EXPERIMENT 7

ANALYSIS OF CHLORPYRIFOS IN WATER BY

SOLID-PHASE EXTRACTION (SPE) AND GAS
CHROMATOGRAPHY-ELECTRON CAPTURE
DETECTOR (GC-ECD)

NAME

: MOHD IQBAL BIN NORAZMAN

STUDENT ID

: 2015840192

GROUP

: AS2452s

PARTNERS NAME

: 1. AKMAL ARSYAD BIN MOHD. RAFFI

2. MUHAMMAD RAHIMI BIN ZAHURI
3. SYARAFUDDIN BIN MOHD SHAMSIBY

DATE OF EXPERIMENT :
DATE OF SUBMISSION

Introduction
Chlorpyrifos is one of about 100 organophosphate (OP) insecticides. This complex pesticide
works by attacking and interrupting the nerve processes of insects and animals. Chlorpyrifos has
an advantage over other products in that it is effective against a wide range of plant-eating insect
pests. As the chemical builds up in the body, it eventually leads to the paralysis and death of the
animal or insect. This is why these types of chemicals are used in agriculture as pesticides. They
are extremely effective and can be highly toxic to humans in high enough doses. In this
experiment, solid-phase extraction (SPE) is used as the extraction method that uses solid and
liquid phase to isolate analyte from the solution.It is selective and rapid sample prepation. The
main purpose of using SPE is to purify, solvent exchange and derivatization. The general method
in using the SPE is the loading of the solution through the SPE phase, wash away the undesired
components, and wash off the desired analytes with other solvent into the collection tube. Steps
of SPE are from column solvation and equilibrium, interferences, sample loading, and the
analyte elution. The objective of this experiment is to calculate the amount of chlorpyrifos and
each waste water sample and also the percentage of recovery.

Method
Instrument used in this experiment was Gas chromatograph (Agilent Technologies 6890N)
equipped with an electron capture detector (ECD) and a 30m x 250m x 0.25m HP5-MS
capillary column. In solid-phase extraction, the water sample was filtered through a glass fiber
filter paper.10mL of methanol was passed through the C 18 SPE cartridge to activate the column.
6mL of deionized water was then passed through the cartridge without applying the vacuum to
remove the excess solvent prior to add the sample. The filtered water sample (50mL) was then
passed through the preconditioned column using a vacuum manifold at about 48-55 drops/min.
The column was not let dry during the sample enrichment step. The column was dried using the
vacuum for 15 minutes. The interference was removed by eluting the column with 10mL of
deionized water and the column was dry again using vacuum for 30 minutes. The pesticide was
eluted by using 5mL of hexane and then was concentrated into about 1mL by gently blowing
with nitrogen. The instrument was set up by the injector temperature was 280 C. The detector
temperature was 300 C and its carrier gas flow rate was 20mL min -1,

while its column

temperature in initial was 165 C for 3 minutes and increase to 260C at 3C min -1 with final
time of 2 minutes. In quanitative analysis of chlorpyrifos,1L of sample was injected onto the
column and to get the reproducible peak, the injection was repeated for each sample. 1L of
standard chlorpyrifos (30ppm) was injected and the injection was repeated to get the
reproducible peak area. By using the data from the standard solution of chlorpyrifos, the
concentration of chlorpyrifos in the samples were calculated.

Result and Calculations

A. Comparison in retention time of standard and samples:
Retention Time of

Sample

Standard (ppm)

Average retention

Sample

time of Sample (min)

Trial 1
6.833
6.832
6.833

1
2
3

6.818

Retention Time of
Trial 2
6.833
6.833
6.833

6.833
6.833
6.833

B. Calculation of Response Factor for standard component:

Response Factor (RF) =

Amount
Peak Area

30
629568

= 4.765 x 10-5 ppm/Hz*s

C. Amount of chlorpyrifos in samples:
Amount of chlorpyrifos in sample = RF standard x peak area sample

Sample

Area (Hz)

Average area

Amount of

(Hz)

chlorpyrifos
(ppm)

1
2
3

Trial 1
228388
403376
392907

Average amount of chlorpyrifos =

Trial 2
211022
393355
395050

10.47+ 18.98+18.77
3

D. Percentage of recovery of samples:

219705
398365.5
393978.5

= 16.07 ppm

10.47
18.98
18.77

Percentage recovery =

Amount of chlorpyrifos
x 100
Amount of chlorpyrifos

Amount of chlorpyrifos in standard = 30 ppm

Sample
1
2
3

Amount of chlorpyrifos in
sample (ppm)
10.47
18.98
18.77

Average percentage recovery of sample =

=

34.90+ 63.27+62.57
3

= 53.58%

Discussion

Percentage recovery (%)

34.90
63.27
62.57

In this analysis, the amount of chlorpyrifos in the water samples was calculated using the
response factor calculation which is based on the standard compound. By comparing each of the
samples, the amount of chlorpyrifos that contained in each samples is quite the same for sample
2 and 3 which are 18.98ppm and 18.77ppm respectively. However, for sample 1, the amount of
chlorpyrifos is quite different compared to sample 2 and 3 which is 10.47ppm. There were
differences between the results because of certain error that involved during the experiment such
as the different in the rate of the filtered water pass through the preconditioned column. Besides,
there error might occur due to presence of some of interference that interfere the column. By
calculating the average amount of chlorpyrifos in the sample, the result obtained was 16.07ppm
which is about half from the amount of the chlorpyrifos in the standard. The average percentage
recovery calculated is 53.58%. Hence, in order to get a higher percentage of recovery, better
precautions step must be applied during the experiment conducted. The instrument used in this
experiment is Gas Chromatography (GC) with the Electron Capture Detector (ECD) as the
detector. ECD detector was used in this experiment because presence of halogenated group
compound in the chlorpyrifos. ECD can only detects compound which has electronegative
functional group compound at which the detector can only functions if there is the presence of
electrons moving through the detector that can be captured through electron capture ionization.
However, this type of detector involves using radioactive components which can cause negative
effects and may harm the analyst.

Conclusion

As a conclusion, the average amount of chlorpyrifos that contained in the waste water sample is
16.07ppm and the average percentage recovery is 53.58%.

References:

Carlo S, S. G. (2008, October). Analysis of chlorpyrifos in water. Retrieved from ResearchGate

Website: http://www.researchgate.net
Chlorpyrifos. (n.d.). Retrieved from Pubchem Website: www.pubchem.nlmh.nih.gov
Nor'ashikin S, R. T. (2014). Analytical Seperation Methods Laboratory Guide. Selangor: UiTM
Press.