RECOMMENDED OPERATING PROCEDURES FOR CWC-RELATED
ANALYSIS
Section 2. Sample preparation
Part B. Established methods
Chapter III. Aqueous liquid samples
NAME : NUR SYUHADAH BINTI NOORDIN
Division of the sample and pH measurement
Divide the 30mL of the
original aqueous sample Transfer the 5ml sub-
into sub sample samples into screw-
capped glass vials and
measure the pH
Liquid-liquid extractions
Dichloromethane
Divide into two portion, each
Neutralise the aqueous portion with volume at one-
sample if: to-two (1:2), which is add Aqueous sample
2.5ml dichloromethane
Acidic – use dilute (water-immiscible high purity
Ammonium hydroxide organic solvent) and 5ml
solution aqueous sample.
Alkaline –use dilute
Hydrochloric acid
LLE time taken 2-5 minutes
5ml of the final extract
(combined extract) and dry
the extracts with Anhydrous
Sodium Sulphate (drying
agent) by adding Sulphate
Analyse with GC and GC-MS or if after Or
approx. 2-10 fold concentration
Non-polar solid phase extraction using C18-SPE cartridge (500mg)
The pH of 5ml aqueous
sample is measured and
adjusted to pH 7 with 1M
HCl and 1% v/v NH4OH
solution
Washing with Na2SO4 and elute sub-
sample with ethyl acetate to end volume
of 1ml. If necessary, concentrate the
dried extract (Section 2, Part A, Chapter
II: Concentration)
Conditioned with 2ml 5ml sub-sample pushing to the
of methanol followed absorbent bed using a plastic
with 5ml of clean syringe adjustable to the
At the end, for SPE pH 7 extract is
water cartridge
analysed for non-polar and pH 11
SPE extract for alkaline CWC
related chemicals
Derivatisation without cation exchange
The derivatised sample is analysed for polar CWC-related chemicals such as thiodiglycol and aminoalcohols
0.5 ml Silylation-grade acetonitrile is
Evaporate the aqueous sample Sonicated for 5 minutes to
added to the dry
from neutral, alkaline or another ensure mixing and heated
residue(concentrated from an
sub-sample with volume 1.0ml in at 60 °C for 30 min
extract) in 1ml reaction vial. Then,
each test tube to dryness using
the vial is capped by using a screw
TurboVap II
cap fitted with a Teflon-coated
silicone septum and 50 μl BSTFA
injected from a syringe through the
septum
The resulting solution is
analysed directly by GC or
Samples stored in a closed vial in GC–MS.
a freezer at -20 °C but care must
be taken to exclude moisture,
particularly on rewarming the
vial to ambient temperature.
SCX cation exchange and derivatisation
Cation exchanged between neutral or alkaline liquid–liquid extraction or another subsample of the original aqueous sample with
inorganic cations, alkali and earth alkali metal ions such as Na+, Ca2+, Mg2+, etc…,
Cation-exchanged samples are analysed for polar alkylphosphonic, alkylthiophosphonic acids and benzilic acid.
Cation exchange can also be useful to remove paramagnetic metal ions from aqueous samples. 0.8 ml of the cation-exchanged
sample is diluted with 0.2 ml of deuterated water and transferred into an NMR tube.
The pH of 5ml aqueous sample or Load 3ml of the aqueous
Condition with 300 μl of
extract is measure and must be 7 or sample or extract slowly
higher in order to make the cation high-purity methanol and
2 ml of high-purity water through the adsorbent bed
exchange start Use dilute using a plastic syringe
ammonium hydroxide solution if through the cartridge
adjustable to the cartridge.
the sample is acidic.
pH of the effluent is measure
to determined to test the
completeness of the cation
exchange, which is repeated
if necessary. The sample
must be more acidic
Take 1ml of the
Derivatisation using Methly The rest effluent is effluent and filter
Method with CH2N2 or TMSCHN2/ evaporate to through a disposable
MeOH or TMPAH as reagent. dryness using syringe filter for LC, CE
Refer Section 2, Part A, Chapter TurboVap II and IC analysis.
III: Derivatisation for gas
Chromatography