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protons and
neutrons.
surrounded by:
electrons
Atomic structure
The structure is notated for element X as:
A Z = number of protons
Z XN N = number of neutrons
A = N + Z = atomic mass
n
N
Atomic weights and abundances
Fractionation
Isotopic molecules behave differently, because:
Examples: 18R
H2O in evaporation: H2Oliquid H2Ogas
13R
H2CO3 in dissociation of CO2: H2CO3 HCO3- + H+
Isotopic ratios
H HO
2
RH2O 1 1
in water it is:
RB
The (kinetic) fractionation factor is: B / A
RA
2
RH O
then gas / liquid 2
2 ( gas )
R H2O( liquid)
Fractionation
RB
eB / A B / A 1 1
RA
12 120
11 110
1000ln (13C, 18O)
10 100
1000ln (2H)
9 90
8 80
7 70
13 -
6 C (HCO3 /CO2) 60
18
5 O (liquid/gas) 50
2
H (liquid/gas)
4 40
0 10 20 30 40 50
o
Temperature ( C)
Kinetic fractionation
Kinetic fractionation results from an irreversible (one-way) reaction
RB
*
r k[ A ] r * k * [A]
RB B AR A
*
r * k[ * A] r k [A]
Phase or Examples:
compound A rapid precipitation of calcite,
RA most redox reactions (methanogenesis
sulphate and nitrate reduction,)
*
r * k * [ A]
RB RB B / AR A
r k [ A]
* '
* ' *
r k [B]
RA RA ' ' A / BRB
r k [B]
r ' k ' [B]
r k[ A] Because RA = RB
r k [ B]
* ' * ' *
*
r * k[ * A]
RB A B R A
e( A B )
B A RB
RA
Equilibrium fractionation
Example: dissociation of carbonic acid in water
CO 2( g) CO 2( a ) e CO2( g ) CO2( a ) 1.1
*
r * k * [ A]
RB RB B / AR A
r k [ A]
* '
* ' *
r k [B]
RA RA ' ' A / BRB
r k [B]
r ' k ' [B]
r k[ A]
r * k ' [ * B]
* '
*
r * k[ * A] Now:
RA RB
RB - Volume reservoir A is decreasing and
- Effective fractionation factor eff e(A-B)
RA
Non-equilibrium fractionation
Example: evaporation of water
h 1
Mass balance: RlNl R v dNl Rl dNl (Rl dR l )(Nl dNl )
1 h 1 h
1 h
Rl dNl R v dNl R
Net evaporating water: 1 h 1 h eff h v
Revap 1 h Rl
(Mook, 1984) dNl
Isotopic ratios in d-notation
RA Rf RA
dA / r 1
Rr Rr
dA / r Is denoted as dA
Standards for isotopic ratios
Examples:
RB
According to the definition: eB / A B / A 1 1
RA
RB 1 dB / r
eB / A 1 1 dB / r d A / r
RA 1 dA / r
Mixing
Mixing of two sources with a different isotopic ratio and concentration
of a single solute
CA
CM CA fA CB 1 fA
fA CM
RA
RB 1 fA B
CA C 1 RM
RM R A f A actually R A is R A
1 RA
CB RM CM CM
fB=1-fA
RB R can be replaced by relative ratios d, if d
variation is less than 100
Mixing
Mixing of two sources with a different isotopic ratio and concentration of
a single solute
Extrapolation of mixing
line indicates the
sources or the mixture
If characteristics of sources
A and B (end members) are
known mixing ratio can be
determined
Mixing
Mixing of two sources with a different isotopic ratio and concentration of
a single solute
In case the solute is water itself and the isotopes are 18O or 2H, then
concentrations are equal to 1.
RB 1 fA B
Then CA C
RM R A f A
CM CM
RM RA fA RB 1 fA
or in d-notation
dM dA fA dB 1 fA
Mixing
Mixing of two sources with two solutes with different concentrations
or isotopic ratios
dM d A fA dB 1 fA
CM CA fA CB 1 fA
d A dB CA dB CBd A
dM CM
CA CB CA CB
Mixing
Determining mixing ratios and discharges
Mixing of two sources with one Mixing of three sources with two
component with different isotopic component with different isotopic
ratios (or concentrations). ratios (or concentrations).
Contribution from
CB various aquifers QM
CA CM
CA
CB
QM
River discharge CM CC
measurement
CM C A fA CB fB CC fC
CM CA fA CB fB
dM d A fA dB fB dC fC
1 fA fB
1 fA fB fC
Rayleigh processes
Reservoir with one sink
R-dR
1
R dR dN
R N
N N-dN
1
R N
Replacing -1 by e and R by Rf(1+d) yields:
R 0 N0
e
N
d (1 d0 ). 1
N0
Raleigh processes
Reservoir with one sink
d ()d ()
E
E40
N
NRR II C
CHHM
MEEN
NTTee =
B
=
B Y
A
Y1100R
R AY
YLLE
E II G
GHH P
PRRO
OCCE
ESSS
S
ffrraaccttiio
onn rreem
maaiin
niin
ngg
20
d0 = 0
ccu
ummu
ullaattiivvee ffrraaccttiio
onn rreem
moovveed
d
-20
1 0.8 0.6 0.4 0.2 0
ffrraaccttiio
onn rreem
maaiin
niin
ngg=
=NN//N
N00
i R o
Ri Ro
fluxI flux
o
R
iRi
or d
1 ei 1 di d e e
o 1 eo
i i o
Raleigh processes
Reservoir with one sink and one source with the same flux
Example stomata in leaf with inflow from uptake and outflow by evaporation
Ri
Ri capillar y v essel
Ri s oil
R leaf w at er = R i/ v/ l
Other example: playa lake with river inflow and outflow by evaporation
Breakdown or mixing ?
Solutes contents may decrease, because of breakdown or dilution (mixing).
EC p
Negatron emission (n p + - + energy)
++
3
1 H 3
2 He
Z n
Positron emission (p n + + energy)
(6429Cu 6428Ni + + energy --
N
Electron capture (p+ + e- n + energy):
40 K + e 40 Ar + energy MO
19 18 ODDE
ESS O
O FF R
RAAD
D II O
OAAC
C TT II V
VEE D
DEEC
CAA
Radioactive Isotopes
N = number of atoms,
dN
N A t = time
dt = rate constant
A = radioactivity
t
N N0e N0= number of atoms at t =0
A0= activity at t =0
A A 0 e t
Radioactive isotopes
Radioactivity
Time to decrease from
1000
A0 to A:
0
800 A
A0
1 A T
T11//22 22T
T11//22
T ln 600
A0
0
400 11//22 A
A0
0
Half-life of a radionuclide 200 11//44 A
A0
ln1/ 2
1 0 10 20 30 40 50 60 70 80 90 100
T1/ 2
time
ln 2 R AA DD II OO AA CC TT II VV EE DD EE CC AA YY
A = A 00 EE -- TT
T1/ 2
Radioactive carbon isotope 14C
14C is formed in the
ccoossm
miicc rraaddiiaattiioonn
stratosphere:
N ++ nn
111444
N 1144
14C C ++ pp C
111444
C N ++
111444
N
14
C 14
C
14
Nn 14
Cp
14
C
111444 1122
C
COO222 ++ 12C CO
O222 111222
C
COO222
14C decays according:
eexxcchhaannggee aassssiim
miillaattiioonn ffoossssiill ffuueell
C N
eexxcchhaannggee 14 14
H 1144
H14C CO
O333 nnuucclleeaarr
sshheellllss hhuum 1144
muuss 14C CO O222
111444 bboom
mbb
CCaa C CO
O333 LLA AKKEE
O
OCCE
EAAN
N ggrroouunnddw a
watert er
O ++ O333
1122 1144 1122
Caa12C
C COO333 ++ H H222O H H14lC eeO
lC vO
vee
333ll + H12C
+H CO
Half-life of 14C:
T1/ 2 5730 yr
11 44
O RR II G
G II N
N A
AN D D II S
ND S TT R
R II B
BUU TT II O
ONN O
O FF C
Radioactive carbon isotope 14C
14C/C concentration in atmosphere is: 10-12 Reported 14C conc. (activity) is:
14 A
in %
14C activity in atmosphere is: 0.25 Bq/gC
(disintegrations per second per gram of C)
14
a sample
14 Areference(1950)
eexxcchhaannggee atmosph.CO2
pprreecciippiittaattiioonn
105%
plants/humus
oceanic HCO3 100% soil H2O
100%
11 44
C II NN G RR O
OUUN
NDDW
WAAT
TEER
R
Radioactive carbon isotope 14C
T1/ 2 a sample
14
Radiocarbon groundwater age
T14 C ln 14
is based on Dissolved ln 2 ainitial
Inorganic Carbon (DIC):
T1/ 2 5730
8267
ln 2 0.693
ii nn ff ii ll tt rr aa tt ii oo nn
oocceeaannss rriivveerr
hh yy dd rr oo ll oo gg ii cc aassll cc yy cc ll ee
Half-life of 3H:
T1/ 2 12.43 yr 33
O RR II G
G II N
N A
AN D D II S
ND S TT R
R II B
BUU TT II O
ON O FF H
N O
Radioactive isotope 3H or Tritium
3H or Tritium is reported in Tritium Units (TU):
1 TU = 0.118 Bq/L as activity,
1 TU = 10-18 as conc. (3H/H).
3
H in precipitation (in TU)
4000
N
Noorrtth
heerrn
nHHeem
miissp
phheerree
3000
1000
0
1955 1960 1965 1970 1975 1980 1985 1990
33
H N P
H II N PRRE
ECC II P
P II T
TAAT
T II O
ONN
3H and 14C in groundwater
3
A (TU)
100
75
rre
ecceenntt
50 m
miix
xeedd ggrro
ou un
nd d--
w
waatte
errs
s w a t
watere r
25
0 v
veerry
yoolld
d o
olld
dggrro
ouun
nddw
waatte
err y
yoou
unng
g
0 25 50 75 100
14
a (%)
3
3 1
144
H
H ,, C
C A
AN D W
ND WAAT
TE R A
ER AGGE
ESS
Other radioactive isotopes
36Cl
half-life = 300,000 yr
produced in atmosphere and deep subsurface
peak created by nuclear bomb tests
used for dating old groundwater and
as tracer for young groundwater
85Kr
Half-life = 10.76 yr
Produced by nuclear fuel processing
Used for dating young groundwater
222Rn
Half-life = 3.8 days
produced in the soil by decay of 226Ra
Used for dating very young groundwater (artificial recharge)
13C isotope in nature
aattm
moossp
phheerriicc C
COO222
m
maarriin
nee H
HC O333
CO
m
maarriin
nee ccaarrb
boon
naattee
m
maarriin
nee p
pllaan
nttss
m
maarriin
nee p
pllaan
nkktto
onn
llaan
nddp
pllaan
nttss C
C444 ttyyp
pee
llaan
nddp
pllaan
nttss C
C333 ttyyp
pee
g
grro
ouun
nddw
waatteerr H
HC O333
CO
ffrreessh
h--w
waatteerr ccaarrb
boon
naattee
w
wooo
odd
p
peeaatt
cco
oaall
o
oiill
n
naattu
urraall g
gaass
b
baacctteerriiaall C
CHH444
aan
niim
maall b
boon
nee
d
diiaam
moon
ndd
13
dVPDB ()
C
CAAR
RBBO
ONN -- 1
13 N N
3 II N NAAT
TUUR
REE
13C isotope in nature
C
CaaC
COO333
s/b
Equilibrium fractionation --
H
HC O333-
CO
of carbonic acid and CO2 0
2
2--
c/b
C
COO3332-
-4
C
COO222((g
g)) g/b
a/b
-8
C
COO222((aaq
q))
-12
0 10 20 30 40
temperature (oC)
11 33
C
C FF R
RAAC
CTT II O
ONNA
ATT II O
ONN
13C isotope in nature
CO2 concentration (ppm)
360
M
Maau
unnaa L
Looaa
355
H aw
Hawaiiaii
350
345 S
Soou
utth
hPPo
ollee
340
335
330
1978
1978 1980
1980 1982
1982 1984
1984 1986
1986 1988
1988 1990
1990 1992
1992 1994
1994 1996
1996
-7.4
-7.5
-7.6 S
Soou
utth
hPPo
ollee
-7.7 M
Maau
unnaa L
Lo oaa
-7.8 H
Haawwaaiiii
-7.9
d(CO2) ()
13
C O 22 C
COONNC CE
ENNT
TRRA AT T II O
ONN A AN
NDD
11 33
d
N PA
II N AC
C II F
F II C
C A AII R
R
13C isotope in nature
plants / humus
oceanic HCO3 25 soil H2O
+ 1
11 33
C II NN G RR O
OUUN
NDDW
WAATT E
ERR
13C isotope in nature
13
d(HCO3-) ()
-6
R
Rhhiinnee
-8
-10
-12
M
Meeuussee
-14
12 2 4 6 8 10 12 2 4 6 8 10 12 2 4 6 8 10 12
0 1967
12 1968
24 1969
36
-6
M
Meeuussee
-7
-8
-9
R
Rhhiinnee
-10
-11
0 12 24 36
18
d(H2O) ()
11 33 11 88
C AANN DD O
II N
N A
A R
RAAII N
NWWA
A TT E
ERR R
R II V
VEER
R( M EE UU SS EE )
A
ANND
D A
A M
MEE LL TT W
WAATT E
ERR R
R II V
VE R (RH
ER H II N
NEE)
18O isotope in nature
for water 18
d VSMOW ()
for carbonate 18
d VPDB ()
-60 -40 -20 0 +20
ocean water
arctic sea ice
mar ine moisture
(sub)tropical
precipitation
Dead Sea/Lake Chad
temperate zone
precipitation
Alpine glaciers
Greenland glaciers
Antarctic ice
Quatern. marine
carbonates
fresh-water
carbonates
ocean water
marine carbonates
igneous rocks
mar ine atmospher ic
CO2
atmospheric oxygen
organic matter
OXYGEN-18 IN NATURE
18O isotope in nature
18
fractionation e ()
50
C
COO22
40
gg//ll
30
C
CaaC
COO33 ss//ll
20 Equilibrium
fractionation between
10 H2O, CO2 and CaCO3
H
H22O
O
0
vv//ll
-10
H
H22O
O vvaappoouurr
-20
0 10 20 30 40
temperature (0C)
11 88
O FR
RAAC
CTT II O
ONNA
ATT II O
ONN
2H or deuterium in nature
ocean water
arctic sea ice
marine moisture
(sub)tropical precipitation
temperate zone ,,
polar ice
Alpine glaciers
Lake Chad
wood cellulose temperate
peat zone
clay minerals
22
H N N
H II N NAAT
TUUR
REE
Mass spectrometry for stable isotopes
Magnetic field
15 to 50 cm
Ion
collectors
Positive ions
low high
High voltage E mass mass
Ionisation chamber
Gas flow
Ion source
Carbondioxide (CO2) for 18O and 13C after equilibration
with H2Osample
Hydrogen (H2) for 2H after reduction H2Osamplewith
uranium
against neutrons
against -radiation