Sampling
Dr Amtul qayoom
A sample must 2
Represent faithfully the properties under
investigation: composition, colour, crystal type etc.
Be of a size that can be handled by the sampler.
Be of a size that can be handled by the analyst.
Keep the properties the object had at the time of
sampling, or change its properties in the same way as
the object.
Be suitable to give the information that the client
wants. e.g. mean, composition, or composition as a
function of time or place
Keep its identity throughout the whole procedure of
transport and analysis.
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Important Terms 4
Bulk materials: a single pile of a material. In some cases, bulk materials
may be partially packaged into smaller units, such as bags or drums. These are
called segments.
packaged goods are comprised of identifiable units, which may be
assigned numbers.
A consignment is defined as a quantity of material transferred on one
occasion and covered by a single set of shipping documents.
A lot is a quantity of material which is assumed to represent a single
population for sampling purposes. A batch is a quantity of material which is
known or assumed to have been produced under uniform conditions.
Increments are portions of the material obtained from the lot/batch by using
a sampling device. Increments are often combined to produce a primary or
gross sample.
Important Terms 5
A number of primary samples are combined and mixed to produce a
composite or aggregate sample.
The laboratory sample is often obtained from the primary or composite
sample by a series of division and reduction processes. The laboratory
sample is the portion of material delivered to the laboratory for analysis.
The test portion is the quantity of material that is actually submitted for
analysis. In the field of analytical chemistry, this is sometimes referred to as
the analytical portion.
There are often a number of other operations that need to take place before a
suitable test portion can be obtained. The intermediate sample that the
analyst obtains from the laboratory sample is called the test (or
analytical) sample
Stages of sampling process
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Defining the population of concern
Specifying a sampling frame, a set of items possible to
measure
Specifying a sampling method for selecting items from the
frame
Determining the sample size
Implementing the sampling plan
Sampling and data collecting
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There are two aspects to sampling process:
Statistical sampling plan (Design Phase)
Physical realization of the statistically
designated portions and the removal and
preparation of them (Implementation Phase)
STATISTICAL SAMPLING PLAN 8
Five questions should be considered when designing
a sampling plan:
From where within the target population should
samples be collected?
What type of samples should be collected?
What is the minimum amount of sample needed for
each analysis?
How many samples should be analyzed?
How can the overall variance be minimized?
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Types of Samples
Representative samples
Selective samples
Random samples
Composite samples
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Representative Sample
A representative sample is the portion of a material taken from a consignment and
selected in such a way that it possesses the essential characteristics of the bulk.
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Selective Sample
This is a sample which is deliberately chosen by using a sampling plan that
screens-out materials with certain characteristics and/or selects only material
with other relevant characteristics. This may also be called directed or focused
sampling.
Random Sample
A sample is selected by a random process to eliminate problems of bias in
selection and/or to provide a basis for statistical interpretation of
measurement data.
Composite Sample
A composite sample consists of two or more portions of material (collected at
the same time) selected so as to represent the material being investigated. The
components of the composite sample are taken in proportion to the amount of
the material that they represent. This type of sample may be appropriate when
carrying out food surveys.
Choose the most appropriate type of sample 12
(representative, selective, random or
composite) for the following parent materials.
(i) River water after a recent thaw. An estimate of the
average concentration of compounds dissolved in the
water is required.
(ii) Cans of baked beans in a warehouse.
(iii) Bars of chocolate suspected of being tampered with.
(iv) Sacks of flour stored near a hydrocarbon source in a
ship’s hold.
(v) Bags of flour in a storeroom, % moisture required.
How many samples/replicates to analyse?
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Rearranging Student’s t equation:
Required number of ts s t 2 s2s
x n
replicate analyses: n e2
e
µ = true population mean
t 2ss2 x = measured mean
n 2 2 n = number of samples needed
X r ss2 = variance of the sampling operation
e = sought-for uncertainty
σr = relative standard deviation
Since degrees of freedom is not known at this stage, the value of t for n → ∞ is
used to estimate n.
The process is then repeated a few times until a constant value for n is found.
Number of samples
a) E 20% of 16
Cadmium concentrations in soil were 0.2 16
measured at a field site during 3.2 ppm
preliminary surveying. The mean ± 2
standard deviation were (16 ± 4) ppm. n
24
3.2
6.25
a) Calculate the number of samples
required to obtain a total uncertainty of
20%. b) E 10% of 16
Between 6 and 7, assuming t=2 0.1 16
1.6 ppm
b) How many samples would be required
to reduce this uncertainty to 10%? n
24
2
25, assuming t=2 1 .6
25
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Example: 16
In analysing a lot with random sample variation, there is a sampling deviation of
5%. Assuming negligible error in the analytical procedure, how many samples
must be analysed to give 95% confidence that the error in the mean is within
4% of the true value?
t 2 s2s
For 95% confidence: n
e2
t = n
The determination of copper in a seawater sample gave a mean value of
77.81 mg/L and a standard deviation ss of 1.74 mg/L. How many samples 17
must be analyzed to obtain a relative standard deviation of 1.7% in the
results at the 95% confidence level?
t 2s s2
n
X 2 r2
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How can the overall variance be minimized?
The analytical result may depend on the method used but it will always
depend on the type of sampling plan used. The standard deviation of a final
result is composed of the standard deviations of each step.
s02 = sS2 + sm2
V0= sS2 + sm2
V0= VS + Vm
V0 = Overall Variance
Vs = Sampling Variance
Vm = Method variance/Analytical Variance
If sampling uncertainty is more than 2/3 of total uncertainty, any
attempt of improve analytical method will be useless
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Ex.1 A quantitative analysis for an analyte gives a mean concentration of 12.6
ppm. The standard deviation for the method is found to be 1.1 ppm and that due to
sampling is 2.1 ppm.
(a) What is the overall variance for the analysis?
(b) By how much does the overall variance change if sm is improved by 10% to 0.99
ppm?
(c) By how much does the overall variance change if ss is improved by 10% to 1.9
ppm?
+ =5.62
+ = 5.39
+ = 4.8
Ex. 1 For a particular analysis, it has been determined that the sampling 20
error is 6% (ss=0.06). A particular analytical technique can give a precision of
1%, what is the overall precision. Is it worth considering a slower technique
which can give a precision of 0.2%.
Ex. 3 For ss=15% and sA=5%. what is the overall precision. If sA is reduced to 1%
what is the total precision.
Analytical samples and methods 21
Sample size Type of analysis
> 0.1g Macro
0.01~0.1g Semimicro
0.0001~0.01g Micro
< 10–4 g Ultramicro
Analytical level Type of constituent
1%~100% Major
0.01%(100ppm)~1% Minor
1ppb~100ppm Trace
<1 ppb Ultratrace
DISSOLVING SAMPLES FOR ANALYSIS
Most analytical techniques require that the samples first be dissolve before
analysis.
It is important that the entire sample is dissolved, else some of the analyte
may still be in the undissolved portion.
We will consider:
Acid dissolution / digestion
Fusion
Wet ashing
Dry ashing
Acid (or wet) digestion
Acid digestion can be used to:
Break down an organic matrix (eg a food)
Dissolve an inorganic matrix (eg geological deposit)
The sample is heated with acid at temperatures normally up to about
100°C.
Digestion releases the analyte from its matrix, thereby making it available
for further work-up
Acid digestion is commonly used for elemental analysis.
Acids commonly used for dissolving inorganic materials:
Non-oxidising acids – HCl, HF, dilute HClO4, dilute H2SO4, H3PO4
Oxidising acids – HNO3, hot concentrated HClO4, hot concentrated H2SO4
A mixture of acids maybe required, e.g.:
HCl:HNO3 , HCl + HClO4, HNO3 + HClO4 + HF
Further Notes
Vessels for acid digestion manufactured from glass, Teflon, platinum, polyethylene
Do NOT use HF in glass
To prevent loss of volatile species – use teflon-lined bombs (sealed container)
Bombs are frequently
manufactured for use in a
microwave oven
FUSIONS
To dissolve refractory substances
Dissolve sample in hot molten inorganic flux.
~10 times more flux than sample (by mass)
Heat crucible to 300 – 1200oC
Crucibles
Automated fusion apparatus e.g. platinum, gold,
nickel, zirconium
Common fluxes used:
Basic fluxes – Na2O2, Na2CO3, LiBO2, NaOH, KOH
for dissolving acidic oxides of Si and P
Acidic fluxes – Li2B4O7, Na2B4O7, K2S2O7, B2O3
for dissolving basic oxides of Group I and II metals,
lanthanides and Al
Then dissolve in diluted acid solution.
Disadvantages of fusions:
Large concentration of flux contamination
Loss of volatile substances
Large salt content in solution when dissolved
ASHING
Heating of a substance to leave only noncombustible ash, which is analyzed
for it's elemental composition.
Problem: loss of volatile species
Wet Ashing
Wet ashing is similar to acid digestion. An organic compound is decomposed
by boiling in oxidizing acid or mixture of acids.
e.g. H2SO4 + HNO3
HClO4 + HNO3
Dry Ashing
Destroying the combustible (organic) portion of the sample by thermal
decomposition using a muffle furnace.
Typical ashing temperatures are 450 to 550 °C.
Charring the sample prior to muffling is preferred. Charring is
accomplished using an open flame.
The solid residue is then dissolved and analysed.
Sample Types: Determination of Pb,
Zn, & Al in Organic Materials
