Environ Geochem Health (2006) 28:519–528
DOI 10.1007/s10653-006-9047-z
R E S E A R C H A RT I C L E
Aluminium in tea plantations: mobility in soils and plants,
and the influence of nitrogen fertilization
Jianyun Ruan Æ Lifeng Ma Æ Yuanzhi Shi
Received: 5 April 2004 / Accepted: 21 September 2004 / Published online: 7 July 2006

Springer Science+Business Media B.V. 2006
Abstract The levels of extractable aluminum
(Al) in soils of tea plantations, Al concentrations
in tea leaves and the impact of nitrogen fertil-
ization on these two parameters were investi-
gated. In addition, the properties of soils from tea
plantations were compared to those from soils of
adjacent non-tea fields to evaluate the effect of
land use conversion (from non-tea soils to tea
soils). Exchangeable Al (extracted in 1 mol l)1
KCl) ranged from 0.03 to 7.32 cmolc kg)1 in 94
tea fields and decreased rapidly with increasing
soil pH. In comparison with non-tea soils, tea soils
had a significantly lower pH and exchangeable
Mg2+ concentration but higher organic matter
contents and exchangeable K+ concentration.
Contents of extractable Al were not different
(P > 0.05) between these two soils. The concen-
trations of Al in mature tea leaves correlated
significantly with exchangeable Al in soil samples
taken at a depth of 20–40 cm and with
exchangeable Al saturations in soil sampled
at depths of 0–20 and 20–40 cm. In the pot
J. Ruan Æ L. Ma Æ Y. Shi
Tea Research Institute of Chinese Academy of
Agricultural Sciences, Key Laboratory of Tea
Chemistry of the Ministry of Agriculture of China,
Hangzhou, Zhejiang 310008, China
J. Ruan (&)
e-mail: jruan@mail.tricaas.com
experiment, nitrogen fertilization significantly
increased extractable Al levels but decreased
soil pH and the levels of exchangeable base
cations. Nevertheless, the levels of Al in mature
leaves and young shoots were significantly
reduced by the application of large amounts of
N fertilizer.
Keywords Al absorption Æ Camellia sinensis Æ
Extractable Al Æ Nitrogen fertilizer Æ
Soil acidification
Introduction
Tea (Camellia sinensis L.) is cultivated in tropical
and subtropical areas on acid soils containing
elevated levels of available aluminium (Al), the
latter having been found to be beneficial to its
growth (Konishi, Miyamoto, & Taki, 1985). In tea
plants Al mainly accumulates in mature leaves
(Ruan & Wong 2001). Commercial teas, despite
being produced from young shoots (one bud with
two or three unfolding leaves), contain high
concentrations of Al and are, therefore, poten-
tially important sources of dietary Al (Ow-
uor,Gone, Onchiri, & Jumba, 1990; Pennington,
1988; Wong, Zhang, Wong, & Lan, 1998). Owing
to health concerns, the concentration of Al in tea
products and its release during infusion have been
123
520
intensively studied (for review, see Flaten, 2002;
Fung, Zhang, Wong, & Wong, 2003; Wong et al.,
1998). Recent studies have demonstrated that the
accumulation of Al in tea plants is significantly
affected by the ontogeny age of organs and the
specific variety (Fung et al., 2003; Ruan & Wong,
2001; Shu, Zhang, Lan, & Wong, 2003). The
variable Al concentrations in tea plants growing
in different types of soils infer that the absorption
of Al is possibly affected by soil conditions and
extractable Al levels (Wong et al., 1998).
Aluminum exists in various forms in the soil: as
soluble species in soil solution, adsorbed forms on
organic and mineral colloidal surfaces, amorphous
and crystalline hydroxy–Al, Al polymerized on
clay surfaces and between clay interlaces, and as a
structural component of secondary clay minerals
(Bertsch & Bloom, 1996; Shuman, 1990; Soon,
1993). The bioavailabilities of these Al fractions
are largely different; the aqueous form of Al in soil
solution is the most readily available to plants,
while other forms, prior to their being released into
soil solution, are not available (Shuman, 1990). A
number of chemical extractants have been adop-
ted for the purpose of extracting these Al fractions
selectively and characterizing their bioavailabili-
ties (Bertsch & Bloom, 1996; Soon, 1993). For
example, a dilute CaCl2 solution (0.02 mol l)1)
extracts Al in concentrations that correlate posi-
tively with Al concentrations in tea leaves (Dong,
Xie, Du, Liu, & Wang, 1999).
The properties of any type of soil are affected
by the vegetation growing on and in it, and they
may change following land use conversion
(Adams, Davis, & Powell, 2001; Dinesh, Ghoshal
Chaudhuri, & Sheeja, 2004; Lilienfein et al., 2000;
Wilcke & Lilienfein, 2002). Tea plants are ever-
green, and tea plantations are characterized by
intensive nutrient recycling from litter fall and
decomposition (Wang, Hu, Chen, 1997). Such
biogeochemical cycling also returns substantial
quantities of Al to the soil, since old leaves are
the most abundant source of Al (Ruan & Wong,
2001; Wong et al., 1998). Comparing soils from
tea plantations of different ages, Ding and Huang
(1991) observed increasing levels of soil
exchangeable Al and Al complexes with planting
time. This observation led them to hypothesize
that Al may accumulate in the soil of tea plan-
123
Environ Geochem Health (2006) 28:519–528
tations as a result of biogeochemical cycling. The
validity of this hypothesis, however, has not yet
been thoroughly investigated. The turnover of Al
forms in the soil is controlled primarily by soil pH
(Bertsch & Bloom, 1996). It is a common practice
of tea farmers worldwide to apply nitrogen (N)
fertilizers that acidify the soil and increase
extractable Al levels (Ruan, Ma, Shi, & Zhang,
2004; Tachibana, Yoshikawa, & Ikeda, 1995).
Consequently, it has been proposed that N fer-
tilization may also affect the uptake of Al by tea
plants.
The objective of the present study was to
investigate the levels of extractable Al in the soils
of various tea fields, the accumulation of Al in tea
leaves, and the impact of nitrogen fertilization. To
further evaluate the influence of land use conver-
sion to tea plantation, extractable Al as well other
properties of soils of tea fields were analyzed and
compared with those of adjacent non-tea soils.
Materials and methods
Soil and plant samples
To obtain general information on extractable Al
in the soils of tea fields, 188 soil samples were
collected at depths of 0–20 cm and 20–40 cm from
94 farmers’ tea fields in the Zhejiang, Jiangsu, and
Anhui provinces of China during July and Octo-
ber 1998. The soil samples were air-dried and
passed through 1-mm sieve for further analyses.
Young shoots (one bud with three unfolding
leaves), when available at the time of soil sam-
pling, were also sampled at 22 fields. Mature
leaves from the spring growth on the surface of
the bush were also taken from these sites (20 sites
at the final count because two samples went
missing). The plant samples were oven-dried and
ground for determination of Al concentrations.
To investigate the effect of tea planting on soil
properties, soil samples were taken from eight
normally managed tea fields with plantation ages
of 10–30 years (tea soil) and from fields adjacent
to the tea fields which were not used for growing
tea (non-tea soil). These latter fields were covered
by natural vegetation (bushes or/and grasses) at
the time of sampling. Each of the eight sampling
Environ Geochem Health (2006) 28:519–528
sites was selected on the basis of the similarity
between the tea soil and non-tea soil: both were
derived from the same parent materials (loess,
sandstone, or Quaternary red clay), had similar
soil depths in the profile, belonged to identical
soil types (red soil or yellow-brown soil), and
were located close by ( < 50 m).
Pot experiment
The pot experiment was conducted to study the
influence of nitrogen fertilization on extractable Al
concentrations in soil and Al uptake by the plant.
Soil samples were taken from a hillside covered by
small bushes, placed in pots and cultivated for
2 years with tea plants to establish a similar
microbiology population as found in tea soil from a
tea plantation. After removal of the plants and root
residues, the soil in the pots was air-dried, passed
through a 5-mm sieve, mixed thoroughly and used
in the experiments described below.
Each pot containing 11 kg air-dried ‘tea’ soil
was planted with four 1-year-old rooted cuttings
of tea cv. Longjing 43 in early November 1996.
Five levels of N were established by applying N
fertilizer in the form of urea at concentrations of
0, 45.5, 91, 182, and 364 mg kg)1 year)1, which is
equivalent to the levels of N fertilization at 0, 100,
200, 400, and 800 kg ha)1 year)1; these levels are
subsequently referred to as N0, N1, N2, N3, and
N4. N fertilizer was applied in two successive
years and two times each year – in March and
April of 1997 and 1998. Therefore, the total
amounts of N treatments within the experimental
period were 0, 91, 182, 364, and 728 mg kg)1. In
addition, total amounts of 0.35 g phosphorus (P)
and 0.84 g potassium (K) in the form of KH2PO4
were applied to each pot. Each N treatment was
repeated four times and arranged randomly. In
mid-August and mid-December of 1997, fresh soil
samples were taken for ammonia (NH+4 ) and ni-
trate (NO)3 ) determinations. Three holes were
drilled in each pot using a plastic tube (diameter:
2.5 cm), and the soil inside the tube was taken for
analysis. In the May of 1998 (18 months after
planting), tea plants were sampled and oven-dried
(60C for 2 days). Soil samples were taken from
each pot, air-dried and passed through a 1-mm
sieve for subsequent analyses.
521
Soil and plant analyses
Ammonium and NO)3 in fresh soil were extracted
using 1 mol l)1 KCl (1:10, w/v). The concentra-
tion of NH+4 in the extract was measured by the
salicylate-hypochlorite colorimetric method, and
NO)3 by the phenyldisulfonic acid colorimetric
method (Li, 1983). The concentrations of NH+4
and NO)3 were converted to per soil dry weight
basis using the moisture content of the fresh soil
samples that was measured concomitantly. Other
measurements were performed on air-dried soils.
Soil pH was determined in water (pH) ( pHH2 O )
or 1 mol l)1 KCl solution (pHKCl) suspensions
(1:1, w/v). The content of organic matter was
measured by the Wakley-Black method
(Li, 1983). Exchangeable Al3+ (Alex) was extracted
in 1 mol l)1 KCl (1:10, w/v), and exchangeable
Ca2+, Mg2+, Na+ and K+ in 1 mol l)1 NH4OAC
(pH 7.0) (Li, 1983); the levels of all extracted ions
were determined by induced coupled plasma
atomic emission spectrometry (ICP-AES) equip-
ped with an axial plasma tube (model IRIS/AP;
Thermol Jarrel Ash, Franklin, Mass.). The cation
exchange capacity (CEC) was calculated as the
sum of exchangeable Al3+, Ca2+, Mg2+, K+, and
Na+. The saturation percentages of Al3+ and Ca2+
were calculated as exchangeable Al3+/CEC · 100
and exchangeable Ca2+/CEC · 100, respectively.
To characterize extractable Al, we extracted the
soils separately using 0.02 mol l)1 CaCl2,
0.1 mol l)1 CuCl2 + 0.5 mol l)1 KCl, 1 mol l)1
NH4OAC (pH 4.0), 0.2 mol l)1 ammonium oxa-
late (pH 3.2), and 0.33 mol l)1 sodium citrate
based on a rationale suggested by Soon (1993). In
the former three extractions, a soil to solution ratio
of 1:10 was used, and extraction times were 30 min,
1 h, and 2 h, respectively. In the latter two
extractions, 0.25 g soil was shaken with 20 ml
ammonium oxalate for 4 h in dark, and 0.2 g soil
( < 60 mesh) with 20 ml sodium citrate was placed
in an oven at 100C for 24 h with occasional
shaking by hand. The concentrations of Al in the
extracts were determined by ICP-AES and are
hereafter referred to as AlCaCl2 , AlK=CuCl2 ,
AlNH4 OAC , AlOxal, and AlCit, respectively. The
concentrations of Al, Ca, Mg, K, Mn, and P in plant
samples were measured by ICP-AES after being
ashed at 500C.
123
522 Environ Geochem Health (2006) 28:519–528

Statistical analysis mum at pH > 5.0. The relationship of Alex and Al

Data on tea soils and non-tea soils were subjected
to the paired-t test to examine their differences.
One-way analysis of variance and Fisher’s LSD
test were used to examine the effect of N fertil-
ization. Correlation coefficients were calculated
from the Pearson Product Moment Correlation
analysis.
Results
Exchangeable Al in tea soils and Al in tea
leaves
The concentration of exchangeable Al (extracted
with 1 mol l)1 KCl; Alex) in soil samples taken
from 94 tea fields ranged from 0.03 to
7.32 cmolc kg)1 and averaged 2.59 cmolc kg)1.
Figure 1 shows that the level of Alex decreased
rapidly with increasing soil pH, reaching a mini-
8 from eight tea fields and adjacent non-tea fields.
0-20 cm
(cmolc kg )
-1
saturation with soil pH was described well by the
semi-empirical equations formerly used by Reuss,
Walthall, Roswall, and Hopper (1990). The level
of Alex decreased as exchangeable Ca2+ or Ca2+
saturation increased. Their relationships could
also be described by the semi-empirical equations
(Fig. 2). In contrast, no clear relationships were
found between Alex and exchangeable Mg2+, and
Alex with exchangeable K+ (Fig. 2).
The concentrations of Al in mature leaves
(2868–4996 mg kg)1) correlated positively with
Al saturation in soil samples from both sampling
depths and with Alex in soil samples from a depth
of 20–40 cm, but not with soil pH (Table 1). No
significant correlations were found between Al
levels in young shoots (393–951 mg kg)1) and soil
pH, Alex, and Al saturation (Table 1).
Properties of tea soil in comparison with those
of non-tea soil
Table 2 shows the properties of soils sampled
The values of pHH2 O and pHKCl were signifi-

20-40 cm
2

6
LogAlex=3.41-0.78pH, r =0.58***
cantly lower, whereas the contents of organic
matter and exchangeable K+ in surface soils were
higher, in the tea soils than in the non-tea soils.
3+

4
Levels of exchangeable Mg2+ were significantly
Exchangeable Al

lower in tea soils (20–40 cm) than in non-tea soils,

2 while the levels of Alex, Al saturation, and
exchangeable Ca2+ were not different between
0 these two soils (Table 2).
The contents of extractable Al in tea soils and
100 adjacent non-tea soils are presented in Table 3.
0-20 cm
20-40 cm
2
For both soils, the CaCl2 solution, which was
80 Log(Alex%)=4.49-0.70pH, r =0.57***
designed to mimic the soil solution, extracted the
Al saturation (%)

least Al ( AlCaCl2 ) while sodium citrate solubilized

60
the highest Al (AlCit). AlK=CuCl2 was higher than
40 Alex, except in a few soil sample in which Alex was
larger (Tables 2, 3). None of these Al fractions
20 were different (P > 0.05) between the tea soils
and non-tea soils. AlCaCl2 , Alex, AlK=CuCl2 , and
0 AlNH4 OAC correlated positively to each other
3 4 5 6 7 and negatively with soil pH, exchangeable Ca2+,
Soil pH and Mg2+ (Table 4). AlOxal and AlCit also corre-
Fig. 1 Relationships of exchangeable Al3+ (Alex) and Al
lated significantly each other but not with other
saturation (Alex%) with soil pH (H2O paste). Al fractions. None of the Al fractions correlated
***P < 0.001 with soil organic matter content.

123
Environ Geochem Health (2006) 28:519–528 523

8 8
0-20 cm
(cmolc kg )

(cmolc kg )
-1

-1
20-40 cm
LogAlex=0.91-0.70Caex, r2=0.52***
6 6
3+

3+
Exchangeable Al

Exchangeable Al
4 4

2 2

0 0

0 1 2 3 0,0 0,2 0,4 0,6 0,8 1,0

2+ -1 + -1
Exchangeable Ca (cmolc kg ) Exchangeable K (cmolc kg )

8 8
0-20 cm
Exchangeable Al3+ (cmolc kg-1)

Exchangeable Al3+ (cmolc kg-1)

20-40 cm
LogAlex=0.95-0.03(Caex%), r2=0.74***
6 6

4 4

2 2

0 0

0 20 40 60 80 100 0 1 2 3 4
Ca saturation (%) Exchangeable Mg2+ (cmolc kg-1)

Fig. 2 Relationships of exchangeable Al3+ (Alex) with exchangeable Ca2+ (Caex), Ca saturation (Caex%), exchangeable K+,
and exchangeable Mg2+. ***P < 0.001

Table 1 Correlation coefficients of Al concentrations in mature leaves (n = 20) and young shoots (n = 22) with soil pH,
exchangeable Al3+ (Alex) and Al saturation (Alex%)
Soil depth Mature leaves Young shoots
pH Alex Alex% pH Alex Alex%

0–20 cm )0.231 0.333 0.509* )0.105 )0.263 )0.074

20–40 cm )0.317 0.648** 0.673** )0.325 )0.142 )0.195
0–40 cm )0.288 0.552* 0.647** )0.215 )0.225 )0.194
*P < 0.05; **P < 0.01

Effect of nitrogen fertilization on soil the levels of both increased with increasing levels
properties and the concentrations of N application (Table 5). Nitrogen fertilization
of elements in plants significantly decreased the soil pH and the levels
of exchangeable Ca2+, K+, and Mg2+ (Table 5).
The concentrations of NH+4 were higher than Conversely, Alex and Al saturation increased up
those of NO)3 in soil during both the growing to the application of N3 and thereafter slightly
(August) and dormancy (December) periods, and decreased (p > 0.05) at the N4 level. AlCaCl2 ,

123
524 Environ Geochem Health (2006) 28:519–528

Table 2 Selected
Parameter Tea soil Non-tea soil Paired-t testa
properties of soils from
tea fields and adjacent Range Mean Range Mean
non-tea soils
Soil depth 0–20 cm
pH (H2O) 3.60–4.73 3.95 3.81–5.28 4.47 *
pH (KCl) 3.41–3.90 3.57 3.38–4.48 3.91 NS
Organic matter (g kg)1) 19.1–40.9 30.0 9.9–30.6 16.4 **
Exchangeable Al3+ (cmolc kg)1) 0.71–6.15 4.28 0.06–7.15 3.31 NS
Exchangeable Ca2+ (cmolc kg)1) 0.20–1.21 0.58 0.25–1.31 0.68 NS
Exchangeable Mg2+ (cmolc kg)1) 0.08–0.44 0.22 0.11–1.16 0.40 NS
Exchangeable K+ (cmolc kg)1) 0.08–0.58 0.19 0.04–0.08 0.06 ***
CEC (cmolc kg)1) 2.37–6.92 5.30 2.64–8.14 4.49 NS
Al saturation (%) 29.9–91.4 76.3 2.3–87.8 68.5 NS
Soil depth 20–40 cm
pH (H2O) 3.46–4.67 4.05 3.85–5.21 4.55 *
PH (KCl) 3.26–3.97 3.58 3.28–4.27 3.85 **
*P < 0.05; **P < 0.01; Organic matter (g kg)1) 12.5–26.8 21.5 4.6–20.4 10.6 NS
***P < 0.001; NS, not Exchangeable Al3+ (cmolc kg)1) 1.22–12.13 5.02 0.22–10.99 4.41 NS
significant Exchangeable Ca2+ (cmolc kg)1) 0.22–0.97 0.51 0.36–1.50 0.69 NS
a
Exchangeable Mg2+ (cmolc kg)1) 0.06–0.35 0.19 0.13–2.06 0.57 *
Paired-t test (df = 8–1) Exchangeable K+ (cmolc kg)1) 0.06–0.38 0.12 0.05–0.10 0.06 NS
examines the differences CEC (cmolc kg)1) 2.64–12.51 5.87 2.60–11.84 5.78 NS
between tea soils and Al saturation (%) 46.2–96.9 80.4 5.6–92.8 68.8 NS
not-tea soils

Table 3 Concentrations (mg kg)1) of extractable Al in tea soils and adjacent non-tea soils (NS not significant)
Extractable Ala Tea soil Non-tea soil Paired-t testb
Range Mean Range Mean

Soil depth 0–20 cm

AlCaCl2 8–196 112 47–149 91 NS
AlK=CuCl2 209–750 488 52–667 395 NS
AlNH4 OAC 402–1020 720 324–939 758 NS
AlOxal 1737–4043 2711 1980–3040 2548 NS
AlCit 2750–7597 5216 4091–8295 5838 NS
Soil depth 20–40 cm
AlCaCl2 3–222 110 1–216 91 NS
AlK=CuCl2 161–702 450 52–1073 435 NS
AlNH4 OAC 295–1023 712 296–1397 858 NS
AlOxal 1729–4445 2966 2144–3564 3002 NS
AlCit 3137–7783 5569 5178–7134 5996 NS
a
Subscripts CaCl2, K/CuCl2, NH4OAC, Oxal, and Cit refer to Al extracted by 0.02 mol l)1 CaCl2, 0.1 mol l)1
CuCl2 + 0.5 mol l)1 KCl , 1 mol l)1 NH4OAC (pH 4.0), 0.2 mol l)1 ammonium oxalate (pH 3.0), and 0.33 mol l)1 sodium
citrate (pH 7.3), respectively
b
Paired-t test (df = 8–1) examines the differences between tea soils and not-tea soils

AlK=CuCl2 , and AlNH4 OAC increased significantly
with increasing amounts of N fertilizer, while
AlOxal and AlCit were unaffected (Table 6).
The biomass production of whole plant and
young shoots increased with the increasing
amounts of N fertilizer up to N3 and decreased
thereafter at N4, showing typical quadric curves
(data not shown). The concentration of Al in
mature leaves slightly (P > 0.05) increased up to
N2, but then decreased significantly at N3 and N4.
The concentrations of K, Mg, Mn, and P in ma-
ture leaves significantly decreased with increasing
N application, while that of Ca was unaffected
(Table 7). In young shoots, the concentrations of
Al, Ca, Mg, and Mn significantly increased at N1
but decreased at higher N and were the lowest at

123
Environ Geochem Health (2006) 28:519–528 525

Table 4 Correlation coefficients of extractable Ala with soil pH and exchangeable cationsa in tea and non-tea soils
AlCaCl2 Alex AlK=CuCl2 AlNH4 OAC AlOxal AlCit

pHH2 O )0.58*** )0.55** )0.53** )0.45** )0.13 0.14

pHKCl )0.69*** )0.73*** )0.68*** )0.53** )0.14 0.21
Organic matter )0.02 )0.03 0.04 )0.10 0.20 0.02
Exchangeable Ca2+ )0.41* )0.46** )0.47* )0.54** )0.52** )0.36*
Exchangeable K+ )0.32 )0.10 )0.27 )0.43* 0.40* 0.09
Exchangeable Mg2+ )0.39* )0.40* )0.43* )0.43* )0.21 )0.11
AlCaCl2 0.85*** 0.88*** 0.78*** )0.01 )0.18
Alex 0.75*** 0.64*** 0.14 )0.19
AlK=CuCl2 0.85*** 0.08 )0.10
AlNH4 OAC 0.24 0.23
AlOxal 0.71***
*P < 0.05; **P < 0.01; ***P < 0.001
Alex, exchangeable Al3+ (1 mol l)1 KCl). For AlCaCl2 , AlK=CuCl2 , AlNH4 OAC , AlOxal, and AlCit, see footnotes to Table 3
a

Table 5 Concentrationsa of NH+4 , NO)3 (mg kg)1), pH and exchangeable cations (cmolc kg)1) in soils supplied with variable
N amounts
N level August 1997 December 1997 May 1998 (final sampling)
NH+4 NO)3 NH+4 NO)3 pH Ca2+ K+ Mg2+ Al3+

N0 7.1a 4.0a 7.5a 2.7a 4.65d 1.17c 0.31c 0.29d 2.22a

N1 5.8a 4.0a 12.2a,b,c 2.6a 4.56cd 1.14b,c 0.24b 0.20c 2.84b
N2 6.7a 4.2a 11.0ab 3.6b 4.51c 1.01b,c 0.22b 0.16b, 3.11b,c
N3 6.3a 6.9b 14.5b,c 3.8b,c 4.36b 0.83a,b 0.17a,b 0.12a,b 3.91d
N4 28.8b 13.1c 17.9c 4.5c 4.21a 0.70a 0.15a 0.11a 3.57c
a
Different letters within columns indicate significant differences among N levels at P < 0.05

Table 6 Concentrationsa of extractable Alb (mg kg)1) in soil supplied with variable amounts of nitrogen (NS not
significant)
N level AlCaCl2 AlK=CuCl2 AlNH4 OAC AlOxal AlCit

N0 36a 319a 502a 2488NS 5537NS

N1 50a,b 373a,b 477a 2543 6205
N2 61b,c 377a,b 513a 2459 5469
N3 76c 417b,c 536a,b 2470 6085
N4 98d 464c 664b 2565 6248
a
Different letters within columns indicate significant differences among N levels at P < 0.05
b
For AlCaCl2 , AlK=CuCl2 , AlNH4 OAC , AlOxal, and AlCit, see footnotes to Table 3

N4 (Table 7). Concentrations of P and K in young
shoots were significantly lower only at N4.
Discussion
Changes in soil properties after a conversion of
land use have been extensively investigated
(Adams et al., 2001; Dinesh et al., 2004; Lilienfein
et al., 2000; Saviozzi, Levi-Minzi, Cardelli, &
Riffaldi, 2001; Wilcke & Lilienfein, 2002). In this
study, tea soils accumulated more organic matter
and exchangeable K+ than non-tea soils. This may
be largely attributable to the effect of litter fall
and agronomic practices such as fertilization with
organic manures and chemical fertilizers. The
significantly lower level of exchangeable Mg2+ in
tea soils was possibly a result of depletion through
the continuous harvesting of young shoots for tea
products and/or increased leaching due to soil
acidification without sufficient repletion with fer-
tilizers. The lower soil pH indicates acidification

123
526 Environ Geochem Health (2006) 28:519–528

Table 7 Elemental concentrationsa (mg g)1) in mature leaves and young shoots of tea plants supplied with variable
amounts of nitrogen (NS, not significant)
Organ N level Al Ca K Mg Mn P

Mature leaves N0 4.72b,c 4.11NS 10.1c 1.42c 3.13c 1.82c

N1 5.06b,c 3.92 8.8b 1.19b 2.76a,b,c 1.35b
N2 5.48c 3.95 8.2a,b 1.20b 2.86b,c 1.46b
N3 4.32b 3.97 8.7b 0.99a 2.63a,b 1.21a,b
N4 2.68a 4.07 7.6a 1.04a,b 2.41a 1.02a
Young shoot N0 1.52a,b 2.79b 14.2b 1.64b 1.48a,b 2.08b
N1 2.74d 3.19c 13.7b 1.90c 2.17c 2.31b
N2 2.28c,d 2.84b 12.5a,b 1.64b 1.89b,c 2.14b
N3 1.96b,c 2.86b 12.1a,b 1.53b 1.82a,b,c 1.94b
N4 1.00a 2.49a 10.0a 1.25a 1.38a 1.33a
a
Different letters within columns of the same organ indicate significant differences among N levels at P < 0.05

as a consequence of tea plantation practices and
has been previously reported (Ding & Huang,
1991). Soil acidification also occurs in other sys-
tems; and example of this is the Oxisols, following
the transformation of savanna into Pinus planta-
tions (Lilienfein et al., 2000). The reasons under-
lining soil acidification with tea plantation
practices, however, have not been clearly eluci-
dated and have been attributed to N fertilization
(Tachibana et al., 1995), accumulation in soil of
inorganic or organic Al derived from litterfall
containing rich Al (Ding & Huang, 1991), and the
rhizosphere effect (Ruan et al., 2000, 2004). The
effect of N fertilization on soil pH and extractable
Al levels reported here was very distinct and is in
accordance with results of experiments reported
earlier (Bouman, Curtin, Campbell, Biederbeck,
& Ukrainetz, 1995; Tachibana et al., 1995).
However, the contents of extractable Al in tea
soils were not different from those of the non-tea
soils from adjacent fields, and both soils contained
levels comparable to those of acidic forest soils
from China (Larssen et al., 1999). This appears to
contradict the hypothesis that tea planting in-
creases exchangeable Al and Al complexes,
thereby leading to soil acidification (Ding & Hu-
ang, 1991). Our experiment mimicking the litter-
fall effect by adding different amounts of litter
materials to soil in pots demonstrated that
extractable Al fractions in the soil were unaffected
after a period of 18 months (Ruan et al., 2004).
Nevertheless, the solutions of CaCl2,
CuCl2 + KCl, and NH4OAC used here appeared
to extract basically the same forms of soil Al as
there were significant correlations among them.
It is possible that Al bound to organic matters was
not effectively extracted by CuCl2 + KCl since in
some soils AlK=CuCl2 was less than Alex (extracted
using 1 mol l)1 KCl) and correlated poorly with
organic matter content as well. We used a reduced
CuCl2 concentration and/or pH rather than that
normally used (0.5 mol l)1, pH3.0–3.5) (Bertsch
& Bloom, 1996) with the objective of reducing the
tendency of CuCl2 to depolymerize sorbed poly-
meric or interlayered hydroxy–Al (Soon, 1993).
The observed relationships between soil pH and
Alex or Al saturation are similar to many others
reported (Aitken, 1992 and references therein).
The concentration of Al in tea products and its
release upon infusion has been a topic of
numerous studies owing to health concerns on the
consumption of Al (for review, see Flaten, 2002;
Fung et al., 2003; Wong et al., 1998). It has been
suggested that higher levels of Al in young shoots
relate to lower pH and hence higher Al avail-
abilities in the soils (Dong et al., 1999; Wong
et al., 1998). However, we did not find a signifi-
cant correlation between Al in young shoots and
soil exchangeable Al or pH, possibly owing to the
fact that the pH of the soil samples in the present
study covered a relatively small range (pH 3.11–
4.41), while soils of wider pH ranges have been
studied in other studies (Dong et al., 1999).
Nevertheless, Al in mature leaves correlated sig-
nificantly with Alex and Al saturation. To a cer-
tain extent, these results confirm previous findings
showing that Al concentration in tea leaves cor-
related well with soil extractable Al using the
dilute CaCl2 solution (Dong et al. 1999), as Alex
and AlCaCl2 correlated significantly (Table 4,

123
Environ Geochem Health (2006) 28:519–528
r=0.85, P=0.001). Both our results and those of
Dong et al., 1999) demonstrate that Al uptake is
related more closely with extractable Al in the
subsoil where more roots are usually found than
in the topsoil.
Fertilization with high N quantities decreased
the concentrations of Al and other elements (Ca,
K, Mg, Mn and P) in young shoots and mature
leaves. However, the mechanism for Al was
apparently different from those for the other
elements. While reduced absorptions of other
elements could be explained by their lower
availabilities in the soil, the contents of extract-
able Al actually increased with the application of
N fertilizer. The decrease in Al uptake following
the application of large amounts of N fertilizer
reported here is in accordance with an earlier
observation in the field experiment, which has
been explained in terms of the inhibitory effect of
competition with NH+4 during root absorption
(Owuor & Cheruiyot, 1989). In the nutrient
solution experiment, the concentration of Al in
the roots and leaves decreased constantly with the
progressively increasing supply of NH+4 (unpub-
lished data). In the present study, the concentra-
tion of NH+4 was higher than that of NO)3 during
both the growing (August) and dormancy
(December) periods. We would expect that the
NH+4 concentration in the soil could actually be
much higher if measured shortly after urea
application as the measured values reported here
were taken on soil samples several months later.
However, it is worth mentioning that the
concentrations of Al and Ca, Mg, Mn in young
shoots did increase when low levels of N fertilizer
was applied (N1) , which may be attributable to
improved root growth.
Acknowledgements This study was supported by funds
from Chinese Academy of Agricultural Sciences and ‘151’
Project of Zhejiang Province, China.
References
Adams, M. L., Davis, M. R., & Powell, K. J. (2001). Effects
of grassland afforestation on exchangeable soil and
soil solution aluminium. Australia Journal of Soil
Research, 39, 1003–1014.
Aitken, R. L. (1992). Relationships between extractable
Al, selected soil properties, pH buffer capacity and
527
lime requirement in some acidic Queensland soils.
Australia Journal of Soil Research, 30, 119–130.
Bertsch, P. M. & Bloom, P. R. (1996). Aluminium. In:
Sparks, D. L., Page, A. L., Sumner, M. E., Tabatabai,
M. A., Helmke, P. A., Loeppert, R. H., Soltanpour, R.
N., & Johnson, C. T. (Eds) Methods of Soil Analysis.
Part 3. Chemical Methods. SSSA Book Series No. 5,
Madison, Wis.
Bouman, O. T., Curtin, D., Campbell, C. A., Biederbeck,
V. O., & Ukrainetz, H. (1995). Soil acidification from
long-term use of anhydrous ammonia and urea. Soil
Science Society of America Journal, 59, 1488–1494.
Dinesh, R., Ghoshal Chaudhuri, S., & Sheeja, T. E. (2004).
Soil biochemical and microbial indices in wet tropical
forests: effects of deforestation and cultivation. Jour-
nal of Plant Nutrition and Soil Science, 167, 24–32.
Ding, R. X., & Huang, X. A. (1991). Biogeochemical cycle
of aluminium and fluorine in a tea garden soil system
and its relationship to soil acidification. Acta Ped-
ologica Sinica, 28, 229–236.
Dong, D., Xie, Z., Du, Y., Liu, C., & Wang, S. (1999).
Influence of soil pH on aluminium availability in the
soil and aluminium in tea leaves. Communication in
Soil Science and Plant Analysis, 30, 873–883.
Flaten, T. P. (2002). Aluminium in tea – concentrations,
speciation and bioavailability. Coordination Chemis-
try Reviews, 228, 385–395.
Fung, K. F., Zhang, Z. Q., Wong, J. W. C., & Wong, M. H.
(2003). Aluminium and fluoride concentrations of
three tea varieties growing at Lantau Island, Hong
Kong. Environmental Geochemistry and Health, 25,
219–232.
Konishi, S., Miyamoto, S., & Taki, T. (1985). Stimulatory
effects of aluminium on tea plants grown under low
and high phosphorus supply. Soil Science and Plant
Nutrition, 31, 361–368.
Larssen, T., Vogt, R. D., Seip, H. M., Furuberg, G., Liao,
B., Xiao, J., & Xiong, J. (1999). Mechanisms for
aluminium release in Chinese acid forest soils.
Geoderma, 91, 65–86.
Li, J. K. (Ed.). (1983). Manual of Soil Agricultural
Chemistry Analyses. Beijing: Science Press.
Lilienfein, J., Wilcke, W., Ayarza, M. A., Vilela, L., do
Carmo Lima, S., & Zech, W. (2000). Soil acidification
in Pinus caribaea forests on Brazilian savanna Oxisols.
Forest Ecology Management, 128, 145–157.
Owuor, P. O., & Cheruiyot, D. K. A. (1989). Effects of
nitrogen fertilizers on the aluminium contents of
mature tea leaf and extractable aluminium in the soil.
Plant and Soil, 119, 342–345.
Owuor, P. O., Gone, F. O., Onchiri, D. B., & Jumba, I. O.
(1990). Levels of aluminium in green leaf of clonal
teas, black tea and black tea liquors, and effects of
rates of nitrogen fertilizers on the aluminium black
tea contents. Food Chemistry, 35, 59–68.
Pennington, J. A. T. (1988). Aluminium content of foods and
diets. Food Additives and Contaminants, 5, 161–232.
Reuss, J. O., Walthall, P. M., Roswall, E. C., & Hopper, R.
W. E. (1990). Aluminium solubility, calcium-alumin-
ium exchange, and pH in acid forest soils. Soil Science
Society of America Journal, 54, 374–380.
123
528
Ruan, J., & Wong, M. H. (2001). Accumulation of fluoride
and aluminium related to different varieties of tea
plant. Environmental Geochemistry and Health, 23,
53–63.
Ruan, J., Zhang, F., & Wong, M. H. (2000). Effect of
nitrogen form and phosphorus source on growth,
nutrient uptake and rhizosphere property of Camellia
sinensis L. Plant and Soil, 223, 65–73.
Ruan, J., Ma, L., Shi, Y., & Zhang, F. (2004). Effects of
litter incorporation and nitrogen fertilization on the
contents of extractable aluminium in the rhizosphere
soil of tea plant (Camallia sinensis (L.) O. Kuntze).
Plant and Soil, 263:283–296.
Saviozzi, A., Levi-Minzi, R., Cardelli, R., & Riffaldi, R.
(2001). A comparison of soil quality in adjacent cul-
tivated, forest and native grassland soils. Plant and
Soil, 233, 251–259.
Shu, W., Zhang, Z. Q., Lan, C. Y., & Wong, M. H. (2003).
Fluoride and aluminium concentrations of tea plants
and tea products from Sichuan Province, PR China.
Chemosphere, 52, 1475–1482.
Shuman, L. M. (1990). Comparison of exchangeable Al,
extractable Al, and Al in soil fractions. Canadian
Journal of Soil Science, 70, 263–275.
123
Environ Geochem Health (2006) 28:519–528
Soon, Y. K. (1993). Fractionation of extractable alumin-
ium in acid soils: A review and a proposed procedure.
Communication in Soil Science and Plant Analysis, 24,
1683–1708.
Tachibana, N., Yoshikawa, S., & Ikeda, K. (1995). Influ-
ences of heavy application of nitrogen on soil acidifi-
cation and root growth in tea fields. Japanese Journal
of Crop Science, 64, 516–522.
Wang, X. J., Hu, X., & Chen, H. (1997). Some biogeo-
chemical characteristics of tea soils. Pedosphere, 7,
275–280.
Wilcke, W., & Lilienfein, J. (2002). Biogeochemical con-
sequences of the transformation of native Cerrado
into Pinus caribaea plantations in Brazil – biogeo-
chemical cycling in Cerrado and Pinus caribaea
forests. Plant and Soil, 238, 175–189.
Wong, M. H., Zhang, Z. Q., Wong, J. W. C., & Lan, C. Y.
(1998). Trace metal contents (Al, Cu and Zn) of tea:
Tea and soil from two tea plantations, and tea prod-
ucts from different provinces of China. Environmental
Geochemistry and Health, 20, 87–94.