University of Chile

Faculty of Agricultural Sciences

Agronomic Production Department

Plant Physiology Seminar

Copper toxicity:
Any Copper would work the same?
December 09, 2015

Colihueque, J.
Márquez, J.
Rojas,I.

1
Introduction
Copper (Cu) is an essential micronutrient
for plant growth, playing a key role in the
function of many proteins. Cu is involved
in electron transport during
photosynthesis, lignin formation and cell
wall metabolism (Burkhead et al., 2009).
Cu can act as a toxin to plants as well,
causing nutrient loss and oxidative stress
(Martins & Mourato, 2006; Reichman et
al., 2006). Under toxic conditions,
damaging hydroxyl radicals are formed
that attack the cell structure, and inhibit
photosynthesis (Fernandes & Henriques,
1991; Yruela, 2009).
+ 2+
Cu and Cu are the species of copper
absorbed by the plants (Murphy, 1972),
however, Copper is taken up by higher
plants largely in the form of Cu2+ and
plants use two types of strategies to absorb
heavy metals, Strategy I and Strategy II.
The importance of these mechanisms in
Cu mobilization and uptake in the soil
environment remains unclear. Although
no studies have confirmed the
mobilization and uptake mechanism of Cu,
there appears to be a strong overlap
between Fe and Cu uptake, with Cu shown
to competitively inhibit Fe uptake
(Schmidt et al., 1997; Michaud et al.,
2008; Yruela, 2009).
Previous work has found that Cu exists as
both Cu+ and Cu2+ in the vegetative tissue
of Larrea tridentata (creosote bush),
despite the fact that Cu absorbed from the
soil is Cu2+, indicating redox changes
within the plant or during uptake (Polette
et al., 2000)
One of the Cu accumulation sites in higher
plants are the chloroplasts, also, this metal
is directly involved as a component of
plastocyanin in the photosynthetic electron
transport chain (Katoh, 1977). However,
Cu content in the chloroplasts is usually
several times higher than that found in the
plastocyanin (Plesnicar and Bendall
1970).
Availability
The total metal concentration of a soil
includes all fractions of a metal, from the
readily available to the highly unavailable.
Other soil factors, such as pH, organic
matter, clay and redox conditions,
determine the proportion of total metal
which is in the soil solution.
In relation to solution pH, it determines
Copper solubility, speciation,
complexation and adsorption, but there is
little relation between soil pH and Copper
concentration (Jeffery and Uren, 1983;
McGrath et al., 1988; Sauve et al., 1997).
The reason for this is the strong affinity of
Cu for organic matter (Norvell, 1991).
This means that the amount of organic
matter dissolved in the soil it’s a more
determining factor on Copper solubility
and therefore availability than any other,
as Copper ions forms strong coordination
complexes with organic matter
(Stevenson, 1976; Stevenson, 1991).
In Chile
Copper mining is by far the major
economic activity of Chile. Given the
underlying geochemistry of the Andean
range one would expect high background
copper levels, at least in the regions where
rich copper ores have been found. In fact,
the surveys carried out so far have shown
rather high copper levels in soils, including
soils from the Antarctic peninsula with as
much as 500 mg/Kg (Carrasco & Préndez,
2
1991). However, the long history of
copper exploitation and beneficiation
associated to certain areas, makes it
difficult to assess the true background
levels of those areas.
The optical mineralogical analysis of the
study soils in the IV Region of Coquimbo
revealed the presence of a number of
copper minerals: chalcopyrite (CuFeS2),
chalcosine (Cu2S), covellite (CuS),
enargite (Cu3AsS4) which in dissociation
releases the free ions Cu2+, Cu+, Cu2+, Cu+
respectively; as well as slag and carbon
particles.
Toxicity
For many crops, ‘total’ soil copper
concentration (perchloric acid extractable)
above 100 mg/kg have been regarded as
high (Landon, 1991), while concentrations
of DTPA-extractable copper above 20
mg/kg are potentially toxic in acid soils
(CFL, 1983). For citrus, soils containing
more than 112 kg/ha total copper in the top
15 cm, using Spencer’s test (Spencer,
1954), are considered at risk, particularly
if the soil pH is below 6.5 (Koo et al.,
1984).
The most widespread visual evidence of
metal toxicity is a reduction in plant
growth as metal toxicity increases.
Toxic levels of Copper rarely occur
naturally in soils. However, copper may
accumulate due to application of organic
amendments or mine slag, though is more
commonly through persistent use of
copper-containing fungicides or fertilisers.
Interveinal foliar chlorosis is a common
initial symptom of Cu toxicity (Taylor and
Foy, 1985; Zhu and Alva, 1993). The
chlorosis often takes the form of cream or
white spots or lesions (Lee et al., 1996a;
O'Sullivan et al., 1997). With increasing
exposure, leaf tips and margins can
become necrotic (Taylor and Foy, 1985;
Yau et al., 1991). In acute Cu toxicity,
leaves may become wilted before
eventually becoming necrotic (Yau et al.,
1991). Copper toxicity can be associated
with a purpling of foliage (Choi et al.,
1996) but this is not apparent in all species
(O'Sullivan et al., 1997).
The principal problem of Copper toxicity
in plants it’s that it has a significant effect
on root growth and form, often before any
effect on above-ground growth (Minnich
et al., 1987). Patterson (1983) found that
the germination of six tree species was less
sensitive to Cu than subsequent root
elongation. In dicot seedlings, toxic
amounts of Cu result in radicles which are
short, blunt tipped, of dark brown/black
colouration (necrotic) and have a
disposition to fungal attack (Patterson and
Olson, 1983).
Any copper would work the same?
According to the consulted literature, It
hasn’t been found any fundamental
difference, in terms of role, between the
different speciations of copper in the
vegetal tissue, which means that its
toxicity doesn’t depend on the oxidation
state that they are found, either Cu+ or
Cu2+. However, in terms of application of
agriculture coppers, in which there’s a
relation between concepts such as
solubility and ionisation potential of every
salt with copper association, there is a
difference as when there is an application
of a product with sulfurized product it
would mean that this product has a rather
high solubility and high ionization
potential, contrary to the application of a
3
copper oxide which releases the copper as Copper speciation and isotopic
free ion faster, however, due to this the fractionation in plants: uptake and
quantity of product to applicate must be translocation mechanisms. New
more. In other words, the first copper Phytologist. Soil Sciences, University of
compound mencioned would produce a Adelaide, Adelaide, Australia. New
higher availability of Cu2+ to the plant Phytologist Vol. 199 page 367-378.
compared to the copper oxide salts,
P. Rodríguez, R. Badilla-Ohlbaum, A.
causing copper phytotoxicity faster.
Birkefield, E. Bustamante, A. Céspedes,
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