Sampling

p g in analytical
y chemistry
y

Leif Anderson
Department of Chemistry
University of Gothenburg
S
Sampling:
Sampling
li :
Sampling is the basis of a reliable analysis!

Definition of a representative sample:

A sample taken in a way that it contains all
relevant characteristics.

Sampling can be performed in different ways

p g on the type
depending yp of
f sample
p to be analysed.
y
 Smoke machine for
Complex samples the identification
and quantification
S
Sampling
li procedure
d of chemical
compounds in
tobacco smoke
smoke.

To the left is a situation

Sample unit Sub sample illustrated where a
shipment consist of several
Mixed sample units. Sub samples are
taken from each of these
units and mixed . The
mixture is homogenised and
Sub sample
sub samples are taken. This
procedure is repeated and
finally a number of replicates
Further sub sample are taken for analysis.
At each h step
t the
th sampling
li
must be representative in
Replicate
p of order to avoid increasing
uncertainty in the result
result..
sample for
analysis
 Samplin off ssolid
Sampling lid material:

Heterogeneity
H i h has to be
b considered
id d when
h
sampling of solid material. Even if the
sample is grinded and mixed a certain
degree of heterogeneity might persist and
cause error in the result. Examples
p of solid
material are:

• drugs
d ((pills
ill and
d powder)
d )
• minerals
• contaminated soil
• agriculture products (grain, leaves)
S b
Sub-sampling
li might
i ht be
b needed.
d d

Sediment samples from the bottom of the sea.

The sediment is dried and rocks are removed.
Sub samples are taken to minimize the volume
before grinding, sieving and storing in clean vials
prior to analysis.

Sampling from a silo is done when its emptying,

p f
preferable
bl att several
s l occasions.
si s

Abandon
Ab d iindustrial
d i l llandd that
h might
i h b
be
contaminated has to be controlled before
reuse. Several discreet samples are
t k as soil
taken il cores.
 St ti ti l sampling:
Statistical li

As lland
A d normally
ll iis heterogenic,
h t i statistical
t ti ti l
sampling of often performed. This is based on Division in squares
the principle that all substances have the same
likelihood to be present in any sample collected.
Such a sampling can be illustrated by a
contaminated land,, where the contamination
only is found in patches.
A number of aspects have to be considered
like; cost,
cost number of samples and the potential Samples
S l ( ) are
accuracy of the result. As they all are taken from random
interdependent one normally makes a squares and
compromise and random sampling according to randomly within any
square.
practise is performed.
The samples are
merged before
analysis, or analysed
individually.
 Sampling of gases and volatile organics:

Ass itt iss difficult

ff cu t to store
stor gas samples
samp s one
on wish
w sh to
perform in situ analysis, if possible, with a suitable
analytical instrument.
This
h type of f analysis
l is regularly
l l d done to f
follow
ll the
h levels
l l
of CO, CO2, SO2 and nitrous oxides in the atmosphere.

Most organic substances can not be determined in situ

pp in a suitable way,
and hence has to be trapped y, e.g.
g on
active carbon, for later analysis in the laboratory. The
reason for this is to low concentrations as well as
variable
i bl concentrations
i andd one wish
i h to get a temporall
mean concentration.
 S
Sampling
li off gases and
d volatile
l til organics:
i

Data illustrating the decrease in

NO2 emission in England between
1970-2000. The determination of
NO2 was performed with either
diffusion tubes or chemiluminescence

Simple traps for the collection of

volatile organic carbons (VOCs) for
analysis
l i iin th
the laboratory:
l b t
diffusion tube containing Tenax,
tube with active carbon
syringe with C18 absorbent
 Classification of Organic Pollutants

Description Boiling point range Sampling methods

from oC to

Very volatile organic <0 50-100 Adsorption on

compounds (incl. Gases) charcoal

Volatile organic 50-100 240-260 Adsorption on

compounds
p Tenaxa or charcoal

Semi-volatile 240-260 380-400 Adsorption on

organic compounds PUFb or XAD
XAD-22c

a Poly
Poly-(2,6-diphenyl-)-p-phenylenoxide
(2,6 diphenyl ) p phenylenoxide
b Polyurethane foam
c Styrene-divinylbenzene copolymer
 Samplin off liquids
Sampling
Liquids in pipes, canals or rivers have
diff
differentt flow
fl conditions,
diti f
for iinstance
t iis
the flow speed faster in the centre then
laminar flow persist while the flow is
very slow at the edge of a pipe or close
to the canal bank. Huddersfield Narrow Canal

In this slow flowing canal the

turbulence and mixing is restricted
Turbulent flow
and several samples
p should
be taken across.

Sampling in a pipe could be

improved by inserting a bend Point of samplingt
that p
promotes mixing.g
Laminar flo
flow

Liquid flowing in a pipe

 Samplin off liquids
Sampling

Errors caused by inhomogeneity

in the sampling matrix should be
minimal in single phase liquids as
mixing easily is achieved. Hence
a single
g samplep is often
f enough.
g A sample is taken away from the ship in
However, if there is a vertical order to avoid contamination from the hull
gradient, as in the sea or in a (e.g. trace metals, anti fouling paint)
The sample is also taken at ~1 m depth to
200 L barrel
barrel, one can not assume avoidd the
h surface
f film
f l at where
h some non
that the surface has the same volatile organic constituents are concentrated.
composition as further down.
Thus more than one sample has
to be collected to get a
representative picture.
In marine waters there are
many aspects of sampling
When organic substances are of
interest one has to consider very
low concentrations. One
alternative is to concentrate the
substance by in situ extraction.
When studying the exchange of
chemical constituents over the
sediment – water boundary one
need special
p equipment,
q p e.g.
g
benthic chambers where the
concentration evolution is
followed in the overlying water
with time.
Traditionally water
is collected in
sampling bottles
attached to a
rosette system.
y
The rosette is transported into a shelter
Samples for the determination of
different constituents are collected
in suitable containers

CFCs

SF6
 C system
C-system
O2
The oxygen is fixed in the
sample by precipitation
with manganese in basic
solution
Mn2+ + 2 OH- + O2 
2MnO(OH)2(s)
 Manganese oxide hydroxide is dissolved by acid
and the iodide ions are reduced
MnO(OH)2 (s) + 4H3O+ +3I-  Mn2+ + I3- + 7H2O

The I3- ions are determined by titration with thiosulfate ions

2S2O32- + I3- S4O62- + 3I-

The thiosulfate is calibrated against

g a I3- standard.
 The determination of
Dissolved Inorganic Carbon
of Total Alkalinity
and of SF6
Example of results from oceanographic expeditions,
sections across the Arctic Ocean

DIC Oxygen

Silicate

Beringia 2005
Seawater can be sampled other
ways. In discrete sample
bottles, some closed when
i th
going throughh th f
the surface
layer into the water column.
m t m by
Sometimes y divers
r if
f special
p ca
areas are to be sampled.
Reliability of the result:

Random and systematic errors

Precision and accuracy
Validation of analytical method
 Random and systematic errors
Random errors
Random errors depends on
variability that is outside the
control of the analytical chemist,
but that effect the analytical
result As these errors are
result.
random the mean error equals
zero if enough analysis are
performed
performed.
mean
Systematic errors
Systematic errors means that the
result deviate from the correct
with a constant factor or in a
foreseeable way, and the error
will not decrease with number of
analysis. These errors can be
corrected for, by for instance
subtract a blank value.
value
mean
Precision and accuracy

Good precision

Good accuracy
 V lid ti off analytical
Validation l ti l method,
th d linearity
li it

In many analytical
I l i l methods
h d theh Calibration graph
result is relative and relies on the 0.6

comparison of the signal from the 0.5

sample with one from a reference

0.4

Signal
0.3

material. 0.2
0.1

Thi could
This ld b
be a problem
bl if th
the signal
i l 0
0 5 10 15 20 25
is not linear in the concentration Concentration

range
g of the samples.
p
Solution: control the linearity in
the range 50 - 150% of the samples
expected concentration.
concentration
V lid ti off analytical
Validation l ti l method,
th d
stability

When routine analysis are performed often a large number

of samples are measured daily. It is then important to
t t th
test the stability
t bilit of
f reagents
t and
d reference
f solutions
l ti th
thatt
are used. This is done by repeating the analysis with on a
stable sample for at least 48 hours.
hours
Limit of stability

Signal

Time
 I.SS. SW
Example 1: Spectrophotometric
determination of p
pH in seawater.
W

RV
Accuracy is determined by KHI as well as
the p
perturbation off the sample
mp by y the
C

Thermostating
SP
C
addition of the indicator and by the
W
temperature control.
TP
C
Spectrophotometer C No calibration, but stability of indicator
is an issue.
 I 2-  
 log10  - 
tot tot
pH = log10 K HI 

 HI 
 Q  e1 
 log10  
tot
pH tot = log10 K HI 

 2
e  Q  e3

1245.69  Q  0.0069 1 
pH =  38275
.  2.11  10  3   35  S   log 10  
T  2.222 0  0133
. 1Q

where Q=A578/A434
Example 2: Determination of Total Alkalinity (TA) and
Dissolved Inorganic Carbon (DIC) in seawater
seawater.
Accuracy is determined by Certified Reference Material.
Precision is set by the analytical performance, involving a
number of aspects; sample storage, sample volume
precision,
i i ttemperature
t control,
t l glass
l electrode
l t d
performance (TA), gas manifold seal (DIC), etc.
Quality control:
planned activities designed to provide a quality
product.

Quality assurance:
planned
l d activities
ti iti d designed
i d tto ensure th
thatt th
the
quality control activities are being properly
implemented.
implemented

(As defined by the Association of Official Analytical Chemists)

 Q lit control:
Quality t l Q lit assurance:
Quality

Quality
Q lit control
t l address
dd th
the Quality assurance refers to
overarching analytical work of each analytical step in the
the laboratory, including; laboratory,
y, as;;

• selection the person that has

the responsibility
p y of
f quality,
q y, • blank of reagents,
reagents
• see to that the equipment is • verified standard solutions,
calibrated to the expected • test samples,
level
level, • blind samples,
samples
• usage of reference material, • replicates, and
and • control schedule
• Perform intercalibration
studies with international
laboratories.
Known from earlier lectures
Remember that the result of the analytical
y
work is never better that the weakest link!