The concentration of cadmium

(Cd) in Ecuadorian cacao: it

nexus with soil-Cd
Chavez E.1,2*, He Z. L.1, Baligar V. C.3, Moyano B.2, Mylavarapu R.4,
Li Y.5, Stoffella P1.
1 Indian River Research and Education Center – University of Florida-IFAS (Fort Pierce, FL)
2 Centro de Investigaciones Biotecnologicas del Ecuador – ESPOL (Guayaquil, EC)
3 United State Department of Agriculture – Beltsville Agricultural Research Center (Beltsville, MD)
4 Soil and water science department – University of Florida (Gainesville, FL)
5 Tropical Research and Education Center – University of Florida (Homestead, FL)

* Presenting author: eduardofchavez@ufl.edu

XX Latin American Congress of Soil Science

Cuzco, Peru
November 2014
Introduction
• Cadmium (Cd) is one of the most concerned elements in
food safety and human health worldwide (Alloway, 2012).
• Cacao (Theobroma cacao, L.) is the main ingredient in
chocolate production, which is mostly consumed by
children and women (Dahiya et al. 2005).
• Cacao have been reported to accumulate excessive level
of Cd in beans (Mounicou et al. 2003).
• The European Union established a critical level of 0.6 mg
kg-1 of Cd in cacao beans and will be implemented by
2019 (ICCO, 2012).
• At this point, there is no information regarding Cd levels
in Ecuadorian soils or cacao beans
Introduction
Cacao is a widely planted
crop in Ecuador with
approximately 500,000
hectares (brown area in
Figure).
Objectives

• To investigate the status of Cd in cacao

tissues and soil profiles in representative
cacao farms.
• To distinguish the source of contamination
based on the vertical distribution of Cd in soil
profiles.
• To study available pools of Cd in soils under
cacao production using single and
sequential extraction methods.
• To correlate the Cd in cacao beans and
tissues with available Cd in soils
Materials and Methods
Material and Methods (cont)
• 19 field sites were selected for this
study in southern Ecuador, Guayas
and El Oro province
• Cacao leaves and pods (beans, and
bean-coating) were sampled from
mature trees.
• Cadmium in leaves and pods: total
concentration (HNO3 digestion)
• Soil profile (4 depths): 0-5, 5-15,
15-30 and 30 – 50 cm.
• Source of pollution: Mehlich 3
(M3) and total recoverable (EPA
3050B), physical – chemical
properties
• Available Cd: M3, 0.1 HCl and 1 M
NH4OAc, sequential extraction (15
sites) (Amacher, 1996). Soil and plant sampling in southern Ecuador
Material and Methods (cont)
The accumulation of Cd in cacao beans and bean
coat from 19 cacao farms in southern Ecuador
Bean-Cd Coa ng-Cd

3.50

3.00
Cd concentra on in nibs and shell (mg kg-1)

2.50

2.00

1.50

1.00

0.50

0.00
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

-0.50
Field sites

Red line represents Cd threshold for cacao beans (0.6 mg kg-1). The
concentration of Cd in cacao leaves were below the detection limit (BDL)
of the equipment (0.1 mg L-1)
Discussion
• Concentrations of Cd in cacao beans ranged from 0.02
to 3.00 mg kg-1, with a mean value of 0.94 mg kg-1.
Twelve sites overpassed the critical level for cacao
beans.
• The distribution of Cd in cacao tree decreased in the
order of beans > shell >> leaves. Cadmium was detected
in shells only when bean-Cd exceeded 1 mg kg-1
• Elevated concentrations of Cd in cacao beans have been
reported previously (Zarcinas et al., 2004). However, in
most cases, Cd concentration has been reported
elevated in chocolate and cacao byproducts (Mounicou
et al. 2003; Dahiya et al., 2005; Yanus et al., 2014).
• This high Cd concentration in beans is carried along the
chocolate production chain, and this contamination may
jeopardize the sustainability of cacao farmers in
developing countries.
The distribution of Cd in soil profiles under cacao
production
M3-Extractable Cd Total recoverable
H1

Soil Cd (mg kg-1)

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
0-15 cm
0-5
Sampie depths (cm)

0 - 15
15-50 cm
15 - 30

30 - 50

In general, soil-Cd decreased with soil depth as

assessed by total recoverable and M3-extractable
Cd.
Diapositiva 10

H1 The font of text with the figure is too small.

He,Zhenli, 09/11/2014
Total recoverable and M3-extractable Cd
in representative soil profile
1.6 Site 1 3 Site 3
1.4 2.5
1.2

Cd (mg kg -1)
Cd (mg kg-1)

1 2
0.8 1.5
0.6 1
0.4
0.2 0.5
0 0
0-5 5 - 15 15 - 30 30 - 50 0-5 5 - 15 15 - 30 30 - 50
Depths (cm) Depths (cm)
1.6
2.5 1.4
Site 5 1.2 Site 20

Cd (mg kg-1)
2
1
Cd (mg kg-1)

1.5 0.8
0.6
1
0.4
0.5 0.2
0
0 0-5 5 - 15 15 - 30 30 - 50
0-5 5 - 15 15 - 30 30 - 50
Depths
Depths

3
2.5
2.5 Site 16 Site 17
2
Cd (mg kg-1)

2
Cd (mg kg-1)

1.5
1.5
1 1
0.5 0.5
0 0
0-5 5 - 15 15 - 30 30 - 50 0-5 5 - 15 15 - 30 30 - 50
Depths (cm) Depths (cm)
Total recoverable
M3 extractable
Discussion
• Total recoverable and M3-extractable Cd was found to
have accumulated at the surface layers (0-15 cm), with
an average concentration of 1.54 and 1.38 mg kg-1 for
total recoverable, and, 0.40 and 0.29 mg kg-1 for M3-
extractable at the depth of 0-5 and 5-15 cm, respectively.
Thirteen sites surpassed critical soil-Cd concentration in
non-polluted soils (< 1.1 mg kg-1), therefore, are
considered polluted (Kabata-Pendias, 2011)
• The accumulation of Cd in upper layers suggests
anthropogenic activities as the source of contamination
in the studied area.
• In similar studies, the vertical distribution of a
contaminant has been used to assess the source of
pollution (Buccolieri et al., 2010, Caridad‐Cancela et al.,
2005).
 Extractable Cd in the soils as estimated by
three single extraction methods
a b
0.7 0.7
a

Extractable Cd mg kg -1
Extractable Cd mg kg-1

0.6 0.6
0.5 0.5 a
b
0.4 0.4
a
0.3 0.3
0.2 0.2
c b
0.1 0.1
0 0
0.1 M HCl M3 1 M NH4OAc 0.1 M HCl M3 1 M NH4OAc
Methods Methods

Extractable Cd at the 0-5 (a) and 5-15 cm depth (b), different letters on
the top of columns indicate significant difference at 5% level.
Soil-Cd fractionation in cacao farms, 0-5 cm
depth
Water soluble Acid-Soluble Reducible Oxidizable Residual
100%

90%

80%

70%
Percentage

60%

50%

40%

30%

20%

10%

0%
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Sites
Soil-Cd fractionation in cacao farms, 5-15 cm
depth
Water soluble Acid-Soluble Reducible Oxidizable Residual
100%

90%

80%

70%
Percentage

60%

50%

40%

30%

20%

10%

0%
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Sites
Correlation coefficients (r) between soil
and tissue Cd

Nomenclature: W-S = Water soluble Cd, Acid-Sol = Acid-Soluble Cd, M3 = Mehlich 3 -

extractable Cd, HCl = 0.1 M HCl – extractable Cd, AA = 1 M NH4OAc – extractable Cd, TR =
total recoverable Cd.
Discussion
• M3- and HCl-extractable Cd were strongly correlated
with bean-Cd concentration at both the surface and
subsurface soil layers (0-5 and 5-15 cm), with similar
correlation coefficients (r = 0.80 and 0.82 for M3, and r =
0.78 and 0.82 for HCl; P < 0.0001). In comparison to M3
and HCl extractable Cd, lower correlation coefficients
were obtained between total recoverable Cd and bean-
Cd (r = 0.56 and 0.61; P < 0.05), and thus total Cd
concentration may not be the best predictor of Cd
availability in cacao beans.
• In contrast, previous studies also suggested neutral
salts, which extract only water soluble and exchangeable
metals, as good predictors of plant-available Cd (Zhang
et al., 2006; Meers et al., 2007)
Discussion (cont)
• In summary, the distribution of Cd fractions decreased in
the following order: oxidizable > acid-soluble > residual >
reducible >> water soluble.
• Soil-Cd was largely bound to organic matter, 34 and 49%
for the 0-5 and 5-15 cm depth, respectively; however,
this pool of Cd is not readily available for cacao plants.
Correspondingly, acid-soluble Cd (also known as
carbonate bound) accounted for 25 and 19% of total Cd,
in contrast with oxidizable-bound Cd, this fraction is
readily available under acid conditions, such as in the
rhizosphere.
• In a similar study, Aikpokpodion et al. (2012) reported a
decreasing order as follows: residual > oxidizable >
water soluble > acid-soluble > reducible.
Conclusions
Twelve out of the nineteen studied farms had a bean
Cd concentration higher than the critical level (0.6 mg
kg-1), attention should be paid to management
practices to reduce Cd availability in soil since cacao
is an important commodity in Ecuador.
Cadmium is highly accumulated in cacao beans, in a
lesser degree in bean’s coat and almost none in
leaves. This phenomena might be linked to the uptake
of nutrients and water of pods directly from the trunk.
In thirteen sites, the concentration of soil-Cd
exceeded the pollution threshold (1.1 mg kg-1).
Furthermore, Cd was mainly in the first 15 cm of the
studied soil profiles, this indicates the occurrence of
anthropogenic activities as the source of pollution in
the area.
The extraction power of Cd among the selected
methods decreased in the following order: 0.1 M HCl
> M3 >> 1 M NH4OAc.
Conclusions (cont)
The fractions of Cd in the soils decreased in order:
oxidizable > acid-soluble > residual > reducible >>
water-soluble/ exchangeable.
The concentration of Cd in beans was highly
correlated with HCl and M3 extractable Cd in soil,
suggesting that these methods are suitable for
predicting plant-available Cd in the soils under cacao
production.
Acid-soluble Cd appears to be the labile pool of Cd in
soil; this fraction was highly correlated with bean-Cd,
HCl- and M3-extractable Cd. Therefore, management
practices to avoid soil acidification should be
implemented to prevent the release of Cd into soil
solution.
The results of this study are applicable only to the
sampling area and are not representative of the
quality of Ecuadorian cacao.
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Acknowledgment
The presenting author want to express their gratitude to the
Centro de Investigaciones Biotecnologicas del Ecuador (CIBE –
ESPOL) for their support in sample collection.
To Francisco Mite and Dr Manuel Carrillo from INIAP for their
valuable advices and Mr Brian Cain for all the lab support.
THANKS