Noble GasesNoble Gases

Groundwater recharge Groundwater recharge temperatures temperatures

HeNe

Ar

Kr

Xe

Gaz nobles Groupe 18Gaz nobles Groupe 18

n 1 18

1 1

H 1

2 13 14 15 16 17 2

He 0

2 3

Li 1

4

Be 2

5

B 6

6

C –4 –2 0

4

7

N –3 0 3 5

8

O –2 0

9

F –1

10

Ne 0

3 11

Na 1

12

Mg 2

3 4 5 6 7 8 9 10 11 12 13

Al 3

14

Si 4

15

P –3 5

16

S –2 0 4 6

17

Cl –1

18

Ar 0

4 19

K 1

20

Ca 2

21

Sc 3

22

Ti 4

23

V 5

24

Cr 3

25

Mn 4 3 2

26

Fe 2 3

27

Co 2 3

28

Ni 2

29

Cu 1 2

30

Zn 2

31

Ga 3

32

Ge 4

33

As 3,5

34

Se –2 0 4 6

35

Br –1

36

Kr 0

5 37

Rb 1

38

Sr 2

39

Y 3

40

Zr 4

41

Nb 3 5

42

Mo 4 6

43

Tc 7

44

Ru 3 4

45

Rh 2 3 4

46

Pd 2 4

47

Ag 1

48

Cd 2

49

In 3

50

Sn 4,2

51

Sb 3,5

52

Te –2 0 4 6

53

I –1

54

Xe 0

6 55

Cs 1

56

Ba 2

57

La 3

72

Hf 4

73

Ta 5

74

W 4 6

75

Re 7

76

Os 3 4

77

Ir 2 4 6

78

Pt 2 4

79

Au 1 3

80

Hg 2

81

Ti 1 3

82

Pb 2

83

Bi 3 5

84

Po 2 4

85

At –1

86

Rn 0

7 87

Fr 1

88

Ra 2

89

Ac 3

58

Ce 3

59

Pr 3

59

Nd 3

61

Pm 3

62

Sm 3

63

Eu 3

64

Gd 3

65

Tb 3

66

Dy 3

67

Ho 3

68

Er 3

69

Tm 3

70

Yb 3

71

Lu 3

90

Th 4

91

Pa 5

92

U 4 6

93

Np 4 5

94

Pu 4

95

Am 3

96

Cm 3

97

Bk

3 4

98

Cf 3

99

Es

100

Fm

101

Md

102

No

103

Lr

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

1.1

0 10 20 30 40Temperature °C

He (C0°C = 5.0 ∙10–8)

C0°C

cc STP/cc H2O

Kr (C0°C = 1.3 ∙10–7)

Ar (C0°C = 5.0 ∙10–4)

Ne (C0°C = 2.3 ∙10–7)

Xe (C0°C = 2.0 ∙10–8)

Re

lati

ve s

olu

bil

ity

(C/C

0°

C)

Noble gas solubilities and temperature

0.20

0.15

0.10

0.05

10 20 30

0.25

0

Sol

ubili

ty (

cc S

TP

/ c

c H

2O

atm

.

Tem perature ( C )O

Solubility in BrinesSolubility in Brines

0E+00

5E-08

1E-07

2E-07

2E-07

3E-07

0 10 20 30 40 50 60

Temperature °C

So

lub

ilit

y cc

/cc

H2O

Fresh water

Seawater

Brine

Neon

0E+00

2E-08

4E-08

6E-08

8E-08

1E-07

1E-07

1E-07

0 10 20 30 40 50 60

Temperature °C

So

lub

ilit

y cc

/cc

H2O

Fresh waterSeawaterBrine

Krypton

0E+00

1E-04

2E-04

3E-04

4E-04

5E-04

6E-04

0 10 20 30 40 50 60

Temperature °C

So

lub

ilit

y cc

/cc

H2O

Fresh waterSeawater

Brine

Argon

0E+00

5E-09

1E-08

2E-08

2E-08

3E-08

0 10 20 30 40 50 60

Temperature °C

So

lub

ilit

y cc

/cc

H2O

Fresh waterSeawaterBrine

Xenon

cradle

p inch zone in c lam p

PINCH IT!

Diffusion Sampler

Diffusion Sampler DesignDiffusion Sampler Design

Ne

Diffusion SamplerDiffusion Sampler

29-May-02 35-BYellowknife B8906.1.1B8906.1.1

Original tracer volume inserted - Mayoriginals1 originals2 originals3

3He/4He 20Ne/22Ne vol Ne 36Ar/40Ar vol Ar 78Kr/84Kr vol Kr 132Xe/136Xevol Xe He 4.69E-05 3.51E-05 ######time (min.) M-57 M-37 30 M-57 1000 M-57 M-57 Ne 3.75E-05 7.91E-06 ######

1 0.0246 0.1023 3.07E+00 0.00599 5.99E+00 9.35 Didn't have the new XwAr 1.26E-05 6.20E-04 ######2 0.0247 0.0975 2.92E+00 0.00595 5.95E+00 9.52 spike yet Kr 5.75E-06 1.64E-06 ######3 0.0245 0.0952 2.86E+00 0.00599 5.99E+00 9.66 4.06E-08 ######4 0.0249 0.0942 2.83E+00 0.00592 5.92E+00 9.86 Vair = Vt * [tXt - airXt*R]/[airXair*R - tXair]5 0.0243 0.0946 2.84E+00 0.00589 5.89E+00 10.04 Mole % of isotope in Tracer Mole fraction of isotope in Air6 0.0241 0.0949 2.85E+00 0.00585 5.85E+00 10.31 Isotope Isotope7 0.0238 0.0947 2.84E+00 0.00582 5.82E+00 10.53 3He 0.9999 3He 1.4E-068 0.0239 0.0942 2.82E+00 0.00575 5.75E+00 10.68 4He 0.0001 4He 19 0.0243 0.0934 2.80E+00 0.00571 5.71E+00 10.80 20Ne 0.0010 20Ne 0.905

10 0.0250 0.0927 2.78E+00 0.00570 5.70E+00 10.96 22Ne 0.9990 22Ne 0.092311 0.0257 0.0922 2.77E+00 0.00564 5.64E+00 11.00 36Ar 1.0000 36Ar 0.003 0.003364 1.0178212 0.0263 0.0913 2.74E+00 0.00563 5.63E+00 11.25 40Ar 0.0000 40Ar 0.997 0.996 1.01781213 0.0267 0.0913 2.74E+00 0.00554 5.54E+00 11.38 78Kr 0.9914 78Kr 0.003 8.7E-0614 0.0268 0.0914 2.74E+00 0.00556 5.56E+00 11.45 84Kr 0.0086 84Kr 0.5715 0.0271 0.0920 2.76E+00 0.00548 5.48E+00 11.50 132Xe 0 132Xe 0.269

0.0 10.7276 0.0060 9.3488 136Xe 1 136Xe 0.089cc sample 1.88E-03 3.86E-06 4.72E-03 9.83E-07mass H2O 8.12 8.12 8.12 8.12cc/ccH2O 2.31E-04 4.75E-07 5.82E-04 1.21E-07

40/36 ratio 302water @ 5° 4.9E-08 2.17E-07 4.4E-04 1.1E-07 1.9E-08brine @ 0° 9.5E-09 3.4E-08 6.6E-05 1.9E-08 2.3E-09overpressuring 2.19 1.33 1.13Air contamination cc 7.5E-08 0.0143637 2.6E-07 1.3E-04 1.6E-08Corr Gl+modern 2.31E-04 2.17E-07 4.48E-04 1.05E-07

1.0000Fraction composition dry air 9.45E-01 1.06E-03 0.0537849He 5.20E-06 3H 24.00 cc/cc at TNe 1.80E-05 % brine 0.0010609 0 TAr 9.30E-03 % glacial 0.0537849 1E-07 Ne 2.3 6.5 averageKr 1.10E-06 % modern 0.9451542 1E-04 Ar 5.0 2.9 5.2Xe 8.60E-08 1E-08 Kr 12.7 6.3 stdev

1E-08 Xe 1.9 0.0 2.02020

0 0.2 0.4 0.6 0.8 1 1.2

He

Kr

Ne

Ar

Xe

02

0 0.2 0.4 0.6 0.8 1 1.2

He

Kr

Ne

Ar

Xe

Case study – Bunter Sandstone, Case study – Bunter Sandstone, UKUK

-10

-9

-8

-7

-10000 0 10000 20000 30000 40000

Corrected 14C age (years)

Modern (3H > 2 TU)Paleo-groundwaters

18O

‰ V

SM

OW

W

0

4

8

12

16

0 10 20 30 40Age ka

Ar/

Kr

pale

o-T

°C

Down-gradient evolution of a14C and 13C in groundwaters from the Bunter sandstone. The inverse correlation of a14C with d13C demonstrates the effect of non-decay reaction in attenuating 14C.

0

20

40

60

80

1 4 6 8 10 12 14 16 18 20 22 25 28 30

Site down-gradient

-14

-13

-12

-11

-10

-9

-8

a14

CD

IC p

mC

C 13C

‰ V

PD

B B

14C13C

3H > 2 TU 3H - free groundwaters

Fig. 8-9 Down-gradient evolution of aC and 13C in groundwaters from the Bunter sandstone. The inverse correlation of aC with 13C demonstrates the effect of non-decay reaction in attenuating C.

-10

-9

-8

-7

-10000 0 10000 20000 30000 40000

Corrected 14C age (years)

Modern (3H > 2 TU)Paleo-groundwaters

18O

‰ V

SM

OW

W

0

4

8

12

16

0 10 20 30 40Age ka

Ar/

Kr

pale

o-T

°C

Noble gas isolation and measurementby quadrupole mass spectrometry

Ian, I don’t thinkit’ll work on Mars.

Isotope dilution Isotope dilution methodmethod

AtmosphereAtmosphere SpikeSpike

Vol - unknownVol - unknown Vol - known Vol - known44HeHe 33HeHe2020NeNe 2222NeNe4040ArAr 3636ArAr8484KrKr 7878KrKr132132XeXe 136136XeXe

Andrews, J.N., N. Hussain, and M.J. Youngman, 1989. Atmospheric and radiogenic gases in groundwaters from the Stripa granite. Geochimica et Cosmochimica Acta 53, 1831-1841.

Poole, Jason C., Gavin McNeill, Stephen R. Langman, and Frank Dennis (1997). Analysis of noble gas in water using a quadrupole mass spectrometer in static mode. Applied Geochemistry 12: 707-714.

Pinti, Daniele L., and Eddy Van Drom (1998). PALEOTEMP: A Mathematica® program for evaluating paleotemperatures from the concentration of atmosphere-derived noble gases in ground water. Computers and Geosciences 24: 33-41.

Isotope DilutionIsotope Dilution

Atmosphere Spike

Vol - unknown Vol - known4He 3He20Ne 22Ne40Ar 36Ar84Kr 78Kr

132Xe 136Xe R84/78 = —––––VKr(atm)

VKr(spike)

3He4He

• geothermal studies• groundwater age (4He from decay)• tritium/He dynamics

Clark, I.D. and Phillips, R.J., 2000. Geochemical and 3He/4He evidence for mantle and crustal contributions to geothermal fluids in the western Canadian continental margin. Journal of Volcanology and Geothermal Research, 104: 261-276