CHAPTERS

AGRICULTURAL APPLICATIONS
OF FLAME PHOTOMETRY

M. Pinta
Office of Scientific and
Technical Research Overseas (ORSTOM)
93-Bondy, France

8.1 Introduction

S.1.1 NATURAL MEDIA

In this chapter on the agricultural applications of flame emission spectrophotometry, we

are dealing basically with the chemical analysis of the following natural media:
a) rocks and soils
b) plants
c) water.
From the chemical point of view, we can distinguish between the major elements and
the trace elements in all these media; the major elements may be said in general to be
those present at a concentration of more than 0.1 %, and the trace elements are those at a
concentration of less than 0.1 %. It goes without saying that this limit between the major
and trace elements is quite arbitrary; in what follows, we will class a given element as
major or trace depending on its mean concentration in the medium in question. This gives
the following classification of the chemical elements in the different natural media:
a) Rocks and soils
major elements: Si, AI, Fe, Na, Ca, Mg, K
trace elements: Mn, Cu, Zn, Ba, Sr, Li, Rb ...
b) Plants
major elements: K, Ca, Mg, Na, Si, S, P
trace elements: Fe, Mn, Cu, Zn, B ...
c) Water. We will limit ourselves here to the types of water which are likely to be in-
volved in agricultural applications: water from streams, rivers and springs. It will be
clear that the concentrations mentioned above are not applicable to this case. We will
therefore define the major elements in water as those present at a concentration of more
than 1 mg/l, namely Na, Ca, Mg, Si, S, P, ... and the trace elements as those present at
concentrations below 1 mg/l, namely Fe, AI, Cu, Mn, Ba, Sr, Li, Rb ...

S.1.2 ELEMENTS WInCH CAN BE DETERMINBD BY FLAME PHOTOMETRY

Flame emission spectrophotometry cannot be used in practice for the chemical analysis

C. T. J. Alkemade et al., Analytical Flame Spectroscopy

© N.V. Philips’ Gloeilampenfabrieken 1970
432 AGRICULTURAL APPLICATIONS OF FLAME PHOTOMETRY [8

of all elements. In general, the elements which can be determined by flame photometry
in the various media are as follows:
a) Rocks and soils: AI, Fe, Na, K, Ca, Mg, Mn, Cu, Sr, Li, Rb, Cs ...
b) Plants: K, Ca, Na, Mg, S, P, Mn, Fe, Cu .. .
c) Water: Na, K, Ca, Mg, S, Mn, Fe, Li, Sr .. .
It should, however, be mentioned that in special cases certain elements for which flame
photometry is not very sensitive (such as barium or caesium) can still be analysed be-
cause of their exceptionally high concentration in the medium under consideration.

8.1.3 ANALYTICAL METHODS

Classical flame photometry is a method for the determination of an element by direct

measurement of one of its spectral emission lines in a flame; this is of particular use for
K, Na, Mg, Mn, Cu ... There are, however, a number of indirect methods which are of
particular interest for the analysis of natural media. We may distinguish:
a) Methods based on interactions between elements.
Under certain conditions, aluminium ions or phosphate ions can form stable molecular
compounds with calcium or strontium in the flame, thus reducing the spectral emission
of the calcium or strontium. Since this reduction is a function of the concentration of the
aluminium or phosphate ions, it can form the basis of a method for the determination of
this concentration.
b) Methods based on the precipitation of metallic salts.
Sulphate ions can be determined by precipitation of the sulphate by means of a known
excess of barium (or lead), followed by photometric determination of the remaining
barium (or lead). Similarly, chlorides can be determined by the photometry of silver.

8.1.4 SAMPLE PREPARATION

Samples must be prepared in accordance with general analytical principles; in particular,

account must be taken of the possibility of interactions, of the sensitivity of emission of the
element to be measured in the flame, of the complexity of the medium and of the calibra-
tion method to be used.
We may mention a number of general principles which apply to this case.
a) The sample is generally dissolved in an acid medium - which should if possible
contain only one acid (HCI, HN0 3 , H 2 S04 , etc.) at a concentration of between 1 % and
5 %. The blank solutions should be made with the same acid medium, to reduce the inter-
action of anions.
Figs. 8.1 and 8.2 show the difference between the calibration curves for sodium and cal-
cium obtained with different acid media.
b) The solution used for analysis should be of such a dilution that the element to be
determined is present at the optimum concentration for the determination. For trace ele-
ments, preliminary chemical separation may be necessary to give a more concentrated so-
lution; for example, copper in plants can be determined by extracting the copper as a Cu-
dithiocarbamate complex, which is dissolved in the minimum volume of methyl isobutyl
ketone.