Effect of phosphate rock and triple superphosphate on soil phosphorus fractions and their...

$: Effect of phosphate rock and triple superphosphate on soil phosphorus fractions and their plant-availability and downward movement in two volcanic ash soils under Pinus radiata plantations$
RESEARCH ARTICLE

Effect of phosphate rock and triple superphosphateon soil phosphorus fractions and their plant-availabilityand downward movement in two volcanic ash soilsunder Pinus radiata plantations in New Zealand

A. A. Rivaie Æ P. Loganathan Æ J. D. Graham ÆR. W. Tillman Æ T. W. Payn

Received: 15 October 2007 / Accepted: 1 February 2008 / Published online: 23 February 2008

� Springer Science+Business Media B.V. 2008

Abstract Changes in phosphorus (P) fractions and

their plant-availability and downward movement in

two strongly P fixing acidic Andosols (Allophanic

and Pumice Soils) under Pinus radiata plantations in

New Zealand were studied 2 years after triple

superphosphate (TSP) and a phosphate rock (BGPR,

origin Ben Guerir, Morocco) application, each at four

rates, to determine the fate and plant availability of

fertilizer-derived P in these soils. The rate of increase

of the concentrations of the P fractions was highest

for NaOH-Pi (inorganic P associated with Fe and Al

oxides and allophane) when TSP was applied and

highest for H2SO4-Pi (predominantly calcium phos-

phates or apatite-type P minerals) when BGPR was

applied. The largest pool of soil P, the NaOH-Po

(labile organic P), was unaffected by the P fertilizer

applications. The rate of NaOH-Pi concentration

increase was higher in the higher P fixing Allophanic

Soil than in the Pumice Soil. Both types of fertilizers

increased resin-Pi (Inorganic P freely available to the

plant) and Bray-2 P concentrations but only the TSP

application increased Olsen P concentration. Phos-

phorus derived from TSP and BGPR applications

moved down to 10–20 cm soil depth within 2 years

of application in the Pumice Soil, but did not move

below 10 cm depth in the higher P fixing and less

porous Allophanic Soil. The fertilizers significantly

increased needle P concentrations 2, 3 and 4 years

after fertilizer application, but did not have any

significant effect on tree growth.

Keywords Fertilizer � Pinus radiata �Phosphorus � Soil phosphorus fractions �Phosphorus availability � Phosphate rock

Introduction

Phosphorus (P) is an important nutrient in New

Zealand Pinus radiata D. Don (P. radiata) planta-

tions as most of the soils are P deficient or marginally

deficient, and this element has been routinely applied

since the 1960s where appropriate (Hunter et al.

1991; Payn et al. 1998). Both soluble and less soluble

P fertilizers can be used in forest production. Many

field trials have shown that direct application of the

less soluble reactive phosphate rocks (RPRs) to

permanent pastures and crops, which have a long

growing season and do not have short-term require-

ments for high levels of P, can be as effective as the

soluble single superphosphate (SSP) or triple super-

phosphate (TSP) in acidic soils (Chien et al. 1987;

Bolan et al. 1990; Indiati et al. 2002; Szilas et al.

A. A. Rivaie � P. Loganathan (&) � R. W. Tillman

Soil and Earth Sciences, Institute of Natural Resources,

Massey University, Palmerston North, New Zealand

e-mail: [email protected]

J. D. Graham � T. W. Payn

Forest Research, 49 Sala St., Private Bag 3020 Rotorua,

New Zealand

123

Nutr Cycl Agroecosyst (2008) 82:75–88

DOI 10.1007/s10705-008-9170-6

2007). Unlike with pastures and crops, only a few

studies have been conducted into the direct applica-

tion of RPRs to P. radiata plantations, especially on

Allophanic and Pumice Soils (Mead and Gadgil

1978; Hunter and Hunter 1991) where P. radiata is

commonly planted in New Zealand.

Readily soluble P fertilizers have the potential to

supply P to plants immediately after application but

the P-availability to plants generally decreases with

time due to the conversion of soluble P to less soluble

forms as a result of reaction with soil constituents,

especially in strongly P-fixing soils of volcanic origin.

In comparison, the plant-availability of P from less

soluble fertilizers such as RPRs is generally low at the

start but may increase with time due to the increased

dissolution of the fertilizer. The P dissolved from these

fertilizers undergoes various reactions with the inor-

ganic and organic constituents of the soil resulting in

products of varying solubility. The rates of transfor-

mation of fertilizer-derived P into the various soil

P fractions can provide information on the plant-

availability of soil P at various times after P applica-

tion. In a recent laboratory incubation study

investigating the changes in soil P fractions following

a soluble P fertilizer (mono-calcium phosphate

(MCP)) application to a Brown Kandosol soil from a

Eucalyptus forest in Australia, Short et al. (2007)

reported that much of the P applied was converted

rapidly to forms with reduced availability; by the time

of the first measurement (4 weeks) only approximately

10% of the added P remained as readily available

resin-extractable P. For the surface soil, much of this

added P was initially converted to the NaOH-extract-

able organic P fraction, before progressively moving

into the NaOH-extractable inorganic P fraction

(P associated with Al and Fe oxide surfaces). For the

mixture of surface and subsoil, the added P was rapidly

converted directly to the NaOH-extractable inorganic

P fraction. Only a few studies have been reported on

determining the effect of P fertilizer application on

P fractions in forest soils under field conditions (Chen

et al. 2003; Liu et al. 2005). Some of these studies

focused mainly on determining the total organic and

inorganic P pools without further separating the

P fractions in each of these pools.

Phosphorus moving downwards in soils has the

potential to reach drainage waters, and can have

adverse environmental effects if it reaches surface

waters. Suggestions have been made that subsoil

sampling should be considered for P prognosis if

significant quantities of P derived from fertilizers or

animal manures applied to surface soils move deeper

in soils (Hountin et al. 2000; Wang et al. 2007).

The objective of the study reported in this paper was

to examine the changes in P fractions and the plant-

availability and downward movement of P, 2 years

following the application of two forms of P fertilizer

with different solubility to an Allophanic Soil (Cryands

and Udands) and a Pumice Soil (Cryand) under second-

rotation P. radiata plantations.

Materials and methods

Site description

Two experiments, one at the Kaweka forest, 50 km

NW of Hastings, New Zealand, located at 740 m

altitude, the other at the Kinleith forest, 15 km NE of

Tokoroa, New Zealand located at 520 m altitude, were

installed in September 2000 by New Zealand Forest

Research Ltd. The soils are classified as Orthic

Allophanic Soil (Cryands and Udands, US Soil Tax-

onomy) at the Kaweka forest and Orthic Pumice Soil

(Vitricryands, U S Soil Taxonomy) at the Kinleith

forest (Hewitt 1998; Soil Survey Staff 1998). Selected

properties of the soils are presented in Table 1.

The climate at the Kinleith forest is cool and humid

(mean annual RH 82%), with a mean annual rainfall of

approximately 1600 mm, and without a pronounced

dry period. Mean annual temperature is 12.2�C, with a

February maximum monthly mean of 17.4�C and a

July minimum of 6.9�C. The climate at the Kaweka

forest is also cool and humid (mean annual RH 70%),

but mean annual rainfall is approximately 1400 mm,

and the area also has no pronounced dry period. Mean

annual temperature is 12.6�C, with a February maxi-

mum monthly mean of 16.3�C and a July minimum of

5.5�C. During the experimental period (2001 and

2002), the total rainfall for 2001 and 2002 was 1285

and 1280 mm at the Kaweka forest and 1491 and

1702 mm at Tokoroa (the closest station to the Kinleith

forest), respectively (National Institute of Water and

Atmospheric Research, personal communication).

At Kaweka forest, the trees were 4- to 5-year-old

second-rotation radiata pines. They were planted

in 1995–1996 at a nominal stocking rate of 1000

76 Nutr Cycl Agroecosyst (2008) 82:75–88

123

stems ha-1. At the Kinleith forest the 3-year-old

second rotation trees were planted in 1997 at a nominal

stocking rate of 670 stems ha-1. Fertilizer had not at

any time been applied to either the first-rotation or to

the second-rotation trees. The predominant understo-

rey species at the Kaweka forest were bracken fern

(Pteridium esculentum), some manuka (Leptospermum

scoparium), and brown top (Agrostis capillaris), while

at the Kinleith forest they were Himalayan honeysuckle

(Leycesteria formosa), buddleia (Buddleja davidii

Franchet), and some toetoe (Cortaderia toetoe).

Experimental design and treatments

The experiments tested the effects of four rates (0, 50,

100, and 200 kg P ha-1) of P applied in two forms of

P fertilizer, a soluble form (triple superphosphate

(TSP)) and a less soluble form (‘‘as received’’ Ben

Guerir phosphate rock (BGPR), mined in Morocco),

in combination with weed control (weed and weed-

free). The water and 2% citric acid soluble

P concentrations of the fertilizers and the particle

size distribution of BGPR are presented in Table 2.

The 2% citric acid solubility of the BGPR in the

as-received state is 28% of the total P content

(Table 2). This value is close to the 30% value above

which PRs are commonly classified as reactive PRs

(White et al. 1989). The treatments were replicated

four times at each site. Each P rate constituted a plot.

Plot sizes were 15 9 15 m plus a treated buffer 5 m

wide. The fertilized buffer was extended to 10 m on

one side of each plot to contain a weed control

treatment. Soil samples were taken from the

15 9 15 m internal plots but no comparisons were

made with the weed control areas as the control had

not been fully effective. The P fertilizers were applied

by hand to the entire surface of the experimental plots

in both forests in October 2000.

Soil sampling

Soil samples were collected in November 2001

and December 2002 at the Kaweka forest, and in

December 2002 at Kinleith forest, using a 2-cm-

diameter soil corer. Twenty soil cores per plot were

taken (spaced uniformly throughout the plot and each

one 1.5 m from the stem of a measurement tree) at soil

depths of 0–10, 10–20, and 20–30 cm, and the cores at

each depth for each treatment were combined. All soil

samples were air-dried and passed through a 2-mm

sieve to remove debris (obvious root and foliage), and

the sieved samples were stored for chemical analyses.

Samples of soils had also been collected from the 4

blocks at each site before the experiment started and

were analysed to determine the soil P status and soil

properties before starting the trials.

Chemical analysis

Soil pH was measured in a water suspension (using a

soil:solution weight ratio of 1:2.5) after the suspensions

were shaken for 24 hours on a reciprocal shaker. The

organic matter content of the soils (expressed as

Table 1 Selected properties of the soils (0–10 cm depth

below the litter layer) at the Kaweka (Allophanic Soil) and

Kinleith (Pumice Soil) forests

Parameter Kaweka Kinleith

pH (1:2.5 H2O) 5.7 5.1

K (cmolc kg-1) 0.29 0.94

Ca (cmolc kg-1) 2.90 9.20

Mg (cmolc kg-1) 0.58 1.36

Na (cmolc kg-1) 0.12 0.10

C (%) 5.6 7.0

CEC (cmolc kg-1) 14 24

P retention (%) 92 83

Bray-2 P (lg g-1) 4 13

Olsen P(lg g-1) 3 6

Resin-Pi (lg g-1) 1 9

NaOH-Pi (lg g-1) 39 43

NaOH-Po (lg g-1) 130 161

H2SO4-Pi (lg g-1) 17 7

Residual-P (lg g-1) 61 45

Total P* (lg g-1) 248 265

* Sum of resin-Pi, NaOH-Pi, NaOH-Po, H2SO4-Pi and resid-

ual-P

Table 2 Chemical characteristics of the P fertilizers used for

the trials

Fertiliser Total Pa (%) 2% Citric acid

soluble Pa (%)

Water soluble

Pa (%)

TSP 20.5 100 93

BGPRb 13.2 28 \1

a Rajan (1985)b Ben Guerir phosphate rock

Nutr Cycl Agroecosyst (2008) 82:75–88 77

123

percentage carbon) was determined by heating the

samples in a stream of high purity oxygen in a Leco

furnace to produce CO2. The CO2 was measured with an

infrared detector (Leco Co. 1996) and the quantity of

that gas used to determine the total organic carbon.

Cation exchange capacity (CEC) and exchangeable

cations were determined by ammonium acetate leaching

at pH 7 (Blakemore et al. 1987). The concentrations of

K, Ca, Mg, and Na in the leachates were determined by

atomic absorption spectrometry (AAS), and the ammo-

nium concentration was determined using an Autoana-

lyser (Blakemore et al. 1987). Phosphorus retention (an

index of P fixation) was determined by measuring the

P concentration in soil solution after 5 g soil was shaken

with 25 ml solution containing 1000 lg P ml-1 for

16 h. Bray-2 P was determined by shaking 2.5 g of air

dry soil for one minute in 25 ml of a solution containing

0.3 M NH4F and 0.1 M HCl and measuring the

P concentration in the solution by the colorimetric

technique of Murphy and Riley (1962) (Blakemore

et al. 1987). Olsen P was determined by shaking 1 g of

air dry soil in 20 ml of 0.5 M NaHCO3 (pH 8.5) for

30 minutes in an end-over-end shaker (Olsen et al.

1954; Blackmore et al. 1987) followed by measuring

the P concentration in the solution by the colorimetric

technique of Murphy and Riley (1962).

Soil P was fractionated using the method of

Hedley et al. (1994) (Table 3) by first extracting

0.5 g air-dried soil with a cation (Na+-form) and

anion (HCO3- form) exchange resin membrane to

determine resin-P, followed by 0.1 M NaOH extrac-

tion and determining inorganic P (NaOH-Pi) and

labile organic P (NaOH-Po) in the extract. The soil

residue was further extracted with 0.5 M H2SO4

(H2SO4-Pi) followed by digestion of the residue with

concentrated H2SO4 and H2O2 to determine the

residual-P. The P concentrations in all the above

extracts and digests were measured by the colorimet-

ric technique of Murphy and Riley (1962).

Plant uptake of Pi from the soil has been shown to

be mainly from the resin-Pi fraction, but 0.1 M

NaOH-Pi fraction can also supply P to plants in the

long-term (Trolove et al. 2003). These two fractions

can be grouped together and called labile-Pi.

Tree growth

At both trial sites, height and diameter at breast

height (DBH) were measured on the 15–22 trees per

plot in September 2002 (24 months after fertilizer

treatments), September 2003, and July 2004. DBH

was measured at 1.4 m above ground and basal area

(BA) was calculated as the sum of the sectional areas

of all stems (1000 stems ha-1 at Kaweka forest and

670 stems ha-1 at Kinleith forest) at breast height,

expressed in square metres ha-1 (MacLaren 1993).

Foliage sampling and chemical analysis

Foliage samples were collected from both trials in

March 2003 (29 months after fertilizer treatments),

March 2004 and March 2005. The needles from

secondary branches in the upper third of the crown

were randomly sampled from 10 trees per plot.

Samples were oven dried at 70�C to constant weight

and then ground to\1 mm before chemical analysis.

Five ml of concentrated HNO3 (99%) was added to

0.25 g dried and ground foliage in a Pyrex tube and

digested at 150�C for about 20 minutes (until the

digest was clear). After cooling, 1.5 ml of 30% H2O2

was added and the digestion continued for 1 hour.

After further cooling, the sample was diluted with

25 ml of deionised water and the P concentration was

determined using inductively coupled plasma (ICP)

spectrometry. All results were corrected to oven dry

weights at 100�C (Leco Co. 1996).

Table 3 The P fractions measured in the sequential

P-extraction procedure (based on Hedley et al. (1994) and

Short et al. (2007))

P fraction Chemical nature of soil P

Resin-Pi Inorganic P weakly adsorbed and

exchangeable with bicarbonate

ion (in resin) and P from

undissolved phosphate rock

0.1 M NaOH-Pi Inorganic P associated with Fe

and Al oxides and allophane

0.1 M NaOH-Po Organic P associated with Fe

and Al oxides and allophane

0.5 M H2SO4-Pi Predominately calcium phosphates

or apatite-type P minerals,

some P occluded in Fe oxides

Residual-P Recalcitrant inorganic P or structural

and stable organic P in

organo-mineral complexes


123

Statistical analysis

Analysis of variance (ANOVA) for a split-plot design

was performed using SAS (SAS Institute 2001). The

least significant difference (LSD) test at P = 0.05,

unless otherwise stated, was used to separate the

means when analysis of variance (ANOVA) results

indicated there were significant treatment effects

(Steel et al. 1997). For the Kaweka forest, resin-Pi

data were square root transformed and NaOH-Pi and

H2SO4-Pi data were loge transformed; while for the

Kinleith forest resin-Pi and H2SO4-Pi data were loge

transformed and NaOH-Pi data were square root

transformed. The data were square root transformed

when the spreads (or standard deviation) were

proportional to the square root of the mean; and the

data were loge transformed when the spreads (or

standard deviation) were proportional to the treat-

ment mean. Unlike the data for soil P concentrations,

the data for foliage P concentrations and tree growth

conformed to the assumptions (in particular, the

homogeneity of variance and normality) underlying

the ANOVA. Therefore, no transformations of those

data were made.

Results and discussion

Needle P concentration and tree growth

Application of both type of fertilizers significantly

(P \ 0.001) increased needle P concentrations at

both forests 2, 3 and 4 years after fertilizer

application (Table 4). However, P application had

no effect on tree height, DBH and BA 1, 2 and

3 years after fertilizer application (data not shown).

This is probably because the needle P concentra-

tions in the control treatment (no P fertilizer added)

soil were approximately at or above the level

considered satisfactory for the growth of P. radiata

(0.12% needle P, Mead and Gadgil 1978) and did

not appear to change with time (Table 4). The soil

P test values, however, were low (Table 1), indi-

cating that P might be limiting tree growth. The

reason for this paradox is that the soil test was not

correctly predicting soil P availability to the tree.

Skinner et al. (1991) also observed that Bray-2

P was not predicting P response in 6 out of 35

forest sites in New Zealand and explained this as

due to the 6 soils having high soil P buffering

capacity. They proposed the use of a sequential

extraction Bray-2 P test to predict soil P availabil-

ity to the trees. Another reason for the failure of

the soil P test to predict P response is that the trees

were taking up P from the rhizosphere soils where

the ectomycorrhizae help the roots to take up more

P (Liu et al. 2004) than that indicated by the soil

P test conducted on bulk soils away from the

rhizosphere.

Soil P fractions

At the Kaweka forest, in 2001 and 2002, application

of TSP and BGPR significantly (P \ 0.0001 and

P = 0.0019, respectively) increased resin-Pi concen-

trations. At the Kinleith forest, however, the

application of P fertilizers significantly (P \ 0.0001)

increased resin-Pi concentrations only in 2001

(Fig. 1). The magnitude of the increase in resin-Pi

concentration due to the addition of TSP was higher

than due to BGPR addition at both forests. This is

Table 4 Needle P

concentrations (%) 2,

3 and 4 years after P

fertilizer application

Values preceding the same

letters in each column are

not significantly (P [ 0.05)

different

P fertiliser

rate

(kg P ha-1)

Kaweka

Year 2

Kaweka

Year 3

Kaweka

Year 4

Kinleith

Year 2

Kinleith

Year 3

Kinleith

Year 4

0 0.136c* 0.122b 0.135b 0.123c 0.111e 0.128c

50 TSP 0.158b 0.153a 0.169a 0.142b 0.124d 0.136bc

100 TSP 0.166b 0.162a 0.168a 0.183a 0.152ab 0.155b

200 TSP 0.188a 0.162a 0.181a 0.181a 0.161a 0.181a

50 BGPR 0.167ab 0.157a 0.164a 0.148b 0.130cd 0.155b

100 BGPR 0.161b 0.157a 0.171a 0.161ab 0.143bc 0.153b

200 BGPR 0.170ab 0.160a 0.181a 0.178a 0.162a 0.183a


123

because of the higher solubility (water and citric acid

solubility) of TSP than of BGPR (Table 2). The

minimum P rate required to significantly increase

resin P concentration at both forests, during 2001, and

at the Kaweka forest in 2002, was lower for the TSP

application compared with the BGPR application.

During 2001, the minimum P rate at both forests was

50 kg P ha-1 for TSP and 100 kg P ha-1 for BGPR

and during 2002, at the Kaweka forest the corre-

sponding rates were 100 kg P ha-1 for TSP and

200 kg P ha-1 for BGPR.

The reason for the increased resin-Pi concentra-

tion, even when the relatively insoluble BGPR was

applied, is that at both forest sites the soils had pH

values (5.7 at Kaweka and 5.1 at Kinleith) lower than

the upper pH limit of 6.0 for PR dissolution (White

et al. 1989). The rainfall in 2001 and 2002 at the

Kaweka and the Kinleith forests (1285 and 1280 mm

at the Kaweka forest and 1491 and 1702 mm at the

Kinleith forest, respectively) was also higher than the

minimum annual rainfall of 800 mm required for PR

dissolution (White et al. 1989).

In 2002 the resin-Pi concentrations in the TSP-

treated soils, especially at 200 kg P ha-1, were lower

than those in 2001 at both forests. This is probably

because with time the amount of P fixation in the soil

may have increased, resulting in an increased

conversion of resin-Pi to NaOH-Pi. Short et al.

(2007) also reported that the resin-P fraction

decreased significantly between weeks 4 and 48

when the soluble P fertilizer, MCP was mixed with

soils and incubated under laboratory conditions. For

the BGPR treatment, however, there was no change

in resin-Pi concentrations between 2001 and 2002.

The difference in the results between the TSP and

BGPR treatments lies in the forms of P extracted by

the resin in the two treatments. The resin extracts

only the exchangeable (weakly adsorbed) P in soils

treated with TSP, whereas it extracts two forms of

P in BGPR treated soils, the dissolved PR weakly

adsorbed to soil and part of the undissolved PR

(Perrott et al. 1993). The undissolved PR appeared to

have remained high even after 2 years of the PR

application, as evidenced by the high concentration of

the H2SO4-Pi fraction (Fig. 2). The resin-Pi concen-

tration in BGPR treatment therefore remained the

same between 2001 and 2002.

The effect of the addition of P fertilizer on NaOH-

Pi concentrations at both the Kaweka and Kinleith

forests in 2002 was also significant (P \ 0.0001 and

P = 0.0003, respectively) (soil samples not analysed

for NaOH-Pi in 2001). Unlike resin-Pi concentrations

(weakly adsorbed P exchangeable by HCO3- in the

resin), NaOH-Pi concentrations, a measure of P

strongly adsorbed onto Fe and Al oxides and

allophane, was higher in the Kaweka soil compared

with the Kinleith soil, for the same rate of P

application (Fig. 2). This is probably because of the

0

20

40

60

80

100

0 50 TSP 100 TSP 200 TSP 50 PR 100 PR 200 PR

P fertiliser rate (kg P ha-1

)

0

20

40

60

80

100



)

0

20

40

60

80

100


)

0

20

40

60

80

100


)

ns ad cd ab bcd bcd bc

c bb

a

cb b b d

bc b

a

cd bc

b

Kinleith

2001 2001

2002 2002

Kaweka

0 50 TSP 100 TSP 200 TSP 50 PR 100 PR 200 PR 0 50 TSP 100 TSP 200 TSP 50 PR 100 PR 200 PR

Res

in-P

i (μg

P g

-1 s

oil)

Res

in-P

i (μg

P g

-1 s

oil)

Res

in-P

i (μg

P g

-1 s

oil)

Res

in-P

i (μg

P g

-1 s

oil)

Fig. 1 Effect of P

fertilizers on resin-Pi

concentrations at 0–10 cm

soil depth, 1 and 2 years

after P fertilizer application.

Statistical analysis was

carried out on H �Ytransformed data for the

Kaweka forest for both

years. For the Kinleith

forest, statistical analysis

was carried out on loge

transformed data for 2001.

Bars having the same letters

at the top are not different at

P = 0.05


123

higher P fixation in the Allophanic Soil at the

Kaweka forest compared with the Pumice Soil at

Kinleith forest (Table 1).

The NaOH-Pi concentrations significantly

increased with the increase in the application rates

of TSP and BGPR at both sites, but the rate of

increase was higher for the TSP treatment than for

the BGPR treatment. The higher rate of increase for

the TSP treatment is probably due to the higher

water solubility of TSP compared with BGPR

(Table 2). When fertilizer P became soluble it might

have quickly mobilized and then transformed mainly

into the NaOH-Pi pool in these high P fixing soils.

Zoysa et al. (2001) also reported that the rate of

increase in NaOH-Pi concentration in a high P fixing

Ultisol was higher when the soils were treated with

TSP compared with when the soils were treated with

a PR.

The application of P fertilizer had significant

effects on H2SO4-Pi concentrations in the soils at

both forests (P \ 0.0001 and P \ 0.0001, respec-

tively). The H2SO4-Pi concentrations were higher for

the BGPR treatment than for the TSP treatment for

each of the rates of P application at both trial sites

(Fig. 2). All rates of BGPR application significantly

increased the H2SO4-Pi concentration in both the

soils. This is due to the high concentration of

undissolved PR (P associated with Ca) remaining in

the soils, which was extracted by H2SO4. In com-

parison, the addition of TSP significantly, but only

slightly, increased the H2SO4-Pi concentrations only

at 100 and 200 kg P ha-1 in the Kaweka soil and at

200 kg P ha-1 in the Kinleith soil. Trolove et al.

(1996) also reported that the application of North

Carolina Phosphate Rock (NCPR) to a Typic Dyst-

rocrept in a glasshouse trial increased the H2SO4-Pi

concentrations, while application of MCP, which is

the main P component of TSP, did not increase the

concentration of the H2SO4-Pi fraction. While the

increase in H2SO4-Pi concentrations resulting from

the increase in BGPR rates of application is due to an

increase in the concentration of undissolved PR, the

increase in H2SO4-Pi with an increase in TSP rates

observed in the current study is due to the increase in

concentrations of di-calcium phosphate (DCP) result-

ing from the conversion of MCP in TSP to DCP

(Hedley et al. 1994).

In general, the magnitude of the increase in

H2SO4-Pi concentrations per unit weight of BGPR

addition at the Kaweka forest was greater than that at

the Kinleith forest. This may be due to the higher rate

of dissolution of BGPR in the Kinleith soil than in the

Kaweka soil, as the former was more acidic than the

latter (pH 5.1 and pH 5.7, respectively, Table 1). The

supply of H+ is a driving force for the dissolution of

PR, along with the removal of the dissolution reaction

products Ca2+, H2PO4- and F- from the site of

dissolution (Khasawneh and Doll 1978). Increases

in PR dissolution in allophanic soils in New Zealand,

from 29.3 to 83.5%, 18.2 to 78.9, and 12.5 to 60.3%,

were reported for North Carolina phosphate rock,

Jordan phosphate rock and Nauru phosphate rock,

respectively, when the soil pH decreased from 6.5 to

3.9 (Bolan and Hedley 1990).

Rainfall at the Kinleith forest during the trial

period was higher than at the Kaweka forest

0

50

100

150

200

250

300

350


P fertiliser rate (kg P ha -1 )

H 2

O

S

4 g

P

g

µ

( i

P

- 1 -

) l i o

s

0

50

100

150

200

250

300

350



H 2

O

S

4 P

-

i g

P

g

µ

(

1 - ) l i

o

s

0

50

100

150

200

250

300

350



P

- H

O

a

N

i g

P

g

µ

(

1 - ) l i

o

s

0

50

100

150

200

250

300

350



P

- H

O

a

N

i g

P

g

µ

(

1 - ) l i

o

s

Kaweka Kinleith

e* c b

a

e de cd

d bc b

a

cd bc bc

e de cd c c

b

a

d cd c c

b

a

cd

Kinleith Kaweka

Fig. 2 Effect of P fertilizer

rates on NaOH-Pi and

H2SO4-Pi concentrations at

0–10 cm soil depth, 2 years

after P application (2002).

Statistical analysis was

carried out on loge

transformed data. *Bars

having the same letters at

the top are not different at

P \ 0.05


123

(annual rainfall for 2001 at Kinleith was 1491 mm

and at Kaweka was 1285 mm; for 2002 they were

1702 and 1280 mm, respectively). It is possible that

this would have resulted in a higher soil moisture

regime at the Kinleith forest, promoting the further

dissolution of BGPR. But the Kaweka soil had

lower exchangeable Ca and resin-Pi concentrations

and higher P fixing capacity compared with the

Kinleith soil, and based on these properties PR

dissolution would have been expected to be higher

at Kaweka (Mackay and Syers 1986). The fact that

the rate of PR dissolution based on the H2SO4-Pi

was lower in the Kaweka soil (higher H2SO4-Pi

concentration) indicates that the effect of the higher

acidity and moisture content in the Kinleith soil

overrides the influences of the P fixing capacity, P

concentration and exchangeable Ca in the soils in

promoting a higher rate of BGPR dissolution in the

Kinleith soil.

An attempt was made to calculate the rate of

BGPR dissolution in the field using the difference in

H2SO4-Pi concentrations in soils between the BGPR

treatment and the control treatment and soil bulk

density (Zoysa et al. 2001), but the results showed

extremely high variability and no meaningful infor-

mation on BGPR dissolution in the field soils was

therefore derived. This high variability in BGPR

dissolution is probably due to the high soil variability

in the field and errors associated with using low

levels of PR dissolution in the dissolution calculation.

Comparison of the fertilizer P contribution

to the different soil P fractions

The data on the concentrations of the various soil

P fractions 2 years after application of P fertilizer

showed that for the TSP treated soils and for the

natural soil (no P added) the P concentration in the

different P fractions, in general, decreased in

the order of NaOH-Po[ residual-P [ NaOH-Pi [H2SO4-Pi C resin-Pi at both sites (Fig. 3). For the

addition of BGPR, the trend was similar to that of

TSP but at the rates of 100 and 200 kg P ha-1 the

concentrations of H2SO4-Pi were higher than the

concentrations of NaOH-Pi at both sites. Further-

more, at the BGPR addition rate of 200 kg P ha-1 at

the Kaweka forest, the concentration for the H2SO4-

Pi fraction was the highest, and at Kinleith forest it is

second highest after NaOH-Po.

The pattern of the rate of change in P concentra-

tion in the different P fractions due to the additions of

TSP was different from that due to the additions of

BGPR. When increased rates of TSP were applied,

the NaOH-Pi fraction increased at a faster rate than

the other P fractions and the rate of increase was

more marked at the Kaweka forest than at the

Kinleith forest (Fig. 3). This suggested that the

proportion of P applied in TSP to the soil that was

adsorbed to allophane and Fe + Al oxides was more

than that converted to any of the other P fractions.

The higher rate of increase of NaOH-Pi

0

50

100

150

200

250

300

350

400

0 50 TSP 100 TSP 200 TSP

P fertiliser rate (kg P ha-1)

gP

gµ(

noitart

necn

ocP

1-)li

os NaOH-Po

Residual P

NaOH-Pi

H2SO4-Pi

Resin-Pi

0

50

100

150

200

250

300

350

400

0 50 TSP 100 TSP 200 TSP


gP

gµ(

noitart

necn

ocP

1-)li

os

0

50

100

150

200

250

300

350

400

0 50 BGPR 100 BGPR 200 BGPR


gP

gµ(

noitart

necn

ocP

1-)li

os

0

50

100

150

200

250

300

350

400

0 50 BGPR 100 BGPR 200 BGPR


gP

gµ(

noitart

necn

ocP

1-)li

os

Kinleith PR

Kaweka PR

TSP TSP Fig. 3 Comparison of the

changes in P concentrations

in different soil P fractions

at 0–10 cm soil depth with

increase in TSP and BGPR

rates 2 years after P

application (2002)


123

concentrations at the Kaweka forest than at the

Kinleith forest is due to the higher P fixation capacity

of the Kaweka soil compared with that of the Kinleith

soil (Table 1). Meanwhile, when increased rates of

BGPR were added, the H2SO4-Pi fraction increased at

a faster rate compared with the other P fractions and

the rate of increase was also more marked at the

Kaweka forest than at the Kinleith forest because of

the presence of a higher proportion of undissolved

BGPR in the higher pH of the Kaweka soil.

At both forests, increased rates of BGPR and TSP

had no effect on the concentrations of NaOH-Po and

residual-P in the 2 years after fertilizers were applied.

Plant-available soil P

Bray-2 P: The Bray-2 P is the common soil test used

for determining P availability in soils under

P. radiata plantation in New Zealand (Ballard

1974; Hunter and Hunter 1991). At the Kaweka

forest, the soils that received no P fertilizer had a

Bray-2 P value of 6 lg P g-1, which is much below

the critical P concentration of 12 lg P g-1 estab-

lished for the maximum yield of 1- to 3-year-old

P. radiata (Ballard 1974), while at the Kinleith forest

the soils had a Bray-2 P value of 15 lg P g-1, which

is higher than the critical soil P concentrations

(Fig. 4). Even though the Bray-2 P concentration at

the Kaweka forest was lower than the critical

P concentration, tree growth was not affected because

foliar P concentrations were not below the critical

foliar P concentration as discussed earlier in the paper

(Table 4). The reasons for the absence of tree

response to P, in spite of low Bray-2 P values, have

been presented at the beginning of this section.

Increased rates of both forms of P fertilizers

significantly increased Bray-2 P concentrations in the

soils at both sites in both years (2001 and 2002), and

the magnitude of the increase in Bray-2 P concen-

tration was higher at the Kinleith forest than at the

Kaweka forest (Fig. 4). These results are similar to

those obtained for the effect of P fertilizers on resin-

Pi concentrations (Fig. 1), which is also an index of

plant P availability (Dias et al. 2000). The Bray-2

P results in this study are consistent with some of the

other studies conducted in New Zealand on

P. radiata. Ballard (1972) reported that 18 years

after application of 2.5 tonnes of superphosphate ha-1

(225 kg P ha-1) to a 20- to 24-year-old P. radiata

plantation on an Ultisol, the Bray-2 P concentration

(soil depth 0–10 cm) in the treated plots (5.4 lg P g-1)

0

20

40

60

80

100

120



g

P

g

µ

( P

2 - y a r

B

1 - ) l i

o

s

0

20

40

60

80

100

120



g

P

g

µ

( P

2 - y a r

B

1 - ) l i

o

s

0

20

40

60

80

100

120



g

P

g

µ

( P

2 - y a r

B

1 - ) l i

o

s

0

20

40

60

80

100

120



g

P

g

µ

( P

2 - y a r

B

1 - ) l i

o

s

0

20

40

60

80

100

120



g

P

g

µ

( P

n

e s l

O

1 - ) l i

o

s

0

20

40

60

80

100

120



g

P

g

µ

( P

n

e s l

O

1 - ) l i

o

s

Kaweka

Kaweka

Kinleith

Kinleith

2001 2001

2002 2002

2002 2002

e d c

a*

d cd b

d c

b

a

cd c

b

e d bc

a

d c

ab

ab ab

c b

a

b bc

c c b a c c c c bc ab

a bc bc bc

Fig. 4 Effect of P fertilizer

rates on Bray-2 P after 1

and 2 years (2001 and

2002) and Olsen P at 0–

10 cm soil depth, after

2 years (2002) of P

application. For Bray-2 P

data, statistical analysis was

carried out on H �Ytransformed data for the

Kaweka forest for 1 year

after P application and on

loge transformed data for

the Kaweka forest for

2 years and for the Kinleith

forest for 1 and 2 years after

P application. For Olsen P

data, statistical analysis was

carried out on loge

transformed data for the

Kaweka data. *Bars having

different letters at the top

are significantly different at

P = 0.05


123

was significantly greater than that in the untreated

plots (2.3 lg P g-1). In another trial, Hunter and

Hunter (1991) reported that 7 years after the appli-

cation of superphosphate or phosphate rock to three

soils of different P retention capacities (P retention of

93%, 48%, and 0%), there were marked increases in

the Bray-2 P concentration in all the three soils.

The Bray-2 P concentrations had a very strong

relationship with resin-Pi, NaOH-Pi and H2SO4-Pi

concentrations (Table 5). This is consistent with the

findings of many others that Bray-2 extractant

solubilises P associated with Fe and Al (NaOH-Pi),

Ca (H2SO4-Pi) (Hahne et al. 1988; Bationo et al.

1991; Saggar et al. 1992) and labile P (resin-Pi)

(Saggar et al. 1992). Because of the strong relation-

ship of Bray-2 P concentrations with resin-Pi, NaOH-

Pi, and H2SO4-Pi concentrations, the effect of

increased P rates on Bray-2 P concentrations was

similar to that observed for these soil P fractions

(discussed previously).

The correlation between the Bray-2 P and NaOH-

Pi concentrations was higher for the TSP treatment

than the BGPR treatment (Table 5). This is because

in the BGPR treatment, the Bray-2 P test not only

extracts P associated with Fe and Al oxides (NaOH-

Pi) but also extracts part of the undissolved BGPR

(H2SO4-Pi), whereas in the TSP treatment, the Bray-2

P extracts only the NaOH-Pi fraction (Perrot et al.

1993). For the same reason, it is expected that the

correlation between the Bray-2 P and H2SO4-Pi

concentrations will be higher for the BGPR treatment

than for the TSP treatment. But correlation results

show that this is only marginally true, probably

because part of the MCP in TSP was converted to

DCP, which was also extracted by H2SO4 as with the

extraction of undissolved PR in the BGPR treatment

(Hedley et al. 1994).

Olsen P: While the Olsen P test is not commonly

used for determining soil P availability to forest trees

in New Zealand, it is commonly used on other crops

(Sinclair et al. 1997) in New Zealand and other

countries (Schoenau and Karamanos 2000; Szilas

et al. 2007). This test was therefore also used in the

current study, but only for the soil samples collected

in 2002.

The main effect of P fertilizer rates on Olsen

P concentrations in the soil at the Kaweka and

Kinleith forests was significant (P \ 0.0001 and

P = 0.0473, respectively). Although increased rates

of TSP application increased Olsen P concentrations,

increased rates of BGPR application had no effect on

Olsen P concentrations at both sites (Fig. 4). Unlike

the acidic Bray test, which extracts resin-Pi, NaOH-Pi

and H2SO4-Pi, the alkaline Olsen test (NaHCO3 pH

8.5) extracts only resin-Pi, NaOH-Pi and some

NaOH-Po (Kumar et al. 1991; Perrott et al. 1992;

Saggar et al. 1992). The Olsen test does not extract

H2SO4-Pi. The reason for BGPR increasing Bray-2

P but not Olsen P is that the addition of BGPR mainly

increases H2SO4-Pi (Fig. 2), which was extracted by

the Bray test but not by the Olsen test. This is

consistent with the absence of any correlation

between Olsen P concentrations and H2SO4-Pi con-

centration when BGPR was applied, as opposed to

significant correlation when TSP was applied

(Table 5). Bray-2 P concentrations, on the other

Table 5 Correlation of Bray-2 P and Olsen P concentrations with soil P fraction coconcentrations (numbers in the table are

correlation coefficients)

Fertilizer Soil Soil test Soil P fractions

Resin-Pi NaOH-Pi NaOH-Po H2SO4-Pi Residual-P

TSP Allophanic Soil Bray-2 0.97*** 0.95*** 0.78* 0.92** 0.44

TSP Allophanic Soil Olsen 0.97*** 0.94*** 0.78* 0.93** 0.47

TSP Pumice Soil Bray-2 0.87** 0.99*** 0.30 0.91** -0.24

TSP Pumice Soil Olsen 0.98*** 0.79* 0.27 0.75* -0.25

BGPR Allophanic Soil Bray-2 0.90** 0.87** -0.05 0.97*** 0.78*

BGPR Allophanic Soil Olsen 0.87** 0.42 0.48 0.49 0.40

BGPR Pumice Soil Bray-2 0.92** 0.76* 0.23 0.92** 0.70

BGPR Pumice Soil Olsen 0.83* 0.34 -0.25 0.45 0.70

Correlation coefficient significant at P \ 0.05; ** P \ 0.01; *** P \ 0.001


123

hand, had a significant correlation with H2SO4-Pi

concentrations for both TSP and BGPR treatments

(Table 5).

The results of this study are consistent with the

findings of many others. For example, Saggar et al.

(1992) reported that the incubation of a range of PRs

and MCP (constituent of TSP) with four New Zealand

soils increased Bray-1 P concentrations in all soils,

whereas Olsen P concentrations increased only in the

MCP treated soils. Mackay et al. (1984) also found that

when different rates of superphosphate or Chatham

Rise phosphorite (CRP) were added to soils at four sites

in the Central North Island of New Zealand, Olsen P

concentrations in the soils did not increase with the

increasing rates of CRP added in three of the four soils,

but Bray P concentrations increased with increasing

CRP rates in all four soils.

The fact that Olsen P did not increase with

increasing PR rate suggests that little PR dissolution

took place to form Fe and Al phosphate (NaOH-Pi) and

the resin-Pi was derived from the undissolved PR. This

confirms previous findings that Olsen extraction is not

a good test to measure PR availability to perennial

crops (Perrott et al. 1993; Saggar et al. 1992) since this

test does not extract undissolved PR, which provides a

significant, if not the main portion of available

P directly to plants compared with P associated with

Fe and Al oxides and allophone.

Downward movement of fertilizer P

The downward movement of P in soils was tested

only for the highest P rate (200 kg P ha-1) 2 years

after fertilizer application. At both forests, the

application of TSP significantly increased both

Bray-2 P and Olsen P concentrations at the

0–10 cm soil depth but the application of BGPR

significantly increased only the Bray-2 P concentra-

tions (Fig. 5). At the 10–20 cm soil depth, however,

the application of either of the two P fertilizers had no

significant effect on Bray-2 P and Olsen P concen-

trations at the Kaweka forest, while at the Kinleith

forest both P fertilizers significantly increased Bray-2

P concentrations, and only TSP significantly

increased Olsen P concentrations. There was no

fertilizer effect on these P concentrations at the

20–30 cm soil depth at either site.

The reason for the differences in the rate of P

movement in the two forests is that in the porous

Pumice Soil at the Kinleith forest, P from both TSP

and BGPR has leached to the lower depth. In the

less porous and higher P fixing Allophanic Soil at

the Kaweka forest it might have been difficult for

fertilizer P to have moved to below 10 cm depth.

The movement of P in Kinleith forest was higher

for TSP than BGPR because of higher solubility of

TSP.

0

5

10

15

20

25

0 10 20 30 40 50 60 70 80 90 100

Bray-2 P (µg P g -1 soil)

) m

c (

h

t p

e

d

l i o

S

Control (no P applied) 200 TSP 200 PR

0

5

10

15

20

25

0 10 20 30 40 50 60 70 80 90 100

Bray-2 P (µg P g -1 soil)

) m

c (

h

t p

e

d

l i o

S

0

5

10

15

20

25

0 10 20 30 40 50 60 70 80 90 100

Olsen P (µg P g -1 soil)

) m

c (

h

t p

e

d

l i o

S

0

5

10

15

20

25

0 10 20 30 40 50 60 70 80 90 100

Olsen P (µg P g -1 soil)

) m

c (

h

t p

e

d

l i o

S

Kaweka

Kaweka Kinleith

NS

NS

NS

NS

NS

NS

Fig. 5 Distribution of

Bray-2 P and and Olsen P

concentrations in the soil

profiles 2 years after

application of 200 kg P

ha-1. Horizontal bars

represent LSD at P = 0.05.

NS denotes not significant

at P = 0.05


123

As the soils from treatments receiving lower rates of

P fertilizer were not analysed it is not known whether

P would have moved below 10 cm depth at lower rates

of P application. The results in the current study are

consistent with the findings from other studies. For

example, Hunter and Hunter (1991) studied the

P movement in soils having different P retention

capacities (0, 48, and 93%) treated with phosphate rock

and superphosphate at the rate of 150 kg P ha-1 and

reported that 7 years after fertilizer application, at the

site with 0% P retention, plant-available P, as measured

by Bray-2 P, was higher in the fertilizer-treated soils

than in the untreated soils and this extended down to

60 cm. This suggests that P from the fertilizer had

moved to 60 cm depth. This P movement was greater

for the superphosphate treatment than for the phos-

phate rock treatment. At the site with 48% P retention,

fertilizer P moved down to only 30 cm, while at the site

with very high P retention (93%) there was no evidence

of P movement below 10 cm. Humphreys and Pritchett

(1971) studied the P movement in some sandy soils

under slash pine (Pinus elliottii Engelm. var. elliottii)

treated with superphosphate and Florida phosphate

rock and reported that 7–11 years after fertilizer

application, P from superphosphate was completely

leached from the top 20 cm of soils with no P sorption

or buffering capacity (Ground water Podzols), while in

a soil with a high P sorption or buffering capacity

(a Low Humic Gley) most of the P added was retained

in the top 20 cm. In contrast, most of the P derived from

phosphate rock was still retained in the top 20 cm even

in soil with no P sorption capacity.

Conclusions

Application of a phosphate rock and triple super-

phosphate, each at four rates (maximum 200 kg

P ha-1) to two second-rotation P. radiata forests, one

each in a Pumice Soil (Cryands) and Allophanic Soil

(Udands), significantly increased needle P concentra-

tions 2, 3 and 4 years after fertilizer application.

However, the fertilizers had no effect on tree growth

1, 2 and 3 years after application. This is probably

because the needle P concentrations in the control

treatment (no P fertilizer added) soil were approxi-

mately at or above the level considered satisfactory

for the growth of P. radiata and did not appear to

change with time.

The labile organic fraction (NaOH-Po) in the

surface soils contained the largest percentage of P.

Therefore, the long-term P supplying power of the

soils largely depends on the mineralisation of this

organic P. Changes in the concentration of the

various P fractions 2 years after P fertilizer applica-

tion depended on the P fertilizer type. The rate of

increase of the concentrations of the P fractions was

highest for NaOH-Pi when TSP was applied and

highest for H2SO4-Pi when BGPR was applied. The

NaOH-Po concentration was unaffected by the

P fertilizer application. The NaOH-Pi concentration

increase was higher in the Allophanic Soil than in the

Pumice Soil, probably because of the higher

P fixation in the Allophanic Soil. Both types of

fertilizers increased plant-available soil P concentra-

tion as measured by resin-Pi and Bray-2 P but only

TSP application increased Olsen P concentration. The

Bray-2 P concentration had a significant relationship

with resin-Pi, NaOH-Pi and H2SO4-Pi concentrations

but the Olsen P concentration was significantly

related to all these soil P fractions only in TSP

treated soils; in BGPR treated soils Olsen P concen-

tration was related only to resin-Pi concentration.

Phosphorus derived from TSP and BGPR application

can move down to 10–20 cm soil depth within

2 years of application in the Pumice Soil, but it did

not move below 10 cm depth in the higher P fixing

and less porous Allophanic Soil.

Acknowledgements The senior author thanks the NZAID for

awarding a scholarship for the PhD study and the Centre for

Sustainable Forest Management at Forest Research Institute,

New Zealand for partial funding of the research. Field and

laboratory assistance by Bob Toes, Ian Furkert, Ross Wallace

and Iynka Loganathan of Massey University is also gratefully

acknowledged.

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Effect of phosphate rock and triple superphosphate on soil phosphorus fractions and their...

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