Journal of Soil Science, 1989,40,359-369

Phosphate reactions with natural allophane,

ferrihydrite and goethite
R. L. P A R F I T T
Division of Land and Soil Sciences, DSIR, Lower Hutt, New Zealand

SUMMARY
The reactions of phosphate with natural samples of allophane, ferrihydrite, hematite and
goethite were measured for up to 30 d. The amount of phosphate sorbed on allophane
showed the biggest increase with time whereas the amount sorbed on goethite showed the
least increase with time. The total amount of phosphate sorbed either at high levels of
phosphate addition or after 10 d followed the order hematite ~ g o e t h i t e<ferrihydrite
<allophane and was probably related to the specific surface. Si was desorbed as
phosphate was adsorbed on the minerals.
The reactions of phosphate on allophane involved rapid, strong adsorption, probably
at defect sites, followed by weaker adsorption, followed, probably, by disruption of the
allophane structure together with precipitation of aluminium phosphates. Previous
suggestions either of diffusive penetration of phosphate into surfaces or about the forma-
tion of aluminium phosphate coatings, are unlikely to hold for allophane, if all the A1 is at
the surface and if the structure can be ruptured.
The reactions of phosphate with iron oxides involved a rapid, strong ligand exchange,
followed by weaker ligand exchange, and, probably, by a relatively slow penetration at
defect sites and pores. Highly crystalline goethite has virtually no slow reaction and
therefore solid-state diffusion of phosphate does not readily occur. The extent of
phosphate uptake during the slow penetration reactions probably depends on the degree
of crystallinity or porosity of iron oxides.
The most reactive adsorbents, such as allophane, ferrihydrite and Al-humus complexes
do not have planar surfaces, and this needs to be considered when modelling phosphate
reactions.

INTRODUCTION

In acid soils the reaction between phosphate and the non-biological components of soils involves
active surface Fe and A1 atoms (Parfitt, 1978). The initial adsorption reaction with Fe and A1 is
followed by a slower diffusion controlled process called the slow reaction (Barrow, 1985). The slow
reaction has been variously considered to arise from penetration of phosphate into oxide crystals or
between aggregates of microcrystals (Barrow, 1987), and from diffusion through a coating of metal
phosphate surrounding an oxide particle (van Riemsdijk et al., 1984).
Work with synthetic oxides and hydroxides of Fe and A1 has shown that the initial adsorption
reaction of phosphate is by ligand exchange with surface OH groups which are in one coordination
with Fe and A1 atoms (Parfitt, 1978). The reaction product is an inner-sphere surface complex
between phosphate and Fe and/or A1 atoms, and this reaction is thought to occur also in soils
(Goldberg & Sposito, 1984). Soil minerals, however, often differ from synthetic minerals in that
defects and substitutions are usually present in soil systems.
In this study relatively pure natural samples of the soil minerals allophane, ferrihydrite and
goethite, and a sample which contains hematite and kaolinite as the reactive species, have been used.

359
360 R. L. ParJitt
These minerals, together with Al-humus complexes, are probably the most active components
which react with phosphate in acid soils (Parfitt, 1978).
The adsorption reaction on allophane is thought to occur initially at defect sites on the surface of
the hollow allophane spherules where one coordinated AlOH groups are exposed (Parfitt & Henmi,
1980). On ferrihydrite, goethite and hematite, the reaction occurs at the surface of the crystals, and
there is good evidence for the formation of a binuclear bridging complex between a phosphate group
and two surface Fe atoms (Parfitt, 1978; Nanzyo, 1986). This reaction is rapid; therefore, the
formation of the binuclear complex is not the mechanism of the slow reaction whereby phosphate
fertilizer becomes less available with time (Barrow, 1987).
In this paper the sorption reactions have been studied and the desorption of Si has been
measured, using natural samples. The data, together with results in the literature, suggest that
different reaction mechanisms occur during the slow reaction on different surfaces. Data for a
well-crystallised synthetic goethite have been included for comparison.

MATERIALS A N D METHODS
Samples
The ferrihydrite sample (PC990) was obtained as a moist suspension from a spring on Mt Ruapehu,
an andesitic volcano (Childs et nl., 1982; sample A2) and the goethite sample (PC1289) was taken
from weathered basalt, excavated at the DSIR campus, Mt Albert, Auckland. The minerals were
concentrated by gentle grinding and sedimentation and then stored as suspensions. X-ray diffrac-
tion, electron diffraction, infrared and Mossbauer spectroscopy data showed that the ferrihydrite
sample contained only small traces of other minerals, possibly magnetite and goethite. The goethite
sample contained traces of hematite and micaceous minerals. The XRF analyses of these samples
are given in Table 1 and electron micrographs were also obtained.

Table 1. Composition of samples by X-ray fluorescence analysis

Sample Fe Si A1 P Mg Na
NO. Yo % Yo % % Yo

Ferrihydrite PC990 46.2 8.55 0.49 0.3 0.4 0.2

Goethite PC1289 50.7 2.76 1.21 1.5 0.8 1.1
Allophane* PC1331 0.9 13.47 21.61 0.08 0.2 0.6

* < 5 pm fraction containing mainly allophane and quartz.

The sample containing hematite came from weathered schist and could not be separated from
kaolinite and micaceous minerals. The sample (Butchers Dam, PC1113) contained 11% hematite,
and this was the only iron oxide detected in the sample (Childs et nl., 1979).
The allophanic sample was obtained from the C horizon of an Aquod (One Tree Point) devel-
oped in quartz sand with some tephra. The C horizon occurred below a pan and the sample
contained only traces of Fe. Analysis of the allophane by acid-oxalate dissolution showed that the
samplecontained 1.2% Al, 0.53% Si and 0.02% Fe, i.e., 4% allophane, the remainder being quartz
sand.
The preparation of the synthetic goethite has been described previously (Parfitt, 1979~).

Sorption studies
Phosphate adsorption was measured by shaking samples containing 0.2-0.4 g of the relevant
mineral with KH,PO, in 7 ml 0.002 M CaCI, for 16 h at 25°C. The phosphate adsorbed was
calculated on the basis of 1 g of allophane or iron oxide.
The slower reactions were measured in a similar batch equipment, but the suspensions were
shaken for a few seconds twice a week. Phosphate was measured by the method of Murphy & Riley
 P reactions with allophane and iron oxides 36 1
(1962), and Si by the method of Weaver et al. (1968). The amount of phosphate sorbed and Si
desorbed were measured by difference between initial and final concentrations in solution. Si
desorption was not measured on the hematite sample because there were large amounts of layer
silicates present.
The pH values of the final solutions in all experiments were (within two tenths of a pH unit) as
follows: allophane, 5.9; goethite (synthetic), 7.3; ferrihydrite, 6.8; goethite (natural), 5.5; hematite,
7.0. When CaCI, is used as background electrolyte, sorption is not strongly dependent on pH in the
pH range 5 to 7 (Barrow, 1987).

RESULTS
Electron micrographs indicated that the ferrihydrite particles had a diameter of about 4 nm. Assum-
ing a density of 4 Mg m-3 the calculated specific surface area is 380 m-' g-'. The calculated specific
surface of the individual goethite particles, which appeared as laths 30 x 3 nm in size, is 310 m2g-'.
The calculated specific surface for allophane is 800 m2g-' (Parfitt & Henmi, 1980).
The phosphate adsorption curves for the reaction of KH,PO, in CaCI,, shaking for 16 h, showed
that the adsorption followed the order hematite < natural goethite c ferrihydrite c allophane which
is the order of the calculated specific surface areas (Fig. 1). The adsorption increased as more
phosphate was added, the curves for allophane and ferrihydrite being significantly steeper. The
synthetic goethite, which has high crystallinity, had a very flat adsorption curve with a defined
adsorption maximum.

Goethite (synthetic)

Hematite
W W
I I I I
20 40 60 80
P in solution (pmol I-')
Fig. 1. Sorption curves for phosphate on 1 g of mineral (25"C, 16 h shaking, 0.002 M CaC1,).

The adsorption curves for 1 to 30 d, are presented as log/log plots (Barrow, 1987) in Fig. 2. The
adsorption of phosphate on synthetic goethite shows only a slight increase between 1 d and 30 d. For
the natural samples, however, the phosphate adsorption increased markedly with time. The increase
with time followed the order goethite < ferrihydrite, hematite < allophane (Fig. 3).
Silicic acid and silicate were displaced when phosphate was added to the natural samples
(Table 2) For allophane I pmol Si was desorbed when 10-20 pmol P was adsorbed. The Si desorp-
tion increased only slightly as more phosphate was adsorbed. With continuous shaking for 1 d, as
 362 R.L. ParJtt
200 /-

30
10
3
- Goethite (natural)

1 50
° i 1

I
m -- I
30 10 3 1

300
Ferrihydrite

1 3 10 30 100 300 pmol I-'

0.1 0.3 1 3 10 rng1-l
P in solution
Fig. 2. Sorption curves for phosphate on 1g of mineral with minimal shaking for 1-30 d (log/log plots).

opposed to minimal shaking, the Si desorption increased from 7 to 9 pmol g-', the phosphate
adsorption increased from 140 to 150 pmol g-', and the phosphate in solution decreased from 270 to
8 pmol I-' (Table 3). Similar results were obtained after 3 d.
More Si was displaced from ferrihydrite than from allophane when phosphate was adsorbed,
and about 1 pmol Si was desorbed when 8 pmol P was adsorbed (Table 2). In these experiments only
about 1% of the total Si was displaced. On shaking, the Si in solution decreased from 1400 to
1300 pmol I-', suggesting that some readsorption took place (Table 3).
On the natural goethite, phosphate desorbed more Si than on the ferrihydrite or allophane.
About 1 pmol Si was desorbed when 3 pmol P was adsorbed. With continuous shaking the Si
desorbed increased from 34 to 38 pmol g-', and phosphate adsorption increased slightly. About 4%
of the total Si was desorbed, but some of the total Si is present in micaceous impurities, so the actual
percentage of Si desorbed from goethite was higher than 4%.

DISCUSSION
A llophane
A natural allophane, which contained only traces of Fe, was used in this work. Therefore the active
sites were mainly A1 and not Fe. 100 pmol P g-' was strongly adsorbed (Fig. l), and the adsorption
 P reactions with allophane and iron oxides 363

200 - Allophane
Ferrihydrite

-- 100 -
1
Goethite

ul
- 50-
E"a
-
D
al
f 20-
$ Hematite
a
- (30PM)
10

5-
I I I 1

Table 2. Phosphate adsorption and Si desorption from natural samples

of allophane, ferrihydrite and goethite after 1d (no shaking)

P P Si Si
adsorbed in solution desorbed in solution
pmol g-' pmol I-' pmol g-' pmol I-'

Allophane 50 4 5 130
100 18 6 180
140 270 7 200

Ferrihydrite 71 6 14 830
95 15 16 950
119 23 17 1000
142 46 18 1090

Goethite 62 9 25 510
115 195 34 685

sites were probably defects in the wall of the hollow allophane spherules (Parfitt & Henmi, 1980).
The allophane (AI/Si = 2.3) has an imogolite-like structure, the outer surface of the allophane
opherulescontaining gibbsite-likeA1.OH.Al groups and the inner surface containing SiOH groups.
The defect sites probably resemble edges of local imogolite structures (Farmer, 1986) and by
-logy with gibbsite edges, the one coordinated AlOH and Al.H,O edge groups will be the most
reactive sites in adsorbing phosphate. These sites are probably associated with the first adsorption
ptocess (Pl), observed on allophane by Imai el ul. (1981), who described them as exposed sites.
A similar amount of phosphate was strongly adsorbed on a synthetic imogolite-like allophane
(Clark & McBride, 1984).
 Table 3. Phosphate adsorption and Si desorption after 1 d and 3 d with and without shaking

Id 3d

P P Si Si P P Si Si
adsorbed in solution desorbed in solution adsorbed in solution desorbed in solution
pmol g-' pmoll-' pmol g-' p o l I-' pmol g-I pmol I-' pmol g-' pmol I-' P
Allophane Standing 140 270 7 200 192 220 9 275 2
Shaking 150 8 9 270 200 10 11 320
3
-
Ferrihydrite Standing 188 200 24 1400 188 110 19 I180
Shaking 189 150 22 1300 190 75 18 1090

Goethite Standing 115 195 34 685 118 108 37 750

Shaking 117 134 38 770 120 70 39 790
 P reactions with allophane and iron oxides 365
The total A1 present in allophane is about 10 000 pmol g-l, and all of the atoms, together with
OH groups, are at the external surface of the spherules. Therefore, the 100 pmol P g-' which is
strongly adsorbed reacts with only a small proportion of the A1 atoms, i.e., the most reactive sites
represent a small proportion of the total Al.
The 100 pmol P g-' which was strongly adsorbed caused the desorption of only 6 pmol Si g-',
compared with the total 5000 pmol Si g-' present in allophane. This indicates that at this level of
phosphate adsorption the allophane structure is not being ruptured, at least not in a manner that
releases large amounts of Si.
Phosphate adsorption increased with time, and over 300 pmol P g-' was sorbed. Rajan (1975)
and Imai et al. (1981) suggested that the allophane structure was disrupted as more phosphate
reacted, displacing structural Si and exposing very reactive sites. It has been suggested that a further
reaction involves the precipitation of an alumino-phosphate such as taranakite or non-crystalline
aluminium phosphate (van Riemsdijk & Lyklema, 1980; Imai et af., 1981; Nanzyo, 1987).
These data suggest the following hypothesis for the reaction of allophane with phosphate.
Initially, phosphate is rapidly and strongly adsorbed by ligand exchange on the most reactive AlOH
defect sites, forming either monodentate or binuclear complexes (Parfitt & Henmi, 1980; Goldberg
& Sposito, 1985). This phosphate is. too strongly adsorbed to be available to plants (Parfitt et al.,
1982). Secondly, as more phosphate is adsorbed it is held on less reactive defect sites, and this
phosphate is available to plants (Parfitt et al., 1982). Thirdly, with time, or at high concentrations,
phosphate reacts with more aluminium, probably located near the defect sites, forming more stable
alumino-phosphate precipitates, disrupting the allophane structure and creating new defect sites.
The products of the third reaction are probably not readily available to fast-growing plants
(Parfitt et al., 1989).
A diffusive penetration reaction (Barrow, 1987) cannot occur with allophane if all the AlOH
groups are at the surface. Neither is it likely that phosphate diffuses through an aluminium
phosphate coating (van Riemsdijk et al., 1984), because the allophane structure can be disrupted
and, being only three atoms thick, is unlikely to support such a coating.

Synthetic Goethite
The phosphate adsorption on the synthetic goethite (Fig. 1) is similar to the adsorption on other
highly crystalline goethite preparations (Parfitt, 1979~).Infrared spectra of moist samples of
phosphated-goethite suggest that a binuclear bridging complex is present (Parfitt, 1979~).Twice as
much fluoride, which forms a monodentate complex with surface Fe atoms on goethite, is adsorbed
compared with phosphate, confirming that one phosphate ion reacts with two surface Fe atoms to
give a binuclear bridging complex on moist samples (Parfitt, 1979~).
The synthetic goethite shows virtually no slow reaction with phosphate (Fig. 2). This probably
results from the absence of defect sites on the goethite. This is consistent with the data and conclu-
sions of Ryden et al. (1977). It demonstrates that solid-state diffusion of phosphate into goethite
(Barrow, 1987) does not readily occur with highly crystalline preparations. The very small amount
of slow reaction could arise either from a few defect sites or from the presence of a small amount of
ferrihydrite, which can form during the preparation of synthetic goethite.
The plant availability of phosphate, adsorbed on synthetic goethite in a bridging complex has
been shown to increase when about half of the surface becomes covered with phosphate (Parfitt,
I9796), although the bridging complex is the only complex detected.

Natural Goethite
The natural goethite contained about 500 pmol ggl of native phosphate. In this study the rapid
adsorption of phosphate on the natural goethite was followed by slower reactions (Fig. 2). During
the rapid adsorption of 62 pmol P g-', desorption of 25pmol Si g-' occurred (Table 2). The Si was
probably held on the most reactive and accessible sites and was desorbed by ligand exchange
(Parfitt, 1978). As more phosphate was adsorbed, presumably at less reactive sites, a smaller pro-
portion of Si was displaced, i.e., 9 pmol Si g-' for 53 pmol P g-' (Table 2). With increasing time or
with increased shaking, phosphate adsorption continued and small additional amounts of Si were
desorbed (Table 3). About one mole of Si was desorbed as one extra mole of P was adsorbed.
3 66 R . L. Parjitt
Electron micrographs showed that the goethite was composed of laths about 30 x 3 nm in size, but
they had an irregular, knobbly appearance, suggesting that defect sites were present. Some laths
appeared to be linked in domains and others appeared to beeither paired or tubular. IfSi is adsorbed
at defect sites or between laths and if P penetrates these sites, this could account for one mole of P
desorbing one mole of Si (Barrow, 1987).It would also account for the small proportion of the total
Si which is displaced by P.
On the basis of previous work it is reasonable to suggest the hypothesis that the reaction of
phosphate with natural goethite occurs in three stages. Initially, phosphate is strongly and rapidly
adsorbed on very reactive sites and Si is desorbed together with OH groups and H,O by ligand
exchange. This phosphate is held too strongly to be available to plants (Parfitt, 19796). Secondly, as
more phosphate is adsorbed, it is held on less reactive sites, and this phosphate is available to plants.
Thirdly, with increasing time, phosphate may penetrate at defect sites or between microcrystals
bonded together by silicate, and the silicate is replaced by the phosphate. The extent of these
reactions depends on the crystallinity and porosity of the iron oxide (Cabrera et al., 1981;Madrid &
de Arambarri, 1985)and the degree of substitution of A1 for Fe (Ainsworth & Sumner, 1985).Under
very acid conditions (pH 3) it has been shown that the iron phosphate, tinticite, can precipitate in
these systems (Jonasson et al., 1988).

Ferrihydrite
The ferrihydrite contained about 100 pmol g-' of native phosphate. In the laboratory the initial
adsorption of phosphate was much less on the natural ferrihydrite (50 pmol g-') than on synthetic
samples (700 pmol g-I) (Ryden et al., 1977), and was similar to the adsorption on natural goethite
(PC1289) (Fig. 1). With increasing time, however, the ferrihydrite, had a greater reaction than the
goethite (Figs 2 and 3). Electron micrographs indicated that the ferrihydrite consisted of aggregates
of rounded, irregular particles which were about 4 nm in diameter and had a larger specific surface
area than the natural goethite. The ferrihydrite and goethite, however, have a similar number of very
reactive sites (Fig. l), so the density of very reactive sites is greater on the goethite. These sites are
probably the one-coordinated Fe-OH groups (Parfitt, 1978).
About 1YOof the total Si was displaced when phospate was adsorbed, which represents a small
proportion of the total Si, suggesting that most of the Si was strongly bonded and/or was held within
the ferrihydrite particles. Unpublished infrared spectra of this ferrihydrite show that the Si is present
mainly as polymerized silicate together with some orthosilicate.
Assuming a density of 4.0 Mg m-3 and a particle diameter of 4 nm, each ferrihydrite particle
contains on average about 700 atoms of Fe, 250 atoms of Si and 1700 atoms of 0 (and/or OH
groups). Up to 25 atoms of P reacted with each particle, desorbing about 3 atoms of Si. Probably
most of the P adsorption and Si desorption occurred at the surface where about 700 OH groups
(or 0 atoms) would be exposed.
With increasing time or shaking, Si was readsorbed by the ferrihydrite (Table 3). This suggests
that the phosphate, during adsorption, had exposed fresh sites which then adsorbed Si. This could
occur if the phosphate, through adding negative charge to the surface, had caused the ferrihydrite
particles to disperse, exposing sites blocked by flocculation. Alternatively, pores and defect sites
blocked by Si may have been exposed as Si exchanged with phosphate. Between 1 d and 30 d about
5&100 pmol P g-' or about 6-12 atoms of P on each ferrihydrite particle are adsorbed. This
involves a small part of the surface and presumably the phosphate penetrates pores or at defect sites.
This is consistent with the results for a synthetic ferrihydrite at neutral pH (Ryden et al., 1977).
Under very acid conditions (PH 2.3-4.9), however, it has been suggested that amorphous iron
phosphate can form (Nanzyo, 1986).
The reaction of phosphate with ferrihydrite can be considered to take place in three stages
similar to those on goethite. There is some evidence that the adsorption reactions in the first two
stages involve the formation of a binuclear complex (Parfitt, 1978;Nanzyo, 1986). During the third
stage the reaction may involve the formation of three bonds between phosphate and iron for both
penetration and precipitation reactions and this would account for the loss of availability of
phosphate.
 P reactions with allophane and iron oxides 367
GENERAL DISCUSSION

It is generally agreed that the initial reaction between phosphate and acid soils involves adsorption
by ligand exchange on reactive A1 and Fe sites (Parfitt, 1978; Berkheiser et al., 1980; Goldberg &
Sposito, 1985; Barrow, 1987).The nature of the slow reaction, however, is not agreed. In this paper,
it is suggested that there are different slow reactions for different minerals.
Skopp (1986) has emphasized that it is necessary to have several mechanistic hypotheses when
a rate law is used to establish a reaction mechanism, implying that kinetic techniques alone cannot
define reaction mechanisms. A review of the literature shows that in addition to kinetic techniques,
procedures using spectroscopy (Nanzyo, 1986), calorimetry (Imai et al., 198I), dissolution
(Ryden et al., 1977) and thermodynamics (Miller et a/., 1986) have given useful information about
the mechanism of the slow reactions. The evidence strongly suggests that aluminium phosphate
precipitates are formed with allophane and that penetration reactions occur with natural iron
oxides. The extent of the penetration reaction with iron oxides depends on the degree of crystal-
linity, and this relates to porosity and the degree of substitution of A1 for Fe (Berkheiser et a/.,
1980).
Ferrihydrite, which is a poorly crystalline (short-range-order) iron oxide, can be estimated in
soils from oxalate-extractable Fe values (Parfitt & Childs, 1988),and the amount of ferrihydrite will
partly control the amount of phosphate adsorbed by a soil during the slow reactions. There is,
however, no simple routine method for estimating the crystallinity of other iron oxides in soils.
Therefore, at present, the extent of slow reactions in soils containing iron oxides of varying
crystallinity can only be estimated by direct measurement.
Although allophane is relatively rare in soils, many soils contain Al-humus complexes which are
very reactive towards phosphate (Gunjigake & Wada, 1981; Le Mare, 1982; Parfitt & Childs, 1988).
These complexes probably have an open microstructure and organic ligands are probably displaced
as more phosphate is added (Imai et al., 1981). Aluminium phosphates are likely to precipitate at
high levels of phosphate addition to soils containing reactive A1 species such as Al-humus complexes
(Norrish & Rosser, 1983; van Riemsdijk et al., 1984).
Al-humus complexes, allophane and ferrihydrite do not have planar surfaces and this needs to be
considered further, together with precipitation reactions in modelling phosphate reactions with soils
(Bolan et a/., 1985). Models can be useful educational tools in studying the effects of changes in
conditions on phosphate adsorption reactions (Barrow, 1987) especially if they point to gaps in
knowledge. Further work, using a variety of techniques, however, is required to test the hypotheses
described here and to fully elucidate the mechanisms of the reactions.

CONCLUSIONS

1. Highly crystalline goethite has virtually no slow reaction with phosphate, and this is interpreted
to mean that solid-state diffusion of phosphate does not readily take place in these crystals.
2. Sorption of phosphate increased with time in the order goethite <ferrihydrite, hematite <
allophane.
3. The total amount of phosphate adsorbed either at high (> 10 pmol I-') levels of phosphate in
solution or after 10 d followed the order hematite < goethite < ferrihydrite < allophane and was
probably related to specific surface area.
4. The reactions of phosphate with allophane can be considered to take place as a rapid, strong
adsorption, followed by weaker adsorption and by disruption of the allophane structure, leading to
precipitation of aluminium phosphates. Since all the A1 atoms in allophane are at the surface
diffusive penetration of phosphate is unlikely to be significant. Coatings of aluminium phosphates
on allophane spherules are also unlikely to form because the spherules may be ruptured.
5. The reactions of phosphate with iron oxides depend on the number of reactive surface FeOH
groups and the crystallinity of the oxides. The reactions probably involve rapid, strong ligand
exchange, followed by weaker ligand exchange and by penetration at defect sites and pores. At very
acid pH values, iron phosphate may precipitate.
368 R. L. Parjitt
ACKNOWLEDGEMENTS
I wish to thank D r R. A. Eggleton of the Geology Department, A N U , Canberra, for the electron
micrographs of the ferrihydrite a n d goethite samples a n d D r C. W. Childs, NZ Soil Bureau for his
help and critical reading of the manuscript.
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(Received 25 July 1988; accepted 5 December 1988)