SPE 108531
Observations and Quantitative Analyses of Waterflood Patterns in a Chalk Reservoir
Using Seismic Data, Halfdan Field, Danish North Sea
Thomas Dons, Ole Jrgensen, and Lars Gommesen, Mrsk Olie og Gas
Copyright 2007, Society of Petroleum Engineers
This paper was prepared for presentation at Offshore Europe 2007 held in Aberdeen,
Scotland, U.K., 47 September 2007.
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Abstract
Reservoir pressure maintenance and sweep of oil with water
are the main objectives of the Halfdan field water flooding.
The lower mobility of water compared to oil in the Halfdan
field facilitates an effective sweep of oil but means that the
water injectors require larger reservoir contact area in order to
replace voidage. In Halfdan this has been the focus from first
development and has been obtained by controlled formation of
10,000-15,000 ft long injection fractures by injection at
fracturing conditions. Modelling has indicated that conditions
for propagating injection fractures along the horizontal
injectors were present, but until recently a field-wide
verification of the expected uniform sweep has been pending
seismic identification of the resulting water flood.
After five years of production, a seismic survey was acquired
covering the developed area. Analysis of the seismic data has
revealed a strong signature reflecting the water flooding of the
reservoir. The seismic imaging of the sweep patterns is
observed directly in the 3-D data without any 4-D processing
and is of an outstanding quality even compared to what is
normally seen in dedicated time lapse seismic studies. The
seismic observations confirm the modelled behaviour of the
Halfdan field water flood.
This paper presents examples of the seismic observations
made and discusses these in a rock physics context including
fluid substitution and pressure effects on acoustic impedance.
It is demonstrated how the seismic results together with simple
analytical models add to the quantitative description of
injection under fracturing conditions by facilitating measures
of fracture height, connectivity and extent.
Introduction
The Halfdan field is located in the Danish North Sea Central
Graben, approximately 250 km west of the West Coast of
Denmark (Figure 1). The Halfdan accumulation was
discovered in 1999 as the latest of the larger Upper Cretaceous
Chalk reservoirs present in the region1 so far. Trapping of
hydrocarbons is caused by a combination of stratigraphic and
fluid dynamic conditions in contrast to other fields in the
region that are trapped below structural closures. An early
assessment of the Halfdan field development was given by
Albrechtsen et al.2. The Halfdan field is operated by Mrsk
Olie og Gas AS on behalf of the DUC partnership (A.P.
Mller-Mrsk AS, Shell Olie- og Gasudvinding Danmark
B.V. (Holland) and Chevron Denmark Inc.).
A regionally extensive but relatively thin oil column
characterizes the Halfdan field. Wells are drilled in a parallel
pattern with horizontal well sections of 10,000-15,000 ft
length and at a well spacing of 600 ft. The Halfdan field is
developed with alternating production and injection wells
giving 1:1 producer-injector coverage. Injection in Halfdan
targets maintenance of the reservoir pressure (PRES) at or
above the initial pressure (PINIT). The conditions are that
water injected has a far lower mobility than the hydrocarbons
produced and that the producing drawdown (PINIT Pp 3,000
psi) is far larger than the pressure head at the injector side
(PINJ PINIT 1,000 psi). These conditions would curtail the
target for pressure maintenance in a 1:1 producer-injector
scenario if injecting under fracturing conditions was avoided.
Fracturing was therefore planned from early on2, 3, 4.
Injection fracturing in Halfdan follows Mrsk Olie og Gas AS
patented FAST concept. The technique builds on flow induced
stresses, which causes injection fractures to grow along the
wellbores of the horizontal injectors. An important element in
FAST is patience, because production and injection for a pre-
defined period must precede fracturing in order to control the
direction of propagation3, 4.
Recently, a seismic survey was acquired over the area. The
interpretations published herein are those important for the
conception of the Halfdan water flood and for water injection
theory in general.
Seismic observations
During the summer of 2005 a new seismic survey covering the
Halfdan field was shot. The survey was subsequently fast
track processed during the winter 2005/6 and has been used as
2 SPE 108531
the basis for a recent review of the Halfdan area geological
model.
Compared to earlier seismic data covering Halfdan, the new
data is characteristically noise free, which allows for better
imaging and mapping. The survey was shot five years after
first production and four years after first injection which
means that water flood patterns were well established for the
first producer-injector pair. The expectation was that this
would allow for detection of possible seismic time lapse
effects after suitable 4-D processing. It was found, however,
that reality exceeded expectations by far and that clear effects
from the production-injection can be detected directly from
the 3-D data.
Figure 2 shows a map of the maximum seismic amplitude in a
time interval corresponding to the upper part of the developed
Maastrichtian reservoir section. As can be seen, there is a very
pronounced correlation between the presence of water
injection wells and a lowering in maximum amplitude. The
difference in maximum amplitude between a paired injector
and producer may be as much as 50%. The insert in Figure 2
shows the cross-sectional view. The effect of the injection-
production is not as evident when viewed in this way. It is
believed that the lack of good response can be attributed to the
effect of the wavelet in the zero phase data.
Figure 3 regards the same cross section but shows seismic data
inverted to relative acoustic impedance. In the inverted data
the wavelet effect has been removed and the only signal left is
from the apparent acoustic impedance in the interval and in
the frequency range resolved by the seismic signal. In this
case a very pronounced effect of the wells can be seen. Higher
relative acoustic impedance (hardening) can be seen around all
the water injectors in the upper part of the Maastrichtian
reservoir interval. Below this upper zone, also at the injector
location, a less pronounced decrease in impedance (softening)
can be seen. In other words, there is a clear response in the
seismic data to the water injection whereas there is no or
limited seismic response to the producers. Mapping of the
relative acoustic impedance response reveals a very similar
picture to that given by the zero phase data.
The clear response in the seismic data can be correlated to the
injectors but it is variable in strength and it may occur
scattered along the wells rather than uniformly distributed
along these. This can be ascribed to the observations being
made directly in the 3-D data, which means that the seismic
response is from a combination of both production induced
heterogeneities and from geological heterogeneity. In order to
reduce the latter effect it was decided to apply spectral
decomposition on the seismic data. The rationale behind this
was to distinguish the two effects in the frequency domain and
then mute the frequencies related to geological
heterogeneities, if possible.
A clear improvement in the definition of the seismic response
to the water injection and a wealth of details can be detected in
the spectral decomposition results (Figure 4). First of all the
injectors both at Halfdan and on the Dan West Flank can be
followed along their entire lengths showing that the injection
response is aligned with the well trajectories and seems to be
evenly distributed along these. In one instance, the HDA-34C
well in the northern part of the Halfdan field, injection has not
yet been initiated and the seismic indicator for injection is
lacking accordingly.
The seismic response is characterised by a very sharp
transition from anomalous to unaffected seismic response. The
lateral distance from the horizontal injection line to the
transition is variable and can be correlated with the duration of
the injection. There are no apparent deviations from this
general pattern.
Quantitative significance of observations
The above observations of production induced seismic
responses are based on spectral decomposition images of the
seismic data. The very good resolution of the images justifies
this approach and is very appropriate for qualitative analysis
of the production imprint as it has been demonstrated in the
previous examples. For the analysis of the possible causes of
the seismic response it is less adequate as the quantitative
analysis of the spectral decomposition is less clear; images
may vary regionally or even locally, they are normalised and
they only represent part of the seismic bandwidth.
The relative acoustic impedance provides a much more
adequate basis for a quantitative analysis of the seismic
response. Even though the absolute acoustic impedance is not
determined, the relative acoustic impedance from the inverted
seismic can be used to estimate absolute changes in acoustic
impedance. The absolute changes can thereafter be used to
estimate changes in rock properties in the flooded rock.
An example of changes in acoustic impedance between
injectors and producers in the Halfdan field can be observed in
Figure 3. In absolute figures the observed changes are around
300,000 m/s kg/m3. Possible causes for the observed
variations are primarily saturation and pressure changes
caused by the water flooding and possibly related porosity
loss. Whether the latter is active depends on the properties of
the chalk, mainly porosity. In the following it is discussed how
the observed changes can be related to these possible causes.
A conceptual quantitative model is presented relating the
observed response to a combination of several causes.
The change in the elastic properties of a porous rock, when
substituting the pore fluids of the rock, is well predicted using
the Gassmann theory5. Using an appropriate rock physics
chalk model one may accordingly estimate the change in e.g.
acoustic impedance as a function of saturation for a given
porosity. Figure 5 is an example of modelled effects
substituting oil with water for four different porosity classes
and variable water saturation. Typical Halfdan field reservoir
chalk will have porosity around or slightly above 30%.
Observations of virgin and flooded reservoir rock have also
shown that the water flooding will reduce the oil saturation
from 80% to 25%. The expected effect of such a change can
be seen in Figure 5 to be in the order of 300,000 m/s kg/m3.
SPE 108531
Changes in the stress acting on the rock lead to changes in the
acoustic properties of the rock frame. Typically, increasing
fluid pressure will cause a lowering of the seismic velocity
and thus a lowering of the acoustic impedance. The reduction
in velocity is believed to be caused by weakening of grain to
grain contacts due to reduced load on the rock frame. In water
flooding the effect of increased fluid pressure and substitution
of hydrocarbons with water has opposite effects on acoustic
impedance. The pressure effect has been experimentally
demonstrated (e.g. Rgen et al.6) in the confining pressure
range 350 1,100 psi but not under producing reservoir
conditions where a wider interval of 0 5,000 psi is relevant.
Rgen et al.6 states an average increase in acoustic impedance
of 4% when increasing confining pressure from 350 psi to
1,100 psi. Generally, porous rocks show declining sensitivity
to pressure variations as the stress acting on the rock increases,
see Avseth et al.7 for a general discussion. The stress-
impedance relationship is considered reversible but not linear.
Accordingly, extrapolation of the laboratory trends is not
applicable. Qualitatively, the pressure will counteract the fluid
effect but whether it is smaller, levelling with or exceeding the
size of the fluid effect has to be established by other means.
Plastic deformation of the chalk and porosity loss as a
response to both depletion and water injection is a well known
phenomenon in chalk reservoirs and is expressed even at
surface as significant seabed subsidence above e.g. the
Ekofisk and Tyra fields. Much research has been done within
this topic8 and it is inferred that plastic deformation in Halfdan
is limited to chalk with porosity exceeding approximately
35%. Since most of the Halfdan field reservoir chalk has
porosity below 35%, compaction is not considered to be
pervasive but may have an effect in the best reservoir
intervals.
Our current understanding of the seismic responses to the
water flooding is that they are a combined result of fluid
substitution and increased pore pressure with an additional
contribution from compaction where porosity is high. In the
upper part of the Maastrichtian reservoir interval, high oil
saturation prevails. Here, the full fluid effect applies giving
rise to an increase in acoustic impedance of ca. 300,000 m/s
kg/m3. The observed impedance increase is similarly
approximately 300,000 m/s kg/m3 and suggests that the
individually opposite effect of compaction and increased pore
pressure levels out although the size of these effects is
undetermined.
The deeper part of the reservoir is a transition zone with
increasingly lower initial oil saturation. Here the water
flooding will reduce a low initial oil saturation of e.g. 40% to
a residual saturation of 20%. The corresponding increase in
impedance is approximately 150,000 m/s kg/m3, which is
less than for the fully saturated reservoir intervals. In the lower
part of the reservoir the observed change in impedance
corresponds to a decrease (softening) by 200,000 m/s kg/m3.
As high porosity intervals are absent in the lower part of the
reservoir no compaction is expected, hence the pressure effect
must amount to a decrease of 350,000 m/s kg/m3.
3
Higher in the transition zone, e.g. in the units characterised by
higher porosity and oil saturation, the same pressure derived
decrease in acoustic impedance is assumed to apply. This
means that a compaction driven increase of 350,000 m/s
kg/m3 is required to achieve the observed total increase of
300,000 m/s kg/m3. At a porosity of 35% this would
correspond to a reduction in porosity of approximately 2
porosity units.
Figure 6 summarizes the conceptual rock physics prediction of
fluid, pressure and compaction effects presented above.
As the current study is based on 3-D analyses, the observed
differences in acoustic impedance caused by the production
effects are estimated from comparisons to unaffected rock and
therefore associated with some uncertainty. Ongoing time-
lapse seismic studies on the Halfdan field are expected to
provide a more accurate determination of the production effect
on acoustic impedance and therefore also expected to allow
for more rigorous quantitative analysis of the effects.
Interpreting the seismic pattern using stress
analysis
The impact of well design on the seismic response can be
studied in detail around the well Skjold-23G, which was
drilled as an early appraisal well on the northwestern part of
the field (Figure 7). The well intersects the later decided
development pattern and has been plugged and abandoned,
and later development wells passing the Skjold-23G well have
been zonally isolated from the formation where crossing
Skjold-23G. None the less, there are clear injection signatures
along the well trajectories, even where the wells are isolated
from the formation. This observation indicates that the fully
developed flow in the reservoir follows a pattern which is
influenced by other factors than the perforations and
completion details. Injection signatures bridging from injector
heel to injector heel across HDA-2X further demonstrate that
injection lines have developed, which form a linear pattern
throughout the entire field, and which extends beyond
completed as well as drilled well sections (Figure 7). By
arguments of force equilibrium, it will be demonstrated that
the observed flow pattern cannot exist without causing large
scale fracturing of the reservoir rock.
Since the seismic indicator correlates with the well pattern, we
will investigate how the well pattern influences the large scale
rupture of the reservoir rock. The development induces
stresses in the rock for two reasons; the rock frame contracts
due to cooling by cold injection water; and the flow of fluids
is associated with gradients in fluid pressure that are balanced
by forces in the rock. In order to derive which reservoir
parameters are of importance to formation parting, linear
displacement in a rectangular cross section is analysed (Figure
8). To keep the problem simple, piece-wise linear pressure
distribution and a step-wise temperature distribution are
modelled. The distribution of horizontal normal stress, x ,
'
along the vertical centre plane (x=0) is found using linear
elasticity theory, thus different load contributions can be
4 SPE 108531

treated independently while their combined effect can be producer and injector is linear. For typical reservoir rock
found by superposition. values between 0.1 and 0.3 are attained. This parameter is of
second order significance to the problem3.
Thermal contribution horizontal stress
' Contribution to horizontal stress from over- and underburden
The contribution to normal stress x,T from cooling can be
When pressures are not uniformly distributed in the reservoir,
assessed by considering the stresses generated due to cooling
over- and underburden loadings will distribute unevenly as
of a finite volume of rock embedded in an infinite
well. For the case under consideration we are interested in the
homogeneous elastic body. Plane strain conditions are
resulting normal stress on the centre plane x=0 (Figure 9).
applicable due to stress and temperature uniformity along the
This resultant is found by integrating the influence of
well axes. The normal stresses within the volume cooled from
magnitude
the original temperature TRES to TINJ are9, p443

E (TRES TINJ ) (PINJ Pp )

thermal contribution : 'x,T = (P0 P(x))dx = (P0 PINJ ) + x dx
2(1 ) L
E is Youngs modulus, is the linear thermal expansion along the top and bottom (y = H and y = -H) of the reservoir.
coefficient, TRES and TINJ denote reservoir and injection water In the equation above P0 is the pore pressure in the over- and
temperature respectively and is Poissons ratio. underburden, which is assumed equal to the initial reservoir
pressure (P0 = PRES). Integration gives the closed form
Contribution to horizontal stress from lateral flow solution:
Following the methods of analyses outlined by Jrgensen3 'x,V (y) =
normal stresses induced at the symmetry plane due to lateral
flow are derived as: (1 ) 1 L L
(PINJ P0 ) tan + tan1

2 H y H + y
'x,L (y) =
(1+ ) L 1 L
+ (PINJ P0 ) tan1 sin 2tan1
(1+ ) tan1 H - y 1 sin 2tan1 H - y 2
H y 2 H y

(PINJ - Pp ) L 2 L

2 (1+ ) L 1 L
1 H - y + (PINJ P0 ) tan1 sin 2tan1
(3+ ) tan L 2


H + y 2
H + y


(1 ) (H- y) L
(3+ ) ln sin tan1 H - y + + (PINJ Pp ) ln cos tan1
(PINJ - Pp ) (H- y)

L
2 L H y


2 L 1 H - y
(1+ ) 1 sin tan
2
(1 ) (H + y) L
+ (PINJ Pp ) ln cos tan1
L 2 L
H + y


(1+ ) tan1 H + y 1 sin 2tan1 H + y (1 ) (H - y) 2 1 L


(PINJ - Pp ) L 2 L + (PINJ Pp )
L
1- cos tan
2
H y
2 1 H+ y
(3+ ) tan L (1 ) (H + y) 2 1 L

+ (PINJ Pp ) 1 cos tan
L

2
H + y
(3+ ) ln sin tan1 H + y +
Discussion and conclusions drawn from analytical stress
(PINJ - Pp ) (H + y) L
modelling
2 L 2 1 H + y Large scale fracturing in the reservoir is strongly affected by

(1+ ) 1 sin tan

L the height-length ratio (H/L) as demonstrated below. For
Halfdan the relevant material parameters are those of 30%
porosity chalk, hence thermal expansion coefficient (=8x10-6
Here is Poissons ratio, = , PINJ, Pp denote injecting
1- (C)-1) Youngs modulus (E=1.1x106 psi) and Poissons ratio
and producing bottomhole pressures respectively and H and L ( = 0.2) are assumed. The well spacing in Halfdan is L=600
define the reservoir height and well spacing. From the above ft, a typical value for producing bottomhole pressure (Pp) is
equation it can be seen that H/L and the pressure difference 1,500 psia and a typical injection pressure (PINJ) is 5,000 psia.
(PINJ Pp) are the key parameters to the problem. If H/L The initial pressure in Halfdan (P0) was 4,200 psia and in the
approaches zero (limited reservoir height or infinite well analysed example, the average pressure is 12 (PINJ + Pp) =
spacing) the induced stress at the centre plane approaches zero
as well. The dependency on pressure difference between
SPE 108531 5

3,250 psia. For calculation of the thermal contribution cooling
by 60 C will be assumed.
With the reservoir and material values listed above, the
effective stress distribution at the centre cross section can be
1 1 1 1
calculated for H/L= 24 , 12 , 8 , 6 (Figure 9). Importantly, a
1
change in sign occurs for H/L around 12 , hence for larger
values the calculated normal stress is tensile. For L=600 ft,
1 lines and 2; these lines are formed continuously across
H/L = 12 corresponds to a flowing interval height of 100 ft
(2H=100 ft). Since chalk has a very limited load carrying
capacity in tension, opening of a fracture would result under
the modelled conditions.
In day to day injection management, parting of the formation
is considered the result of injecting at higher rates than the
current injectivity allows under non-fracturing conditions.
Hence, from a well surveillance standpoint, fracturing occurs
to accommodate an imposed rate flow. This view set may be
used to formulate leak-off models for dynamic fracture size
but it cannot offer any explanation for observed patterns in
fracture geometry.
In the present analysis linear flow in the reservoir causes the
parting of the formation. The analysis builds on fluid and solid
mechanics theory and explains why the seismic indicator for
injection is observed, not only where the injectors are drilled
and completed, but along the continuous lines of symmetry
defined by the reservoir flow.
The fact that the flow geometry determines the direction of
large scale fracturing means that the lateral flow in the
reservoir is developed across a certain height. Quantitative
analyses show that flow must have developed vertically across
100 ft of reservoir column or higher in order to produce the
observed fracture pattern (H/L > 1/12 generates tension,
Figure 9). Based on this finding it is concluded that the
Halfdan water flood is likely to sweep the full height of the oil
column.
So far, the development of the Halfdan field has only been
verified from indirect observations of production performance
being in agreement with modelled expectations. The Halfdan
3-D survey provides direct and independent evidence of
parallel injection fractures formed field-wide and aligned with
the injection well pattern. The seismic signatures related to
injection conform to the location of the wellbores, thus
confirming the survey data. Most importantly, it is observed
that 1; the water signature is distributed evenly along injection
unperforated intervals and across intervals not intersected by
injection wells.
The fact that the injection signatures form parallel lines, which
on the one hand align with injectors and on the other hand
extend beyond the well and completion intervals, proves that
the development pattern affects injection fracture propagation.
Analyses of flow induced stresses in Halfdan show that this
influence is evident when linear flow is developed to a height
of 100 ft or higher. The regularity observed in the seismic
response is thereby a strong indicator of vertical as well as
lateral flow distribution. Given the data and analyses presented
in this paper, it can be concluded that the sweep of oil most
likely includes the deeper part of the transition zone and
confidence in the recovery process is thus strengthened.
Acknowledgements
We would like to thank Mrsk Olie og Gas AS and the DUC
Partners, A.P. Mller-Mrsk AS, Shell Olie- og Gasudvinding
Danmark B.V. (Holland) and Chevron Denmark Inc. for their
permission to publish this work.

Conclusion
Many modelling studies over the years have been inconclusive
as to whether it is possible to monitor production induced
effects from 4-D analysis in relatively low porous chalk. The
current data effectively ends this discussion by demonstrating
a very strong seismic response to water injection in the
Halfdan field. It is concluded that the seismic response is a
combined effect of fluid substitution and compaction of the
rock, both increasing the acoustic impedance hardening the
rock and from increasing the pore pressure leading to lower
acoustic impedance softening the rock. In the upper part of
the reservoir the fluid- and compaction effect dominates over
the pressure effect resulting in a hardened response, however,
in the transition zone this changes to an apparent softening
because the fluid substitution effect diminishes with
decreasing initial oil saturation, compaction ceases with lower
porosity whereas the pressure effect remains constant.
6 SPE 108531

References

1. Surlyk, F., Dons, T., Clausen, C.K., Higham, J., Upper

Cretaceous in The Millennium Atlas: Petroleum Geology of the
Central and Northern North Sea", Evans, D., Graham, C.,
Armour, A. and Bathurst, P. (eds. and co-ordinators). 2003, The
Geological Society of London, 213-233.

2. Albrechtsen, T., Andersen, S.J., Dons, T., Engstrm, F.,

Jrgensen, O., Srensen, F.W., Halfdan: Developing Non-
Structurally Trapped Oil in North Sea Chalk, 2001 SPE ATCE,
New Orleans, Louisiana, U.S.A. SPE 71322.

3. Jrgensen, O., Using Flow Induced Stresses for Steering of

Injection Fractures, SPE/ISRM Rock Mechanics Conference,
20-23 October 2002, Irving, Texas, U.S.A. SPE/ISRM 78220.

4 . Rod, M. H. & Jrgensen, O., Injection Fracturing in a Densely

Spaced Line Drive Waterflood The Halfdan Example., 14th
Europec Biennial Conference, Madrid, Spain, 13-16 June 2005.
SPE 94049.

5. Gassmann, F, ber die Elastizitt Porser Medien, Vier.

Natur Gesellschaft, 1951, 96, 1-23.

6. Rgen, B. , Fabritius, I. L., Japsen, P., Hier, C., Mavko, G.,

Pedersen, J. M., Ultrasonic Velocities of North Sea Chalk
Samples- Influence of Porosity, Fluid Content and Texture,
2005, Geophysical Prospecting, 53, 481-496.

7. Avseth, P. Mukerji, T. and Mavko G., Quantitative Seismic

Interpretation, 2005, Cambridge University Press, Cambridge
UK.

8. Andersen, M., Petroleum Research in North Sea Chalk, 1995,

RF-Rogaland Research, Stavanger Norway.

9. Timoshenko, S.P., Goodier, J.N., Theory of Elasticity, Third

edition, 1970, McGraw-Hill Book Company.
SPE 108531 7

Figure 1: Halfdan field basic information

Figure 2: Production responses as observed in seismic amplitude data

8 SPE 108531

Figure 3: Production response in relative Acoustic Impedance, Cross-sectional view.

Figure 4: Production response in spectral decomposition. Injection along entire length of wells. Similar images with well paths in map view
overlain on right image.
SPE 108531 9

Figure 5: Effect of Fluid Substitution on Acoustic Impedance

Figure 6: Conceptual model of acoustic impedance variations with reservoir properties and production.
10 SPE 108531

Figure 7: Water injection lines detected by seismic with and without wells overlain (left and right images respectively). The injection
signatures form parallel lines, which align with injectors while extending beyond these due to fracture propagation. The hydraulic fracturing
and water flooding seems unaffected by wells crossing the general pattern (Skjold-23G and HDA-2X).

Figure 8: Cross-sectional model of linear displacement. For the stress analysis, a constant pressure gradient and a stepwise temperature
distribution are assumed. The cooling (TRES-TINJ) and the pressuere gradient (PINJ Pp)/L, together with the geometric parameter H/L
determines the stresses induced by production.
SPE 108531 11

Figure 9: Effective stress at centre plane for different H/L and constant injection and production pressures of 5,000 psia and 1,500 psia
respectively . Resulting normal stresses below zero causes fracturing, hence the criterion for fracturing is fulfilled for H/L > 1/12 under the
modelled pressure conditions.