Published 1986

18 Porosity

R. E. DANIELSON AND P. L. SUTHERLAND

Colorado State University
Fort Collins, Colorado

18-1 INTRODUCTION

The structure of the soil is related to many important soil physical prop-
erties, especially those pertaining to the retention and transport of so-
lutions, gases, and heat. Soil structure can be measured in various ways,
but perhaps it is most meaningfully evaluated through some knowledge
ofthe amount, size, configuration, or distribution of soil pores. It is often
the information concerning these pore spaces, rather than the soil par-
ticles, that is most useful in characterizing the soil as a medium for plant
growth or other uses. Within the soil matrix there exists an array of
complex interaggregate and intraaggregate cavities which vary in amount,
size, shape, tortuosity and continuity. Precise quantification of these char-
acteristics of soil pores is essentially impossible, due to their extremely
complicated nature. However, the total pore space can be determined
with relatively high precision, and by making certain assumptions, the
size distribution of the larger pores can be made with at least useful
accuracy for both laboratory and field purposes.
An important problem associated with the characterization of soil
pores is the lack of standard terminology related to their classification
into distinct size ranges. The need for a standard classification scheme
has been identified by various researchers, and suggestions for such a
classification have been made. Typical examples are the proposed index
for soil pore size distribution of Cary and Hayden (1973), the suggested
classification of micro-, meso- and macro porosity by Luxmoore (1981),
and the responses of Bouma (1981), Beven (1981) and Skopp (1981). A
second problem relates to the need for identifying pore size in terms of
an equivalent cylindrical diameter. This results from the complex and
variable pore shapes and their interconnected nature. Commonly these
equivalent diameters are estimated from liquid retention and capillary
pressure considerations, and the computed size may be somewhat de-
pendent upon the method used.
A thorough discussion relating to the general subject of pore structure
may be found in the text of Dullien (1979), and a review of techniques
that have been used for measuring pore sizes in soil is provided by Law-
Copyright 1986 © American Society of Agronomy-Soil Science Society of America, 677
South Segoe Road, Madison, WI 53711, USA. Methods of Soil Analysis, Part 1. Physical
and Mineralogical Methods-Agronomy Monograph no. 9 (2nd Edition)
443
444 DANIELSON & SUTHERLAND

renee (1977). Nitrogen sorption is an estabished practice for determining

pore-size distribution, but although it has been used, the method appears
to have limited potential for evaluating a wide range of pore sizes in
soils. Wilkins et al. (1977) have described a procedure for direct mea-
surement of soil pores larger than 20 }Lm by vacuum impregnation with
a fluorescent polyester resin followed by sectioning and photographing
under black light.
Although the porosity and pore size distribution of many porous
materials have been satisfactorily measured by a variety of techniques,
only a few have been adequately evaluated and commonly accepted for
use with soils. In this chapter, two methods, calculation from density
measurements and direct evaluation by the gas pycnometer, are provided
for determining total pore space. Also, two methods, water retention and
mercury intrusion, are described for identifying the pore size distribution.

18-2 TOTAL POROSITY

18-2.1 Calculation from Particle and Bulk Densities

18-2.1.1 PRINCIPLES
Total soil porosity may be calculated if the particle density, PP' and
the dry bulk density, Pb, are known. The ratio Phi Pp is the fraction of the
total volume occupied by solids, and this value subtracted from unity
gives the fraction of the total volume occupied by pores. Total porosity,
Sh is therefore calculated by:

[1]

18-2.1.2 APPARATUS
The apparatus required for the various methods used in measuring
bulk and particle densities are described in chapters 13 and 14, respec-
tively.

18-2.1.3 PROCEDURE
Measure the particle density and the bulk density of the soil using
one of the procedures described in chapters 13 and 14. The procedure
to be chosen depends upon the accuracy desired in calculating the total
porosity. The number of soil samples to be obtained must be based on
the spatial variability of the soil. Using the density values, or averages
of values, calculate total porosity using Eq. [1].

18-2.1.4 COMMENTS
Particle density of soil is essentially constant over a reasonable time
period. Thus, the value obtained for total porosity will vary with bulk
POROSITY 445

E
-
~ 1.0
o
~ 0.98
"0
.
>~ 096

~., 0.94
0::
0.92

0.91~~---:-' ___- - - - ' - - - - L - - - - - . . L_ _--'-_ _--I

2,.50 2.55 2.60 2.65 2.70 2.75 2.80
Actual Particle Density. Mg m- 3
Fig. 18-1. Relative error in calculation of total porosity of soil when particle density is
assumed to be 2.65 Mg m- 1• The three curves represent bulk density values of 1.2, 1.4,
and 1.6 Mg m- 1.

density variations. If an aggregate (clod) is used for the evaluation of Ph,

the calculated porosity will reflect only the aggregate and not the inter-
aggregate pore volume. The influence of shrinking and swelling of the
soil must be taken into consideration when bulk density is measured.
The bulk volume of the sample must be determined at the water content
of interest to allow calculation of St at that degree of wetness.
When a highly accurate determination of total porosity is not re-
quired, an estimate of soil particle density may be satisfactory. For many
mineral soils Pp is approximately 2.65 Mg m- 3 • If this value is used instead
of the actual measurement, the error in calculating St by Eq. [1] is shown
in Fig. 18-1. As an example, if the true values for Pp and Pb are 2.55 and
1.40 Mg m- 3, respectively, the error resulting by estimating the particle
density as 2.65 will be < 5%.

18-2.2 Gas Pycnometer Method

18-2.2.1 PRINCIPLES
The pycnometer method for measuring gas-filled volume is based on
Boyle's Law of volume-pressure relationships. Assume a given amount
of gas (moles) confined in a given volume at a specified temperature and
pressure. Boyle's Law states that the product of temperature (1) and
pressure (P) will remain constant if the gas is compressed or allowed to
expand and again brought to the previous temperature. Thus, PI VI =
P2 V2, where the subscripts refer to the initial and final pressure and vol-
ume.
446 DANIELSON & SUTHERLAND

In practice a sample chamber is used in conjunction with a reservoir

chamber. Either of two methods may be utilized. The volume of the
reservoir may be changed after sealing the system and the resulting pres-
sure change measured, or the reservoir and sample chamber may initially
contain gas at different pressures and the resulting pressure change in the
sample chamber measured after they are pneumatically connected.
Sketches of systems utilizing these two methods are shown in Fig. 18-2.
When the variable volume pycnometer is used, the volume of gas in
the complete system after compression, Vb may be calculated using Eq.
[2]. Since PI VI = P 2 V2 and VI = V2 + Ll V (where Ll V is the change in
volume after the system is sealed), it follows that PI (V2 + Ll V) = P 2 V2•
Thus, V2 = (PI Ll V)/(P2 - PI) or

[2]

where M is the change in gas pressure resulting from Ll V. It must be

remembered that Eq. [2] holds only when the amount of gas is constant
(no leaks) and the temperature is constant (all materials are at ambient
temperature and heat resulting from gas compression has dissipated). If
the sample chamber is sealed at atmospheric pressure, PI may be obtained
from a barometer reading, M is read from the pressure gage, and Ll V
must be known.
The volume of gas in the system after compression, V2, may be de-
termined with and without a soil sample in the chamber. The difference,
[V2 (without sample) - V2 (with sample)], is the volume of solids and
liquids in the sample. If this value is subtracted from the sample bulk
volume, the result is the volume of gas-filled pores in the soil sample.
When the constant volume pycnometer is used, the volume of gas
in the sample chamber, Vc, may be calculated by equating the sum of the

A B

Reservoir Gas In let

Bellows
Merc ury
valve -1~~~~_ To Pressure Gage
Manometer
or Appropr ia te Gage
Vent

Fig. 18-2. Diagrammatic sketches of two types of gas pycnometer, the variable volume
system (A) and constant volume system (B).
POROSITY 447
pressure-volume products ofthe chamber and the reservoir to that of the
combined system after the valve is opened (Fig. 18-2). This is expressed
as V,Pc + V,Pr = (Vc + Vr)P, where subscripts c and r refer to the sample
chamber and the reservoir, respectively, and P is the pressure in the
combined system after equilibration. Solving for Vc:

[3]

As with the previous case, the volume ofliquid and solid in a soil sample
may be obtained from the difference in Vc determined with and without
the sample in the chamber. The gas-filled porosity is then calculated from
the bulk volume of the soil sample.

18-2.2.2 APPARATUS
Construct the gas pycnometer as indicated in Fig. 18-2. The aid of
a professjonal machine shop will usually be required. The sample cham-
ber must be designed for easy closing after a soil sample of known bulk
volume is inserted. It is expedient to have the chamber just large enough
to contain a sampling cylinder used to obtain bulk samples from the field.
A volume of 80 to 100 cm 3 should be useful for most purposes. A leak-
proof vent must be available on the sample chamber to establish at-
mospheric pressure when desired. A bellows, with reproducible open and
closed stops, is recommended for the variable volume pycnometer. The
change in volume, .:1 V, when the bellows of the variable volume pyc-
nometer is collapsed, and the volume of the reservoir of the constant-
volume instrument may be approximately one-third the volume of the
sample chambers for effective use over a range of soil porosity values.
An automobile tire valve may be used for a gas inlet device on the
reservoir. Tubing required for connections on the pycnometer should be
rigid and of small bore. Any suitable pressure-sensing device may be
installed, providing it has a sensitivity suitable to the results desired. A
mercury manometer is ideally suitable, providing the pycnometer is ad-
equately supported in an upright position to prevent spillage. The device
should be capable of measuring gage pressure to approximately 40 kPa.
Construct a set of identical sampling cylinders with outside diameter
and length to easily fit into the sample chamber of the pycnometer. If
the calibration method is to be used, prepare solid calibration discs which
fit closely into the sampling cylinders and which occupy specific fractions
of the total cylinder volume. Discs of 5, 10, 20, 25, and 50% are suggested.
Various commercial gas pycnometers are available. They are rela-
tively expensive and are capable of higher precision than is usually war-
ranted for soil porosity measurements, because sampling errors are usu-
ally significantly larger than measurement errors.

18-2.2.3 PROCEDURE
18-2.2.3.1 Variable Volume Pycnometer. Obtain a soil core sample
in a sampling cylinder designed for the pycnometer. Oven-dry the sample,
448 DANIELSON & SUTHERLAND

cool to ambient temperature, insert the cylinder with the soil into the
sample chamber of the pycnometer, and seal. Open the vent to establish
atmospheric pressure in the chamber, open the reservoir bellows to the
maximum, close the vent, and collapse the bellows to the stop. Read and
record the pressure gage, M, as soon as a constant pressure is attained.
If the pressure decreases, a leak exists in the system and the measurement
is invalid. Open the vent to return the pressure to atmospheric. A second
measurement may be obtained, if desired, before removing the sample
from the chamber. Calculate the volume of air in the pycnometer after
compression, V2 , using Eq. [2]. Repeat the procedure when the sample
chamber contains a clean sampling cylinder without soil.
The volume of solid phase in the soil sample is obtained by sub-
tracting V2 measured with the soil in the chamber from V2 measured
without soil. The total porosity, Sf' of the soil sample may be calculated
from Eq. [4]. '

S = [(V2 without soil) - (V2 with soil)

[4]
( volume of sampling cylinder

In order to use Eq. [2], the atmospheric pressure, PI, may be measured
with a barometer. The volume change due to collapse ofthe bellows, Ll V,
is usually difficult to measure directly; however, the value may be cal-
culated from the values of Eq. [2] obtained when the sample cylinder is
filled with air and when it is filled with solid calibration discs. Let the
symbols of Eq. [2] represent the conditions when the cylinder is air-filled
and let LlP* be the change in pressure resulting from Ll V when the sample
cylinder of volume Vs is completely filled with calibration discs. Then

Thus

[5]

18-2.2.3.2 Constant Volume Pycnometer. Obtain a soil sample in a

sampling cylinder designed for the pycnometer. Oven-dry, cool to am-
bient temperature, insert into the sample chamber of the pycnometer,
and seal. Close the vent on the chamber and open the valve between the
chamber and reservoir. Using an appropriate pump, inflate the system
to give a gage pressure of approximately 35 kPa. The desired gage pressure
may be obtained by over inflation followed by careful release of air through
the vent. Test for leaks by observing the gage for a few minutes. Measure
atmospheric pressure with a barometer and record the absolute air pres-
sure, P" in the reservoir. Close the valve between sample chamber and'
reservoir. Open the vent to establish atmospheric pressure in the cham-
ber, Pc> and then close it again. Open the valve to allow equilibration
POROSITY 449
between chamber and reservoir, allow time for thermal equilibrium and
record the absolute pressure, P, of the combined system. The volume of
air, Ve, in the sample chamber may be calculated by Eq. [3]. Repeat the
procedure using a clean sampling cylinder without soil. Calculate the total
porosity of the soil, St, using Eq. [4] when V2 is replaced by Vc.
18-2.2.3.3 Use of Calibration Curves. The above procedures require
that the barometric pressure and certain volume values of the pycnom-
eters are known so that Eq. [2] and [3] can be solved. It may be expedient
to use calibration curves rather than the equations for determining the
air-filled pore space ofthe soil sample. This is accomplished by measuring
the value Mor P, in case of the variable or constant volume pycnometers,
respectively, when the sampling cylinder contains known fractions of air-
filled volume. The appropriate procedure described above for soil samples
is used repeatedly to obtain gage pressure readings when a clean sampling
cylinder, containing various combinations of calibration discs, is inserted
into the sample chamber. Prepare a graph relating gage reading to air-
filled pore space, St. Use this curve to determine St when soil samples
are used in the pycnometer. When the calibration method is used with
the constant volume pycnometer, the system must be inflated to precisely
the same gage pressure when measuring porosity of soil samples and when
using the calibration discs.
A calibration curve prepared under a specific value of atmospheric
pressure is not applicable if the pycnometer is used at a different elevation.
Thus, separate calibrations must be obtained for each value of atmos-
pheric pressure at which the instrument is to be used. Usually, the var-
iation in barometric pressure at a given elevation is not of sufficient
magnitude to be of concern; however, it is advisable to check the cali-
bration curve periodically by measuring the gage pressure at one or two
known values of St.
When the barometric pressure is measured and the characteristics of
the pycnometer are known, so that Eq. [2] or [3] together with [4] are
used, the instruments may be used at any elevation.

18-2.2.4 COMMENTS
Further details ofthe construction and operation of gas pycnometers
for use in the field are given by Russell (1950) for the variable-volume
type and by Page (1948) for the constant-volume system. Commercial
instruments are usually designed to use helium as the gas instead of air,
since helium does not absorb on most solids and more closely obeys the
perfect gas law. Identical temperature is required before and after the
pressure change in the system but may vary from one measurement to
another. The soil in the pycnometer sampling cylinder may shrink to
some degree when oven-dried. As a result, the "pore space" within the
cylinder may not all be within the soil core; however, the total porosity
measured represents the soil at sampling time.
450 DANIELSON & SUTHERLAND

Since the gas pycnometer may be used to determine the volume of

solid phase in an oven-dried soil sample, the particle density may be
determined in this manner. Accuracy will not equal that·of the method
described in chapter 14 for particle density measurement unless com-
mercial pycnometers using helium gas are utilized.
If the calibration method is to be the only method used, the pressure-
sensing system on the pycnometer does not have to accurately measure
gage pressure. The gage reading may be used for the calibration curve
even though it is not a true pressure measurement. This is useful when
a mercury manometer serves as the pressure sensor, because the scale
does not have to be set for a true zero reading.
Although the procedure is written to use an oven-dried soil sample
in order to measure total porosity, a wet sample may also be used in the
pycnometer. The method then measures the air-filled porosity at the water
content of the soil. This might be useful for evaluating soil aeration
potential at a given time; for example when the soil is at the "field ca-
pacity." Total soil porosity, S" can be calculated by adding the volumetric
water content to the air-filled porosity measured by the pycnometer.

18-3 PORE SIZE DISTRIBUTION

18-3.1 Water Desorption Method

18-3.1.1 PRINCIPLES
Evaluation of the size, configuration, and distribution of the soil pores
is essentially impossible due to their extremely complicated nature. How-
ever, by making certain assumptions, the size distribution of the larger
pores can be measured with at least useful accuracy. If we start with a
saturated soil sample, drain it by steps, and measure the volume of water
removed between consecutive steps, we can equate the volume of water
removed to the soil pore-volume drained. Then, if the size-range of pores
drained during each step can be calculated, the pore-size distribution can
be determined. In theory, the largest pores should drain first, followed
by successively smaller and smaller pores. Actually the drainage of the
"pore" will be determined by the size of the largest "opening" of that
pore to a larger one.
The pressure difference (ill» across an air-water meniscus, as in a
capillary tube, is expressed as

[6]
where (1 is the surface tension of water (J m- 2), rcis the radius of curvature
of the meniscus (m), 8 is the contact angle (degrees) of water to the solid,
and rp is the radius of the tube (m). ill> is then expressed as pascals. If
the contact angle is assumed to be zero, the cosine of 8 becomes unity
POROSITY 451

and the radius of meniscus curvature is equal to the radius of a circular

capillary tube of size equivalent to that of the pore. Thus, Eq. [6] can be
altered to

[7]

where rp is considered to be the equivalent cylindrical pore radius.

As water is removed by any means from the porous medium, the
radius of curvature of air-water interfaces will decrease. When rc decreases
to the effective radius of a given pore, that pore will drain as further
water is removed. All pores with effective radii of a lesser value will still
be water filled. When a given water content in a soil sample is attained
by bringing the water matric potential to a desired value using a porous
plate, the pore size dividing water-filled pores and drained pores may be
calculated from Eq. [7]. When equilibrium has been reached, the pressure
difference across the meniscus (6.P) will be equal to the pressure difference
across the porous plate.

18-3.1.2 APPARATUS
A device is required whereby a saturated soil sample can be drained
stepwise to known matric potentials and a volume measurement obtained
of the water removed during each step. A filter funnel modified as shown
in Fig. 18-3 is ideal. For less precise measurements the funnel may be
simply attached with flexible, thick-walled, transparent tubing to a suit-
able buret fitted with a stopcock. In this case the pressure differential
established across the porous plate of the funnel is limited by the extent
to which the buret can be lowered below the level of the plate. When a
water column of 2 m is established, the smallest soil pores drained at
equilibrium would have an equivalent diameter of approximately 15 J.lm.
The filter funnel should be of convenient size to contain the soil
sample in an appropriate sampling cylinder. Funnels of various diameters
and with a wide range of air-entry values are commercially available.
Plates with maximum pore diameter of approximately 5 J.lm are appro-
priate. Those with smaller pores have reduced permeability values and
require longer times for sample equilibration during drainage steps.
The funnel system diagrammed in Fig. 18-3 may be easily con-
structed by an experienced glass-blower. The welds attaching the inner
and outer tubes to the funnel should be made as close to the porous plate
as possible. A battery of funnels of this construction is shown in the
photograph of Fig. 18-4. The plate diameter and overall length of these
units are 65 mm and 60 cm, respectively. A good quality stopcock is
required at the bottom to avoid inadvertent loosening under the pressure
of mercury in the outer tube. The inner tube should be of uniform inside
diameter along its length and carefully centered within the outer tube.
A cathetometer for precision measurements of elevation is essential
to determine the volume of water removed from the soil sample during
452 DANIELSON & SUTHERLAND

---------------,...- - Cover

.~-- Soil Sample

(l!) -r~~~~~~~-- Porous Plate

+ - -- - Water
(a)

¥ -- - Filling Stem

(y)-+-- --l

(b)

( z) -'--~-\,-,{!!

VN.! Mf;t---- - - Mer cu r y

Fig. 18-3. Porous funnel apparatus for determining pore-size distribution in soil.

each drainage step. This instrument, shown in Fig. 18-4, should allow
easy readings to 0.1 mm.

18-3.1.3 PROCEDURE
Specific instructions for measuring pore-size distribution of a soil
sample using water desorption data will depend on the specific equipment
used. The procedure provided in this section relates to the use of porous
funnel systems comparable to the design shown in Fig. 18-3 and 18-4.
The general methodology is comparable for use of equipment of other
design.
Prepare the apparatus, as shown in Fig. 18-3, by inverting the funnel,
opening or removing the stopcock, and slowly adding previously boiled
water at room temperature through the filling stem (boiling under vacuum
is an ideal way to remove air from the water). When the entire system
is full of water, close the stopcock, return the funnel to the upright po-
sition, and clamp it to a ring stand or other support. Check to be sure
POROSITY 453

Fig. 18-4. Filter funnels used for pore-size distribution and a cathetometer for measuring
elevations.

there are no air bubbles under the porous plate or anywhere within the
inner glass tube.
Add water through the filling tube until it overflows; then slowly add
mercury to force water out of the filling tube and upward through the
porous plate. Add mercury until the Hg-H 20 interface (y) is a short
distance below the weld of the inner tube and the Hg-air interface (z) is
approximately level with y. Make certain there are no air bubbles below
the porous plate. Remove the water from above the porous plate and
from above the mercury in the outer tube. Cover the funnel to eliminate
evaporation.
Calibrate the funnel as follows. Lower the level of z about 5 cm by
removing mercury through the stopcock. Measure the level of y with the
cathetometer and record to the nearest 0.1 mm. Lift cover to pipette 1.00
cm 3 of water onto the porous plate. Establish equilibrium, measure, and
record the resulting level of y. Repeat as needed to obtained a series of
values, lowering z when necessary. Calculate the changes in the elevation
of y for each addition of 1.00 cm 3 of water, and record the average value
as the calibration factor, k.
The soil sample to be used for pore-size distribution analysis should
be contained in a metal or plastic cylinder about 1 cm high and of such
diameter that it can be placed in, and removed from, the funnel with a
large tweezers or forceps. Refer to chapter 13 section 13-2.2.1 for field
sampling techniques. Secure high-density filter paper to the bottom of
the sample cylinder by forcing the cylinder into a larger ring to hold the
paper in place, or secure paper with an elastic band. Trim away excess
454 DANIELSON & SUTHERLAND

filter paper. If a disturbed sample is used, secure the paper across the
sample cylinders, add the soil, and pack as desired.
Prepare the funnel apparatus and adjust the Hg-H 20 interface, y, as
described above for calibration. Place the soil sample in the funnel. Add
mercury through the filling tube so that water is forced through the plate.
Continue to add as much mercury as possible, add water around the
sample as needed, and allow time for the soil to become saturated. Refer
to soil sample wetting technique (chapter 26, section 26-6.2.2).
Lower the Hg-air interface, Z, and continue adjusting until y is in
the calibrated portion of the tube and the distance b is as small as possible.
The objective is to bring the system to equilibrium at as small a suction
as possible, so that the soil sample remains saturated. It is possible, with
careful adjustment, to have the value of b approximately 1 mm. Water
may be removed or added above the porous plate to adjust the level of
y. When the system is at equilibrium, with the funnel sealed to prevent
evaporation, measure and record the elevations of x, y, and Z to the
nearest 0.1 mm. A convenient format for recording measured and cal-
culated data is shown in Table 18-1.
Withdraw mercury to lower the level of y, to establish the second
equilibrium at a value for b of approximately 1 cm. Again measure and
record elevation of y and z. Continue to establish equilibrium steps with
values for b of approximately 2.5,5,10,15, and 20 cm of mercury. Longer
and longer equilibrium times will be required as the matric potential of
the soil water decreases. Periodic readings of y with the cathetometer will
allow detection of equilibrium. A day or so may be required at the greatest
suction, depending on soil type and depth of sample.
Table 18-1. Data for determination of pore-size distribution using the
water desorption method. An example.
Funnel no. _1_ Calibration factor, k ~ Elevation of x 94.33 cm
Temperature 22°C Surface tension 0.07244 J m- 2
Max diameter
Eq. saturated
no. (Y) (Z) (a) (b) h pore
- - - - c m - - - - cmH,O /tm
1 80.82 80.41 13.51 0.41 19.1 0.243 0.388 1.00 155
2 80.46 79.55 13.87 0.91 26.2 0.229 0.366 0.94 113
3 79.70 77.94 14.63 1.76 38.5 0.199 0.318 0.82 77
4 78.21 73.99 16.12 4.22 73.3 0.142 0.227 0.58 40
5 77.10 67.42 17.23 9.68 148.3 0.098 0.157 0.41 20
6 76.87 61.23 17.46 15.64 229.2 0.089 0.142 0.37 13
7 76.65 56.05 17.68 20.60 296.6 0.081 0.129 0.33 10
8 ...
Gross wet wt. soil sample 36.56 g Calculated bulk density, Qb ~Mgm-3
Gross dry wt. soil sample 34.81 g Calculated total porosity, St 0.3879
Tarewt. 13.17 g Particle density 2.61 Mg m- 3
Ow at final equilibrium 0.0809
POROSITY 455

When values for the final equilibrium have been recorded, remove
the soil sample from the funnel, transfer the soil and filter paper to a
weighing dish, obtain wet and oven-dry weights, and calculate the final
water content on the weight basis (Ow). Record the laboratory temperature
and the surface tension of the water.
Calculate the soil water suction, h, in cm of water at each equilibrium
by

h = a + PHg b [8]

where PHg is the density of mercury in Mg m- 3 at the laboratory tem-

perature. Calculate the water content, Ow, at each of the other equilibrium
values by

Ow = final Ow + PH20 (ar - a}/w k [9]

where PH20 is the density of water (1.00 Mg m- 3 may be used), aris the
value of a at the final equilibrium, w is the oven-dry mass of the soil
sample, and k is the calibration factor for the funnel.
Multiply Ow at each equilibrium by the sample bulk density to obtain
the volume fraction of water, Ov. The bulk density, Mg m- 3, may be
calculated from the sample dry mass and bulk volume or determined by
assuming the soil sample is saturated at the first equilibrium value. The
latter case will be appropriate for many soils, since the matric potential
is only negative 1 or 2 kPa. In that case, the bulk density may be calculated
if the particle density is known. The total porosity, Sf) may be expressed
as:

Sf = (Pb) (Ow at equilibrium no. 1). [10]

Combining with Eq. [1] results in:

Pb = 1/[({lw at eq. no. I} + (l/p p )] • [11]

Calculate Sf using Eq. [1] or [10]. Divide the value of Ov at each

equilibrium by Sf to obtain the fraction of total pore space occupied by
water. Calculate the diameter in ,urn of the largest water-filled pore at
each equilibrium by:

[12]

where u and Pw are surface tension (J m - 2) and density (Mg m - 3) of water,

g is the gravitational acceleration (m S-2), and h is the matric suction
(centimeters of water).
Table 18-1 provides an example of a convenient manner for record-
ing data and demonstrates the results for a typical soil core. The fraction
456 DANIELSON & SUTHERLAND

1.00
•8 0.90
Q.
II) 0.80
!
~ 0.70
2 0.60
~
.... 0.50
o
~ 0.40

...e0.30
~ 0.20
:s
"60.10
>
°o~--~--~--~~--~--~--~----~--~--~
20 40 60 80 100 120 140 160 180
Pore Diameter. I'm
Fig. 18-5. Pore-size distribution for two soils. Data for the sandy loam are given in Table
18-l.

of total pore space filled with water, ()v!S/o may be plotted as a function
of pore diameter to express the pore-size distribution (Fig. 18-5).

18-3.1.4 COMMENTS
Certain errors are inherent to the water desorption method of pore-
size distribution. Some plate drainage could occur as suction is increased.
This may be checked during calibration of the funnel by measuring the
change in elevation of y when the elevation of z is lowered. With good
quality equipment this drainage is negligible. The calculation of pore size
is based on the assumption that the pores are of capillary-tube shape and
that the contact angle of water to soil (Eq. [6]) is zero. It is customary
to ignore these obvious problems by expressing pore size in terms of
"equivalent" radius or diameter. The use of filter paper to contain the
sample, and thus allow complete removal of all soil from the plate, enters
into the determined pore-size determination. This error is minimized by
having a small ratio of paper to sQil sample. Evaporation losses during
establishment of equilibrium should be avoided as far as possible. A cover
of waxed paper or plastic sheet may be secured over the funnel with tape
or elastic bands, so that it is water-vapor-tight but flexible to maintain
the air around the sample at atmospheric pressure. Errors due to normal
temperature changes are minimal, the greatest influence being on the
calculation of pore size from Eq. [12]. Water density (Pw) changes are
negligible, but the value for surface tension (0-) changes about 0.2% for
each degree change in temperature. A constant-temperature room is pref-
erable, but ordinary laboratory conditions may be satisfactory if caution
is used to prevent temperature change due to air currents or direct sun
radiation on the equipment.
The greatest chances for error undoubtedly relate to determination
of sample volume or bulk density and to assurance of sample saturation.
POROSITY 457

When soil is wetted its bulk volume will increase to an extent depending
on the particular soil. Thus, the use of cylinder size to represent sample
volume may not be satisfactory for calculating bulk density and total pore
space. Since it is very difficult to measure the soil bulk volume when it
has swelled, it is probably most precise to use Eq. [10] and [11] if care
is taken to have minimum matric suction at equilibrium no. 1. The effort
expended to achieve complete saturation and to prevent errors due to
gas production within the sample by microorganisms depend upon how
the data are to be used. For some soils, the assumption that the contact
angle is zero may be the dominant error of the determination.
The matric suction values established at each equilibrium will depend
on pore-size values desired. The values for b indicated in the described
procedure will provide points to plot a satisfactory pore-size distribution
curve for most soils. Intermediate steps may be utilized if desired.
As pointed out by Russell (1949), bimodal pore size distribution
curves are commonly found for well aggregated soils as a consequence
of the intraaggregate and interaggregate pores. Voorhees et al. (1966) have
used a unique method for measuring the pore volume between aggregates.
They utilized small glass beads as a non-imbibing "fluid" to fill the in-
tercrumb space. The volume of these macropores was calculated from
the mass of the beads and their predetermined bulk density.
Regardless of the limitations to the water desorption method for
measuring pore size distribution, it serves as the most commonly used
technique.

18-3.2 Mercury Intrusion Method

18-3.2.1 PRINCIPLES
Mercury intrusion porosimetry has been utilized as a reliable method
for determining pore-size distribution of a wide variety of porous solids
(Ritter & Drake, 1945a, 1945b; Winslow & Diamond, 1970). The tech-
nique has been further expanded for use with clay systems (Aylmore &
Quirk, 1967; Diamond, 1970; Sills et aI., 1973a, 1973b) and with soil
(Klock et aI., 1969; Nagpal et aI., 1972; Sills et aI., 1974; Lawrence, 1977;
Ragab et aI., 1982).
The theoretical basis for using mercury intrusion to determine pore-
size distribution is similar to that for the water desorption method, except
that pressure is required to force the mercury into the pores instead of
suction to remove water from a saturated system. Because mercury is a
nonwetting liquid for most materials, the contact angle, 8, has a value
greater than 90°. Thus, it will enter the pores of a solid only if an external
pressure is applied. The pressure required is dependent on the value of
the contact angle, the size and geometry of the pore, and the surface
tension. If the porous material is initially evacuated, Eq. [6] may be
restated as:
458 DANIELSON & SUTHERLAND

rp = -20" cosO P-I [13]

where rp is the calculated pore radius (m), 0" the surface tension of mercury
(J m -2), 0 the contact angle of mercury on the porous solid, and P is the
absolute pressure applied (N m- 2). Since cosO is negative for the obtuse
angle of contact, a negative sign is required in the equation to obtain a
positive value for the radius of the pore, rp.
The porous sample is dried, evacuated, and inundated in mercury,
and pressure is applied hydraulically in discrete steps. The diminution
of the bathing mercury is measured and equated to the volume of pores
invaded at each pressure step. Equation [13] is used to calculate the
equivalent radii of the smallest pores filled with mercury, assuming a
model of cylindrical capillary tubes of differing sizes. Because the pore
geometry is not that simple, it may be necessary to use a correction factor
in order to obtain "effective" pore size-volume relationships that are
useful in predicting certain soil properties.

18-3.2.2 APPARATUS
Two types of mercury intrusion porosimeters are commercially avail-
able. One type is designed to obtain data by applying pressure incre-
mentally; the second type is the scanning porosimeter which provides
for a constant increase or decrease in pressure and the recording of in-
truded or extruded mercury volume on a continuous basis. The mercury
volume is measured using a capacitance bridge.
Although the commercial porosimeters differ in certain aspects, each
instrument consists of two components. One is used for mercury intrusion
into the porous material by pressures less than atmospheric. This requires
allowance for evacuation of the sample and subsequent mercury-filling
by desired fractions of atmospheric air pressure. The second component
consists of a system for establishing pressures greater than atmospheric.
The most advanced instruments have an upper pressure limit of over
400 MPa (4000 bars), which allows evaluation of equivalent cylindrical
pore radii to a minimum of approximately 1.5 nm.

18-3.2.3 PROCEDURE
Specific step-by-step procedures are dependent on the porosimeter
chosen for the analysis. The instructions for the equipment should be
followed. An oven-dried soil sample is placed in the penetrometer as-
sembly. The penetrometer is then inserted into the filling device, sealed,
and evacuated. Pressure on the mercury in the penetrometer is increased
by small increments and readings of pressure and mercury volume are
recorded for each step. When a continuous scan porosimeter is used,
pressure and mercury volume are recorded continuously.
The equivalent pore radius at each applied pressure value is calcu-
lated from Eq. [13]. It has been observed that pore radii are consistently
underestimated using the mercury intrusion technique. Thus, an empir-
POROSITY 459
ical correction factor may be necessary. Klock et al. (1969) suggested that
the correction factor required for their measurements was 1.31, to be
multipled by the calculated pore size. It has been observed by Nagpal et
al. (1972) that the correction factor may not be the same for all soils.
They suggested that it varies linearly with the clay content of the soil.
Ragab et al. (1982) compared the water desorption and mercury intrusion
methods of determining pore size distribution for use in evaluating soil-
water characteristic curves and hydraulic conductivity relationships. A
correction factor of 2.60 for the mercury method was found to be nec-
essary for their data. Once the "effective" pore size is calculated by mul-
tiplying the equivalent value obtained from Eq. [13] by the desired cor-
rection factor, the pore volume obtained from the amount of mercury
intruded into the sample can be related to the size of pores.
Pore-size distribution may be determined in a manner similar to that
described for the water desorption method. The volume of pores not
intruded with mercury at the maximum applied pressure may be deter-
mined by subtracting the volume of intruded mercury from the total pore
volume, St, as calculated from Eq. [1]. A check on the volume of intruded
mercury may be made by weighing the sample assembly containing the
soil and mercury after the final pressure step. Subtracting from this the
mass of the sample holder and of the oven-dry soil provides the mass of
mercury in the pores, and when divided by PHg the volume is obtained
(Nagpal et aI., 1972).

18-3.2.4 COMMENTS
The mercury intrusion porosimetry method for determining pore-
size distribution in soils is a very convenient and fast method. However,
several sources of error have been identified. The value of the mercury-
particle contact angle is uncertain. Reported values range from 112 to
150 0 for various types of porous materials (Lawrence, 1977). The value
for clay-mercury systems has been reported to range from 139 0 for mont-
morillonite to 147 0 for illite and kaolinite (Diamond, 1970). A value of
130 0 has been used by Sills et al. (1973a) and Nagpal et al. (1972). Contact
angle hysteresis may also influence the accuracy of the mercury porosi-
metry measurements when a continuous scan instrument is used. The
effect has been observed with several porous media (Lowell & Shields,
1981a, 1981 b). The result is a greater mercury volume at a given pressure
during extrusion than during intrusion.
Uncertainty also exists concerning the surface tension of mercury.
Values have been reported to range from 0.43 to 0.52 J m- 2• The most
probable range is from 0.472 to 0.487; a value of 0.473 has commonly
been used for soil porosimetry measurements. Lawrence (1977) points
out that the error associated with surface tension variation is not very
important when compared to those related to contact angles. A rise in
temperature with a consequent decrease in surface tension is expected
when the pressure is increased. The error associated with this effect can
460 DANIELSON & SUTHERLAND

be alleviated by waiting for temperature equilibrium between pressure

steps.
Further sources of error may be associated with mercury compres-
sion, nonuniform pressure distribution within the soil sample, impurities
in the mercury, and entrapped air in the sample after initial evacuation.
The collapse of the pores and subsequent compression of the soil sample
during the measurement period may also be a source of error. There
appears, however, to be little information available concerning the effect
of mercury intrusion on pore distortion.

18-4 REFERENCES

Aylmore, L. A. G., and J. P. Quirk. 1967. The micropore size distribution of clay mineral
systems. J. Soil Sci. 18:1-17.
Beven, K. 1981. Micro-, meso-, macroporosity and channeling flow phenomena in soils.
Soil Sci. Soc. Am. J. 45:1245.
Bouma, J. 1981. Comment on "micro-, meso-, and macroporosity of soil." Soil Sci. Soc.
Am. J. 45:1244-1245.
Cary, J.W., and C.W. Hayden. 1973. An index for soil pore size distribution. Geoderma
9:249-256.
Diamond, S., 1970. Pore size distributions in clays. Clays Clay Miner. 18:7-23.
Dullien, F. A. L. 1979. Pore structure. p. 75-155. In Porous media. Academic Press, New
York.
Klock, G. 0., L. Boersma, and L. W. DeBacker. 1969. Pore size distributions as measured
by the mercury intrusion method and their use in predicting permeability. Soil Sci.
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Lawrence, G. P. 1977. Measurement of pore sizes in fine-textured soils: a review of existing
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Lowell, S., and J. E. Shields. 1981a. Influence of contact angle on hysteresis in mercury
porosimetry. J. Colloid Interface Sci. 80:192-196.
Lowell, S., and J. E. Shields. 1981b. Hysteresis, entrapment, and wetting angle in mercury
porosimetry. J. Colloid Interface Sci. 83:273-278.
Luxmoore, R. J. 1981. Micro-, meso-, and macroporosity of soil. Letter to the editor. Soil
Sci. Soc. Am. J. 45:671-672.
Nagpal, N. K., L. Boersma, and L. W. DeBacker. 1972. Pore size distributions of soils from
mercury intrusion porosimeter data. Soil Sci. Soc. Am. Proc. 36:264-267.
Page, J. B. 1948. Advantages of the pressure pycnometer for measuring the pore space in
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Ragab, R., J. Feyen, and D. Hillel. 1982. Effect of the method for determining pore size
distribution on prediction of the hydraulic conductivity function and of infiltration.
Soil Sci. 134:141-145.
Ritter, H. L., and L. C. Drake. 1945a. Pore-size distribution in porous materials: pressure
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Chern. Anal. Ed. 17:782-786.
Ritter, H. L., and L. C. Drake. 1945b. Pore-size distribution in porous materials: macropore-
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Russell, M. B. 1949. Methods of measuring soil structure and aeration. Soil Sci. 68:25-35.
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Sills, I. D., L. A. G. Aylmore, and J. P. Quirk. 1973b. A comparison between mercu!),
injection and nitrogen sorption as methods of determining pore size distributions. Soil
Sci. Soc. Am. Proc. 37:535-537.
POROSITY 461
Sills, I. D., L. A. G. Aylmore, and J. P. Quirk. 1974. Relationship between pore size dis-
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Am. J. 45:1246.
Voorhees, W. B., R. R. Allmaras, and W. E. Larson. 1966. Porosity of surface soil aggregates
at various moisture contents. Soil Sci. Soc. Am. Proc. 30: 163-167.
Wilkins, D. E., W. F. Buchele, and W. G. Lovely. 1977. A technique to index soil pores
and aggregates larger than 20 micrometers. Soil Sci. Soc. Am. J. 41: 139-140.
Winslow, D. N., and S. Diamond. 1970. A mercury porosimetry study of the evolution of
porosity in Portland cement. J. Mater. 5:564-585.