EXPERIMENT 7: MEASUREMENT OF TRACE METALS IN WATER, TOBACCO AND CIGARETTE ASH BY INDUCTIVELY-COUPLED PLASMA ATOMIC EMISSION SPECTROSCOPY (ICP-AES)

OBJECTIVES From the experiment, we are able: 1. to analyze trace metals present in cigarette tobacco, the cigarette filter, and the ash obtained when the cigarette is burned. 2. to learn the uses of inductively-coupled plasma atomic emission spectroscopy (ICP-AES).

INTRODUCTION Inductively-coupled plasma atomic emission spectroscopy (ICP-AES) and Inductively coupled plasma mass spectrometry (ICP-MS) are techniques well suited for the determination of trace elements in water samples, as the low levels of most elements in these samples eliminates the use of other, less sensitive, analytical techniques. It is a type of emission spectroscopy that uses the inductively coupled plasma to produce excited atoms and ions that emit electromagnetic radiation at wavelengths characteristic of a particular element. The intensity of this emission is indicative of the concentration of the element within the sample. The ICP-AES is composed of two parts, the ICP and the optical spectrometer. Components of ICP typically include sample introduction system (nebulizer), ICP torch, high frequency generator, transfer optics and spectrometer, also computer interface. ICP-AES is often used for analysis of trace elements in soil, and for that reason it is often used in forensics to ascertain the origin of soil samples found at crime scenes or on victims by taking one sample from a control and determining the metal composition and taking the sample obtained from evidence and determine that metal composition allows a comparison to be made.

Advantages of using the ICP is including its ability to identify and quantify all elements; since many wavelengths of varied sensitivity are available from ultratrace levels to major components; detection limits are generally low for most elements with a typical range of 1 - 100 g / L. Probably the largest advantage of employing ICP when performing quantitative analysis is the fact that multi-elemental analysis can be accomplished, and quite rapidly. A complete multielemental analysis can be undertaken in a period as short as 30 seconds, consuming only 0.5 ml of sample solution. Although in theory, all elements except Argon can be determined using and ICP, certain unstable elements require special facilities for handling the radioactive fume of the plasma. Also, ICP has difficulty handling halogens--special optics for the transmission of the very short wavelengths become necessary. Determination of any one element, the ICP is suitable for all type of concentrations. The most important advantages of ICP-MS include multi-element capability, high sensitivity, and the possibility to obtain isotopic information on the elements determined. Disadvantages inherent to the ICP-MS system include the isobaric interferences produced by polyatomic species arising from the plasma gas and the atmosphere. The isotopes of argon, oxygen, nitrogen, and hydrogen can combine with themselves or with other elements to produce isobaric interferences.

CHEMICAL Camel cigarette 15.9M HNO3 19M NaOH 40-50mL of ice Deionized water

APPARATUS ICP-AES Syringe Mortar and pestle Stir rod Beaker pH paper Fritted glass and acrodic

METHODOLOGY Tobacco preparation: The camel cigarette was weighed with its outer wrap. To continue with the preparation of tobacco, the outer wrap was removed and tobacco was grind with mortar and pestle. After enough grinding, tobacco was dissolved in 15 mL of concentrated 15.9M HNO3. While dissolving, tobacco mixture was mash-up with stirring rod until the tobacco was properly dissolved. Tobacco mixture was then placed in 40-50mL of ice to give a low temperature condition for reaction with dropwise addition of 19M NaOH. Addition of NaOH was continued until the pH of solution was reaching pH 2. Solution was then diluted to 20 times by diluting 5mL of mixture to 100mL. Before taking the sample for analysis using the ICP-AES, further filtration was done on the sample solution. These steps were continued on preparation of solution with the pH of 11. Ash preparation: To prepare ash, cigarette was lighted and the ash was collected in a beaker. The weight of ash was taken and dissolved in 5 mL of HNO3. NaOH was added to the mixture until the pH of the mixture was reaching 2-3. This step was done by monitoring the change in pH by using pH paper. The sample was then prepared for ICP-AES analysis by filtering with fritted glass and acrodic. Blank solution: Blank solution for the tobacco preparation and ash preparation experiments was prepared by adding the same chemicals without dissolving tobacco and ash. The step for preparing tobacco and ash was repeated to the blank solution without adding tobacco and ash.

RESULTS A) Standards

B) Samples Camel cigarette tobacco at pH 2 Elements As Sb Zn Co Se Fe Cr Cu Concentration (ppm) [Jeremy] -0.00039 -0.00075 0.01690 -0.00015 0.000173 0.026912 0.000234 0.003316 Concentration (ppm) [Fenny] 0.001173 0.000621 0.008584 -0.00014 0.002687 0.044853 0.000255 0.003594 Average X 20 (20 = dilution factor) 0.01173 0.00621 0.25484 ND 0.02860 0.71765 0.00489 0.06910

Camel cigarette tobacco at pH 11 Elements As Sb Zn Co Se Fe Cr Cu Concentration (ppm) [Ain] -0.00076 0.000101 0.003733 -0.00015 0.001810 0.008805 0.000445 0.000793 Concentration (ppm) [Razi] 0.000105 -2.71E-05 0.002329 -0.00021 0.001108 0.010682 0.000264 0.000692 Average X 20 (20 = dilution factor) 0.00105 0.00101 0.06062 ND 0.02918 0.19487 0.00709 0.01485

Camel cigarette tobacco ash Elements As Sb Zn Co Se Fe Cr Cu Concentration (ppm) [Khaliq] 0.000174 -0.00043 0.028860 -7.18E-05 -5.62E-05 0.134739 0.000402 0.010131 Concentration (ppm) [Faezah] -0.00097 0.000204 0.02824 -2.24E-05 -0.00023 0.136729 0.000448 0.010469 Average X 20 (20 = dilution factor) 0.00174 0.00101 0.00204 ND ND 2.71468 0.00850 0.20600

Water samples Elements Concentration (ppm) [Water cooler] As Sb Zn Co Se Fe Cr Cu -3.79E-05 0.000250 0.000149 1.82E-05 0.001281 -0.00052 0.000154 0.000207 Concentration (ppm) [Distilled water] -0.00063 -0.00035 0.000411 -7.84E-05 -0.00034 -0.00066 0.000129 4.63E-05 Concentration (ppm) [Tap water] -0.00015 7.87E-05 0.004675 -0.00015 0.001344 -0.00044 6.95E-05 0.000126 Concentration (ppm) [Drinking water] 0.000171 -0.00042 0.001503 -0.00015 -0.00015 -0.00050 9.30E-05 -8.5E-05

DISCUSSION Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) is one of several techniques available in analytical atomic spectroscopy. Its high specificity, multi-element capability and good detection limits result in the variety of applications. All kinds of dissolved samples can be analyzed, varying from solutions containing high salt concentrations to diluted acids. ICP-AES utilizes plasma as the atomization and excitation source. A plasma source is used to dissociate the sample into its constituent atoms or ions, exciting them to a higher energy level. They return to their ground state by emitting photons of a characteristic wavelength depending on the element present. This light is recorded by an optical spectrometer and when calibrated against standards, the technique provides a quantitative analysis of the original sample. Plasma is an electrically neutral, highly ionized gas that consists of ions, electrons, and atoms. The energy that maintains analytical plasma is derived from an electric or magnetic field. Most analytical plasmas operate with pure argon or helium, which makes combustion impossible. Plasmas are characterized by their temperature, as well as their electron and ion densities, where analytical plasmas typically range in temperature from 600 to 8,000 K. There are six steps involved in the sample detection of ICP-AES; sample preparation, nebulization, desolvation/volatilization, atomization, excitation/emission and separation/detection. Figure 1 summarizes the steps involved in determining the elemental content of an aqueous phase sample by ICP-AES. For sample preparation, some sample requires special preparation step, including treatment with acids, heating or microwave digestion. The next step is nebulization, where the sample which is in liquid is converted to aerosol. Followed by desolvation/volatilization, where water is driven off and the remaining solid and liquid portions are converted to gases. When all the samples are in gaseous state, it is atomized by atomizer, where gas phase bonds are broken leaving only atoms in here. At this stage, plasma temperature and inert chemical environment are important. The atoms present then are gaining energy from collisions, thus excited from the low energy level to higher energy level, emitting the light of a characteristic wavelength. Lastly, grating dispersers light is quantitatively measured by a detector. In ICPAES, air or nitrogen is not use as the carrier gas in an ICP-AES, but Argon. Argon is used here because of 0.9% of the earths atmosphere, so it is readily available. N2 emits several molecular

bands in the ultraviolet and visible, so overlaps with analytical lines are possible which might interfere with the results.

Figure 1: steps involved in the analysis of aqueous samples by ICP-AES The typical limits of detection obtained with ICP-AES are for over 70 elements. The units are in parts per billion (ng mL-1 or g L-1). Inert gases and some prominent nonmetals (C, N, O, and H) are not analyzed by ICP-AES, but most of the nonmetals for example P, S, and halogens have strong emission lines that are in the vacuum ultraviolet. As more instruments come equipped with UV/Vis capabilities, analysis of nonmetals by ICP-AES will expand. In this experiment, we used ICP-AES to measure trace metals in cigarette tobacco at pH 2 and pH 11, cigarette ash and four types of water sample which are water cooler, distilled water, tap water and drinking water. For the standard solution, the calibration curve for each trace metal is linear. For cigarette tobacco at pH 2, the highest element that is contained in it is iron (Fe) which the value is 0.71765. For cigarette tobacco at pH 11, iron (Fe) also the highest element determined, which the value is 0.19487. From the data, we could see that most of the

elements in acidic pH are in higher concentration than the alkaline. It could be the reason of in acidic condition; these trace metal elements are easily dissolved. Thus the concentrations of these metal ions are higher. Most of heavy metals are likely preferred to dissociate in acidic solution, thus which is the reason why in pH 2, the concentration for each trace elements are higher. Same with both cigarette tobacco at pH 2 and 11, element that contains the most in cigarette ash is iron (Fe) and its value is 2.71468. Among three of these samples, the highest amount of Fe found is cigarette ash. The amount of element in the cigarette depends on cigarette brand because of different brand contains different amount of element in it. So, for Camel brand, the results show that iron (Fe) has the highest amount in it. Furthermore, in cigarette, the amount of heavy metals presence are vary, as we know that cigarette is one of dangerous kind of thing to human as it contains a lot of carcinogenic and toxic substances. For water sample, there is not much to compare between the elements contained in each sample. For water cooler, an element that contains the most is Selenium (Se) which the value is 0.001281 and for distilled water, tap water and drinking water, they have the same element that contains the most in them which is Zinc (Zn). Their values are 0.000411, 0.004675 and 0.001503. In water sample, the trace elements could be presence from the waste from industrial factory, or from water pollutants. But the concentration is not much higher compared to the tobacco, and especially the cigarette ash as the tobacco which being burned in the presence of oxygen will have some chemical reaction that will forming other substances, making the concentration become higher.

CONCLUSION The most abundance trace metal element in cigarette ash and tobacco sample is Fe ion, with 0.71765 for pH 2 tobacco, 0.19487 for the pH 11 tobacco and 2.71468 for cigarette ash. While for water samples, each of the race metal is present in a small concentration.

QUESTIONS 1. Why can you measure many elements simultaneously with ICP-AES but typically only one at time with AA? ICP-AES is able to measure many elements simultaneously since all of the elements are emitting at once in the plasma compared to AA. With AA, we have to use a lamp which was specific for the particular element of interest. In addition, the sensitivity of ICP-AES is generally greater than AA.

2. ICP-AES is generally more sensitive than AA, i.e. has lower detection limits for most elements. Explain why this is might be expected, based on how the two technique work. Think about what signals you are actually measuring to obtain the concentrations. Each run of a set of samples must be accompanied by a set of known standards. Only by drawing a calibration curve plotting the emitted intensities from these standards versus their known concentrations can the emitted intensities from the unknown samples be converted to a meaningful concentration value. ICP-AES is used to determine levels in the parts per million and higher. It is easier to detect a small signal in the absence of background (emission), than a small change in signal in the presence of a large background signal (absorption). This is why emission techniques are more sensitive than absorption techniques.

3. Compare your results for the acid and basic tobacco samples. Is there any difference? Why might this be the case? There is a bit different between the acid and basic tobacco samples, where the concentration of each trace metal is higher in acidic condition compared to the basic. It is because most of the heavy metal is easily dissolves and dissociates in acidic solution rather than the basic. The metal then dissociates to become ion and easily detected by ICP-AES. Most of the heavy metal like Fe, As, Sb, Co, Cu and Cr is reactive in acidic solution. Thus, it results to the higher concentration in acidic solution than the basic solution.

4. You will see that some elements such as Arsenic have quite high background signal with Millipore water alone, while the other elements have much smaller signals. a) Comment on why this might be the case The applicability of ICP emission spectrometry to various elements is different. The detection limit for the best line for each of the element is indicated by the colour and degree of shading. The area of shading indicates the number of line for each element that yields a detection limit within a factor of 3 of the best line. The more such lines that are available, the greater the chance that a usable line can be found that is free from interference when the matrix yield a line-rich spectrum. Arsenic, in comparison to the other element have detection limit of 100-300 (ng/mL) and 3-6 detection lines. Arsenic yields a detection limit within a factor of 3 and it found free from interference. These causes the Arsenic have quite high background signal compare to other elements. b) The detection limits typically cited for As, Se and Sb are about an order of magnitude worse than for the other elements and much worse for Cr. Why would this be the case? (hint: look at the blank counts and at the wavelengths used). For all three As, Se and Sb their number of lines for detection limit are in the 3-6 range. However, for Cr, its detection limit is in the range of 7-10. Other elements, such as Fe have 1116 number of lines, thus, it detects better than As, Sb and Se. As for Cr, although the numbers of lines are 7-10, but, its detection limit is below than 10. Element Sb Se As Cr Wavelength 206.836 196.026 188.979 267.716

REFERENCES Tyler, G. 1992. AA or ICP - which do you choose? Chemistry in Australia. Vol. 59 (4). 150-152 pp. Olesik, J. 1991. Elemental Analysis Using ICP-AES and ICP-MS. Anal. Chem. Vol. 63 (1). 12A-21A pp. Manning, T. J. and Grow, W. R. 1997. Inductively Coupled Plasma-Atomic Emission Spectrometry. The Chemical Educator. Vol. 2 (1). 1-19 pp. Holler, F. J., Skoog, D. A., Crouch, S. R. 2007. Principles of Instrumental Analysis. 6th Edition. Thomson Higher Education: Belmont, Canada. 267-269 pp.