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Multiele
ment Analytical Spectroscopy in Plant Ionomics
Research
Journal:
Applied Spectroscopy Reviews
Manuscript ID:
Draft
Manuscript Type:
Reviews
Date Submitted by the Author:
n/a
Complete List of Authors:
Djingova, Rumyana; University of Sofia “St. Kliment Ohridski”, Department
of Analytical Chemistry, Faculty of Chemistry and Pharmacy
Mihaylova, Veronika; University of Sofia “St. Kliment Ohridski”,
Department of Analytical Chemistry, Faculty of Chemistry and Pharmacy
Lyubomirova, Valentina; University of Sofia “St. Kliment Ohridski”,
Department of Analytical Chemistry, Faculty of Chemistry and Pharmacy
Tsalev, Dimiter; University of Sofia “St. Kliment Ohridski”, Department of
Analytical Chemistry, Faculty of Chemistry and Pharmacy
Keywords:
Spectroscopy, Analytical, Multielement plant analysis, Ionomics,
Environmental
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Multielement Analytical Spectroscopy in Plant Ionomics Research
Rumyana Djingova, Veronika Mihaylova, Valentina Lyubomirova, Dimiter L. Tsalev*
Department of Analytical Chemistry, Faculty of Chemistry and Pharmacy, University of Sofia
“St. Kliment Ohridski”, Sofia, Bulgaria
* Address correspondence to Dimiter L. Tsalev, Department of Analytical Chemistry, Faculty of
Chemistry and Pharmacy, University of Sofia “St. Kliment Ohridski”, 1 James Bourchier Blvd.,
Sofia 1164, Bulgaria. E-mail: tsalev@chem.uni-sofia.bg; Phone: +359 2 8161 318; Fax: +359 2
9625438.
Abstract: The study of the ionome (ionomics) is defined as quantitative and simultaneous
measurement of the element composition of living organisms and changes in this composition in
response to physiological stimuli, development stage and genetic modifications (Salt et al. 2008).
The necessity to understand the regulation processes of elements in the organisms demands
determination of many elements in organism, tissue and cell (Baxter 2009). Potential prospect for
ionomics is environmental pollution where great variety of conditions and pollutants exist
resulting in concentration and interelement changes in the plant ionome. Capabilities and
problems of several multielement analytical techniques: instrumental neutron activation analysis,
X-ray fluorescence, inductively coupled plasma atomic emission spectrometry, inductively
coupled plasma mass spectrometry and atomic absorption spectrometry which are adequate and
most promising in ionomic and environmental studies of plants are reviewed. References are
confined mainly to the last 10–15 years. Information about concentrations, role, binding forms
and pollution sources of the elements and comparison between methods in respect to limit of
detection, determined elements, interferences and economic considerations are tabulated. Some
combinations of instrumental techniques supplementing each other are highly valued, namely
ICP-MS and ICP-AES; INAA and AAS or ICP-AES.
Keywords: Spectroscopy, Analtyical, Multielement plant analysis, Ionomics, Environmental
INTRODUCTION
All living organisms are composed of chemical elements which are interconnected and correlated
in dependence on their functions, chemical properties and biochemical behavior. Although a
limited number of elements have been established as essential for plants, different investigations
have indicated that complex relationships among elements in organisms exist (1–3). The binding,
transport, distribution and accumulation of elements in plants are extremely important processes
controlled by different genes. Lahner et al. (4) first described the ionome as the mineral nutrient
and trace element composition (including all metals, metalloids and nonmetals) of an organism,
representing the inorganic component of cellular and organism system. The study of the ionome,
called ionomics, is defined as quantitative and simultaneous measurement of the element
composition of living organisms and changes in this composition in response to physiological
stimuli, development stage and genetic modifications (5). The necessity to understand the
regulation processes of elements in the organisms demands determination of as many elements
out of the 92 in the Periodic table as possible in the organism, tissue and cell (2). One of the
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potential perspectives for ionomics is environmental pollution where broad variety of conditions
and pollutants exist probably resulting in concentration and interelement changes in the plant
ionome. The changes in the soil chemical environment are expected to affect more than one
element (2) and lead to respective changes in the genome. Thus it is important to rationalize the
analytical methodology to develop highly accurate and precise methods for determination of as
many elements as possible at various concentration levels.
At present ionomic research relies on two analytical techniques ICP-AES and ICP-MS
used for determination of 13 (6, 7), 14 (8) and 15 elements (9) in yeast, rice, Arabidopsis and
Lotus japonica. Focused are the essential elements and some of the potentially toxic elements,
often determined in environmental studies such as As, Cd and Pb. Obviously at this early stage of
ionomic investigations the interests are towards smaller number of variables in the system since
the combination of the ionome with the regulating genetic networks is an extremely complicated
task. This however prevents the recognition of analytical challenges in ionomic research, the use
of the whole potential of analytical techniques focused on development of highly reliable
analytical methods for determination of a maximum number of elements. Such methods should
be a compulsory prerequisite in ionomic research to permit functional analysis of genes and gene
networks that control development and physiological processes affecting the ionome.
The aim of the present contribution is to present the possibilities and some of the
problems of several analytical techniques which are adequate and most promising to be used in
ionomic and environmental studies of plants. Basic information on the role, toxicity and behavior
of elements is included to link the analytical spectroscopy to plant science and to illustrate the
necessity for close interdisciplinary collaboration in this field. Since the number of publications is
very large mainly contributions published during the last 10–15 years and reviews are cited.
ELEMENTS AND THEIR IMPORTANCE IN LIVING ORGANISMS (PLANTS)
Table 1 presents essential information on the concentrations, functions, toxicity, binding and
pollution sources of the elements in plants. Lanthanoids are considered as a group (REE), all
other 56 elements are given separately. In a few cases no information was found either for
concentrations at background level (e.g. platinum metals), or toxic effects, or binding forms.
Nevertheless the data in Table 1 prove that practically all elements in the Periodic table might be
expected to influence positively or negatively the plant organism especially when changes in the
normal concentration levels appear irrespective of the reasons (genetic, environmental, etc.). This
information illustrates the necessity to determine large number of elements in plants especially at
background levels.
ANALYTICAL ASPECTS
Sampling and Sample Preparation
Representative sampling of plants demands serious consideration of a number of biotic and
abiotic factors and sometimes needs a lot of preliminary investigations, depending on the aim of
research. For biomonitoring purposes a good estimate of biological and seasonal variations in the
elemental composition is necessary as well as evaluation of local factors such as soil properties,
anthropogenic factors, etc. A number of contributions over the years discuss different aspects of
representative sampling of plants (10–26). Keeping in mind that sampling may introduce error
exceeding orders of magnitude the analytical error, standardized sampling procedures are
nessesary (18, 21, 23, 26). In ionomic research where usually until now different mutants are
grown under specific conditions, the sampling procedure is simplified in comparison to field
sampling since seedlings with the same genetic line are being analyzed. This however leads to the
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problem of accurate determination of the sample weight (4, 27) since samples are very small (1–
10 mg), a problem that does not exist in field sampling. To overcome this problem Lahner et al.
(4) have proposed a method for calculating the weight by using the elemental profile. This
method is found to work only if the samples are the same tissue and approximately the same size
(27).
Sample pretreatment also depends on the aim of research. In food chain studies sample
cleaning is usually omitted. In all other cases cleaning of samples is strongly recommended to
avoid soil contamination and in the case of field sampling – to minimize the effect of
precipitation. For deciduous trees, shrubs, grass and herbage different procedures have been
proposed (23–25, 28, 29). Generally washing with tap and distilled water seems to be the easiest
and effective approach. For conifers treatment with chloroform has been be recommended (30,
31).
In the laboratory the samples are dried usually for several hours at temperatures between
60 and 100ºC (results are always presented for DW). The effect of three drying procedures on the
concentration of metals and metalloids in plants has been investigated and reported in Anawar et
al. (32). For small samples drying is also considered a problem (27) and as a probable solution of
this problem the method of Lahner et al. (4) is also recommended.
Most of the analytical methods work with liquid samples, therefore digestion of plant
samples is necessary. This can be easily performed using inorganic acids and either open vessel
or MW assisted digestion. The MW digestion has the advantage of shorter time, smaller amounts
of reagents and preventing losses of volatile elements. In ionomic research however the capacity
of open vessel digestion (possibility to digest simultaneously large number of samples) is
considered an advantage (33). A comparison between the two approaches has been done using
the same reagents, and the results indicate that the concentrations of the determined elements do
not differ significantly in dependence on the digestion method used (Mihaylova et al., 2012,
unpublished information). The mixture HNO
3
+ H
2
O
2
is widely used for digestion of plant
material and in the majority of samples and elements it is successful. However a lot of papers
report uncomplete digestion of plant samples using this mixture. For bioindication studies (and
ionomic research) it is important to achieve complete decomposition of samples (34). A lot of
comparative digestion studies have been performed using: HNO
3
+ H
2
O
2
vs. HNO
3
–HCl (35, 36);
HNO
3
+ H
2
O
2
vs. ashing + HCl +HNO
3
+ HClO
4
+ HF (34); HNO
3
+ H
2
O
2
vs. HNO
3
+ H
2
O
2
+
HBF
4
(37); HNO
3
+ H
2
O
2
vs. HNO
3
+ HBF
4
(38).
According to Sucharova and Suchara (37), at Si concentration > 2000 µg g
–1
the results
for Cu, Li, Ni, Sn, Th, Tl, V, Zn, Ba and Rb are considerably lower when HF is not used for
digestion of plants. If the number of determined elements is extended than lower results when
using acid mixtures without HF have been obtained for Be, Hf, Sb, Ti, U and W even for samples
with Si content below the 2000 µg g
–1
(Myhailova et al., 2012 unpublished information)
Therefore depending on the type of samples and elements to be determined the use of HF may be
necessary which includes an additional step in the digestion, namely discarding of the unreacted
HF either by addition of H
3
BO
4
or HBF
4
(37, 38) or fuming off the HF.
Instrumental Measurement
The choice of an appropriate method for analysis depends on several factors: type and size of
sample, elements to be determined, concentration range, accuracy and precision, speed and cost
of analysis, available instrumentation and other considerations. In most environmental studies the
number of determined elements is limited to macro and micronutrients and specific
environmental pollutants and potentially toxic elements usually: As, Cd, Cu, Pb, Zn, etc. at
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higher concentrations. In ionomic research the same elements are being investigated although the
concentration ranges are considerably lower. This has predefined the choice of methods to AAS
and nowadays to ICP-AES and ICP-MS. Recently, however, a lot of less studied elements such
as REE and platinum metals are increasingly used in different technological processes and
present potential ecological problem on one hand and on the other hand some of them may be
beneficial to plant growth (39, 40) or correlate with other elements in the plant (1, 2). Thus the
necessity to determine as many elements as possible in different concentration intervals demands
the use of methods and/or combination of methods permitting multielement analysis with high
accuracy and precision.
Instrumental neutron activation analysis (INAA)
INAA is a very suitable method for analysis of plants thanks to the fact that digestion of samples
is not performed since the method works preferably with (dried) solid samples. Therefore sample
preparation is reduced to grinding and homogenization of the material and packing in appropriate
containers for neutron irradiation. Thus a lot of possible errors during the sample preparation step
are eliminated in comparison to other analytical techniques. Thus INAA may be a very suitable
technique in ionomic research where large number of small samples has to be analyzed. The peak
in application of activation analysis was in the 70-ies and 80-ies (25, 41–43). Although the
application of INAA is declining due to the close down of many research nuclear reactors (44),
still the method is used in environmental, botanical and agricultural investigations, e.g. Refs (45–
58). Besides the simple sample preparation the general advantages of the method are: possibility
to determine 60–70 elements with very good precision and accuracy, very large dynamic range,
permitting to work with a single standard instead of calibration curve, high selectivity and
sensitivity. A serious limitation of the method is the necessity of an irradiation facility
(experimental nuclear reactor) which seriously confined its application nowadays, as well as the
rather long time of analysis, implied by the long waiting periods to reduce short-lived
radionuclides. Thus in comparison to other methods INAA is the most time consuming but the
least labor consuming analytical technique. With an available irradiation facility the cost of
analysis (instrumentation) is commensurable to FAAS (25). In the schemes for INAA a
combination between irradiation time, cooling time, neutron flux and/or neutron energy permits
the determination of almost all elements in Table 1 with the exception of O, N, F, P and for the
determination of Pb special high speed pneumatic facility is required since
207m
Pb obtained in
neutron irradiation by (n,γ) reaction has a half-life of 0.8 s. Many essential or beneficial elements
in plants (Ca, Mg, K, Mn, Cl, Cu, Na, Se, Si, Mo, S, V) are determined only after short
irradiation in the reactor facility. Usually irradiation times vary between 20 s and 2 h, depending
on the neutron flux density. After cooling times of up to 2 h and several short time measurements
the concentrations of the above elements is determined. Additionally after short time irradiations
information about elements such as Br, As, Al is also obtained (54, 59). The usual approach is a
combination between short and long irradiations and the number of determined elements is
impressively raised to 44 (48, 50, 55, 59–64). Using such approach INAA has been used in the
certification of many reference materials (25). To use however short irradiation times it is
necessary to use a pneumatic system and perform the measurements in a laboratory situated at the
irradiation facility which in many cases might be a problem and limits the use of this approach.
Extension of the possibilities of the method is the use of irradiations with neutrons with different
energies. While activation with thermal neutrons (E < 0.1 eV) eliminates a lot of possible
interferences caused by parallel nuclear reactions (n,n’, n,α, n,p) leading to the formation of
interfering radionuclides, the use of epithermal neutrons (0.4 eV < E < 1 keV) is beneficial for
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the determination of As, Ba, Br, Rb, Sb, Sr, U, Ta, Th, etc. Besides epithermal activation
suppresses one of the basic spectral interferences due to higher concentrations of Na and K in
plants. Their nuclides are high energetic gamma emitters and might interfere in the determination
of other elements by their Compton peaks. Additionally Na and K are preferably activated by
thermal neutrons. Using epithermal NAA, up to 38 elements in mosses were determined by
Frontasyeva and Steinnes (65), and even 41 elements by Baljinnyam et al. (56). A combination of
pile and epithermal irradiation without short time irradiations permitted the determination of over
30 elements (66).
The large number of elements, determined by several analytical techniques (INAA, ICP-
MS) demands reference materials (CRM, SRM
®
, ERM
®
, etc.) with certified concentrations of
50–60 elements and reasonable assortment of matrices and different concentration levels of
elements for adequate evaluation of the quality of analytical results. At present such materials in
plant analysis are still not available and in this respect INAA has another advantage versus other
analytical techniques. The monostandard or K
o
-method (67–70) permits the determination of all
elements, present in the sample by using a single comparator (32, 55, 49, 57, 58, 71).
Energy dispersive X-ray fluorescence spectrometry (EDXRF)
X-ray fluorescence techniques are advantageous and promising in environmental analysis. The
technique is non-destructive, multielement, suitable for numerous elements with Z > 18 with
broad dynamic range, and the cost of analysis is generally low. While XRF is extremely popular
for soil analysis its LODs do not permit the determination of more than 10–15 elements in plants
at background concentrations. Nevertheless skipping sample digestion, environmental friendly
sample preparation, multielement capability and high sample throughput are all attractive assets
that render EDXRF usable in plant analysis (72).
Sample preparation usually includes grinding and homogenization of the samples and
preparation of pellets with suitable geometry for measurement. If the sample consists of particles
with various size or particle size varies between the samples, the resulting X-ray intensities might
be difficult for interpretation (73). The intensity of characteristic radiation is inversely
proportional to particle size. Reduction of the particle effect may be achieved be preparation of
pellets with appropriate thickness using binding agents with good homogeneity and low
absorption parameters.
In EDXRF different excitation sources provide different possibilities in the analysis. The
conventional EDXRF fitted with X-ray tube is most widely used and permits the determination of
5 (74), 8 (75), 9 (72, 76, 77), 12 (59, 78), 14 (79, 80), and even up to 17 analytes (81) in various
plant materials. Usually K, Ca, Al, Ti, V, Mn, Cu, Zn, Sr are determined, in some cases S, Cl and
Pb, and rarely As, Co and P, depending on the concentration in the samples.
The use of radioactive excitation sources with small dimensions and intensity of radiation,
independent of the energy supply has been popular in EDXRF plant analysis in the 80-ies and 90-
ies of the last century (73, 82). The choice of the most appropriate radionuclide for excitation is
extremely important in EDXRF and depends on the elements to be determined. Either single
radionuclide sources (83–85) are used for determination of up to six elements, or otherwise the
combination of several radionuclide sources increases the number of determined elements up to
18 (72).
PIXE uses proton excitation and the same detection system for X-rays. An excellent
review on the possibilities of PIXE in plant analysis was recently published (86). The method
permits the determination of a larger number of elements (P, K, Ca, heavier metals and
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metalloids) as well as a microprobe technique may be used for elemental mapping. PIXE requires
accelerators as excitation source hence the cost of analysis is higher than by EDXRF.
Micro PIXE might be used for quantitative analysis only by precise proton dose
determination (72, 87–89). Using this approach determination of S, K, Ca, Mn, Fe, Zn, Pb, Rb, Sr
and Cd is reported (72).
TXRF has better possibilities than the conventional EDXRF thanks to the total reflection
module included in the system. Determination of up to 15 elements (Si, S, Cl, K, Ca, Ti, Cr, Mn,
Fe, Ni, Cu, Zn, Pb, Br, Rb) in plant samples has been reported (70, 90, 91). Determination of Cd
by TRXF in plants is not possible due to the very strong interference of potassium K-series X-
ray. The method however demands digestion of the samples which eliminates the major
advantage of XRF over destructive techniques.
Inductively coupled plasma atomic emission spectrometry (ICP-AES)
ICP-AES is an established technique and its capacity for environmental analysis is well explored
(25, 92–94). The method is multielement and is characterized by LODs in the range ng g
–1
–µg g
–
1
, high sample throughput, dynamic range about 5 orders of magnitude, low chemical
interferences. In the 80-ies and 90-ies the method has been used for the determination of up to 26
elements in plant samples and plant RMs (25). Even after appropriate digestion, concentration
and optimized instrumental corrections (95) determine 36 elements in CRMs. Presently ICP-AES
widely used in plant analysis (95–110), mostly for determination of Al, Ba, Ca, Fe, K, Mg, Mn,
Na, P, Sr, and Zn, elements that are present at sufficiently high concentrations in plants and need
serious dilutions to be determined by ICP-MS (111–116). Additionally ICP-AES has been used
for determination of Cd, Co, Cr, Cu, Mo, and in rare cases for B, S and Ti in plants with higher
concentrations of these elements such as tea leaves (96), tobacco leaves (97) or in active
biomonitoring study with lichens (115). Thus the number of determined elements varies between
7 (98), 8 (99, 100), 9 (24), 10 (101, 102), 11 (103, 104), 12 (105, 106), 13 (107), 14 (96, 108,
109), 19 (110, 112), 20 (114), and up to 23 analytes (115). The authors seldom discuss matrix
interferences in the determination of microelements although higher concentrations of Ca, Mg, K,
Na, Fe entail spectral problems in the determination of microelements. Attention has been paid to
applicability of different digestion procedures for total solubilization of the samples (97, 110) as
important source of error and means of increasing the number of determined elements. To
overcome the necessity for digestion, the use of ETV has been demonstrated for analysis of solid
plants samples at optimized conditions and the concentrations of 8 elements had been reported
(100). Practically in all papers accuracy has been evaluated using different CRMs and unanimous
conclusions that the strength of the method lies in the direct determination of the
macrocomponents has been reached. The recoveries in the determination of 14 elements are
reported to vary between 0.15% and 8.1% (109).
The strength of ICP-AES to determine macrocomponents in plants is the main reason that
the method nowadays is used in combination with ICP-MS in a variety of studies incl. ionomic
research.
Inductively coupled plasma mass spectrometry (ICP-MS)
During the last decades ICP-MS has emerged as the most promising technique for multielement
trace analysis of environmental samples (25, 111, 112), and it is routinely used for the
determination of up to 18 elements in ionomic research studies. The main advantages of the
method are:
- multielement determination of more than 50 elements with LODs below 1 ng g
–1
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- dynamic range is six to seven orders of magnitute
- precision below 1% RSD
- high sample throughput
- instrumental and methodological development in progress.
In spite of these advantages ICP-MS has been usually applied for rather limited number of
elements compared to its capabilities, the reason being most probably due to the research aims in
the respective studies. Using ICP-MS the determination of 13 (7), 18 (4); 14 (8), 15 (9, 38), 17
(113), 18 (4), 21 (36), 28 (116), 31 (107), 33 (117), 35 (118), and up to 36 elements (34, 37) in
various plant materials has been achieved. Using optimized procedure for sample preparation,
calibration of the spectrometer with CRMs, cold plasma conditions for determination of
macrocomponents and dynamic reaction cell for determination of Pd, Pt, Ni and Se, 60 elements
have been determined by Mihaylova et al., unpublished information (2012). In special research
studies ICP-MS was used for very limited number of elements e.g. determination of platinum
metals in plant materials as the most sensitive techniques for their determination in plants (119,
120).
The analysis of plants could be accompanied by difficulties due to the formation of
polyatomic and molecular ions with concomitant Ar, O, H, N, Cl, Ca, P, K, Na which might
influence the determination of As, Ni, Cr, Se, etc. Therefore special care has to be devoted to
sample preparation, calibration and optimization of instrumentation, and use of dynamic reaction
or collision cells for some of the elements is necessary.
At present the use of HR-ICP-MS (high resolution ICP-MS) is a way to overcome most
interferences although the cost of analysis increases manifold. The number of determined
elements increases from 30 up to 63 (62, 121–123).
A promising alternative to quantitative ICP-MS is semi-quantitative ICP-MS which
enables the determination of all elements in the mass range from 7 (Li) to 238 (U). It uses a
simple calibration procedure and provides information for about 70–80 elements in plant samples
(112). Although the accuracy is worse than in quantitative ICP-MS the advantages are
information for the concentration levels of most of the elements in the Periodic Table with a
single standard calibration and low data acquisition time. Accuracy better than 70% recovery is
reported for 14 elements and in conjunction with chemometrics, the discrimination power of
semi-quantitative results was even better than of full quantitative analysis (124). Zuluaga et al.
(125) obtained recoveries close to 100% for half of the determined elements at RSD < 10%, and
only Si, Al and P required the use of quantitative ICP-MS.
Although LA-ICP-MS is still not widely used in plant analysis it provides a possibility to
analyze solid samples, and permits sensitive visualization of elemental distribution within the
plant (126–128). Additional advantage especially in ionomic and genetic research is to
investigate thin sections of biological tissues both quantitatively and by visualization. Problem in
the quantitative analysis using this technique is the lack of plant CRMs with appropriate form –
pellets or discs. This limits the applicability of the method. Quantitative determination of 7
elements by using
13
C
+
as an internal standard is reported by Wu et al. (126). Wang et al. (129)
use NIST-610 (Glass Standard Reference Material
®
) to determine 13 elements in plants analyzing
pressed discs of the plants sample.
Atomic absorption spectrometry (AAS)
AAS is nowadays a classical, well established and documented, widely available and affordable,
robust and reliable analytical technique for the determination of numerous chemical elements in
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environmental, biological, food and plant samples. The main limitation of the method is that it is
a typically single element technique.
Metrological and technical performance characteristics and application scope of various
AAS techniques differ substantially between the methods: flame AAS (FAAS), electrothermal
AAS (ETAAS) also widely known as graphite furnace AAS (GFAAS), vapor generation AAS
(VGAAS), viz. hydride generation AAS (HGAAS) and cold vapor technique (CVAAS), and their
combination with each other (VG–ETAAS) and with other sample introduction/treatment,
enrichment and speciation analysis techniques: flow injection (FI-FAAS, FI-ETAAS, FI-
VGAAS, FI-VG-ETAAS, etc.), slurry sampling (SS-ETAAS), solid sampling (SoS-ETAAS), etc.
Detailed discussion, comparison and profoundly referenced treatment of these AAS
techniques could be found in several specialized monographs (130-140), book chapters (141–
145) and critical reviews (146–150). Essential speciation and fractionation analysis topics often
rely on single-element approaches and are outside the scope of this review –see e.g. References
(86, 112, 147, 151–154).
Analytical procedures for the determination of up to 27 elements by FAAS, up to 39
analytes by ETAAS and 8−11 hydride forming elements by VGAAS and VG–ETAAS are
available in the vast AAS literature. This elemental scope could be reasonably reduced by at least
factor of two for real concentrations of trace elements at background levels: Al, Ca, Cu, Fe, K,
Mg, Mn, Na and Zn in sample digests or leachates by FAAS without preconcentration; Al, Cd,
Cr, Cu, Fe, Mn, Ni, P, Pb, Zn by ETAAS in digests, slurries or solid microsamples (≤ 0.2−0.5
mg); and As, Hg, Sb and Se in digests/leachates by VGAAS or VG–ETAAS. Enrichment by
means of liquid-liquid extraction (LLE), mainly as dithiocarbamates in batch or FI mode (131,
139, 155–157) or elsewhere by co-precipitation in FI-FAAS or FI-ETAAS (131, 139) and other
preconcentration approaches does extend the number of determined elements and help improving
LODs by 1−2 orders of magnitude (147, 148).
Although generalizations may prove risky in such a broad application field, several
comments on AAS techniques could be made:
AAS techniques inherently exhibit limited potential for simultaneous multielement
analysis; in this respect they are seriously rivaled by ICP-AES and ICP-MS. AAS is primarily
strong as a single element technique for a large number of samples. True simultaneous
determinations with multichannel/multiplex instruments are technically possible with some
instruments (2–6 elements) but at compromise conditions and within limited dynamic range of
2−3 orders of magnitude. Multielement determinations are usually performed element by element
in a ‘fast sequential mode’. Because of extensive chemistry involved in VGAAS techniques
(matrix decomposition, pre-reduction of As(V), Sb(V), Se(VI) and Te(VI) to their lower
oxidation states, effect of acid concentration in digests, etc. (130), the number of hydride-forming
elements that could be simultaneously determined is limited as well (e.g. As + Se; As + Sb; As +
Sb + Bi; Sn + Ge + Bi, depending on reaction medium) (148).
Dissolution of solid samples is typically needed for most FAAS, HGAAS and ETAAS
applications, since liquids are more conveniently homogenized, diluted, handled by autosamplers
and introduced into atomizers than are solids, powders, suspensions (slurries) and emulsions.
Analyses of slurries (1−50 mg mL
–1
, i.e. injection into the graphite atomizer of 10–20 µL of 1–
5% m/v slurry) and solid microsamples (0.05−1 mg) are nowadays successfully commercialized
and automated in ETAAS. This approach exhibits numerous advantages and is highly valued in
literature—see recent reviews and discussions on SS-ETAAS (141, 150, 158, 159) and on SoS-
ETAAS (133, 150, 160). Multielement analysis of slurries (5−6 elements) is possible with SS-
ETAAS (158) and, even better, by true simultaneous SS-ICP-AES (133, 161), ETV-ICP-AES
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(162) as recently reviewed by Resano et al. (150). Solid samples treated by carbonization at 300
o
C (163) or by dry ashing may also be slurried for ETAAS or ETV-ICP-AES quantification—see
reviews by Ebdon et al. (161) and Resano et al. (150). Nebulization of plant slurries in FAAS,
although described for some elements (Ca, Cu, Fe, K, Mg, Mn, Zn) with modified sample
introduction systems, cannot be recommended with commercial instruments because of risk of
nebulizer clogging, matrix accumulation in spray chamber and other complications.
Comparison of analytical techniques
Table 2 gives comparison of the techniques based on LODs, necessity for sample digestion, time
of analysis and cost of equipment. The elements, routinely determined at normal concentration
levels in plants are presented in Table 3. As already discussed the highest number of elements is
determined by ICP-MS, followed by INAA. It should be mentioned however that in order to
reach this number of elements INAA has to be performed in a laboratory at a reactor site for short
lived isotopes irradiation and measurement. The usual practice however is to combine the
analytical techniques whenever possible instead of optimizing the analysis to reach high
performance. Usual combination has been INAA and AAS (71, 164, 165) to overcome the
inability of INAA to determine lead and the difficulties in determining Cd and Cu. At present the
practice is the combination of the two ICP techniques: ICP-AES for determination of
macroelements and macronutrients and ICP-MS for trace elements and micronutrients (2, 4, 27,
166–169). Besides these “popular” combinations others are successfully used either to compare
the possibilities of the methods or to use each method for its most suitable elements. Frontasyeva
et al. (170, 171) combined INAA and ICP-MS and achieved the determination of a lot of
elements not routinely determined in moss samples. Steinnes et al. (172) compared the
possibilities of INAA/AAS with ICP-AES and ICP-MS in the analysis of mosses and reachd the
conclusion that ICP-MS is a good alternative of INAA/AAS. Reimann et al. (173) use ICP-MS,
ICP-AES and CVAAS (for Hg) and determine 38 elements in different plant species. Rashed
(174) used a combination of ICP-MS, ICP-AES, CVAAS and FAAS for determination of 13
elements in plants and soils.
QUALITY CONTROL
The question for quality control in analytical determinations is of vital importance especially
when a large number of elements is to be determined (292). The plant CRMs with certified or
information values for numerous elements are rather limited, therefore analysis of only one or
two CRMs usually cannot cover all determined elements. To overcome this problem either a
number of CRMs should be analyzed or comparison with other established methods should be
performed and reported. Table 4 gives an overview of the elements, that are possible to be found
either as certified or information values in different CRMs and links to the respective cites with
CRM information are provided.
CONCLUSIONS
Multielement techniques like ICP-MS and INAA are undoubtedly advantageous in the analysis of
various plants and plant tissues aiming the determination of a large number of elements. Usually
a combination of analytical techniques (e.g. ICP-MS and ICP-AES; INAA and AAS or ICP-AES)
is preferred to achieve best results. Although AAS is a single element technique in special cases
of interest it still has its importance. In the investigations sampling and sample preparation need
special attention since incorrect performance at this stage may introduce such gross errors that
render the following analytical measurement steps meaningless.
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GLOSSARY OF ABBREVIATIONS
AAS Atomic absorption spectrometry
ADP Adenosine diphosphate
ATP Adenosine triphosphate
BCR Community Bureau of Reference
CF Continuous flow
CRM Certified reference material
CVAAS Cold vapor atomic absorption spectrometry
DNA Deoxyribonucleic acid
DW Dry weight
EDXRF Energy dispersive X-ray fluorescence spectrometry
ERM® European Reference Material
ETAAS Electrothermal atomic absorption spectrometry
ETV Electrothermal vaporization
FAAS Flame atomic absorption spectrometry
FI Flow injection
GFAAS Graphite furnace atomic absorption spectrometry
GP Glycerophosphate
HG Hydride generation
HGAAS Hydride generation atomic absorption spectrometry
IAEA International Atomic Energy Agency (Vienna)
ICP Inductively coupled plasma
ICP-AES Inductively coupled plasma atomic emission spectrometry
ICP-MS Inductively coupled plasma-mass spectrometry
INAA Instrumental neutron activation analysis
IRMM Institute for Reference Materials and Measurements (Geel, Belgium)
LA Laser ablation
LOD Limit of detection
MW Microwave
NAA Neutron activation analysis
NADH2 Nicotinamide adenine dinucleotide
NAD(P)H Nicotinamide adenine dinucleotide phosphate oxidase
NIST National Institute of Standards and Technology
PEP Phosphoenolpyruvate
REE Rare earth element (lanthanoid)
RM Reference material
RNA Ribonucleic acid
RSD Relative standard deviation
SoS Solid sampling
SS Slurry sampling
SRM® Standard Reference Material
TXRF Total reflection X-ray fluorescence spectrometry
VIRM Virtual Institute for Reference Materials
XRF X-ray fluorescence spectrometry
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List of Table Captions
Table 1. Concentrations (µg g
–1
), role, toxicity and binding forms of chemical elements in
plants
Table 2. Comparison of analytical techniques
Table 3. Elements determined in plant samples by different analytical techniques at
background concentration levels
Table 4. Availability of RMs or CRMs for elemental contents in plant tissues
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258. Messer, R.L., Lockwood, P.E., Tseng, W.Y., Edwards, K., Shaw, M., Caughman, G.B.,
Lewis, J.B., and Wataha, J.C. (2005) Mercury(II) alters mitochondrial activity of monocytes at
sublethal doses via oxidative stress mechanisms. J. Biomed. Mat. Res. B, 75: 257–263.
259. Diatloff, E., Asher, C.J., and Smith, F.W. (1999) Foliar application of rare earth elements
to maize and mung bean. Aust. J. Exp. Agric., 39: 189–194.
260. Wen, B., Yuan, D.A., Shan, X.Q., Li, F.L., and Zhang, S.Z. (2001) The influence of rare
earth element fertilizer application on the distribution and bioaccumulation of rare earth elements
in plants under field conditions. Chem. Speciat. Bioavailab., 13: 39–48.
261. Huang, Z.W., Chen, G.C., and Du, J.W. (2003) Influence of lanthanum on the uptake of
trace elements in cucumber plant. Biol. Trace Elem. Res., 95: 185–192.
262. Shi, P., Huang, Z.W., and Chen, G.C., 2006. Influence of lanthanum on the accumulation
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263. Hong, F.H., Liu, C., Zheng, L., Wang, X.F., Wu, K., Song, W.P., Lu, S.P., Tao, Y., and
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264. Tian, H.E., Gao, F.Y., Zeng, F.L., LI, F.M., and Shan, L. (2005) Effects of Eu
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267. Werner, A.K., Sparkes, I.A., Romeis, T., and Witte, C.P. (2008) Identification,
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268. Khan, A.S., Van Driessche, E., Kanarek, L., and Beeckmans, S. (1992) The purification
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270. Schwarz, G., Mendel, R.R. (2006) Molybdenum cofactor biosynthesis and molybdenum
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271. Lang, C., Popko, J., Wirtz, M., Hell, R., Herschbach, C., Kreuzwieser, J., Rennenberg, H.,
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272. Yadav, S.K. (2010) Heavy metals toxicity in plants: An overview on the role of
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273. Raskin, I., Smith, R.D., and Salt, D.E. (1997) Phytoremediation of metals: using plants to
remove pollutants from environment. Curr. Opinion Biotech., 8: 221–226.
274. Gimeno-Garcia, E., Andreu, V., and Boluda, R. (1996) Heavy metal incidence in the
application of inorganic fertilizers and pesticides to rice farming soils. Environ. Poll., 92: 19–25.
275. Bai, C., Reilly, C.C., and Wood, B.W. (2006) Nickel deficiency disrupts metabolism of
ureides, amino acids, and organic acids of young pecan foliage. Plant Physiol., 140: 433–443.
276. Freyermuth, S.K., Bacanamwo, M., and Polacco, J.C. (2000) The soybean Eu3 gene
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277. Sharma, P. and Dubey, R.S. (2005) Lead toxicity in plants. Brazil. J. Plant Physiol., 17:
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Uncommon heavy metals, metalloids and their plant toxicity: a review. Environ. Chem. Lett., 6:
189–213.
281. Yong, P., Rowson, N.A., Farr, J.P.G., Harris, I.R., and Macaskie, L.E. (2002)
Bioaccumulation of palladium by Desulfovibrio desulfuricans. J. Chem. Technol. Biotechnol., 77:
593–601.
282. Maeda, S., Fukuyama, H., Yokoyama, E., Kuroiwa, T., Ohki, A., and Naka, K. (1997)
Bioaccumulation of antimony by Chlorella vulgaris and the association mode of antimony in the
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283. Pratas, J., Prasad, M.N.V., Freitas, H., and Conde, L. (2005) Plants growing in abandoned
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285. DeLaHaba, P., Aguera, E., and Maldonado, J.M. (1990) Differential effects of ammonium
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List of Captions
Multielement Analytical Spectroscopy in Plant Ionomics Research
Rumyana Djingova, Veronika Mihaylova, Valentina Lyubomirova, Dimiter L. Tsalev*
Table 1. Concentrations (µg g
–1
), role, toxicity and binding forms of chemical elements in
plants
Table 2. Comparison of analytical techniques
Table 3. Elements determined in plant samples by different analytical techniques at
background concentration levels
Table 4. Availability of RMs or CRMs for elemental contents in plant tissues
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Table 1. Concentrations (µg g
–1
), role, toxicity and binding forms of chemical elements in plants
El
em
ent
a
Conc
. in
plant
s
Toxici
ty
Role Uptake
form
Deficiency or
excess
Accumulating species Anthropoge
nic sources
Binding to
Ag 0.06
−0.3
Toxic Without
biological
function
Ag
+
,
AgCl
2
−
Chlorosis, damage
of chloroplast and
mitochondria,
oxidative stress,
reduction of ATP,
damage to the
ultrastructure of
organelles
Eriogonum
ovalifolium (175)
Photographi
c material,
alkali
batteries,
catalysts
Interacts metabolically with Cu and
Se and replaces H
from the
sulfhydryl groups of the
photosynthetic enzymes, changing
their structure
Al 90−5
30
Toxic
(0.1−3
0 mg
L
–1
)
Without
biological
function
Al
3+
,
Al(OH
)
4
,
Al(OH
)
3
Inhibition of root
growth, altering
root architecture,
disturbing root
elongation (179)
Festusa arundinacea
(180); Diapensiaceae,
Ericaceae,
Melastomaceae,
Symplocaceae,
Theaceae, Orites,
Excelsa (175);
Plantago
almogravensis (181)
Industries Pectic substances (182, 183),
phospholipids (184), nucleotides
(185, 186)
As 0.01
−1.5
Toxic
(0.02−
7.5 mg
L
–1
)
As(III)
>
As(V)
Without
biological
function
HAsO
4
2−
,
H
2
AsO
4
−
Inhibits plant
growth and fruit
yield, changes in
peroxidase activity,
changes in
chloroplast
pigments
Pteris vita (187),
Pityrogramma
calomelano (188),
Agrostis tenuis,
Holcus lanatus (189)
Industrial
and
agricultural
activities
Dimethylarsinic acid (190),
monomethylarsonic acid; enzymes
Au 0.01
−0.0
4
Slightl
y
toxic;
Au(III
) >
Au(I)
Without
biological
function
Au(O
H)
3
Necrosis, inhibitors
of aquaporins (191)
Brassica juncea (192) Ores
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B 30−7
0
1−5
mg L
–1
Cell division,
glycometabolism
, sugar transport,
flavonoid,
nucleic acid
synthesis, cell
wall formation,
membrane
integrity,
calcium uptake,
flowering, pollen
germination;
carbohydrate
synthesis;
nucleotide
biosynthesis
(112)
B(OH)
3
,
B(OH)
4−
Deficiencies kill
terminal buds
leaving a rosette
effect on the plant
Cruciferae,
Leguminosae (175)
Glass,
ceramic and
enamel
industries
Rhamnogalacturonan II (193)
Ba 10−1
00
500
mg L
–1
Without
biological
function
Ba
2+
Leaf withering, leaf
growth inhibition,
interferes plant’s S
and Ca nutrition
(194)
Bertholletia excelsa
(Bowen, 1979)
Cement and
glass
industry,
electronics,
manufactur
e of alloys,
paints, fuel
oils
Analogous to Ca
Be 0.00
1−0.
4
Toxic
0.5 mg
L
–1
Without
biological
function
BeOH
+
Inhibits the
germination of
seed, the uptake of
Ca and Mg by
roots; degrades
some proteins.
Inhibits splitting of
GP and ATP (195)
Vaccinium myrtillus Alloys;
aerospace,
electronics;
coal-fired
power
plants;
nuclear
weappons
production/
disposal;
strongly
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toxic and
carcinogeni
c to humans
(196)
Bi 0.06 Hardly
toxic
(27
mg L
–
1
)
Without
biological
function
? Oxidative stress Lycopodium sp. Medicine,
pharmaceuti
cal and
cosmetic
articles,
catalysts,
industry
Nuclear proteins (197)
Br <40 15−60
0 mg
L
–1
Essential for
plant growth
Br
−
,
BrO
−
,
HBrO
Reduction plant
growth, causes
chlorosis followed
by leaf tip necrosis
Red and brown algae Fumigants,
insecticides,
flame-
proofing
agents
C 45% Toxic
compo
unds
in the
form
of CO
2
Structural,
biochemical and
metabolic
functions,
manufacture of
sugar during
photosynthesis
CO
2
,
HCO
3
−
Death All plants Technical
processes
Organic compounds, carbohydrates
Ca 1% Hardly
toxic
Activates
enzymes,
structural
component,
influences water
movement, cell
growth and
division, signal
transduction.
(112)
Ca
2+
,
CaOH
+
Deficiency causes
stunting of new
growth in stems,
flowers and roots,
deformed buds,
distored leaves,
failure to grow,
poor fruit
development
Red algae Cement
factories,
fertilizers
and dust
Calmodulin, albumin
Cd 0.03
−0.5
Toxic
(0.2−9
mg L
–
Without
biological
function
Cd
2+
,
CdOH
+
Excess causes
reduction in
photosynthesis,
Brassica chinensis
(200) Thlaspi
caerulescens (201),
Sewage
sludge,
urban
−SH groups of cysteine residues in
proteins, metallothioneins, displace
Zn in Zn enzymes, replaces Ca
2+
in
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1
) water uptake, and
nutrient uptake;
visible symptoms
of chlorosis;
growth inhibition;
browning of root
tips; and finally
death (198, 199)
Phaeodactylum
tricornutim (202),
Datura innoxia (203)
Thlaspicae rulescens
and Arabidopsis
halleri (204–206)
composts,
fertilizers,
municipal
waste
incinerators
, residues
from
metalliferou
s mining;
smelters
albumin
Ce 0.25
−0.5
5
Slightl
y toxic
Promotes
growth, plant
development in
very low
concentrations,
metallic
activated factors
Ce
3+
,
CeOH
2
+
Oxidative stress Tree Carya spp.,
Dryopteris,
Asplenium,
Adianthum,
Dicranopteris (207,
208)
Oil-refined
petroleum
products
Chlorophyll (replaces Mg) (210),
Phytochelatin (209)
Cl 0.2−
2%
Rel.
non-
toxic
Osmolytic
function, enzyme
activation, ionic
balance,
photosynthesis
(211),
electroneutrality,
electrical charge
balance
Cl
−
Deficiency causes
wilting, stubby
roots, chlorosis
(yellowing) and
bronzing
Chenopodiaceae,
Frankeniaceae,
Plumbaginaceae,
Avicennia, Bruguiera,
Rhizophora (175)
Natural
sources
As free ions (?)
Co 0.02
−0.5
Weakl
y toxic
(0.1−3
mg L
–
1
)
N-fixation
system, redox
catalysis, Part of
vit. B
12
;
increases growth
in legumes (179)
Co
2+
,
CoCO
3
Deficiency could
result in N
defficiency
symptoms. Adverse
effect on shoot
growth and
biomass (212)
Families of
Lamiaceae,
Scrophulariaceae,
Asteraceae, and
Fabaceae (213);
Clethra barbinervis:
Crotalaria
cobalticola, Nyssa
sylvatica (175)
Fossil fuels;
wearing of
Co
containing
alloys,
sewage
sludge and
manure
(214)
Vit. B
12
(215)
Cr 0.2− Toxic Carbohydrate Cr(OH Excess of Cr Leptospermum Tanning Tyrosine, Glutathione, carbohydrates
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1 (1 mg
L
–1
Cr(VI)
metabolism. )
3
,
CrO
4
2−
causes inhibition of
plant growth,
chlorosis in young
leaves, nutrient
imbalance, wilting
of tops, and root
injury (216–219),
inhibition of
chlorophyll
biosynthesis (220);
alterations in the
germination
process
scoparium, Pimelia
suteri (175)
industry,
cement
industry
(pentoses), NAD(P)H, FADH
2
(221)
Cs 0.03
−0.4
4
Rel.
harmle
ss
Without
biological
function
Cs
+
Induces K
starvation in plants
Calotropis gigantean
(222, 223)
Natural
sources
Similar to K (224)
Cu 2−20 Toxic
(0.5−8
mg L
–
1
)
Enzyme
activation;
electron
transport;
oxidative stress
protection (112).
Photosynthesis
and
mitochondrial
respiration;
carbon
metabolism
(225)
CuOH
+
,
CuCO
3
Deficiencies cause
brown spots. Cu
toxicity can result
in reduction of Fe
uptake (226).
Cytotoxic role;
induces stress,
injury to plants;
plant growth
retardation and leaf
chlorosis (227)
Brassica juncea,
Aeolanthus biformi
folius, Becium
homblei,
Cryptosepalum
maraiense, Elsholtzia
haichowensis,
Gypsophila patrinii;
Lychnis alpina;
Polycarpaea
spirostylis; Silene
dioica; S. vulgaris,
Triumfetta
welwitschi; Uapaca
spp: Vernonia
glaberrima (175)
Industrial
and mining
activities,
slemting of
Cu-
containing
ores
Plastocyanin, cytochrome oxidase
(228); Mattalochaperones. Ascorbate
oxidase (229), Polyphenol oxidase
(230), Cu-Zn superoxide dismutase
(231), Cytochrome c oxidase (232),
Cu-metallothionein (233), Ethlyene
receptor (234), Mo-cofactor
biosynthesis (235)
F 2−20 Toxic
(5 mg
L
–1
)
Stimulates plant
growth, essential
role in plant
metabolism
F
−
, HF Oxygen uptake
decrease,
respiratory
disorders,
Acacia georginae,
Dichapetalum spp:
Gastrolobioum
grandiflorum (175)
Ceramic,
cement and
brick-
making
Dehydrogenase
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assimilation
decrease, reduction
of chlorophyll
content, inhibition
of pyrophosphatase
function, altered
metabolism of cell
organelles,
disturbance of
DNA and RNA
industries
Fe 5−20
0
Hardly
toxic
(10−2
00 mg
L
–1
)
Enzyme
activation,
electron
transport,
chlorophyll
biosynthesis,
oxidative stress
protection (112).
Electron transfer,
bind oxygen and
transport
Fe
2+
,
Fe(OH
)
2
+
Deficiency causes
loss of green color
due to loss of
chlorophyll. Fe
deficiency
symptom first
appears in the
younger plant
tissue
Acarospora
smaragdula (175)
Industry Hemoproteins, ferritins (236);
Aconitase (237); Succinate
dehydrogenase (338); NADH-Q
oxidoreductase (239); Thioreduxin
reductase (240); Xanthine
dehydrogenase (241); Aldehyde
oxidase (242); Ferredoxin (243);
Cytochromes (224); Catalase,
Peroxidase (244); Cytochrome c
oxidase (245); Nitrate reductase
(246); Nitrite reductase (247);
Cytochrome P450 (248), Leg
hemoglobin (249). Fe-superoxide
dismutase (250), Lipoxygenase
(251), Alternative oxidase (252)
Ga 0.01
−0.2
3
Toxic Without
biological
function
Ga(OH
)
4
−
Disruption of Fe
uptake (253),
disruption of Al
uptake (254)
Brassicaceae Medicine Lactoferrins
Ge 1−2.
4
Hardly
toxic
(apart
from
GeH
4
)
Without
biological
function
Ge(OH
)
4
Inhibit germination
and plant growth
Medicine
Hf 0.00
01–
Hardly
toxic
Without
biological
?
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1.1 function
Hg 0.00
5−0.
2
Toxic Without
biological
function
Hg(O
H)
2
,
HgOH
Cl
Visible injuries,
physiological
disorders, in plants,
inducing leaf
stomata to close
and physicall
obsctruction of
water flow in
plants (255)
Interfere the
metochondrial
activity, induces
oxidative stress,
disruption of
biomembrane
lipids and cellular
metabolism in
plants (256–258)
Minuartia setacea
(175)
Emissions
from
combustion
sources,
smelters,
metallurgy,
cement
production
Sulphydryl groups in proteins
I 0.07
−10
Rel.
non-
toxic
(1 mg
L
–1
)
Iodine cycle I
−
, IO
3
−
Oxidative stress Feijoa, sellowiana
(175), red and brown
algae
Chemical
industry,
paint
industry,
medicine
Proteins
In 0.00
05−0
.002
Toxic Without
biological
function
In(OH)
4
−
Semiconduc
tor industry
Ir ? ? Without
biological
function
? Plant cell death Automobile
catalytic
convertors,
medicine
K 0.5−
3.4%
Rel.
harmle
ss
Electrochemical,
catalytic enzyme
activation;
translocation,
osmoregulation,
K
+
Disturb water
balance, leaf
curling, root rot
All plants Natural
sources,
fertilizers
As free ions
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pH homeostasis,
enzyme
activation (112)
La 0.15
−0.2
5
Slightl
y toxic
Promotes
growth, plant
development in
very low
concentrations
(259–262);
metallic
activated factors
(263, 264)
La
3+
,
LaOH
2
+
Oxidative stress Carya spp. Tree
Carya spp.,
Dryopteris,
Asplenium,
Adianthum,
Dicranopteris (207,
208)
Industry,
medicine
Replaces Ca(II) (265), replaces
Mg(II) (210)
Li 0.01
−3.1
Slightl
y toxic
Without
biological
function
Li
+
Plant growth,
changes in lipids,
leaf and roots
B. cerinata Reactor
fuel, rocket
fuel
M
g
1000
−900
0
Hardly
toxic
Enzyme
component;
chlorophyll
structure;
electrochemical
and catalytic
functions;
germination of
seeds. Fixation
of carbon in
chloroplasts
(266)
Mg
2+
,
MgOH
+
Chlorotic
appearance of
deficient plants
All plants Natural
sources,
fertilizers
ADP
4
−
, ATP
4
−
N-and O-binding, chlorophyll
M
n
1−70
0
Slightl
y toxic
Enzyme
activation,
photosynthesis,
electron
transport,
sunthesys of cell
wall
components,
oxidative stress
Mn
2+
Chlorosis, not too
dissimilar to
symptoms of Mg
deficiency
Ericaceae; Camellia
spp. (175)
Metallurgy Mn-superoxide dismutase (231);
PEP-carboxykinase (226);
Allantoate amidohydrolase (267);
Malic enzyme (226); Isocitrate lyase
(268) PEP carboxylase (269)
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protection (112)
M
o
0.03
−5
Slightl
y toxic
(0.5−2
mg L
–
1
)
Enzyme
activation,
nitrogen fixation,
nitrate reduction.
(112) sulfur
metabolism
(270)
MoO
4
2
−
Relation to N
deficiency.
Restricted plant
growth and flower
development
Grindelia fastigiata
(175)
Steel
industry.
Molybdenum-enzyme aldehyde
oxidase, Nitrate reductase (270),
Sulfite oxidase (271), Aldehyde
oxidase (270), Xanthine
dehydrogenase (241)
N 1–
7%
Essent
ial
Structure
component;
metabolic
physiological
functions;
protein synthesis,
nucleic acid
(112)
NO
3
−
,
NH
4
+
,
N
2
Reduce yield,
cause yellowing of
the leaves and stunt
growth. Yellow
leaves, stunted
growth, lower
leaves turn brown,
leaves abort
All plants Natural
sources
Urea, biotin, thiamine, niacin and
riboflavin, nucleic acids (DNA and
RNA)
Na 35−1
000
Rel.
harmle
ss
Electrochemical
enzyme
activation; water
movement;
osmotic and
ionic balance.
Increases plant
growth; can
replace K (179)
Na
+
Disturbs water
balance, leaf
curling, root rot
Atriplex, Custuta
attenuate (179)
Natural
sources,
metallurgy
As free ions
Nb 0.02
–
0.45
Slightl
y toxic
Without
biological
function
? Rubus arcticus Steel
industry
Ni 0.4−
4
Toxic
(0.5−2
mg L
–
1
)
Interaction with
iron resorption,
redox catalysis.
Seeds germinate.
Enzyme
activation, urea
metabolism
(112)
Ni
2+
Physiological
alterations and
diverse toxicity
symptoms
(chlorosis,
necrosis). Excess
Ni causes
impairment of
Brassica juncea
(273), Thlaspi
goesingense Alyssum
bertolonii; A. murale,
Dicoma spp.;
Geissois spp.;
Homalium spp.;
Hybanthus
Mining
works,
smelters,
coal and oil
burning,
sewage,
phosphate
fertilizer;
Ni-metallochaperone (275); Urease
(276)
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nutrient balance
and disorder of cell
membrane
function; decreases
in water uptake
(272)
floribundus; Pimelea
suteri; Planchnella
spp.; Psychotria spp.
Rinorea bengalensis;
Sebertia spp;
Strychnos ignatii
seeds;
Trichospermum spp
(175)
pesticides
(274)
O 40−4
4%
Toxic
in the
form
of O
3
and
peroxi
de
Constituent of
many organic
compounds,
provides
oxidation
equivalents in
metabolism
O
2
,
CO
2
Oxidative stress,
plant death
All plants Natural
sources
Organic compounds, proteins,
enzymes
P 120−
3000
0
Energy
metabolism,
phosphorylizatio
n, structural
functions seed
germination,
photosynthesis,
protein
formation; all
aspects of
growth and
metabolism in
plants. Fruit and
flower
formation.
Energy transport,
biomembranes
(112)
HPO
4
2
−
,
H
2
PO
4
−
Deficiency
symptoms are
purple stems and
leaves; maturity
and growth
retarded
All plants Military
industry,
semiconduc
tor industry
DNA and ATP, enzymes, proteins
Pb 0.1−
5
Toxic
(3−2
Without
biological
PbCO
3
Inhibiton of
enzyme activities,
Brassica juncea, Zea
mays, Ambrosia
Mining and
smelting
Peptides
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mg L
–
1
)
function water imbalance,
alterations in
membrane
permeability and
disturbs mineral
nutrition (277),
induces oxidative
stress (278)
artemisiifilia (279),
Amorpha canescens,
Minuartia verna (175)
activities,
Pb
containing
paints,
paper and
pulps,
gasoline
and
explosives
Pd ? Toxic Without
biological
function
? Cell cycle, cell
division (280)
Desylfovibrio
desulphuricans (281)
Automobile
catalytic
convertors
Carbohydrates
Pt ? Slightl
y toxic
Without
biological
function
? Cell cycle, cell
division (280)
Sinapis alba, Lolium
perenne (280)
Automobile
catalytic
convertors,
medicine
Carbohydrates
Rb 1−50 Slightl
y toxic
Replaces K
+
Rb
+
Stimulates growth Some fungi Semiconduc
tor industry
Similar to K
Rh ? ? Without
biological
function
? Cell cycle, cell
division (280)
Desylfovibrio
desulphuricans (281)
Automobile
catalytic
convertors
Carbohydrates
S 600−
1000
0
SO
x
ecotox
ic
Constituent of
amino acids,
vitamins and
enzymes.
Essential to
prodice
chlorophyll.
Protein synthesis
and functionality
(112)
SO
4
2
−
,
HSO
4
−
Deficiencies shows
light green leaves.
Slow growth, low
vigor, no response
to applied nitrogen,
low crop yield and
quality
Cruciferae; Alliums
spp (175)
Emission of
SO
2
; soil
acidificatio
n
Cysteine and methionine
Sb 0.00
1–1
Toxic Without
biological
function
Sb(OH
)
6−
Chlorosis Chlorella vulgaris
(282), Calluna
vulgaris, Digitalis
purpurea (283)
Coal
burning,
smelters;
Sb-
containing
Phytochelatins carbohydrates
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Sc 0.01
−0.2
Slightl
y toxic
Without
biological
function
Sc(OH
)
3
2−
Chlorosis Uranium
smelting
Se 0.01
−2
Toxic
(1−2
mg L
–1
Se(IV)
)
Redox catalysis;
affects
metabolism of
many higher
plants. Trace Se
promotes
growth, has an
antioxidant
capacity and
protects plants
from biotic stress
(179)
SeO
3
−
Chlorosis and
oxidative stress
Asteraceae, Allium,
Brassicaceae,
Astragalus and
Leguminoseae
families (112),
Stanleya, Astragalus
(179)
Coal and oil
combustion,
industrial
and
agriculture
processes
Glutathione peroxidase
Si 2000
−800
0
Scarce
ly
toxic
Structural
component.
Increases plant
growth,
resistance to
abiotic stress
(179)
Si(OH)
4
Biotic stress,
growth
disturbances
Families of
Equisetaceae and
Poaceae (179),
Cyperaceae,
Gramineae,
Juncaceae, Moquilea
spp.
Cement and
glass
industry
Phenol-carbohydrate complexes,
lignin-carbohydrate complexes
(Inanaga and Okasaka, 1995)
Sn 0.8−
7
Hardly
?
Without
biological
function
SnO(O
H)
3−
Growth
disturbances
Silene vulgaris? (175) Industry
Sr 3−40
0
In the
form
of
90
Sr
Without
biological
function
Sr
2+
Chlorosis Brown algae Nuclear
explosions
Similar to Ca
Ta <0.0
01
Slightl
y toxic
Without
biological
function
? Stylea plicata
Te 0.01
−0.3
Toxic
(6 mg
Without
biological
HTeO
3
–
Unknown Industry Unknown
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5 L
–
1
) function
Th 0.03
−1.3
Toxic Without
biological
function
Th(OH
)
4
4−n
Plant growth Mining
activity
Phosphoryl groups
Tl 0.03
−0.3
Toxic
(1 mg
L
–1
)
Without
biological
function
Tl
+
Inhibits
monovalent cation-
activated enzymes
Iberis intermedia,
Biscutella laevigata,
brassicaceae, Lolium
perenne (280)
Coal
mining, Zn
and
nonferrous
smelters;
cement
industry
Sulhydryl groups of proteins
Ti 0.02
−56
Hardly
toxic
Plays positive
role in cereal
growth
Ti(OH
)
4
Inhibits plant
growth; chlorotic
and necrotic spots
Cosmetics;
glass
industry
U 0.00
5−0.
06
Highly
toxic
Without
biological
function
UO
2
(CO
3
)
3
4−
Growth anomalies Coprosma arborea.
Uncinia leptostachya
(175)
Mining
activity
Phosphoryl groups
V 0.00
1−10
Toxic
(10−4
0 mg
L
–1
)
Redox catalysis H
2
VO
4
−
,HVO
4
2−
Growth reduction,
changes in lipid
metabolism
Petroselinum sativum
(175), Amanita
muscaria
Steel
industry
Amavadine
W 0.00
05−0
.15
Slightl
y toxic
(10
mg L
–
1
)
Antagonist of
Mo
WO
4
2
−
Inhibition of root
nitrate reductase
activity, growth
depression, and
plant death (285)
Penus cembra,
Digitalis purpurea,
Cistus ladanifer,
Erica umbellate (283)
Industry
and military
Xantine oxidase
Y 0.15
−0.7
7
Slightl
y toxic
Without
biological
function
Y(OH)
3
Growth inhibition Cerua spp. Electronics
industry
Zn 15−1
50
Toxic
(60−4
00 mg
L
–1
)
Chlorophyll
formation, Gene
expression,
enzyme
activation,
hormone and
nucleic acid
Zn
2+
,
ZnOH
+
,
ZnCO
3
Zinc deficiency:
chlorosis in the
interveinal areas of
new leaves; plant
and leaf growth
become stunted
Thlaspicae rulescens
and Arabidopsis
halleri (204–206).
Minuartia verna;
Silene vilgaris, Voila
tricolor (175)
Sewage
sludge,
urban
composts,
fertilizers,
emissions
from
Zn-finger containing proteins,
transcription factors,
oxidoreductases, metalloproteases
(225), SPP (286), Carbonic
Anhydrase (287), Cu-Zn superoxide
dismutase (231), Alcohol
dehydrogenase (288) Peptide
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synthesis,
oxidative stress
protection (112)
municipal
waste
incinerators
, residues
from
metalliferou
s mining,
the metal
smelting
industry
deformulase (289), α-Mannosidase
(290), Matrix metalloproteinase
(291), Auxin
Zr 0.3−
2
Slightl
y toxic
Without
biological
function