Академический Документы
Профессиональный Документы
Культура Документы
Mr. S. D. Joshi
Scientist
Introduction
The air besides containing gaseous pollutants like S02, NO x , CO, HC also
Ion Chromatography
halides (Cr,F~) and the oxides (NO3", SO4"). For ambient air monitoring, IC is
the most suitable technique though it is expensive. The anions SO4", NO3", CI",
F" are being monitored in ambient air using IC 2000i/SP and DX-100 models
under NAQM project, NEERI.
For anion exchange separation the sample ions X" are in competition with
the mobile phase ions Y" for the ionic sites R+ of the ion exchanger. Sample ions
that interact weakly with the ion exchanger, in the presence of competing mobile
phase ion will be retained on the column for a shorter duration whereas sample
ion interacting strongly to with the ion exchanger will be retained for larger.
The second column called the stripper or the suppresser complicates the
use of ion chromatography. The stripper column needs periodic regeneration
and furthermore ion exclusion effects and some band broadening in the
suppresser column deteriorates the analysis.
iii
low unity being desirable but values upto 10 acceptable. Regeneration
requirements are minimised by using low capacity pellicular particles or surface
modified resins in separating columns, low ionic strength mobile phase, small
sample size and conventional high capacity porous ion exchange resin in the
stripper. Typical low capacity separator column can be used alongwith
conventional high capacity suppresser column for 8 to 10 hours without requiring
regeneration. Automatic - regeneration feature in commercial instruments
further simplify the analysis. However suppresor should not react with the
sample ions in a way that would remove them from the eluant or reduce their
conductivities or retain them permanently undergoing irreversible changes.
iv
UV absorbance has been coupled with several separation modes for variety of
samples. However, the major drawback of these methods is the low sensitivity
even after employing high purity solutes to minimise background absorbance.
The sample contains the chromospheres and when they elute and pass
through the detector, absorption of light takes place and positive peak is
recorded.
A large number of organic and and inorganic ions have been studied by
this technique. Analogous schemes for cation analysis have also been reported.
Simultaneous analysis of anions and cations in a single chromatogram also can
be done by this system.
Refractive index detector also has been used in this indirect mode. Both
UV & Rl methods are more sensitive than conductivity detection and they give
less baseline noise.
Interference : Any substance that has retention time coinciding with that
of any anion to be determined will interference. For example relatively high
concentrations of low molecular weight organic acids interfere with the
determination of chloride and fluoride. Sample dilution over comes many
interferences. Spurious peaks may result from contaminants in reagent water,
glassware or sample processing apparatus.
are near 0.1 mg/l for Br, CI", NO3-, N0 2 ", P 0 4 3 " and S 0 4 2 " with a 25 pi loop
For ambient air anion sampling and analytical technique being used for
these pollutants require a large volume of air to be sampled in order to reach
needed detections limits. This has been accomplished utilising the high volume
(1400 Ipm) air sampler for the collection of total suspended particulate matter.
The filter papers are dried in desiccators for hours before, use. To ensure
acceptable filters, they are extracted with water and extracts are analysed by ion
chromatography. A filter blank of less than 0.1 pg per filter is considered
acceptable for field use.
vi
Construct a best fit curve for the points generated and use this relationship
for future work employing the flow sensor device.
Sample Retrieval
At the end of the desired sampling period the power is turned off.
Carefully remove the sampling head containing the filter. Remove filter from the
upper chamber using clean, teflon tipped forceps. Fold the filter in half twice
(Sampled side inward) and place it in an labeled envelope. These filters should
stored in dessicator containing dry silica gel. If the time span between sample
collection and laboratory analysis is to exceed 24 hour samples must be kept
Analysis
Regenerant Solution
vii
Combine Working Standard Solution
From the exposed filter paper 18 circles of 1.5 cm diameter each were
taken by punching with steel punch (area 31.8 cm 2 ) in a clean 100 ml beaker. To
these circles 20 ml deionised water was added and extracted for 5 min in
ultrasonicator. The extract was vacuum filtered with the help of G4 sintered glass
crucible in a clean plastic bottle. Again 20 ml water was added and extraction
was done for 10 min. The filtrate was collected in same bottle. The extraction
procedure was repeated third time for 15 minutes. The extracted samples were
stored in fridge till analysis.
Calibration Curve
System Equillibration
Turn on ion chromatograph and adjust eluant flow rate. Adjust detector to
desired setting and let system come to equilibrium (20 to 30 min). A stable
baseline indicates equilibrium conditions. Adjust detector offset to zero out eluant
conductivity; with fibre or membrane suppressor adjust the regeneration flow rate
to maintain stability usually 2 to 3 mL/min.
ix
For each analyte the retention time window must be established, verified
on a daily basis and established for each analyte throughout the course of a 72
hour period.
For each analyte the mid level standard must fall within the retention time
window on a daily basis as a qualitative performance evaluation of the IC system.
The surrogate standard recovery must not deviate by more than 20%.
Calibration
Retention Time
The retention time is the time required for complete elution of a component
from the point of injection of sample. The retention time windows for each analyst
was determined. The retention time window is defined as plus or minus three
times the standard deviation of the absolute retention times for each standard.
The minimum detectable limit for chloride ion at sensitivity 100 is 2.44 pg.
The minimum detectable concentration of chloride ion for particulates collected
on one glass fiber filter of approximately 400 cm 2 is 0.064 pg if 480 m3 of air are
sampled in the ambient atmosphere. The minimum detectable limit for SO4 is
3 pg for fluoride 0.4 pg and for nitrate 0.5 pg at sensitivity 100 on 2000 i/SP
Dionex ion chromatograph.
The blank fiber filter paper was spiked by known concentration of anions
and extracted ultrasonically. The relative standard deviation (RSD) for 3
ultrasonic extract for SO4 was ±1.35. For nitrate 5.54% for chloride 4.23% and for
fluoride 4.5%. The percentage recovery for SO4 is 98.02 for chloride 97.4, for
is 97.01 for chloride 95.2 for nitrate 95 and for fluoride 90.58%.
Calculations
The concentration of different ions is calculated in ug/m 3
xi
F
SAMPLE