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Mr. S. D. Joshi Scientist Air Pollution Control Division, NEERI, Nagpur - 440020 Introduction The air besides containing gaseous pollutants like S02, NO x , CO, HC also contains particulate matter which is made up of complex organic compounds, inorganic elements and their oxides and secondary particulates viz, sulphate, nitrate etc. processes. These secondary particulates are formed from their precursors in The acid precursors viz. sulfate and nitrate, and chloride require presence of sunlight humidity and metal ion species by oxidation or reduction more concern as these have deleterious effects on aquatic and forest ecosystems and are potentially harmful for a variety of building materials, accelerate corrosion of metals, damage sculptures and cause chronic respiratory problems in human beings. ambient air. These particulates are emitted in the atmosphere by different in the The Acid In view of possible large social, economic, ecological and aesthetic value, it has become important to analyse these pollutants in the
anthropogenic and natural sources.
Sulphate (SO4-) is formed
atmosphere by reduction or oxidation in presence of hydroxy! ion (OH"). industries, oil refineries, coal burning and domestic use of fuels.
main sources of sulfur oxides are power houses, sulphuric acid, petroleum manufacturing, automobile exhaust, explosive industry, fuel burning etc. are the main sources of nitrogen oxides. Chloride occurs predominantly in coastal cities. Other sources of chloride are coal burning, waste incineration, automobile exhaust, burning of chlorinated hydrocarbons. atmosphere by fertiliser industry, making industries. Fluoride is emitted in the aluminium industry, steel making and acid
Analytical Techniques Different methods are available for the analysis of anions. conventional methods, viz., titrimetric, colorimetric, gravimetric and ion selective electrode The
methods though commonly used, are
ion specific, time consuming and less sensitive. Ion Chromatography (IC) is the only instrumental technique which can be used for rapid, sequential analysis of different anions simultaneously. Ion Chromatography Chromatography encompasses wide range of techniques of separation of the components of a mixture as a result of differential migration of the component molecules between stationary phase and mobile phase. It was Hamish, Small of DOW chemical corporation whose pioneering work in mid seventies in the analysis of multiple -ion mixture developed into, 'Ion Chromatography" Ion chromatograph provides a single instrumental technique for rapid sequential analysis of different anions present in a sample. Ion chromatograph eliminates the need to use hazardous reagents and it effectively distinguishes among the 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.
Several approaches have been initiated to solve the problem of separation and detection of ions either independently or in integrated fashion. Three major approaches are:
i) ii) iii)
suppressed ion chromatography non-suppressed ion chromatography and indirect detection ion chromatography
Suppressed Ion chromatography In the group of separation techniques employing ionic interactions ion exchange is the oldest one. The separation is carried out with the packing that possess charge bearing functional groups. The most common with the charged groups R of the stationary phase. X" + R + Y _ X + + R"Y + Y" + R + X" Y + + R"X + anion exchange cation exchange retention mechanism is simple ion exchange of sample ions X and mobile phase ion Y
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. Conductivity being universal property of ionic species in solution, showing simple dependence on the concentration of ions, has been considered to solved detection problem since long. However, in ion exchange separation conductivity response is masked by the mobile phase electrolyte. This problem was tackled by employing a novel combination of ion exchange columns to remove the background electrolyte leaving only the ionic solute of interest as conducting species in the column effluent.
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. To optimise the regeneration and chromatographic are adjusted. efficiency of
conventional suppressor column, the relative volumes and specific ion exchange capacities of separator and stripper columns For good chromatographic efficiency volume ratio of stripper and separator column is kept
low unity being desirable but values upto 10 acceptable.
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 Automatic - regeneration feature in commercial instruments conventional high capacity suppresser column for 8 to 10 hours without requiring regeneration. 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.
Non Suppressed Ion Chromatography The ion chromatographic systems with suppresser columns are generally dedicated and relatively costly. Analysis by non-suppressed systems depends on existence of a significant measurable difference between sample ions and the prevailing eiuent ions. For improving sensitivity low capacity exchanges and proper displacing ions are required. Low capacity exchanger match the low ionic strength eiuent employed, which enable detection of small amounts of samples and proper displacing ions can display a useful difference in equivalent conductance in comparison with common inorganic ions. Low capacity micro porous anion exchange resin also have been developed for the separation of inorganic anions. The resins used macro reticular cross-linked polystyrene beads as substrate. The conductivity detector used for this method requires a large electronic offset range for nulling the background conductivity of the eiuent and small cell currents to minimise heat dissipation in the cell and resulting baseline drift and noise. This detector given best results when used with low background conductivity of the eiuent and fine temperature stability.
Indirect Detection Ion Chromatography Many inorganic ions display strong absorbance in UV region but at wavelengths that were previously inaccessible to liquid chromatography photometers. With the development of UV detectors that reach down to 190 nm. These ions are easily amenable to sensitive monitoring and determination. Direct
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. Recently the method of indirect detection is gaining applications.
Generally in ion exchange or ion pair separation ultraviolet detector is used in conjunction with mobile phases with very low absorbance at the monitoring wavelength. The sample contains the chromospheres and when they elute and pass through the detector, absorption of light takes place and positive peak is recorded. Generally low capacity ion exchange columns are employed as separators and an aqueous solutions of potassium hydrogen phthalate (10~4 to 10" 3 M) as mobile phase. This salt gives suitable absorption at the wavelength 265 mm. The choice of the mobile phase and its strength is decided by the anions of interest and analysis time. 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. determination of chloride and fluoride. For example relatively high interfere with the concentrations of low molecular weight organic acids
Sample dilution over comes many
Spurious peaks may result from contaminants in reagent water,
glassware or sample processing apparatus. Minimum Detectable Limit The minimum detectable concentration of an anion is a function of sample size and conductivity scale used. Generally, minimum detectable concentrations 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 and a 10 pS/cm full scale setting on the conductivity detector. Air Monitoring/Sampling Collection 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. While for respirable suspended particulate matter, respirable dust sampler is used. flow rate. Preparation of Sample Filter 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. Calibration of Sampling System Each sampler is to be calibrated i) when new ii) after major repairs or maintenance iii) whenever any audit point deviates from the calibration curve by more than 7% iv) when a different sample collection media, other than that which the sampler was originally calibrate to will be used for sampling, v) before and after each test series. This sampler can be adapted with an optional PM-10 aerodynamic aerosol inlet cut-point design which is insensitive to small variations in sampling
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 refrigerated at 4°C. At least on field filter should be returned to the laboratory with each group of samples. A field blank is treated exactly as a sample except that no air is drawn throughout the filter. Analysis Reagents : Deionised or distilled water free from minimum detection limit of each constituent. Eluant Solution : Eluant solution is a mixture of 1.7 mm sodium bicarbonate and 1.8 mm Sodium Carbonate. interferences at the
Regenerant Solution Regenerant solution is all glass double distilled water for continous regeneration. Standard Anion Solution Prepare a series of standard anion solutions by weighing the inducted amount of salt, dried to a constant weight at 105°C to 1000 ml. Store in plastic bottles in a refrigerator. These solutions are stable for at least one month. Verify stability.
Combine Working Standard Solution Prepare a combined working standard solution by mixing appropriate quantity of stock solution and store in plastic bottle protected from light. Prepare fresh daily. Ultrasonic Extraction Method The extraction of anions is carried out by ultrasonic compact cleaner model SW 45 (Toshniwal). The tank volume of extractor is 4.5 lits. It has a
sonifer cell disrupter .40 KHz power ultrasonic generator capable of dialing 150/130 w accurately with 127 cm horn distrupter sonabox. 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 Prepare standards of different concentration by mixing known volume of different ions. Inject standards containing single anion or a mixture and determine approximate retention time. Inject atleast three different concentrations for each anion to be measured and construct a calibration curve by plotting peak height or area against concentration on linear graph paper. Recalibrate whenever detector setting is changed. Record the peak height or area and retention time for calculation of the calibration factor CF. Total area of peak Calibration Factor CF = Mass injected (in microgram)
if the percent relative standard deviation (% RSD) of the calibration factor is less than 20% over the working range, linearity through the origin can be assumed, and average calibration factor can be used in place of a calibration curve. The working calibration curve or calibration factor must be verified on each working day by the injection of one or more calibration standards. If the response factor for any analyte varies from the predicted response by more than + 20% a new calibration curve must be prepared for that analyte. Calculate the percent variance by the following equationPercent variance = [(R 2 -Ri)/R<|] X 100 Before analysis can be performed the retention time windows must be established for each analyte. Make three injections of the standard containing all compounds for retention time window determination. The retention time window is defined as the plus or minus three times the standard deviation of the absolute retention times for each standard. 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.
Ion Chromatography with Conductivity Detector Under the calibration procedures (external)the % RSD of the calibration factor should be <20% over the linear working range of a five point calibration curve. Under the calibration procedures (external) daily working calibration curve for each analyte should not vary from the predicted response by more than + 20%.
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 The stock standard solutions were prepared by adding exactly weighed known amount of compound to a one litre volumetric flask and voiume was made up by deionised water. A series of different concentrations of standards were prepared by diluting stock standard solution. 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.
Range and Sensitivity 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. Precision and Accuracy 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 nitrate 98.0 and for fluoride 95.0. Similarly the exposed filter papers were also spiked by known
concentration of anions. The RSD for 2 ultrasonic extract for sulphate was 1.44 for nitrate 5.8 for chloride 5.2 & for fluoride 5.5. The percentage recovery for SO4 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 concentration = (ug/m 3 ) peak height of sample (cm) X peak height of standard (cm) concentration Volumeof of standard (ug) X sample X Total area of filter paper(cm 2 ) X Area taken for extraction(cm 2 ) 1
volume of air (m 3 )
Anions Separation in Rain Water Sample by Ion-chromatograph
C a t i o n s S e p a r a t i o n in Rain Water Sample by lon-'chromasograph
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