Paradox of groundwater age

Craig M. Bethke*
Thomas M. Johnson
Department of Geology, University of Illinois, Urbana, Illinois 61801, USA

ABSTRACT
Groundwater in aquifers is generally older than expected on the basis of flow velocity,
and this observation has important implications for interpreting radiometric age deter-
minations. Hydrologists commonly account for the aging of water as it flows along stream-
tubes, but not for the effects of mixing old water from aquitards (or confining layers) into
aquifers, because the rate of mass exchange between aquifers and aquitards can in many
cases be assumed to be small. We show, however, that the effect on age of such mixing
does not depend on the mixing rate; this is the paradox of groundwater age. Surprisingly,
the contribution of aquitards to the age of groundwater in aquifers depends only on the
ratio of fluid volume in aquitards to aquifers. This result has broad importance for un-
derstanding the relationship between groundwater flow and the distribution of radiometric
age.

Keywords: groundwater age, residence time, radiometric age dating.

INTRODUCTION
Groundwater residence time, or age, is
among the most fundamental parameters de-
scribing a subsurface flow regime, and is the
conceptual link between flow modeling and
radiometric age dating. The age of a ground-
water sample is the average over its water
molecules of the time elapsed since they re-
charged the subsurface (Goode, 1996). Only
imperfect measures of the quantity exist, but
it is nonetheless of central importance in phys-
ical and chemical hydrology. Radiometric de-
terminations of groundwater age are used rou-
tinely to estimate groundwater velocity in
order to predict, e.g., the rate at which a con-
taminant migrates through the subsurface, or
the sustainable yield of a water supply.
The distribution of groundwater age is pre-
dicted fully by models describing transport,
i.e., advection, hydrodynamic dispersion, and
molecular diffusion, within a flow regime. If
a perfect flow model could be constructed, it
would give the exact age distribution. The
quantity would also be predicted by an ideal
radiometric dating technique. To give the ex-
act age distribution, an ideal isotope would
need to accumulate within groundwater at a
uniform rate per unit volume water, not react
chemically, and diffuse through water at the
rate of a water molecule.
Hydrologists most commonly take the age
of water flowing along an aquifer as distance
to the point of recharge divided by ground-
water velocity averaged over the flow path.
This conceptualization (Fig. 1) is referred to
as the piston flow age (or streamtube age). Old
water molecules in aquitards (the confining
layers), however, affect age in neighboring
aquifers when they mix into the aquifers by
diffusion, dispersion, and cross-formational
flow (Fig. 2). Whereas piston flow age reflects
only advection in one dimension, the actual
age of a groundwater is that determined ac-
counting for transport by these processes in
three dimensions (Etcheverry and Pierre,
2000; Goode, 1996; Varni and Carrera, 1998).
In invoking the piston flow model, hydrol-
ogists commonly assume that the rate of mass
exchange between aquifers and aquitards is
small enough that it has little effect on the age
in the aquifer. As we show here, however, this
effect is independent of the rate of mass ex-
change; whereas mixing increases age in aqui-
fers, it has the counter-balancing effect of de-
creasing age in aquitards. This unappreciated
result is the paradox of groundwater age, and
has broad implications in groundwater
hydrology.
TRANSPORT OF GROUNDWATER
AGE
Age is similar to solute concentration in
that the distribution of each in a groundwater
Figure 1. Piston flow (or
streamtube) age t of
groundwater is distance x
to fluid packet’s point of
recharge divided by dis-
tance-averaged flow ve-
locity v̄x; variation in age
along direction of flow is
at any point reciprocal of
velocity.
flow is controlled by molecular diffusion, hy-
drodynamic dispersion, and fluid advection. In
considering the distribution of a solute, the
quantity conserved during transport is solute
moles, not concentration. Similarly, age t (s)
itself is not conserved during transport, but the
product rVt of mass and age, where r is den-
sity (kg m23) and V is volume (m3), is con-
served. This quantity is called age mass (Goo-
de, 1996) and has units such as kg s or kg yr;
e.g., mixing 1 kg of 10-yr-old water with 1 kg
of 30-yr-old water yields 40 kg yr of age mass,
or 2 kg of 20-yr-old water.
To model solute transport, we solve a dif-
ferential equation written in terms of concen-
tration. An analogous equation in t (Goode,
1996)
]t ]2 t ]t
5 D 2 2 vz 1 1 (1)
]t ]z ]z
describes how in a homogeneous domain age
varies in time t along a single dimension z. D
in this equation is the coefficient of hydro-
dynamic dispersion (m2 s21), which accounts
for diffusion and dispersion within the do-

*E-mail: c-bethke@uiuc.edu.

q 2002 Geological Society of America. For permission to copy, contact Copyright Permissions, GSA, or editing@geosociety.org.
Geology; February 2002; v. 30; no. 2; p. 107–110; 5 figures. 107

Figure 2. Actual age of groundwater in
aquifer is affected not only by flow ve-
locity within aquifer, but by mass ex-
change with neighboring aquitards. Dou-
ble arrows represent mass exchange
between aquifers and aquitards, a pro-
cess ignored in interpreting age accord-
ing to piston flow model.
main, and vz is flow velocity (m s21). Coeffi-
cient D 5 Dw/f 1 aL vz, where Dw is the
self-diffusion coefficient of water (;23 3
10210 m2/s at 20 8C, and rising sharply with
temperature), f is sediment tortuosity (typical
values are in the range 2–100), and aL is lon-
gitudinal dispersivity.
The 1 in equation 1 represents the aging
with time of water molecules at unit rate; it is
a source term analogous mathematically to a
reaction source of solute. Replacing t with
concentration and the 1 with reaction rate
gives the familiar equation of solute transport.
AGE DISTRIBUTION WITHIN AN
AQUITARD
Given sufficient time for the regime to ap-
proach a steady state, equation 1 becomes
Figure 4. Excess age within aquitard in absence of cross-formational flow. A:
Dimensionless age vs. relative position within aquitard. B: How age at aquitard
centerline depends on aquitard thickness and value of coefficient D, which rep-
resents diffusion and hydrodynamic dispersion within aquitard.
108
Figure 3. Coordinate system for
calculating distribution of age in
aquitard within interlayered sys-
tem of aquifers and aquitards.
When considering effects of
cross-formational flow (equa-
tions 5 and 6), coordinate origin
(z 5 0) is shifted from center of
aquitard to top.
dt d2t
vz 2 D 2 5 1. (2)
dz dz
We can use this equation to solve for the dis-
tribution at steady state of age within an aqui-
tard of half-width , bounded by aquifers (Fig.
3), assuming that there is no cross-formational
flow (vz 5 0). Age t9 5 t 2 taqf in excess of
age taqf in the bounding aquifers is given by
solving
Figure 5. Effect of cross-formational flow on
excess age within aquitard for various flow
velocities vz .
d 2 t9 1
2 50 (3)
dz 2 D
subject to the boundary conditions dt9/dz 5 0
at the centerline z 5 0 and t9 5 0 at the aqui-
fer contacts, z 5 6,. The result,
,2 2 z 2
t9 5 (4)
2D
(Carslaw and Jaeger, 1959), shows that excess
age within the aquitard follows a parabolic
distribution, reaching a maximum along the
centerline. The extent to which age within the
aquitard exceeds that in the aquifers depends
on , and D, as shown in Figure 4.
Whether the age distribution reaches a
steady state depends on how the time elapsed
since the boundary conditions assumed stable
values compares to the relaxation time. In the
absence of flow, tr 5 ,2/D (Carslaw and Jae-
ger, 1959). The relaxation time for a 20-m-
thick aquitard (, 5 10 m) for which D 5 1028
m2/s, e.g., is 300 yr; that for a 200 m aquitard
with D 5 10210 m2/s is 3 3 106 yr.
In the presence of cross-formational flow,
the governing equation becomes
dt9 d 2 t9
vz 2 D 2 5 1. (5)
dz dz
To solve this equation, we shift our coordinate
system so that z 5 0 and z 5 2, correspond
to the top and bottom of the aquitard, where
we again set t9 to zero. The result
t9(z) 5
1
[
vz
z 2 2,1
1 2 exp(vz z/D)
1 2 exp(2vz ,/D) 2 ] (6)
shows how cross-formational flow decreases
age by flushing age mass from the aquitard
(Fig. 5). The corresponding relaxation time, tr
5 2,/vz, is necessarily shorter than for the no-
flow case already discussed.
GEOLOGY, February 2002
EFFLUX FROM AN AQUITARD
Using these results, we can calculate the ef-
flux of excess age mass from aquitard to ad-
joining aquifer. At the point of contact, the
entire flux Jz (kg m22) is given by Fick’s law
dt9
Jz 5 2naqt rD (7)
dz
(Goode, 1996), where naqt is porosity of the
aquitard. (Because t9 equals zero precisely at
the boundary, the advective flux here disap-
pears.) For the case of no cross-formational
flow, the derivative of equation 4 is
dt9 z
52 . (8)
dz D where vx is flow velocity along the aquifer. For
Substituting this result into equation 7 gives
Jz5, 5 2Jz52, 5 naqt r,, (9)
where the flux is positive (or downward) at z
5 , and negative (upward) at z 5 2,. In the
presence of cross-formational flow,
1 2
dt9 1 2, exp(vz z/D)
5 1 . (10)
dz vz D 1 2 exp(2vz ,/D)
Substituting into equation 7, the average flux
in this case is
1 DISCUSSION
(J 2 Jz50 ) 5 naqt r,, (11)
2 z52,
which is the same result as in the absence of
flow.
Equations 9 and 11 constitute a striking re-
sult in that they contain no variables such as
D or vz that describe mass exchange between
aquitard and aquifer. The efflux of age mass
from the aquitard is simply the mass of
groundwater within the aquitard per unit area
of contact with the aquifer. These equations
represent a simple fact: the rate at which age
mass accumulates within an aquitard must at
steady state be balanced by the rate at which
it is dissipated into available sinks, either
neighboring aquifers or the surface. Because
the water molecules age at unit rate, the rate
of age mass accumulation (and hence dissi-
pation) is simply the mass of groundwater
contained in the aquitard.
AGE VARIATION ALONG AN
AQUIFER
The efflux of age mass from an aquitard
affects the distribution of age along neighbor-
ing aquifers, causing it to differ from that pre-
dicted by the piston flow model. Assuming
that the aquifer is well mixed by transverse
dispersion (or, equivalently, that it is sampled
GEOLOGY, February 2002
across its thickness), the rate at which a fluid
packet ages as it flows along the aquifer, ac-
counting for the efflux from aquitards (equa-
tions 9 and 11), is
Dt naqt ,
511 , (12)
Dt naqf L
where D/Dt represents the Lagrangian deriv-
ative, taken in the reference frame of the mi-
grating packet, and naqf is aquifer porosity.
The equivalent Eulerian derivative is
naqt ,
1 2
dt 1
5 11 , (13)
dx vx naqf L
comparison, the piston flow model holds that
dt/dx 5 1/vx (Fig. 1).
These results illustrate an important prin-
ciple. There are two contributions to ground-
water age in an aquifer: the aging at unit rate
predicted by the piston flow model (the 1 in
equations 12 and 13), and the contribution
(naqt ,)/(naqf L) of the neighboring aquitards.
The latter term can be seen to represent the
ratio of pore space in aquitards to aquifer.
Where aquitards dominate aquifers, which is
the common case, the evolution of ground-
water age in aquifers is dominated by the sim-
ple presence in the subsurface of aquitards.
The concepts and analysis presented here
provide a rigorous and useful approach to un-
derstanding the nature of groundwater age.
The approach focuses on the transport of age
mass, which is generated continuously
throughout the flow regime and dissipated to
the surface. Age mass can be dissipated by
advection along aquifers, or through cross-
formational flow, dispersion, and diffusion
across aquitards. Once a flow regime reaches
a steady state, the rate of dissipation must bal-
ance that of generation.
This approach accounts for the contribu-
tions to groundwater age of the entire subsur-
face, in contrast to the common perspective
(i.e., the piston flow model), which is based
on the aging of water packets as they migrate
along streamtubes. Rigorous analysis (equa-
tion 13) shows that at steady state the contri-
bution of aquitards to the age of groundwater
in aquifers is proportional to the mass fraction
of the regime’s groundwater they contain, and
independent of the rate of mass exchange be-
tween the formations. Groundwater in aqui-
fers, therefore, is invariably older than ex-
pected from the rates of flow along them.
Conversely, flow rates along an aquifer are
higher than predicted by the distribution of
groundwater age.
In estimating groundwater age from the dis-
tribution of a radioactive or radiogenic iso-
tope, or a marker molecule, we should start by
considering the extent to which the isotope or
molecule mirrors the behavior of age mass.
An ideal age tracer would accumulate within
groundwater at a uniform rate per unit volume
water, be transported in three dimensions by
diffusion, dispersion, and advection without
reaction, and would diffuse at the rate of water
molecules. Techniques based on noble gas iso-
topes such as 4He and 40Ar (e.g., Castro et al.,
1998, and references therein) give perhaps the
closest examples of such an ideal.
To figure flow velocity along an aquifer
from the distribution of radiometric ages, we
should account for the influx of age mass from
neighboring aquitards. Consider two radio-
metric age determinations t1 and t2 from lo-
calities a distance Dx apart. Assuming that the
dating technique is nearly ideal, we can rear-
range equation 13 to give velocity in an in-
terlayering of aquifers and aquitards as
2@1
naqt ,
1 2
t2 2 t1
vx 5 1 1 . (14)
naqf L Dx
Velocity calculated using the piston flow mod-
el, for comparison, is Dx/(t2—t1). The actual
velocity will differ significantly from the pis-
ton flow model, therefore, where aquitards
dominate aquifers; e.g., where aquitards com-
prise 90% of the section, groundwater mi-
grates 10 times faster than expected from con-
ventional analysis.
Dating methods that rely on the decay of a
radioactive isotope such as 3H, 14C, or 36Cl
can differ significantly from the ideal case be-
cause their concentrations follow a negative
exponential trend with time, whereas age mass
increases linearly. If young water rich in the
isotope mixes with water many times older
than the isotope’s half-life, the apparent radio-
metric age of the mixture will be much less
than its actual age (Park et al., 2002). Dating
using the CFC method (Plummer and Fried-
man, 1999) is similarly complicated, because
the relationship between CFC concentration
and model age is based on historical curves,
which are nonlinear. To evaluate the distribu-
tion of groundwater age in such cases, it may
be necessary to calibrate to observed data a
multidimensional model of isotope transport
and decay.
The assumption of steady state employed
here does not apply to all natural flow re-
gimes. Shale in very old sedimentary rocks
that have only recently become active as
freshwater aquifers, for example, may harbor
water older than expected at the steady state,
and hence have a greater impact on the age in
neighboring aquifers. At the other extreme,
109
water in thick clay beds deposited by recent
glacial events may be younger than in the
steady-state case. Nonetheless, the effects of
aquitards on groundwater age will be at least
qualitatively similar to those presented, and
cannot be ignored.
The discussion here, although formalized in
terms of aquifers and aquitards, has clear par-
allels to problems of flow in fractured media
and karstic rocks (see Goode, 1998, p. 17–18;
Shapiro, 2001). Just as aquitards leak age
mass into aquifers, matrix blocks leak it into
fractures, and limestone leaks it into karst
channels. Where the volume of fractures or
channels is very small compared to pore vol-
ume in the matrix (e.g., in many silicic tuffs
and karst aquifers), velocity in the fractures is
many times greater than might be suggested
by the age distribution.
A final point is that deep aquifers might be
expected to derive age mass from below their
flow regime, absent a barrier to diffusion. A
basal aquifer in a sedimentary basin, for ex-
ample, might acquire age from an unknown
depth within the underlying crystalline crust.
This result is of special interest in light of the
observation (e.g., Castro et al., 1998; Bethke
et al., 1999) that deep aquifers in basins
worldwide accumulate 4He and 40Ar, noble
gas isotopes useful for dating very old
groundwater from deep within the crust. Such
accumulation may reflect the contribution to
age of very old water derived from the crust
and entrained in the aquifer flow.
CONCLUSIONS
Arguments in this and other recent papers
(e.g., Goode, 1996) portray groundwater age
in a new and useful manner: its distribution is
controlled by the transport in three dimensions
110
of a quantity called age mass. Simple transport
calculations lead to a surprising result: in a
system at steady state, age mass passes from
aquitards to aquifers at a rate controlled solely
by the ratio of water mass in aquitards to that
in aquifers; it is independent of rate of mass
transfer. We might expect that a highly im-
permeable aquitard would little affect the age
of water in a neighboring aquifer, but it in fact
has the same effect as would a more perme-
able aquitard. This conclusion, the paradox of
groundwater age, is the inescapable result of
the necessity of transporting age mass from a
flow regime at its rate of generation.
This approach has important implications
for using radiometric methods to date ground-
water, and for using age dating studies to in-
terpret groundwater flow velocities. Isotopes
that accumulate linearly with time can serve
as direct tracers of age mass, allowing age to
be estimated directly. Transport modeling,
however, may be required to accurately deter-
mine the relationship between age and the dis-
tribution of an isotope that decays radioac-
tively. Flow velocity in aquifers (as well as in
fractures and karst channels) is generally more
rapid than predicted by the variation of age
along flow paths, unless the effects of aqui-
tards (or the rock matrix) on age have been
taken into account.
ACKNOWLEDGMENTS
This paper arises from discussions with many
people, especially Jungho Park and Thomas Tor-
gersen. Allen Shapiro derived equation 6. This ma-
terial is based on work supported by National Sci-
ence Foundation grant EAR-94-17768. We thank
M.C. Castro, D.J. Goode, and A.M. Shapiro for
thoughtful reviews.
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Manuscript received June 4, 2001
Revised manuscript received October 15, 2001
Manuscript accepted October 22, 2001
Printed in USA
GEOLOGY, February 2002