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Agricultural Sciences in China

2007. 6 ( 3 ) .330-337 ScienceDirect March 2007

Release Characteristicsof Different N Forms in an Uncoated Slow/Controlled

Release Cornpound FertiIizer

DONG Yan and WANG Zheng-yin

College of Resourcec and Environmental Sciences, Sorrthuest University, Chongqing 400716, P.R.China

Abstract
This study examined the release characteristics of different N forms in an uncoated slow/controlled-release compound
fertilizer (UCRF) and the N uptake and N-use efficiency by rice plants. Water dissolution, soil leaching, and pot
experiments were employed. The dynamics of N release from the UCRF could be quantitatively described by three
equations: the first-order kinetics equation [N,= N o( 1 -e-")], Elovich equation (N,= a + blnt), and parabola equation (N,= a
+ btos), with the best fitting by the first-order kinetics equation for different N ( r = 0.9S69**- 0.9999**). The release
potentials (Novalues estimated by the first-order kinetics equation) of different N in the UCRF decreased in the order of
total N > DON > urea-N > NH,+-N > NO,--N in water, and total N > NH,+-N > DON > urea-N > NO,--N in soil, respectively,
being in accordance with cumulative amounts of N release. The constants of N release rate ( k values and b values) for
different N forms were in decreasing order of total N > DON > NH,+-N > NO,--N in water, whereas the k values were urea-
N >DON > NH,+-N > total N > NO,--N, and the b values were total N > NH,+-N > DON > NO,--N > urea-N in soil. Compared
with a common compound fertilizer, the N-use efficiency, N-agronomy efficiency, and N-physiological efficiency of the
UCRF were increased by 1 1.4%, 8.32 kg kg-1, and 5.17 kg kg-1, respectively. The ratios of different N to total N in the UCRF
showed significant correlation with N uptake by rice plants. The findings showed that the first-order kinetics equation
[N,=N,(l-e-k~)jcould be used to describe the release characteristics of different N forms in the fertilizer. The UCRF
containing different N forms was more effective in facilitating N uptake by rice compared with the common compound
fertilizer containing single urea-N form.

Key words: slow/controlled release compound fertilizer, nitrogen forms, release kinetics, nitrogen use efficiency

In recent years, research on slow and controlled re-

INTRODUCTION
Slow/controlled release ferti 1izers play an important
role in improving fertilizer use efficiency by plants by
reducing the frequency of fertilization, thereby miti-
gating environmental pollution and leading to the de-
velopment of sustainable agriculture. Therefore, tech-
nologies to slow down and/or control nutrient release
from fertilizers have been a new topic in fertilizer stud-
ies (Elizabeth 2000; Peng et al. 2002; Li er al. 2005).
lease fertilizers in China has been mainly focused on
regulating N-release rate and on coating slow and con-
trolled release fertilizers (Shavit et al. 1997; Walher
2001; Zhang et al. 2003; Mao et al. 2004). However,
the research on only N without considering other nutri-
ents such as P and K may not meet the requirements
of plants for multiple nutrients. Furthermore, use of
coating materials may result in high production costs
and even soil contamination after their release into soil.
To solve these problems, some researchers have re-

This paper is translated from its Chinese version in Sc~entioAgriculrura Sinica

DONG Yan. Ph D candidate. E-mail: pipi-cq@ 163.com; Correspondence WANG Zheng-yin, Professor, Tel: +86-23-68251249,E-mail: wangzy@swau.edu.cn

02007,CAAS.All rights reserved.Publishedby ElsevierLtd.

Release Characteristics of Different N Forms in an Uncoated Slow/Controlled Release Compound Fertilizer
cently developed new uncoated slowkontrolled release
organic-inorganic compound fertilizers, such as the fer-
tilizers prepared using plastic-starch and clay-polyes-
ter as cementing agents (Wang R F et al. 2005), those
by mixing common urea with industrial organic wastes
and controlled release inorganic materials (Song et al.
2003), and those by mixing inorganic compound fer-
tilizer with N-rich and high-quality organic fertilizer
(Wang Z Y et al. 2005). In the current study, the
release characteristics of different N forms in an un-
coated slow and controlled release compound fertil-
izer (UCRF) in water and soil, and N uptake by rice
plants from the UCRF in pot experiment were examined.
These results will provide critical information regard-
ing development and application of new slow and con-
trolled release fertilizers.
MATERIALS AND METHODS
Materials
A high-quality organic material-based UCRF produced
by the Southwest University, China, was used in this
experiment. It was characterized as uncoated organic
and inorganic nutrient frame types (Wang Z Y et al.
2005). The cementing material was complex and was
composed of natural mineral materials and macromol-
ecule carbohydrates. The release time of the fertilizer
lasted over 90 d (Zhang et al. 2004) and the N:P,O,:
K,O ratio of the fertilizer was 12:9:12. Nitrogen in the
UCRF existed as NH,+-N, NO;-N, urea-N, and dissolv-
able organic nitrogen (DON). A common compound
fertilizer (CCF) containing urea (N, 46%), ammonium
dihydrogen phosphate (N, 10%; P,O,, 44%), and po-
tassium chloride (K,O, 60%) with a N:P,O,:K,O ratio
of 12:9:12 was used as a control.
Two purple soils derived from the Shaximiao Group
parental rock were used in the experiment. Their basic
agrochemical properties are given in Table 1.
Table 1 Basic properties of soils used in the experiment
Soils pH
Grey-brown purple soil 1 (incubation) 5.20
Grey-brown purple soil 2 (pot experiment) 5.39
'O.M., soil organic matter; Av-P and Av-K, soil available P and K, respectively.
33 1
Methods
Nitrogen dissolution in water Nitrogen dissolution
experiment was conducted following the method by
Yamazoe et al. (1983). Ten grams of fertilizer samples
were accurately weighed, transferred into nylon bags
(160 mesh), and then placed in 250-mL plastic bottles
containing 200 mL of distilled water. The bottles were
incubated at 25 f 2°C and 35 +2"C, respectively. At 1,
2, 3, 4, 5 , 6, and 7 d of the incubation, the bags were
taken out of the bottles, and transferred into 250-mL
new plastic bottles containing 200 mL of distilled water.
The solutions were filtered and collected for N analyses.
Total N, NH,+-N, N03--N,and urea-N in the solutions
that were obtained each time were analyzed.
Release of N from UCRF in soil Nitrogen release
from the UCRF in soil was measured using Stanford
and Smith's acrobic incubation-leaching method (1972).
There were two treatments, i.e., CK (no fertilizer
control) and UCRF (12-9-12) with three replicates for
each treatment. Twenty grams of air-dried soil (< 2
mm) were mixed well with 20 g quartz sand and 0.5 g
fertilizer, and were then transferred to glass tube (14.5
cm in length and 3 cm in diameter) containing 3-cm
thick quartz sand and 160-mesh nylon net with a drain
hole (0.5 cm diameter) at the bottom. A 2-cm thick
layer of quartz sand was then placed on the top of the
soil to avoid interruption by watering activity. The tubes
were covered with polyethylene film that was pierced
with a small hole (1 mm) to maintain aeration. All tubes
were incubated in incubator at 35 f 2°C. At the sched-
uled times, e.g., 1,3,7,14,21,28, and 42 d of incubation,
all tubes were leached with 100 mL of 0.01% CaC1,.
The leachates were collected for N analyses (total N,
NH,+-N, NO;-N, and urea-N).
Pot experiment A pot experiment was carried out in a
greenhouse of the Southwest University, China. The
experiment consisted of 3 treatments: CK (no fertilizer
control), UCRF (200 mg N kg-' soil), and CCF (200
O.M. (g kg-1)' Alkali-hydrolyzed N (mg kg-1) Av-P (mg kg-I) Av-K (mg kg-I)
16.98 107.6 15.5 95.0
14.50 57.5 22.5 100.0
8 2007, CAAS. All rightsreserved. Publishedby ElsevierLtd.
332 DONG Yan et al.

mg N kg-' soil). Each treatment had 10 replicates. Two
rice plants were grown in each pot (14 cm x 9 cm)
filled with 2.5 kg of soil. At 30,35,40,45, 5 0 , 5 5 , and
60 d of growth, plant samples were collected, thor-
oughly washed, and then placed in oven at 90°C for 15
minutes to inactivate enzymes, after which the samples
were oven dried at 60°C for 24 hours. Plant dry mass
was recorded. The samples were ground to pass through
a 0.5-mm sieve for N analysis.
Analyses
The basic agrochemical properities of soils and total N
of plant samples were measured using traditional analysis
methods (Peiqi and Mile 1991; Bao 2000).
N-efficiency parameters (Peng ef al. 2002,) were
calculated as follows:
Apparent N-use efficiency (N-use efficiency, NUE,
9%)= 100 x [Total plant N accumulation in the pot with
N fertilizer (T,) - total plant N accumulation in the pot
without fertilizer (T,)]/the amount of N fertilizer ap-
plied (FJ.
N agronomic efficiency (NAE, kg kg-') = [Grain yield
in the pot with N fertilizer (G,) - grain yield in the pot
without fertilizer (G,,)]/FN.
N physiological efficiency (NPE, kg kg-')= (GN-Go)/
(T,-To).
RESULTS
Release of different N forms from UCRF in water
Various N forms (total-N, NH,f-N, NO,--N, urea-N,
and DON) in the UCRF exhibited differences for the
cumulative N release amounts in pure water at both
temperatures (25 and 35°C); however, their cumula-
tive release curves showed similar patterns (Fig. 1). On
the first day, the release amounts of different N ac-
counted for more than 50% of their respective total
release amounts. After 3 d, the cumulative releases of
total N, NH,+-N, NO;-N, urea-N, and DON became
stable, suggesting that N release was easy when UCRF
was in water. During day 7, the cumulative amounts
of N release of all N forms were less at 25°C compared
to those at 30°C indicating that higher temperature en-
hanced N releases from UCRF in water.
The cumulative releases of different N forms from
the UCRF at both temperatures could be described by
the first-order kinetics equation [N, = N o ( I&)], Elovich
equation ( N , = a + blnt), and parabola equation (Nr= a

+25C B +25% C

:E
-0-30-C 24 +30%

NH, -N NO, -N Urea-N

6 9
6
6
3
03 0 1 2 3 4 5 6 7
~~ 00 1 2 3 4 5 6 7
0 1 2 3 4 5 6 7

DON

- 0
0 1 2 3 4 5 6 7 0 I 2 3 4 5 6 7

Time (d) Time (d)

Fig. 1 Effect of temperature on N cumulative release of different forms from UCRF in water.

02007,CAAS. Ail rights resewed.Publishedby ElsevierLM.

Release Characteristics of Different N Forms in an Uncoated Slow/Controlled Release ComDound Fertilizer 333

+ b t 0 9 (Table 2). According to the correlation

coefficients, the fitting of the first-order kinetics equa-
tion was the best for different N forms (r=0.9569**- 2 100
1 800
0.9999**),and the least was the parbola equation ( r =
1500
0.8553**- 0.9792**). At both temperatures, the maxi-
1200
mum releases (No value) of different N forms esti-
mated by the first-order kinetics equation decreased -
m
900
-
in the order of total N > DON > urea-N > NH,+-N > z
0
600
300
NO;-N, which was correlated with their respective 0
0 7 14 21 28 35 42
cumulative release amounts.
Time (d)
The release rates ( k values) of different N decreased
in the order of NO;-N > total N > DON > urea-N >
Fig. 2 The cumulative release of different form N in soil.
NH,+-N. Apparently, NO,--N had the greatest release
rate among different N forms although its release
amount was the lowest as it is a readily mobile ion crement in NO,--N. During the entire incubation, the
(Tinker and Nye 2000). Unlike the release amounts, cumulative release amounts of four different N decreased
the effect of temperature on k values varied with the N in the order of DON > NH,+-N > urea-N > NO, -N.
forms. The k values of total N and NH,+-N increased, The fitting of the cumulative releases of different N
but those of DON, urea-N, and NO,--N decreased with to kinetic equations is given in Table 3. Based on their
temperature. correlation coefficients, the first-order kinetics equa-
tion was the best to describe N releases for different N
Release of different N forms from UCRF in soil forms ( r = 0.9759**- 0.9994**),followed by Elovich
equation (r=0.7705**-0.9933**),similar to those in water.
Under soil conditions, the cumulative releases of total The maximum releases (No values) of different N esti-
N, NH,+-N, and NO,--N from the UCRF increased mated by the first-order kmetics equation were in the
gradually during the first 4 weeks (Fig.2), and the in- order of total N > NH,+-N > DON > urea-N > NO, -N,
crease was slower compared to that in water. DON being correlative with their actual cumulative releases.
and urea-N showed release patterns that were different The release rate coefficients ( k value) followed the or-
from those of other N forms, and this is attributed to der of urea-N > DON > NH,+-N > total N >NO,--N,
their microbial decomposition and transformation in the which correlated with the experimental results.
soil. During the first 14 d of incubation, NH,+-N had
the greatest cumulative release increment due to de- N-uptake and N-use efficiency by rice plants
composition of urea-N. After 14 d of incubation,
however, nitrification resulted in greater cumulative in- Compared with the CCF, N uptake by rice plants was

Table 2 Kinetic parameters of release of different N forms in water at 25 and 30°C

The first-order kinetics equation N,=N,(l -e-") Elovich equation q,= u + blnr Parabola equation 9,= a + bP
Temperature N form
No k r a b r U h r

25°C NH,+-N 15.04 0.5923 0.9960" 10.85 2.306 0.9737" 8.680 2.586 0.9324"
NO,--N 13.50 1.759 0.9937" 10.12 2.047 0.8693" 8.407 2.186 0.7925"
Urea-N 23.30 0.6332 0.9567" 18.47 2.151 0.9369" 16.47 2.403 0.8936"
DON 50.15 0.661 2 0.9868" 44.89 2.950 0.9774" 42.00 3.366 0.9521"
Total N 100.6 0.8030 0.9970" 84.33 9.543 0.9607" 75.55 10.54 0.9145"
35°C NH,+-N 16.18 0.6082 0.9962" 11.54 2.554 0.9771" 9.118 2.874 0.9385"
NO,--N 14.20 1.4983 0.9999" 10.43 2.231 0.8553" 8.577 2.372 0.7764"
Urea-N 24.05 0.5523 0.9773" 19.39 1.823 0.9170" 17.75 2.006 0.86 1 I '*
DON 55.01 0.6126 0.9790" 47.42 4.739 0.9792" 43.30 4.824 0.9513"
Total N 107.4 0.8131 0.9981" 88.78 10.85 0.9598" 78.74 12.08 0.9121"
"Significance at P<O.Ol leve1 (n=7, r0,=0.707, r,,,=O.834).

02007,CAAS. All nghtsreserved.Publishedby Elsevwrltd.

334 DONG Yan et al.

lower in the UCRF treatment on d 3 1 of transplantation, samples collected on d 61 of transplantation showed

whereas higher after 31 d, with an exception of 45- that application of UCRF increased the N-use efficiency,
d sample, especially after 51 d (Fig.3). The UCRF N-agronomy efficiency, and N-physiological efficiency
enhanced the plant N uptake by 7.05-19.*3% com- by 11.4%, 8.32 kg kg", and 5.17 kg kg-', respectively,
pared with CCF. as compared to CCF.
The N-use efficiency was higher in UCRF than in
CCF treatments, except for the samples collected at d Ratios of different N to total N (Nx/N,) and their
31 and 46 (Table 4). The measurements of the final relationship with N uptake by rice plants

400 - -cct The ratios of different N released to total N in the UCRF

-CRF
350 - decreased in the order of DON > urea-N > NH,+-N >
-? 300 - NO;-N under both water and soil conditions during 7 d
250 -
of experiment (Tables 5 and 6). However, they had
24 200 -
- different changes over time. At both temperatures in
150
'00 - ,7
water, the ratios of the released NH,C-N and NO,--N to
total N increased, but those for DON decreased with
0 ' time during the first 3 d. After 3 d, the ratios for differ-
31 36 41 46 51 56 61
ent N showed a slight change. In soil, the ratios of
Time ( d )
NO;-N and NH,+-N to total N showed a profound in-
Fig. 3 Dynamics of N uptake with different treatment. crease with time, with the increase being 1.41 and 2.04

Table 3 Kinetic parameters of N release of different forms from UCRF in soil

The first-order kinetics equation N , = N , ( I -ekO Elovich equation q,=a+blnt Parabola equation q,= a + b P 5
N form
Nu k r a h r a h r
NH,+-N 754.5 0.1201 0.9863" 142.8 173.8 0.9859" 132.3 110.7 0.8746"
NO,--N 225.5 0.0960 0.9762" 36.32 47.38 0.8998" 24.33 32.68 0.9363"
Urea-N 402.5 0.6175 0.9994" 356.5 14.61 0.7705' 359.3 8.289 0.5426
DON 718.2 0.1318 0.9759" 553.4 47.83 0.9473" 548.8 30.93 0.8664"
Total N 2 098.6 0.1139 0.9976" I089 283.6 0.9933" 1064.7 182.5 0.9003"

"Significance at P<O.O1 level, 'Significance at P<O.OS level ( n = 7 , r,,,=0.707. ro,,=0.834).

Table 4 N-use efficiency by rice plants during growth stage in UCRF and CCF treatments
Samoling dates (d)
N use N agronomy N physiological
. I

Treatment efficiency efficiency efficiency

31 36 41 46 51 56 61
("/) (kg kg I)- (kg kg-')
Common fertilizer (CCF) 12.68 14.79 29.92 42.7 53.04 54.98 5Y.14 59.14 24.24 40.99
Slow and controlled release fertilizer (UCRF) 5.466 21.34 31.38 40.12 56.78 61.26 70.54 70.54 32.56 46.16

Table 5 The ratios between different N forms and total N in water (N,/N,) (%)
lncuhation time (d)
Temperature N form
____ 1 3 7 14 21 28 42 X (average value)
25°C NH,+-N 12.62 13.91 14.29 14.43 14.58 14.76 14.86 14.21
NO; -N 10.96 13.66 13.69 13.49 13.37 13.33 13.31 13.12
Urea-N 22.10 21.42 22.20 22.27 22.07 22.00 21.96 22.00
DON 54.32 51.01 49.83 49.81 49.98 49.91 49.86 50.67
35°C NH,*-N 12.87 13.86 14.38 14.55 14.71 14.87 14.98 14.32
NO, -N 10.58 13.55 13.41 13.20 13.07 13.03 13.01 12.84
Urea-N 21.93 21.15 21.51 21.16 20.97 20.90 20.86 21.21
DON 54.62 51.45 50.70 5 1.08 5 I .24 51.21 51.15 51.64

02007,CAAS. All rights resewed.Publishedby ElsevierLtd.

Release Characteristics of Different N Forms in an Uncoated SlowKontrolled Release Compound Fertilizer 335

times greater on d 42 than on d 1, respectively (Table 6).
However, the ratios of DON and urea-N to total N de-
creased with time, with the decrease being 33.9 and
38.7% on d 42, respectively, compared with d 1.
Correlation analysis showed that there were signifi-
cant and very significant correlations between the ra-
tios (N,/N,) and N uptake by rice plants at different
growth stages. The Nx/N, ratio for NH,+-N and urea-
N obtained from the water dissolution experiment had
very significant positive correlations with N uptake by
rice (r= 0.8437**- 0.9347**),whereas significant nega-
tive correlation was found for DON (Table 7). The Nx/
N, for NH,+-N and NO,--N obtained from soil incuba-
tion experiment showed very significant positive cor-
relation with N uptake by rice (r=0.8947**- 0.9540**),
but very significant negative correlation was observed
for urea-N and DON (r=-0.9146**--0.9619**). These
results showed that the quantity and ratios of different
N released from the UCRF at different periods impacted
N uptake by the plant, having implications for develop-
ment of uncoated slow and controlled release fertilizers
with nutrient configuration.

Table 6 The ratios between different N to totaLN in soil (NJN,) (%s

Incubation time (d)
N form
1 3 7 14 21 28 42 X (average value)
NH,+-N 11.82 22.76 31.07 34.26 34.44 34.94 35.94 29.32
NO,--N 4.390 6.992 6.463 6.691 9.560 10.54 10.59 7.889
Urea-N 31.92 27.13 24.42 21.48 20.17 19.59 19.17 23.41
DON 51.87 43.12 38.05 37.58 35.83 34.94 34.29 39.38

Table 7 Correlation coefficients between the ratios (Nx/N,) and N uptake by rice plants ( r )
N form
Medium and temperature
NH,+-N NO,--N urea-N DON
In water 25°C 0.9073" 0.5494 0.8437" -0.7626'
30°C 0.9347" 0.5133 0.8824" -0.7524'
In soil 35°C 0.8947" 0.9540" -0.9619" -0.9146"
"Significance at P<0.01 level; 'Significance at P<0.05 level (n=7. roo,=0.707,ro,,=0.834).

DISCUSSION simultaneous decomposition of DON and urea-N from

the UCRF under soil conditions, this fertilizer exhibits a
Effects of medium on release of different N forms better performance with regard to sustainable N supply
from UCRF to plants compared with other fertilizers.

Medium not only affects the rate and quantity of N
release from a fertilizer, but also alters the transforma-
tion of different N forms. The results of this study
showed that the different N in the UCRF dissolved eas-
ily and released rapidly in water, which did not fully
meet the definition of slow and controlled release fertil-
izer by Europe Standard Committee. However, many
researchers have recently suggested that the release of
slow and controlled release fertilizer should be evalu-
ated in soil-plant system (Du et al. 2003) or fertilizer-
soil-plant system (Xi 2003; Liao et al. 2003). This has
been demonstrated in the current study. Moreover,
because of both release of NH,+-N and NO,--N and
Kinetic characteristics of release of different N
forms from UCRF
The first-order kinetics equation, Elovich equation, and
parabola equation could be used to describe the N re-
lease characteristics, as evidenced by high correlation
coefficients with the best for the first-order kinetic
equation. Stanford and Smith (1972) and Wang and
Qing (1994) have successfully described long-term min-
eralization of organic N in soil using the first-order ki-
netics equation. Under soil conditions, the k value for
urea-N was the greatest among different N forms, which
is attributed to rapid decomposition and transformation

02007,CAAS. All rights reserved. Published by Elsevierltd.

336
of urea at 35"C, whereas the k value for total N was
the lowest, indicating slow release of N from the UCRF.
The slow mineralization and transformation of DON
and urea-N in the UCRF during plant growth sustained
NH,+-N and NO;-N levels in the soil, which may meet
plant requirement for N, while avoiding the toxicity
caused by NH, to the plants and the effect of N leach-
ing on the environment that results from use of com-
mon fertilizers that can cause rapid increase in NH,+-N
after application.
Effects of UCRF on rice plants
The nutrient release rate of CCF was higher during the
initial growth stages of rice, which resulted in higher
nitrogen uptake. For the UCRF, however, the N re-
lease rate was slower at the prophase of rice growth,
whereas it increased with increase in temperature and
with prolonged growth period, thus showing that UCRF
could sustain N supply for rice growth, thereby in-
creasing the N-use efficiency at the anaphase. The
findings that there were significant positive or negative
correlations between the NK/N,of four N forms and N
uptake by rice have important implications for develop-
ment of slow and controlled release fertilizers with nu-
trient configuration. Optimum ranges for the ratios of
different N to total N in a fertilizer need further
investigation.
CONCLUSIONS
The release characteristics of different N forms in UCRF
showed significant differences for water and soil. The
UCRF release parameters obtained from soil incubation
better reflect N uptake and utilization by rice plants
compared with those from water. The first-order ki-
netic equation could be successfully used to describe
N release from UCRF. Compared with the common
compound fertilizers with only urea-N, the UCRF with
multiple N forms significantly improved the NUE, NAE,
and NPE by rice plants during later growth stage.
Acknowledgements
The project was supported by National 863 Program
of China (2001AA246022,2004AA246020).
DONG Yan et al.
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(Edited by ZHAO Qi)
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