Atomic structure

An atom of an element consists of nucleus with:

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

Number of protons (Z) is equal to the number of electrons.

Z defines its chemical characteristics and position on the periodic table

In light elements Z (protons) are equal to N (neutrons).

In heavier elements neutrons become more abundant.
 Isotopes
Isotopes are atoms of the same element (i.e., same number of protons
and electrons) but different numbers of neutrons

rare oxygen isotope

(0.20 %)
18
8 O8 18
O

abundant oxygen isotope

(99.76 %)
16
8 O8 16
O
 Stable and unstable isotopes
Stable isotope are not radioactive; usually the numbers of protons
and neutrons are similar (the less abundant isotope is often
heavy, i.e., it has an extra neutron or two)
Unstable or radioactive isotopes decay 16
O 17
O 18
O
into daughter atoms while emitting: 14 15
-radiation (4He2+), N N
-radiation (electrons or positrons) 12
C 13
C 14
C
-radiation (electro magnetic radiation) 10 11
Z B B
9 10
Be B
6 7 e
Li Li
3
He 4He unstable
1 2 3
H H H

n
N
Atomic weights and abundances
 Fractionation
Isotopic molecules behave differently, because:

heavier isotopic molecules are less mobile

(lower diffusion velocity and collision frequency)

heavier isotopic molecules have higher binding energies

(more energy needed for separation)

Isotopic ratios change during transition from one phase or molecule to

another. This is isotopic fractionation.

Examples: 18R
H2O in evaporation: H2Oliquid H2Ogas
13R
H2CO3 in dissociation of CO2: H2CO3 HCO3- + H+
 Isotopic ratios

Isotopic ratio in a certain molecule abundance of rare isotope

R
is defined as: abundance of abundant isotope

For the 13C-isotope

13
CO2

13
RCO2 12
in carbondioxide it is expressed as: CO2

For the 2H-isotope (or deuterium)

H HO
2 1

H HO
2
RH2O 1 1
in water it is:

abundance of rare isotope R

NB: Isotopic concentration is: C
abundance of all isotopes 1 R
 Fractionation

Isotopic ratio R changes after chemical or physical transition

from compound or phase A to B.

RB
The (kinetic) fractionation factor is: B / A
RA

Ex.: hydrogen fractionation during evaporation: H2O(liquid) H2O(gas):

2
RH O
then gas / liquid 2
2 ( gas )

R H2O( liquid)
 Fractionation

Fractionation factor B/A is generally close to 1

Often the fractionation eB/A or deviation of from 1 (in ) is used:

RB
eB / A B / A 1 1
RA

e > 0 = isotopic enrichment

e < 0 = isotopic depletion

 Fractionation
Fractionation is temperature dependant

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,)

2NO 3 2CH2O N2 2HCO 3 H2O (15RNO3 , 15RN2)

 Kinetic fractionation

Kinetic fractionation also takes place during diffusion, as molecules

with light isotopes move faster than those with heavy isotopes.

Diffusion according to Fickss law:

dC
F D
with F = diffusive flux, dx
C = concentration,
D = diffusion coefficient

Maximum fractionation factor along the diffusion pathway is: *D

e 1
D
with *D = diffusion coefficient of molecules with the rare
and (generally heavy) isotopes
 Equilibrium fractionation
Equilibrium fractionation occurs when the reaction(s) are
reversible and in thermodynamic equilibrium.

*
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

H2 0 CO2( a ) H HCO 3 eCO2( a ) HCO3 9.0

HCO3 H CO32 eHCO3 CO3 0.4

CaCO3 Ca 2 CO32 e sc 1.3
 Non-equilibrium fractionation
Non-equilibrium fractionation occurs when reactions are
reversible, but there is a net discharge of reactants (open system)

*
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

Water vapor In equilibrium (closed system) relative

humidity h = 1
h Rv
Rl
1 In non-equilibrium vapor is continuously
Rv h
dNl dNl removed and h < 1,
1 h 1 h
while Nl, Rl and Rv vary during process
Nl dNl
Nl Rl
Rl dR l
Liquid water body Next step

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

Usually isotopic ratios are reported with reference to a certain standards

RA Rf RA
dA / r 1
Rr Rr

There is international agreement on these standards, therefore

dA / r Is denoted as dA
 Standards for isotopic ratios
Examples:

Primary standard(s) Isotope(s) Ratio Rr Reference

(mean 95% CI) materials
Standard Mean Ocean 2H/1H 0.00015576 0.00000010 GISP, SLAP, NSB-1
Water (SMOW), Vienna- 18O/16O 0.00200520 0.00000043
SMOW 17O/16O 0.0003799 0.0000016
PeeDee Belemnite 13C/12C 0.0112372 0.0000090 NSB-19, NSB-20,
(Vienna PDB) 18O/16O 0.0020671 0.0000021 NSB-21
17O/16O 0.0003859 0.0000016
Atmospheric nitrogen 15N/14N 0.0036765 0.0000081 Air, NSB-14
(air)

Caon Diablo Troilite 34S/32S 0.0450045 0.0000093 CDT

meteorite
 Isotopes applied in hydrology
Isotope compound

2H, 3H H2O, CH4, org. cont.

3He, 4He He2
13C, 14C CO2, HCO3-, CH4, Org. cont.
15N NO3-, NH4+, N2
18O H20, NO3-, SO42-
34S S042-, H2S, FeS2
36Cl, 37Cl Cl-, org. cont.
87Sr Sr2+
85Kr Kr2
222Rn Rn2
 Fractionation and fractionation factors

RB
According to the definition: eB / A B / A 1 1
RA

If B/A is small (0.95 to 1.05) then: eB / A B / A 1 ln( B / A )

If dvalues are small (50 to 50 ) then:

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

Plotting Rm against 1/Cm of the mixture gives straight mixing line:

Example of mixing of strontium from two water types

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

Example: Mixed coastal water of North Sea M = mixed water

and Schelde origin, seen on the d18O and A = North Sea water
chloride mixing line B = Schelde River water
fA = contribution of North Sea water

dM d A fA dB 1 fA

CM CA fA CB 1 fA

Equation of the mixing line

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

Kinetic and non-equilibrium fractionation, leads to continuous changes in

isotopic ratios of mother and daughter reservoirs
Mass balance:
dN R
RN R dRN dN RdN

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

After removal of small fractions (or small changes in concentrations) isotopic

effects are large.
Accuracies of ratios are often less than 0.1
 Raleigh processes
Reservoir with one sink

An example of sulphate reduction (reservoir with one sink)

SO24 2CH2O 2HCO3 H2S eH2SSO4 20
 Raleigh processes
Reservoir with one sink and one source with the same flux

i R o
Ri Ro
fluxI flux
o

Equilibrium will arise after some time with

flux i flux o and Ri R 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 / v/l plant leaf

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).

If Rayleigh fractionation occurs with breakdown, the two processes can be

discriminated by plotting RA or dA versus ln(CA)

Example of nitrate reduction: 2NO 3 2CH2O N2 2HCO 3 H2O

Straight line indicates

breakdown
 Radioactive isotopes
Three main mechanisms for radioactive decay:

Emission of -particle or 42He (larger radionuclide):

238 U 234 Th + 4 He + energy (-rays)
92 90 2

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

Radioactive isotopes lose nuclear material at a fixed rate:

radioactive decay

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%

humus CO2 dissolved CO2

100% 100%

marine CaCO3 soil CaCO3

< 100% eerro
ossiio
onn // sseed
diim
meen
nttaattiio
onn 0%

groundwater DIC groundwater HCO3

>50% 50%

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

For true groundwater ages T14C has to be corrected for:

secular variations in atmospheric 14C activity

dissolution of DIC with dead carbon
exchange with the atmospheric carbon
 Radioactive isotope 3H or Tritium
3 3
H 3 H
3H is formed in the 3
H
H 3
H
stratosphere:
N ++ nn H Hee ++
1144 12 3
12C
33 3
3
H N C ++ 3HH H 3H
14
Nn 12
C 3H
33 11
hh yy dd rr oo ll oo gg ii cc aa ll cc yy cc ll ee HHH H
OO

3H decays according to:

pprreecciippiittaattiioonn

3
H He
3
ssuurrffaaccee rruunnooffff
eevvaappoorraattiioonn

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

Nuclear bom tests in atmosphere

2000

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

-80 -60 -40 -20 0 +20

13
dVPDB ()

C
CAAR
RBBO
ONN -- 1
13 N N
3 II N NAAT
TUUR
REE
 13C isotope in nature

carbon isotope fractionation e ()

13

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

eexxcchhaannggee atmosph. CO2 pprreecciippiittaattiioonn

7.5

plants / humus
oceanic HCO3 25 soil H2O
+ 1

humus CO2 dissolved

25 CO2
25
marine CaCO3 soil CaCO3
+ 1 eerroossiioonn // sseeddiim
meennttaattiioonn + 1

groundwater DIC groundwater HCO3

11 to 16 12 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

-20 0 +20 +40 +60

18
d VSMOW ()

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

-200 -150 -100 -50 0 +50

2
dVSMOW ()

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

Schematic view of mass separation in a mass spectrometer.

 Radiometry for radioactive isotopes
Protection of counters and samples
Proportional gas counter

against neutrons

against -radiation

Liquid scintillation counter