio
n, p
er m
il
3H/3He (Springs)SF6 (Springs)CFC-12 (Springs)3H/3He (Wells)SF5 (Wells)CFC-12 (Wells)
Average Seasonal∆ δ18O = 0.12 per milAverage Age ∼ 5 years
"Average" Spring
Conclusions from Blue Ridge (SNP)
• δ 18O data: Mean residence time of 5 years. (Range 0-10 yrs.)
• Ages based on CFCs and SF6 young; generally consistent with stable isotope data; do not include uz travel time.
• Ages based on 3H/3He biased young (0-2 yrs, most 0)
• Water from wells have ages of 0 to 25 yrs. 3H/3He dating works well for these (and applies to the young fraction).
• Some wells discharge mixtures; ratios of CFCs can define age of young fraction and percent young water in mixture.
• Excess CFCs-- Anthropogenic sources? Evidence of shallow recharge?
Chesapeake Bay Watershed
Region of 165,000 km2 over parts ofNY, PA, MD, DE, VA, and WV.
Evaluate residence times and nitratetransport in groundwater dischargingto streams in the watershed.
Assess lag time between changes at theland surface and the response in thebase-flow component of groundwaterdischarge to the bay.
Washington D.C.
Lindsey and others, 2003, USGS WRIR 03-4035, http://pa.water.usgs.gov/reports/wrir03-4035.pdf
Layered fracture density model(Gburek, Folmar, and Urban (1998)Depth (ft)
0
20
40
80
60
Layered fracture density model
Burton et al. 2002
CFC ratio plot
0 200 400 600CFC-12 Concentration in pptv
0
40
80
120
CFC
-113
Con
cen
trat
ion
in p
ptv
Piston FlowBinary MixingEast TransectWest Transect
19902000
1980
1985
1994
1975
Bedding
Cleavage
NE SW
NW SE
drainage
East Piezometer Transect
West Piezometer Transect
..although these ages are really mixture ages!
--Preferred CFC-12 ages NE of stream are older...
19.942.5
47.2
41.4
49.647.6
42.8
31.5
13.413.9
25.4
16.9
15.9
12.9
8.9
13.4
5.4
5.5
..than those underneath and SW of stream
22/94
--Ages are even more mixed, but % of young water (2nd #) shows older waters generally prevailing to NW 28.1
28/959/23
17/4117/17
21/24…and younger to SE
12.511/45
6/38
14/63
11.9
0.0
Piezometerage animation
Burton et al. 2002
USGS Chesapeake Bay watershed nutrient study
• SF6 vs 3H, CFCs• Monitoring
wells, springs from watersheds Valley and
Ridge
Piedmont/ Blue Ridge
Coastal Plain
Muddy Cr.
Polecat Cr.
East Mahantango Cr.
Upper Pocomoke R.
0 1 2 3 4 5SF6 Concentration, pptv
0
200
400
600
CFC
-12
Con
cent
rati
on, p
ptv
Piston FlowRecharge DateBinary MixingExponential MixingResidence Time, Yrs.
50
5
10
200
100
20
1
19991995
1990
1985
1980
1975
1970
0 1 2 3 4 5SF6 Concentration, pptv
0
10
20
30
40
3 H D
ecay
ed t
o Y
ear
1999
, TU
Piston FlowRecharge DateBinary MixingExponential MixingResidence Time, Yrs.
50 510
200
100
20
1
19991995199019851980
1975
1970
Winchester
Harrisonburg
Staunton
Waynesboro Charlottesville
38º30'N
39º30'N
39ºN
38ºN
78º3
0'W
79ºW
78ºW
77º3
0'W
0 15 30 MILES
Virginia
Maryland
WestVirginia
Virginia Aquifer Susceptibility StudyValley & Ridge Carbonate
Valley & Ridge Siliciclastic
Blue Ridge
Piedmont
Shenandoah National Park StudySpring
Well
Chesapeake Bay StudyCarbonate Spring
EXPLANATION
PD-20
VR-24
VR-17
VR-16
VR-46
VR-27
VR-26
VR-20 VR-45
Stanley
Shenandoah
Waynesboro
VR-25
BR-10
PD-24
BR-07
BR-06
PD-17
PD-16
BR-01 BR-02
BR-03
PD-19
VRC9 VRC15
VRC12VRC23
VRC16
VRC20
VRC2
Soil & RegolithSoil & Regolith
AlluviumAlluvium
LimestoneLimestone
Younger Ground WaterYounger Ground Water
Older Ground WaterOlder Ground Water
Mixture of Younger and OlderMixture of Younger and OlderGround WaterGround Water
Modified from Brahana and others, 1986Modified from Brahana and others, 1986
SPRINGSSPRINGSSOLUTIONSOLUTIONCHANNELSCHANNELS
NOT TO SCALENOT TO SCALE
FRACTURESFRACTURES
Hydrogeology of Carbonate Hydrogeology of Carbonate TerranesTerranesof the Valley & Ridge Provinceof the Valley & Ridge Province
Blue Hole Spr., VA
Piston FlowRecharge DateBinary MixingExponential MixingResidence Time, Yrs.C-Bay SpringsMuddy Creek Sprs.Muddy Creek Dom. wellsMuddy Creek Mon. wellsShenandoah Sprs.Shenandoah WellsVAS Sprs.VAS Wells
0 200 400 600CFC-12 Concentration, pptv
0
10
20
30
403 H
Dec
ayed
to
Yea
r 19
99, T
U
1990
19801960
19951975
1970
15
100
200
1050
20
1985
1999
Tritium vs CFC-12
• Young, piston flow•Binary mixtures of young and old•Few CFC-12 contamination
Valley and Ridge CarbonatesC-Bay Sprs.Muddy Creek Sprs.Muddy Creek Dom. wellsMuddy Creek Mon. wellsShenandoah Sprs.Shenandoah wellsVAS Sprs.VAS wells
Mixture
s
Bear Lithia Spring • 2 samples beyond dating range of 3H/3He.• 9 samples may be unmixed.• 13 samples look like mixtures.
0 20 40 603H/3He Age in Years
0
20
40
60
CF
C-1
2 P
isto
n-F
low
Age
in Y
ears
1:1 L
ine
Beyond 3H/3HeDating range
0 10 20 30CFC-113/CFC-12 Age of Young Fraction, Years
0
20
40
60
80
100
120P
erce
nt Y
oun
g W
ater
in M
ixtu
re Valley and Ridge CarbonatesC-Bay Sprs.Muddy Creek Sprs.Muddy Creek Dom. wellsMuddy Creek Mon. wellsShenandoah Sprs.Shenandoah wellsVAS Sprs.VAS wells
Ages and mixing fractions determined from CFC-113/CFC-12
5-22 years and 10-100%young water in mixture.
Some are inconsistent with 3H (CFC contam.)
Valley and Ridge CarbonatesC-Bay Sprs.Muddy Creek Sprs.Muddy Creek Dom. wellsMuddy Creek Mon. wellsShenandoah Sprs.Shenandoah wellsVAS Sprs.VAS wells
Numbers are % ofYoung fraction inMixture.
3H + 3He(tritiogenic)as function of 3H/3Heage.
Bear LithiaSpr.
1940 1960 1980 2000Date
0
10
20
30
40
50T
riti
um
in P
reci
pita
tio
n in
TU
18
31
5
11
34
839
32
42
78
45
64
1
47
6
Bear Lithia Spring (9/2/99)
Piston-Flow AgesCFC-11 27.2 yrsCFC-12 27.2 yrsCFC-113 >Modern (100 pptv)3H/3He 30.0 yrs
Agreement in ages suggestsPiston flow (30 yrs in pipe flow).
Major Contradiction:Tritium = 1.2 ± 0.2 TU1969.6 water would containedabout 130 TU; decays to 25 TU
Piston FlowRecharge DateBinary MixingExponential MixingResidence Time, Yrs.C-Bay SpringsMuddy Creek Sprs.Muddy Creek Dom. wellsMuddy Creek Mon. wellsShenandoah Sprs.Shenandoah WellsVAS Sprs.VAS Wells
0 200 400 600CFC-12 Concentration, pptv
0
10
20
30
403 H
Dec
ayed
to
Yea
r 19
99, T
U
1990
19801960
19951975
1970
15
100
200
1050
20
1985
1999
Bear Lithia
Without multipleTracers, we would not know this is aMixture.
GC-ECD Chromatograms
• Analysis by GC-ECD: Purge and trap gas chromatography with electron-capture detector.
• Detects halogenated VOCs (examples: CFCs, CCl4, Halons, TCE, TCA, etc.
• Traditional analysis: GC-MS < 0.1 ug/L (= 100 ng/L = 100,000 pg/L)
• GC-ECD: < 1 pg/L (= 5 orders of magnitude below normal reporting levels)
Shenandoah National ParkSpringDrinking WaterModern Clean Water
Spring Yorktown, VADrinking Water
Spring, Clean Modern Water 10 Year Old Water
CFC-12 CFC-12
CFC-11 CFC-11
CFC-113 CFC-113
CCl4 120 pptv in air
Chloroform?Low ppb range
CCl4
A Town well in VADrinking Water WellDepth: 190 metersValley and Ridge
A Town well in VADrinking Water WellDepth: 115 metersBlue Ridge
CFC-12 CFC-12
Vinyl Chloride?, Methyl chloride?
CFC-11 CFC-11DCA?, TCA?, CH3Br?CFC-113?
CCl4 ppb rangeCCl4 natural range
???
Chloroform ? Others?, ppb? Chloroform ?
PCE Tetrachloroethene ??
???
?
Vulnerable, fingerprintsof sources of contamination
Nelms, D.L. and others,2003, USGSWRIR 03-4278
http://water.usgs.gov/pubs/of/2003/ofr03-246/ofr03-246.htm
LALF-1 LALF-9
CFC
-12
CFC
-11
LALFLALF--9, 6/29/969, 6/29/96
?CFC-12: 45,000 pg/kgCFC-11: 5,700 pg/kgCFC-113: 31,000 pg/kg
TD 233 ft, Screen 10 ft, 146 feet water above top of open interval
Halon 1211Drilling Tracer
Minutes0 1 2 3 4 5 6 7 8 9
milli
volts
0
2
4
6
8
10
12
14
1.
65
258
1.
79
1005
0
1.87
59
31
2.0
2 5
866
2
.14
166
CF
C-1
2 2
.29
227
06
2.
52
5067
2.
90
5833
62
3.
13 9
4
CF
C-1
1 3
.75
721
07
4
.03
386
4
4
.86
756
2
CF
C-1
13
6.21
49
75
6
.43
264
46
7
.44
210
828
8
.18
2
8
.65
179
3
8.67
10
32
9.
29
1588
9
.40
987
9.
52
271
9.
61
48
Detector 2ORhinkle011603c20
NameRetention TimeArea
Minutes0 1 2 3 4 5 6 7 8 9
mill
ivol
ts
0
2
4
6
8
10
12
14
1.
60
775
1
.68
192
1
.85
682
75
2.0
1 1
1083
CFC
-12
2.3
0 8
9941
2.
54
2608
2.
65
475
2.
83
865
2
.93
133
5
CF
C-1
1 3
.52
938
3.
80
1097
263
3
.99
480
8
4
.95
129
15
5.
27
91
CF
C-1
13
6.18
273
04
6.
47
3276
5
7.
49
5212
23
8
.65
238
3
Detector 2ORhinkle011603c23
NameRetention TimeArea
Well MW-N3D. Large Halon peak.CFC-11 and CFC-12 indicate mid- tolate 1970s. Since CFCs came withHalon, water is older than 1970s, butcannot be dated further with CFCsbecause of contamination withdrilling air. Possible mixture of oldwater and water contaminated withdrilling air. Without the Halon data,we would have interpreted a CFCage that is too young.
Halon-1211
Well MW-N4D. Trace or no Halonpresent. CFC data probably unaffectedby drilling air. CFC data suggest a modernage for the water. Without the Halon data,we would not know that the CFCs are valid in this sample.
Halon-1211?
CFC-11
CFC-12 CFC-11
CFC-12
CFC-113
CONCLUSIONS• Dating with environmental tracers can help answer the
“When?” in forensic hydrology.
• Use of multiple tracers and “tracer plots” can help to eliminate some mixing models, and refine estimates of mean tracer age.
• To a first approximation, the ages and mixing fractions of many samples from karst or fractured rock can be interpreted using a simple binary mixing model.
• Young ages in Blue Ridge. Mixtures from wells.
• About half of the 3H/3He samples from the Valley and Ridge karst have initial tritium consistent with piston flow (0-15 yrs, unmixed). Rest are mixtures of 0-25 yrs (apparent age) mixed with old (pre-bomb) water.
CONCLUSIONS (cont.)
• Dating with ratios can be very useful. Demonstrate cases of piston flow and binary mixing, but can be affected by contamination. (3H/CFC-12, CFC-113/CFC-12, SF6/CFC-12)
• Most ground water from fractured rock or karstic aquifers is vulnerable to contamination.
• Should include tracers in well drilling.
• Use of patterns in low-level VOC detections to identify and trace sources.
CONCLUSIONS (cont.)
“… the concept of groundwater age has little significance” (Fontes, 1983).
Investigation of multiple environmental tracers in groundwater systems can often help to refine interpretation of age, and refine conceptualization of ground-water flow.
•Chesapeake Bay Study. Scott Phillips, Bruce Lindsey, Gary Spieran, Mike Focazio, J.K. Bohlke, Bill Burton, Colleen Donnelly, Ed Busenberg.
•Virginia Aquifer Susceptibility Study. Dave Nelms and George Harlow.
•Shenandoah National Park Study. Ed Busenberg, Dave Nelms, Jerry Casile, Julian Wayland, WandeeKirkland, Stephanie Shapiro, Brian Norton.
•Reston Chlorofluorocarbon Laboratory.
•Noble Gas Laboratory of Lamont-Doherty Earth Observatory, Columbia University.
Thanks