Nama : Simson Paulus Taifa

Nim : 1806060004
Tugas : G.3
Summary Chapter III
Principles of Trace Analysis

The practical effectiveness of any geochemical method of exploration depends in large part on the
availability of an analytical procedure that is properly suited to the problem at hand. The procedure must be
sensitise enough to detect elements present in very small concentrations: it must be reliable enough that the
chances of missing an important anomaly are negligible; and, for most types of survey, it must be economical
enough that sexy large numbers of samples can be processed. Added desirable features are simplicity techniques.
so that the analysis can be entrusted to relatively untrained personnel, and portability of equipment. so that the
analytical laboratory can, if desirable. he set up near field operations.
Four steps are invoked in almost every trace analysis procedure. Firstt,he sample must be treated to prepare it for
transport. storage, and subsequent steps in the analytical procedure. Then the sample must be partially or
completely decomposed. so that the element to be determined is released in a form that can be easily manipulated.
The third step is the separation of the element from other constituents that might interfere with later
measurements. And, finally, the quantity of the clement present must be estimated. In some trace-analysis systems,
as in X-ray spectrography, one or two of the intermediate steps may be omitted. Also, in some systems, such as
cold-extraction colori-metry and emission spectrography, several of the steps may be carried out essentially
simultaneously as a single process.
In this chapter, the mode of occurrence of trace elements in natural materials is discussed as a basis for
understanding the behavior of elements both during chemical treatments in the laboratory and geochemical
processes in nature. The techniques of sample preparation, decomposition, separation and estimation are briefly
reviewed, with emphasis on the methods used in geochemical exploration. Finally, methods of determining and
expressing precision and accuracy of analyses are discussed.

(i) As a major elemnts in trace trace material. such as Ph on anglesite (PhSO4) i n m a l a c h i t e ( Cu2 Co32 ¿.

(ii As a trace constituent in the crystal structure of a well crystallized mineral,such as Zn in mahnetict Pb in K-
feldspar,or Cu in biotite.

(iii) Are trace element in a poorly crystallized material, or occluded as a trace mineral in such a phase. or
adsorbed on such a material and trapped by further precipitation.

(iv) As a trace element adsorbed on the surface of a colloidal particle of Fe-Mn-oxide, clay or organic material,
or in the exchange layer of a clay mineral Elements in these sites are controlled mainly by ion exchange
equilibria. Even minor changes in composition of surrounding solutions may liberate the trace element to
solution.
 From the above classification, it is clear that a trace element enclosed by a host mineral that is inert in either the natural
or laboratory environment will remain in the solid phase and can only be affected by physical processes, such as sorting
by size or density of the particle. In contrast. a trace element occurring as a trace mineral or as an adsorbed ion may be
directly taken into solution by appropriate changes in the surrounding solution. Trace elements in the lattice of major
minerals can go into solution only after decomposition of the host.

I.MODE OF OCCURRENCE OF TRACE ELEMENTS IN SOLID

A. Stability of Important Minerals

The minerals formed during weathering are generally fine grained. poorly crystalline, and have a large surface
area, and, as a result. may be dissolved or modified by relatively mild chemical treatments The silicates of igneous
and metamorphic rocks (and their detrital grains in sedimentary rocks. sods. and stream sediment) generally require
more drastic chemical treatment for decomposition. Trace minerals haver wide range of properties, ranging from phases
soluble m water to zircon and otheo heavy resistant minerals.
The stability of Fe-Mn-oxides is a function of acidity (pH) and oxidation potential a (Eh). Oxides of both Fe and
Mn are dissolved by either acid or reducing solutions. The Mn-oxides are more easily dissolved than the Fe-oxides. By
an appropriate choice of acids or reducing agents, Fe- or Mn-oxides or both may be selectively dissolved from samples of
soil or stream sediment, leaving more-resistant minerals behind. Conversely. if the chemical conditions are kept w
ithin or near the field of stability of the Fe- and Mn-oxides, trace metals enclosed in them should be unaffected.
Similarly, organic materials and sulfides are stable only under reducing conditions and may therefore be dissolved by
strongly oxidizing treatments . Clays. micas. feldspars, and mafic silicates are only slowly decomposed by weak acids
or buses because silica and alumina are relatively insoluble in such solutions. Many of these silicates are only slowly
decomposed even in hot concentrated acids and therefore arc relatively unaffected by conditions that dissolve Fe- or Mn-
oxides.

II. PREPARATION OF SAMPLES

Samples of naturally occurring material almost always require some kind of preparatory treatment before they are
ready for chemical analysis. The pur¬pose of such treatment may be (i) to put the sample into a form that can he
readily transported and stored. (ii) to homogenize the sample so that sub-sample variations are minimized, or (iii) to
effect a preliminary separation of the elemental constituents according to their occurrence in the different kinds of
particle. All such treatments must be designed to avoid contamination of the samples, and if large numbers of
samples are to be processed, they must be handled with minimum of time and effort. Also, the fewer steps and mani-
pulations involved in preparation and determination, the less chance there is for contamination and error, other
factors being equal. General aspects of sampk preparation are discussed by Lavergne (1965).
Water is normally removed from samples before shipment to the labora¬tory. Water is not only an unnecessary
component of elastic or organic.
Soils and stream sediments arc usually sieved before analysis. This stevine has two purposes rejection of coarse
fragments of quart. organic later, and other materials relutisely posit in trace metals. and tut production of a tine-
grained homogeneous product from which representative subsamples may he consemently taken. Sues of sloes
should be specified by the dimension of the sieve opening. because sieses of the same nominal mesh may differ in
opening by as much as a factor of two.
 When small portions of pulverized rock,soil or sediment arc removed from a larger solume for further processing
or analysis. care must he taken that these samples are representative.

III. DECOMPOTITION OF SAMPLES

Many methods of extracting trace metals from rock, soil, sediment, and other materials are used in geochemical
exploration. The user must choose a method going optimum contrast between anomalies and background, within the
constraints of cost, linse, equipment. and subsequent analytical steps. In many geochemical surveys. contrast can be
improved by sckctise extraction of only certain forms of the clement. rather than the total content of the element.
Methods of selective extraction arc based on differing modes of occurrence of the element (Section I of this
chapter).
The terms "total" ,"readily extractable", "hot extractable", "cold extract-able", and similar expressions are widely
used in geochemical exploration but have no well-defined meanings. "Total" frequently refers to decomposition by
fusion or treatment by hot concentrated acid. which usually extracts 80100% of heavy metals from most samples,
but may extract less than 50% from some minerals and types of samples. Such methods are better termed "near-
total", Alternatively, "total" may refer to analyses by emission spectrography, X-ray fluorescence or neutron
activation, or decomposition by HF combined with strong acids, which give essentially total metal content for most
natural materials.
The characteristics of some common methods of extraction and sample decomposition arc summarized below.

A.Volatilization

The sample may be di.voinisowd 11), solatliiiation in the extreme heat or An electric discharge lemission
spectrography ). releasing essentially the total content of the element. or on the more adjustable heat of an electric furnace
(distillation of Hg) or induction furnace The volatilized material may be determined directly by optical or other
methods, or trapped by condensation or absorption in water for later determination.

B. Fusion

An effectise method of attack is fusion of the sample with an inorganic salt that melts at a reasonably low
temperature but. at the same time. is capable ol' a sigorous attack on the sample. Fusion in potassium bisulfate
(CHS%) has been commonly used because, in contrast to most other fluxes. the fusion can be carried out in Pyrex test
tubes, Some fluxes, in addition to having a high temperature. attack the sample analogously to an acid. us in the case of
KHSO4; others arc alkaline (Na,CO3) or oxidizing (Na303).

C. Vigorous Acid Attack

Hot concentrated acids arc widely used as agents for decomposing samples:
HNO3, HC104, HC1, H2SO4, and HI' have all been used. An acid attack by relatively concentrated HNO3, HO.
HCI03, or mixtures of these with each other and other acids decomposes ft- and Mn-oxides, clay minerals, carbonates,
and some other silicates, especially olivine, but trace elements in pyroeyes and amphiboks arc only partly released.

D. Attack by Weak Aqueous Extractants

The trace metal content in exchange sites of clays and on the surfaces of colloidal particles can be released by
displacing an exchange reaction of the type :

Tr-X + Me 2+¿ ¿ = Me-X 4-Tr 2+¿ ¿ (3.1)

to the right, where Tr is the trace cation. Mc a major cation (both assumed to be divalent for purposes of illustration),
and X the substrate (clay or colloidal particle), The H 'of dilute or weak acids, such as HCI. HNO 3, or acetic acid,
acts as the major cation Me and displaces the trace metal.

E. Oxidation Reduction Agents

Hydroxslamine,dithtionitc, oxalate,and hydroquinone act as selective reducing for Me and Mn-oxides.

The rate of dissolution of various phases can be important in designinig analytical procedures and understanding
the occurrence of elements.

IV. SEPARATION
Once the trace element under study has been released from the sample,it may be necessary to separate it
from interfering elements liberated from the sample at the same time Separation is especially needed prior to most
colon-metric methods, but it not usually required before determination by atomic absorption The process of
separation may also aid by concentrating the ek merit in the separate phase. thus increasing the effective sensitivity
of the overall method Where the element is present in extremely low concentrations. as is often the case in natural
waters. enrichment of the element is often necessary for its determination
A. Separation in Liquid Phase
Many separations in trace analysis involve liquid-liquid solvent extraction rimitting the transfer of
dissolved material between two immiscible liquid phases, usually water and an organic liquid Solvent extraction
requires rigorous mechanical shaking of the system to emulsify the two component phases and thus increase the
effective surface area across which the transfer of dissolved components takes place. Separation may be facilitated
by the use of appropriate completing agents that modify the solubilities of the trace element in the two phases .

B. Separation in Solid Phase

A solid phase containing the desired elements may be separated from a liquid phase by ion exchange or by
precipitation. These methods may be applied to sarnp!es of natural water or to aqueous solutions obtained by some
of the sample extraction procedures mentioned earlier.

V. ESTIMATION

Some of the advantages and disadvantages of these methods in geochemical prospecting work are
mentioned in the follow-ing summary.
A. Colorimetry
 The formation of colored compounds in solution by reaction of an element with a specific chemical reagent
is the basis of colorimetry. Quantitative estimation of the element is possible if the intensity of the color, as
measured by the absorption of light over a small range of waselengths. is proportional to the concentration of the
colored compound A few colorimetne reagents form colored compounds only wit'i one element, but most react
with seseral elements, so preliminary exclusion of interfering elements by compleung or separation is usually
required. Very commonly, the colored complex is ex-tracted from aqueous solution into an organic solvent, thereby
concentrating It and separating it from many interferences. Dithizone is a common colon-metric reagent which can
be used to separate and estimate many elements by varying the pH of extraction and adding completing agents for
unwanted elements (Hawkes, 1963. Sandell, 1959).

B. Emission Spectrometry and Spectrography

Almost all elements, when vaporized and ionized an the Intense heat of an electric discharge or other
source of energy, emit radiation of characteristic wavelength in the visible and ultraviolet range as a result of
electrons refilling the outer electron orbitals . The element can be identified by the wavelength emitted, and the
quantity of the element can be determined by the intensity of the light.
C. Atomic Absorption
Uncharged atoms in a vapor state are capable of absorbing photons of light having energy appropriate for
exciting the outer electrons. In atomic absorption, a sharp spectral line of the element to be analyzed is generated in
a source lamp and passed through the vaporized sample.

D. X-Ray Fluorescence Spectrometry

The inner electrons may be actuated by an X-ray beam In such a way that fluorescent X-rays of a
wavelength characteristic of the activated element are emitted Advantages of X-ray fluorescence include multi-
element capability. high precision, and low cost per determination.Disadvantages ate high cost of equipment and
detection limits of about 50 ppm, inadequate for many ele-ments of interest in mineral exploration. However.
nearly all ektnents uttl an atomic weight greater than Xlg can be detected, many at levels lower than by emission
spectrometry .
Normal laboratory X-ray fluorescence units use an X-ray tube as the source of exciting radiation. but
because gamma rays and X-rays are identical, a gamma-emitting radioactive source can also be used to excite
fluorescent radiation Portable units using a radioactive source have been designed for evaluation of outcrops and
drill holes

E. Fluorimetry
Samples containing U,when fused with a suitable flux and cooled, emit visible under ultraviolet activation. Under
proper's controlled conditions, the luminescence is quantitatisely proportional to the amount of U present down to
extremely low concentrations.
F. Radiometric Methods
The elements U, Th, and K and some of their decay products may be detected and measured by their
natural radioacusity. Non-radioactive elements may be converted into radioactive elements by bombardment with
neutrons or other atomic particles (neutron-activation analysis). The identity of the radioactive element may be
determined by the energy of the emitted eanuna rays or other radiation, and the amount in a sample can be
estimated from the intensity of the radiation.
G. Electroanalytical Methods

Measurements of electrical potentials and electrical currents in solutions have several applications in analyzing
for trace elements. Measurement of pH by the potential of a glass electrode and Eli by potential of a platinum electrode
are the hest known procedures cif this group.
Other electroanalitycal methods include the measurement of dissolved by oxygen in water by electrical measurement
of the current derived from decomposition of oxygen diffusing through a membrane selectively permeable to oxygen,
and measurement of conductivity of solutions as a means of estimating the content of ionized solutes in water.
H. Chromatographic Methods
The adsorption or partition of solutes between a flowing fluid and a station¬ary sorbent is the basis of
chromatographic methods. As the solvent flows. the less strongly sorbed atoms and molecules tend to be carried
along by the solvent at a faster rate than the more strongly sorbed species. In gas-liquid chromatography, the
solvent is a gas and the sorbent is liquid coating the surface of solid particles in a tube or column. In gas-solid
chromatography,the same configuration is used, except that the sorbent is a surface-active solid. la both types, the
sample containing the volatile compounds is injected into the column, carried along by an inert gas, and separated
into atomic and molecular components after traversing a suitable length of column. In paper chromatography, the
liquid flows by capillary action through an adsorbing paper.

I .Mass Spectrometry
The mass spectrometer consists of an evacuated chamber into which a sample of gas is injected and in
which the molecules or atoms are ionized. The tons are accelerated in a strong electric field and then passed
through magnetic held, which separates them according to their ratio of mass to charge.
Mass spectrometers are used in isotopic studies (because they can resolve individual isotopes of the same element),
in organic geochemistry, and in gas analysis.
J. Other Methods
A wide variety of other methods has been used for gcochemical analyses, including gravimetry (used in
fire assay for Au, Ag, and Pt metals), turbidi-metry ( absorption or scattering of light by a suspended precipitate,
used for BaSO4),spot tests (formation of a colored spot), and flame spectrometry .
K. Units for Reporting Chemical Analyses
The common units for reporting trace element analyses are parts per million (ppm) by weight. For
example. 20 ppm Cu indicates that the sample contains 20 grams of Cu in 10" grams of sample, or 20
micrograms (0 pg) per gram Oilier common units for solid samples are percent (%)) and parts by billion
(ppb). where a billion is 10^9, following the American usage To convert from percent to ppm, multiply
by 10^4 that is, I % = 10 000 ppm. To consort from ppm to ppb. multiply by 10^3. that is, I ppm = 1000
ppb.
In water samples, the sample is usually measured by volume rather than by weight, and results arc
commonly reported in milligrams per liter (mg/I) or micrograms per liter (pg/1). For dilute solutions with
a density of 1 g ml, mg/ I = ppm and ug/1 = ppb, by weight.
 VI. Re l ia bi li t y of ge oc he mi c al a nal ys e s

Reliable analyses are required if significant anomalies and patterns are to he detected with any degree of
confidence. The reliability of analyses may be conseniently evaluated in terms of precision and accuracy.
Precision is a measure of the reproducibility of replicate determinations without regard to how close their
average is to the true value. Accuracy deals with the closeness of the measured salve to the true value.

In most geochemical surveys, precision is more important than accuracy, because if precision is poor,
weak anomalies cannot be recognized and spurious anomalies may be created However, if results are to be
compared with other surveys or with data from the literature, then accurate results are also needed.
Inaccurate results may take the form of a constant bias or a bias that varies from sample to sample (Miesch,
1967).

A.Precision

The precision of an analytical method can be determined by multiple analyses of it single sample or,
preferably, by multiple analyses of many samples from the area being surveyed. The determinations
commonly approximate to a normal (Gaussian) distribution (for major ekments) or a log-normal
distribution (for trace elements) If the errors are normally (or log-normally) distributed, then statistical
techniques can be used to express the confidence that the content of the clement is greater than or less than a
certain value, such as the threshold, or the probability that the content falls within a certain range. The
improvement in precision from multiple determinations on a sample and the results of other
manipulations of the data can also be estimated.

B. Accuracy
Ideally. in order to evaluate the accuracy of a geochemical analysis, the true content of an element in some sample
must be known and compared with determinations by the analytical method in question. The simplest type of
inaccuracy is a constant deviation or constant percentage deviation of the determinations from the true value. In
more complicated cases, the error depends on the form of the indicator element or on the content of some other
element. If the error is constant or a constant percentage, the result may be very usable within the group of
samples analyzed, but comparison with values from the literature or with other surveys may be misleading. With
increasing use of computerized data hanks and comparison of data from different sources, verification of the
accuracy of geochemical data is becoming increasingly important. In large surveys, minor changes in analytical
method during the survey may make it impossible to interpret the data properly.
Other methods of evaluating accuracy include the analysis of synthetic samples made up to contain known
amounts of elements. and the analysis of unknown samples spiked with known amounts of the element in question.
Flanagan 119741 lists some synthetic samples available on request. All of these methods arc capable of
detecting a simple bias in the analytical method, but not all are capable of detecting bias related to differing
behavior of elements in different chemical forms.

C. Routine Checks of Precision and Accuracy

In any geochemical project, the precision and accuracy of the analyses must be evaluated and monitored during
the progress of the project_ For small projects. one or more samples may he split and included for analysis
under new numbers. In addition, one or more reference samples of known content should be analyzed.

In large projects, check samples should be included with each hatch of samples or at a regular internal.
Replication of every 10th or 20th sample, submitted under a different number, allows a measure of routine
precision. as described by Garrett (1969). In addition, a reference sample. or possibly a composite of samples from
the project, should be analyzed regularly. Plant et al. (1975) describe procedures used in monitoring precision and
accuracy in a large geochemical survey and some errors uncovered by the procedure.

VII. ANALYTICAL PROCEDURES

Selecting an analytical system that combines the most suitable procedures for the preparation and
decomposition of the sample, and for the separation and estimation of the desired constituents must be based on
an appraisal of a number of factors. The principal of these are (i) the mode of occurrence of the element in the
material sampled. (ii) the number and nature of the elements to be determined, (iii) the sensitivity and precision
required, and (iv) the economics and logistics of the operation.

The economics of an operation make themselves let where the capital investment of a large sum of money for
an expensive instrument is required. For very large projects, many of the instrumental methods of estimation are
far cheaper per unit than the methods that do not require any substantial investment. Thus. if hundreds of
samples per day are to he processed con¬tinuously user a long period of time an X-ray spectrometer or a
radiometric instrument could easily be amortired by the savings in cost per sample.

The logistics of the operation are involsed where the problem of prompt reporting of analytical data and hence
the desirability of a field analytical laboratory arises. Many of the expensive instruments that offer a real
economy in cost per unit determination are too heavy or delicate to transport to the field. The need for a high-
capacity power supply for many of the instru¬mental methods may also limit their applicability.