2Atomic Emission Spectroscopy Atomic emission spectroscopy (AES), in contrast to AAS, uses the very high temperatures of atomization sources to excite atoms, thus excluding the need for lamp sources. Emission sources, which are routinely used in AES, include plasma, arcs and sparks, as well as flames. We will study the different types of emission sources, their operational principles, features, and operational characteristics. Finally, instrumental designs and applications of emission methods will be discussed.
3Plasma SourcesThe term “plasma” is defined as a homogeneous mixture of gaseous atoms, ions and electrons at very high temperatures. Two types of plasma atomic emission sources are frequently used:Inductively coupled plasmaDirect current plasma
5Inductively Coupled Plasma (ICP) A typical ICP consists of three concentric quartz tubes through which streams of argon gas flow at a rate in the range from 5-20 L/min. The outer tube is about 2.5 cm in diameter and the top of this tube is surrounded by a radiofrequency powered induction coil producing a power of about 2 kW at a frequency in the range from MHz. This coil produces a strong magnetic field as well.
6Ionization of flowing argon is achieved by a spark where ionized argon interacts with the strong magnetic field and is thus forced to move within the vicinity of the induction coil at a very high speed. A very high temperature is obtained as a result of the very high resistance experienced by circulating argon (ohmic heating). The top of the quartz tube will experience very high temperatures and should, therefore, be isolated and cooled.
7This can be accomplished by passing argon tangentially around the walls of the tube. A schematic of an ICP (usually called a torch plasma) is shown below:
13The viewing region used in elemental analysis is usually about 6000 oC, which is about cm above the top of the tube. It should also be indicated that argon consumption is relatively high which makes the running cost of the ICP torch high as well. Argon is a unique inert gas for plasma torches since it has few emission lines. This decreases possibility of interferences with other analyte lines.
14Sample IntroductionThere are several methods for sample introduction; the most widely used is, of course, the nebulization of an analyte solution into the plasma. However, other methods, as described earlier, are fine where vapors of analyte molecules or atom from electrothermal or ablation devices can be driven into the torch for complete atomization and excitation. For your convenience, sample introduction methods are summarized here again:
15Samples in Solution 1. Pneumatic Nebulizers Samples in solution are usually easily introduced into the atomizer by a simple nebulization, aspiration, process. Nebulization converts the solution into an aerosol of very fine droplets using a jet of compressed gas. The flow of gas carries the aerosol droplets to the atomization chamber or region.
16Ultrasonic Nebulizers In this case samples are pumped onto the surface of a piezoelectric crystal that vibrates in the kHz to MHz range. Such vibrations convert samples into homogeneous aerosols that can be driven into atomizers. Ultrasonic nebulization is preferred over pneumatic nebulization since finer droplets and more homogeneous aerosols are usually achieved. However, most instruments use pneumatic nebulization for convenience.
17Electrothermal Vaporization An accurately measured quantity of sample (few mL) is introduced into an electrically heated cylindrical chamber through which an inert gas flows. Usually, the cylinder is made of pyrolytic carbon but tungsten cylinders are now available. The vapors of molecules and atoms are swept into the plasma source for complete atomization and excitation.
18Hydride Generation Techniques Samples that contain arsenic, antimony, tin, selenium, bismuth, and lead can be vaporized by converting them to volatile hydrides by addition of sodium borohydride. Volatile hydrides are then swept into the plasma by a stream of an inert gas.
20Introduction of Solid Samples A variety of techniques were used to introduce solid samples into atomizers. These include:1. Conductive SamplesIf the sample is conductive and is of a shape that can be directly used as an electrode (like a piece of metal or coin), that would be the choice for sample introduction in arc and spark techniques. Otherwise, powdered solid samples are mixed with fine graphite and made into a paste. Upon drying, this solid composite can be used as an electrode. The discharge caused by arcs and sparks interacts with the surface of the solid sample creating a plume of very fine particulates and atoms that are swept into the plasma by argon flow.
21Laser AblationSufficient energy from a focused intense laser will interact with the surface of samples (in a similar manner like arcs and sparks) resulting in ablation. The vapors of molecules and atoms are swept into the plasma source for complete atomization and excitation. Laser ablation is becoming increasingly used since it is applicable to conductive and nonconductive samples.
22The Glow Discharge Technique The technique is used for sample introduction and atomization as well. The electrodes are kept at a 250 to 1000 V DC. This high potential is sufficient to cause ionization of argon, which will be accelerated to the cathode where the sample is introduced. Collision of the fast moving energetic argon ions with the sample (cathode) causes atomization by a process called sputtering. Samples should thus be conductive to use the technique of glow discharge. The vapors of molecules and atoms are swept into the plasma source for complete atomization and excitation by flowing argon. However, nonconductive samples were reported to be atomized by this technique where they were mixed with a conductor material like graphite or powdered copper.
23Plasma Appearance and Spectra A plasma torch looks very much like a flame but with a very intense nontransparent brilliant white color at the core (less than 1 cm above the top). In the region from 1-3 cm above the top of the tube, the plasma becomes transparent. The temperatures used are at least two to three orders of magnitude higher than that achieved by flames which may suggest efficient atomization and fewer chemical interferences.
24Ionization in plasma may be thought to be a problem due to the very high temperatures, but fortunately the large electron flux from the ionization of argon will suppress ionization of all species.
25The Direct Current Plasma (DCP) The DCP is composed of three electrodes arranged in an inverted Y configuration. A tungsten cathode resides at the top arm of the inverted Y while the lower two arms are occupied by two graphite anodes. Argon flows from the two anode blocks and plasma is obtained by momentarily bringing the cathode in contact with the anodes. Argon ionizes and a high current passes through the cathode and anodes.
26It is this current which ionizes more argon and sustains the current indefinitely. Samples are aspirated into the vicinity of the electrodes (at the center of the inverted Y) where the temperature is about 5000 oC. DCP sources usually have fewer lines than ICP sources, require less argon/hour, and have lower sensitivities than ICP sources. In addition, the graphite electrodes tend to decay with continuous use and should thus be frequently exchanged. A schematic of a DCP source is shown below:
29A DCP has the advantage of less argon consumption, simpler instrumental requirements, and less spectral line interference. However, ICP sources are more convenient to work with, free from frequent consumables (like the anodes in DCP’s which need to be frequently changed), and are more sensitive than DCP sources.
30Advantages of Plasma Sources No oxide formation as a result of two factors includingVery high temperatureInert environment inside the plasma (no oxygen)2. Minimum chemical interferences3. Minimum spectral interferences except for higher possibility of spectral line interference due to exceedingly large number of emission lines (because of high temperature)
314. Uniform temperature which results in precise determinations 5. No self-absorption is observed which extends the linear dynamic range to higher concentrations6. No need for a separate lamp for each element7. Easily adaptable to multichannel analysis
32Plasma Emission Instruments Three classes of plasma emission instruments can be presented including:1. Sequential instrumentsIn this class of instruments a single channel detector is used where the signal for each element is read using the specific wavelength for each element sequentially. Two types of sequential instruments are available:
33Linear sequential scan instruments where the wavelength is linearly changed with time. Therefore, the grating is driven by a single speed during an analysis of interestb. Slew scan instruments where the monochromator is preset to provide specific wavelengths; moving very fast in between wavelengths while moving slowly at the specific wavelengths. Therefore, a two-speed motor driving the grating is thus used.
34Radial vs. Axial Viewing Radial – traditional side view, better for concentrated samples.Axial – direct view into plasma, lower sensitivity, shifts detection range lower.
36Sequential vs. multichannel Sequential instrumentPMT moved behind aperture plate,or grating + prism moved to focus new l on exit slitPre-configured exit slits to detect up to 20 lines, slew scancharacteristicsCheaperSlowerMultichannel instrumentPolychromators (not monochromator) - multiple PMT'sArray-based systemcharge-injection device/charge coupled deviceExpensive ( > $80,000)Faster
37Slew scan spectrometer Two slew-scan gratingsTwo PMTs for VIS and UVMost use holographic grating
382. Multichannel Instruments This class of instruments is also referred to as simultaneous instruments in which all signals are reported at the same time using two types of configurations:
39a. PolychromatorsMultiple detectors, usually photomultiplier tubes are used. Beams of radiation emerging from the grating are guided to exit slits (each representing the wavelength of a specific element) are focused at several PMTs for detection. Detection, thus, takes place simultaneously
41b. Array-based systemsThis multichannel type instrument uses a multichannel detector like a charge injection device or a charge-coupled device. Diffracted beams from a grating pass through a prism where further resolution of diffracted beams takes place by a prism. The prism will disperse the orders of each diffracted beam. The multichannel detector can also be a linear photodiode array as in the figure below:
463. Fourier transform instruments (FT) Instruments in which the signal is coded will need a decoding mechanism in order to see the signal. FT is a very common technique for decoding time domain spectra. In such instruments, the detector records the change of signal with time, which is practically not useful. However, Fourier transformation of the time domain signal yield a frequency domain spectrum, which is the usual signal, obtained by conventional methods. Instruments that rely on decoding a coded signal is also said to have a multiplex design.
47Applications of Plasma Sources 1. Since plasma sources result in a very large number of emission lines, these sources can be used for both qualitative and quantitative analysis.2. The signal obtained from plasma sources is stable, has a low noise and background, as well as freedom from interferences.3. Requires sample preparation similar to AAS
484. Plasma sources are usually best suited for operation in the ultraviolet region, therefore, elements having emission lines below 180 nm (like B, P, S, N, and C) can be only analyzed under vacuum since air components absorb under 180 nm. Also, alkali metals are difficult to analyze since their best lines under plasma conditions occur in the near infrared.5. An analytical emission line can easily be located but will depend on the other elements present since spectral line interferences are encountered in plasma sources due to the very high temperatures used.
496. Linear calibration plots are usually obtained but departure from linearity is observed at high concentrations; due to self absorption as well as other instrumental reasons. An internal standard is often used in emission methods to correct for fluctuations in temperature as well as other factors. The calibration plot in this case is a plot between the concentration of analyte and the ratio of the analyte to internal standard signal. The internal standard is a substance that is added in a constant amount to all samples, blanks, and standards; therefore it must be absent from initial sample matrix. The internal standard should have very close characteristics (both chemically and physically) to analyte.
50Elements by ICP-AESDifferent elements have different emission intensities. Alkalis (Na, K, Rb, Cs) are weakly emitting. Alkaline Earths (Be, Mg, Ca, Sr, Ba ) are strongly emitting.
51Concepts, Instrumentation, and Techniques in Inductively Coupled Plasma Optical Emission Spectrometry, Boss and Freeden, Perkin Elmer
52ICP/OES INTERFERENCES Spectral interferences:caused by background emission from continuous or recombination phenomena,stray light from the line emission of high concentration elements,overlap of a spectral line from another element,or unresolved overlap of molecular band spectra.CorrectionsBackground emission and stray light compensated for by subtracting background emission determined by measurements adjacent to the analyte wavelength peak.Correction factors can be applied if interference is well characterizedInter-element corrections will vary for the same emission line among instruments because of differences in resolution, as determined by the grating, the entrance and exit slit widths, and by the order of dispersion.
53Physical interferences of ICP causeeffects associated with the sample nebulization and transport processes.Changes in viscosity and surface tension can cause significant inaccuracies,especially in samples containing high dissolved solidsor high acid concentrations.Salt buildup at the tip of the nebulizer, affecting aerosol flow rate and nebulization.Reductionby diluting the sampleor by using a peristaltic pump,by using an internal standardor by using a high solids nebulizer.
54Interferences of ICP Chemical interferences: include molecular compound formation, ionization effects, and solute vaporization effects.Normally, these effects are not significant with the ICP technique.Chemical interferences are highly dependent on matrix type and the specific analyte element.
55Memory interferences: When analytes in a previous sample contribute to the signals measured in a new sample.Memory effects can resultfrom sample deposition on the uptake tubing to the nebulizerfrom the build up of sample material in the plasma torch and spray chamber.The site where these effects occur is dependent on the element and can be minimizedby flushing the system with a rinse blank between samples.High salt concentrations can cause analyte signal suppressions and confuse interference tests.
56INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY (ICP-MS)- Very sensitive and good for trace analysis- Plasma produces analyte ions- Ions are directed to a mass spectrometer- Ions are separated on the basis of their mass-to-charge ratio- A very sensitive detector measures ions- Very low detection limits
57SUMMARY Inductively Coupled Plasma Emission - High cost - No lamp required- Low background signals- Low interference- Moderate sensitivityInductively Coupled Plasma-Mass Spectrometry- Very high cost- Least background signals- Least interference- Very high sensitivity
58Techniques for elemental analysis ICP-MS ICP-AES FAAS GFAAS Detection Limits Excellent Good Good ExcellentProductivity Excellent Very good Good LowLDR / HDDPrecision 1-3 % % % %Spectral interference Few Common Almost none Very fewChemical interference Moderate Few Many ManyIonization Minimal Minimal Some MinimalMass efffects High on low none none noneIsotopes Yes none none noneDissolved solids % up to 30 % % up to 30 %No. of elements ~75 ~73 ~ ~50Sample usage low medium high very lowSemi-quantitative yes yes no noIsotope analysis yes no no noroutine operation Skill required easy easy skill requiredMethod development skill required skill required easy skill requiredRunning costs high high low mediumCapital costs very high high low medium
59Emission Spectroscopy Based on Arcs and Sparks Samples are excited in the gap between a pair of electrodes connected to a high potential power supply (200 VDC or VAC). The high potential applied forces a discharge between the two electrodes to occur where current passes between the two separated electrodes (temperature rises due to very high resistance).
60The very high temperature ( oC) realized in the vicinity between the two electrodes provide enough energy for atomization and excitation of the samples in this region or when the sample is, or a part of, one of the electrodes.Arc and spark methods are mainly used as qualitative techniques and can also be used as semiquantitative techniques.
6110B. Arc and Spark AES Arc and Spark Excitation Sources: Limited to semi-quantitative/qualitative analysis (arc flicker)Usually performed on solidsLargely displaced by plasma-AESElectric current flowing between two C electrodes
62Sample Handling and Preparation If the sample is conductive and is of a shape that can be directly used as an electrode (like a piece of metal or coin), that would be the choice for sample introduction in arc and spark techniques. Otherwise, powdered solid samples are mixed with fine graphite and made into a paste. Upon drying, this solid composite can be used as an electrode. The discharge caused by arcs and sparks interacts with the surface of the solid sample creating a plume of very fine particulates and atoms that are excited and emission is collected. The figure below shows some common shapes of graphite electrodes used in arc and spark sources.
63Carbon electrodesSample pressed into electrode or mixed with Cu powder and pressed - Briquetting (pelleting)Cyanogen bands (CN) nm occur with C electrodes in air -He, Ar atmosphereArc/spark unstableeach line measured >20 sneeds multichannel detection
64Instruments for Arcs and Sparks In most cases, emission from atoms in an arc or spark is directed to a monochromator with a long focal length and the diffracted beams are allowed to hit a photographic film. This typical instrument is called a spectrograph since it uses a photographic film as the detector.
65spectrograph Beginning 1930s photographic film Cheap Long integration timesDifficult to develop/analyzeNon-linearity of line "darkness“
68The blackness of the lines on the photographic film is an indication of the intensity of the atomic line and thus the concentration of the analyte. The location of emission lines as compared to standard lines on a film serves to identify the wavelengths of emission lines of analyte and thus its identity. The use of spectrographs is not very convenient since a lot of time and precautions must be spent on processing and calibrating the photographic film.
69Qualitative analysis is accomplished by comparison of the wavelengths of some emission lines to standards while the line blackness serves as the tool for semiquantitative analysis.Polychromators are also available as multichannel arc and spark instruments. However, these have fixed slits at certain wavelengths in order to do certain elements and thus they are not versatile.
71Recently, arc and spark instruments based on charge injection and charge coupled devices became available. These have extraordinarily high efficiency and performance in terms of easier calibration, short analysis time, as well as superior quantitative results.
73Characteristics of Arc Sources 1. Typical temperatures between oC are high enough to cause atomization and excitation of sample and electrode materials.2. Usually, cyanogens compounds are formed due to reaction of graphite electrodes with atmospheric nitrogen. Emission bands from cyanogens compounds occur in the region from nm. Unfortunately, several elements have their most sensitive lines in this same region which limits the technique. However, use of controlled atmosphere around the arc (using CO2, Helium, or argon) very much decreases the effect of cyanogens emission.
743. The emission signal should be integrated over a minute or so since volatilization and excitation of atoms of different species differ widely. While some species give maximum signal, others may still be in the molecular state.4. Arc sources are very good for qualitative analysis of elements while only semiquantitative analysis is possible. It is mandatory to compare the emission spectrum of a sample with the emission spectrum of a standard. In some cases, a few milligrams of a standard is added to the sample in order to locate the emission lines of the standard and thus identify the emission wavelengths of the different elements in the sample. A comparator densitometer can be used to exactly locate the wavelengths of the standard and the sample components.
75StandardSampleThe lines from the standard are projected on the lines of the combined sample/standard emission spectra in order to identify sample components. Only few lines are shown in the figure.
79Why use Carbon in Atomic Spectroscopy? We have previously seen the use of graphite in electrothermal AAS as well as arc and spark AES, even though molecular spectra are real problems in both techniques due to cyanogens compounds absorption and emission. The reasons after graphite common use in atomic spectroscopy can be summarized below:
80It is conductive.It can be obtained in a very pure state.Easily available and cheap.Thermally stable and inert.Carbon has few emission lines.Easily shaped.
81Spark SourcesMost of the instruments in this category are arc based instruments. Spark based instruments are of the same idea except for a spark source substituting an arc source. The spark source is constructed as in the figure below where an AC potential in the order of KV is discharged through a capacitor which is charged and discharged through the graphite electrodes about 120 times/s; resulting in a discharge current of about 1000 A.
82This very high current will suffer a great deal of resistance, which increase the temperature to an estimated oC. Therefore, ionic spectra are more pronounced.TransformerPotential Source