In-Situ Monitoring of the Structure of a Goethite-Based Catalyst During Methane Oxidation by X-ray Absorption Near-Edge Structure (XANES) Spectroscopy

Assisted by Chemometric Methods

CLEITON A. NUNES, ELIANE C. RESENDE, IARA R. GUIMARAES, ALEXANDRE S. ANASTACIO, and MARIO C. GUERREIRO*
Department of Chemistry, Federal University of Lavras, P.O. Box 3037, 37200-000, Lavras, MG, Brazil (C.A.N., E.C.R., I.R.G., M.C.G.); and Department of Zootechnics, Federal University of Esprito Santo, P.O. Box 16, 29500-000, Alegre, ES, Brazil (A.S.A.)

A goethite-based catalyst was evaluated using in-situ X-ray absorption near-edge structure (XANES) spectroscopy during methane oxidation under increasing reaction temperature. Determination of rank by median absolute deviation (DRMAD), evolving factor analysis (EFA), and multivariate curve resolution (MCR) were used to detect the species present in the catalyst during the reaction and determine their concentration proles and their pure spectra. The reactants and reaction products were monitored on-line by mass spectrometer. The goethitebased catalyst was active for methane oxidation, with CO2 and H2O as the main products. DRMAD and EFA were useful to determine the number of chemical species present in the catalyst structure during reactions. The catalyst presented phase transition during the reaction from goethite to maghemite according to XANES spectra determined by MCR. On the other hand, it was veried that the catalyst presented phase transition from goethite to wustite in the process in the absence of the oxidant (O2). Index Headings: Goethite; Methane oxidation; X-ray absorption near-edge structure spectroscopy; XANES spectroscopy; Chemometrics; Determination of rank by median absolute deviation; DRMAD; Evolving factor analysis; EFA; Multivariate curve resolution; MCR.

INTRODUCTION
Iron is a versatile chemical element that can be present in different substances and consequently with different oxidation states, such as Fe, FeO, Fe3O4, Fe2O3, and FeOOH. Due to its versatile redox behavior, low toxicity, and low cost, iron has been used extensively for technological applications, primarily related to catalytic reactions.1 Various industrial syntheses consist of reactions catalyzed by iron compounds, including the synthesis of NH3 (Harber Bosch process), the high-temperature water gas shift reaction (CO H2O!CO2 H2) for the production of hydrogen, and the desulphurization of natural gas. Other important reactions include the synthesis of hydrocarbons from hydrogen and carbon monoxide (FischerTropsch synthesis), dehydrogenation of ethyl benzene to styrene, and oxidation of alcohols to aldehydes and ketones.1 Goethite (a-FeOOH) is one of the most thermodynamically stable iron oxides, with a diaspore structure based on hexagonal close packing of the anions.1 This iron oxide has been reported as an active catalyst for the oxidation of organic
Received 2 December 2010; accepted 1 March 2011. * Author to whom correspondence should be sent. E-mail: guerreiro@dqi. ua.br. DOI: 10.1366/10-06202

compounds, such as methane,2 and the mitigation of organic contaminants.3,4 During these catalytic processes, alterations of the catalyst structure can occur concomitantly with product formation. Mainly phase transitions are observed, which can inuence the performance of the catalyst. Knowledge of the catalyst changes is indispensable in understanding the behavior of these catalysts in the process. X-ray absorption spectroscopy (XAS) is a very useful analytical technique for studying these phenomena and evaluating their stability.1 In XAS, absorption spectra are obtained by increasing the energy of the incident photons. As soon as the energy is high enough to eject the core electrons, an abrupt increase of the absorption (absorption edge) is observed. The XAS spectrum is commonly divided into two parts, that originating from the extended X-ray absorption ne structure (EXAFS) and that from the X-ray absorption near-edge structure (XANES). In EXAFS, the outgoing electrons are backscattered by neighboring atoms and interference of these backscattered electrons with the outgoing electrons produces a ne structure in the spectrum at energies that are greater than the absorption edge. The XANES spectra show the near-edge (lower energy part) structure of the absorptions, attributed to transitions of core electrons to a continuum state. With the increasing oxidation state of the absorbing atom, the absorption edge shifts to higher energies, which allows determination of the valence of the atom.1,5 The XAS spectra can be obtained quickly using a chargecoupled device (CCD) detector. Thus, an in-situ study of the structure of the material used as catalyst can be easily carried out while the reaction is in progress. In these experiments, a large amount of data is generated and the use of chemometric tools can be useful to extract data information helpful in the interpretation of the results. On the other hand, at some moments (e.g., during a phase transition), the spectra obtained cannot give separate information about each existent phase, but they are characteristic of the phases that co-exist at that moment of the reaction. However, it is desirable to know the phase and composition of the material at each reaction time. Here, chemometric methods can be a useful tool. From the spectra obtained at certain time intervals during the progress of the reaction, the number of pure components in the system can be veried, i.e., the number of pure existing species (or phases) on the catalyst during the reaction. This can be carried out with the aid of chemometric methods based on the matrix rank, such as the recently proposed determination of rank by median absolute deviation (DRMAD),6 or by evolving factor analysis (EFA).7 EFA also provides information about

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FIG. 1. Simplied schematic of the catalytic tests.

the intervals in which each phase exists, which is essential for the following stage: the determination of concentration proles of each species present in the system by multivariate curve resolution (MCR).8 MCR also allows the pure spectra of each species to be obtained, which is useful for its identication. Some of these chemometric methods have been successfully used in the evaluation of catalyst structures by in-situ XAS techniques, as shown for copper,9 cobalt,10 and copper-zinc11 based catalysts. In this article, a goethite-based catalyst was evaluated by insitu XANES spectroscopy during methane oxidation. The catalyst structure was also evaluated in the absence of the oxidant (O2). The DRMAD, EFA, and MCR chemometric methods were used to detect the species present in the catalyst during the reaction and to determine their concentration proles and pure spectra. The reactants and products of the reaction were monitored on-line by mass spectrometry.

EXPERIMENTAL
Catalyst Synthesis. The catalyst used in this study was a material based on goethite, in which 10% of the iron atoms were substituted by nickel atoms. The synthesis consisted of adding 100 mL 5.0 mol L1 NaOH drop wise to 100 mL aqueous solution of Fe(NO 3 ) 3 9H 2 O (27.0 g) and Ni(NO3)26H2O (0.9 g) under stirring. The resulting mixture was diluted to 2.0 L with distilled water and kept at 70 8C for 72 h. After this time the material was washed with distilled water at room temperature until it reached neutral pH. The material was then ltered and dried at 50 8C for 24 h. This material has been synthesized and characterized in previous work.12 Monitoring of the Catalytic Reaction. The catalytic reaction was carried out as shown in the scheme in Fig. 1. A

quartz tubular reactor with 30 mg of the catalyst was used for the gas ows (CH4 and O2 diluted in He) at 150 mL min1. The reaction system was heated from 25 8C to 800 8C at a rate of 10 8C min1. The reactants and products were monitored on-line by mass spectrometry. The catalyst was analyzed in situ by Fe K-edge XANES spectroscopy using sample disks diluted in boron nitride. The experiments were carried out at the Brazilian Synchrotron Light Laboratory. Chemometric Methods. In this study, chemometric methods were used to extract information from the XANES spectroscopic analysis and evaluate the transformations that occurred on the catalyst structure. The data matrix (XANES spectra) was preprocessed using multiplicative scatter correction (MSC)13 for baseline adjustment because spectra stacking was observed, caused by energy decay of the synchrotron radiation beam over time. The number of phases present in the catalyst during each run was determined using DRMAD and EFA. EFA was also used to provide information on the intervals of each existing phase. The concentration proles of each species present in the system were obtained and the determination of XANES spectra of each species was carried out using MCR. The calculations were performed in Matlab (The Mathworks Inc., Natick, MA) using the appropriate algorithm for DRMAD6 and the MCR-ALS toolbox for EFA and MCR routines.14 Temperature-Programmed Reduction Analysis. The goethite-based catalyst was analyzed comparatively by temperature-programmed reduction (TPR) before and after methane reaction at 400, 600, and 900 8C in the absence of O2. The reactions were carried out in a quartz tube at a total methane (4% in helium) ow of 150 mL min1 for 3 h at the specied temperature. The materials were then analyzed by TPR at an H2 (4% in N2) ow of 80 mL min1 and temperature range from 50 to 900 8C at a rate of 10 8C min1.

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FIG. 2. XANES absorption spectra of the goethite-based catalyst recorded in situ during methane oxidation.

RESULTS AND DISCUSSION

Catalyst Evaluation. The catalyst was initially evaluated for methane oxidation. A mixture of 2% oxygen and 4% methane in helium at a total ow of 150 mL min1 was used. The reaction was carried out using a temperature program of 25 to 800 8C at 10 8C min1. XANES catalyst spectra were recorded every 15 s during the reaction progress. Selected XANES spectra obtained during the reaction are shown in Fig. 2. In this series of XANES spectra it was not possible to observe signicant alterations in the spectra prole during the reaction with increasing temperature. A more elaborate data evaluation is required to distinguish any alteration in the spectra during the progress of the reaction. In order to verify any difference obtained in the XANES spectra, EFA was used. EFA was applied on the Fe-K edge spectra looking for different Fe phases on the catalyst during the reaction. In EFA, a rank analysis by singular value decomposition is performed t times, in which t is the number of spectra in the data set. This analysis is performed in the forward and backward mode in an evolutionary process in which one spectrum is added at every step. When a new chemical species appears, an eigenvalue evolves from the pool of noise in the forward mode, increasing the value in relation to its contribution to the enlarged data set. On the other hand, the backward mode indicates when any species disappears. An eigenvalue plot of both modes indicates the number of components of the system and the range in which each one exists.7 The EFA of the XANES spectra of the goethite-based catalyst recorded during methane oxidation is shown in Fig. 3a. The EFA graph clearly shows the existence of two species and suggests the presence of a third. However, the noise level threshold is uncertain. In order to determine the number of species in the system and to help establish the noise level, a determination of rank by median absolute deviation (DRMAD) was performed. The DRMAD determines the number of principal factors responsible for a data matrix by direct application of the residual standard deviation of eigenvalues obtained from principal component analysis (PCA).6 The output of the DRMAD displays the factor level (n), the associated

FIG. 3. (a) EFA of XANES spectra set, (b) prole concentration determined by MCR, and (c) on-line mass spectrometry analysis recorded during methane oxidation.

eigenvalue (EV), the residual standard deviation (RSD), and the results of an outlier test for RSD, using the median absolute deviation (MAD) algorithm. A zero in the TEST column indicates that the RSD based on n factors is an outlier. Unity indicates that the next associated RSD is not an outlier. The DRMAD of the rst ten eigenvalues for the XANES spectra set of the goethite-based catalyst obtained during methane oxidation are shown in Table I. The analysis indicates the existence of three species in the system, based on the TEST output and due to the fact that the RSD did not vary beyond three factors. Referring to the EFA graph (Fig. 3a), the threshold (shaded area) was dened below three species (approximately 0.35) according to DRMAD indications. The EFA graph suggests that the rst species is present at the beginning of the reaction for approximately 20 min (or to 250 8C). Just before disappearing, a new line, suggesting the appearance of another species, emerges from the noise. This species disappears after 60 min (at 620 8C). Finally, the existence of a third species is observed after 25 min (at 290 8C), which remains until the reaction ceases. After determining the number of existing species (or phases) on the catalyst and their survival at increasing temperatures,

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TABLE I. DEMAD results for the rst ten eigenvalues of the XANES spectra set of the goethite-based catalyst obtained during methane oxidation. n 1 2 3 4 5 6 7 8 9 10 EV 2.7 3 10 1.8 3 101 1.3 1.2 3 101 4.0 3 102 7.9 3 103 4.3 3 103 2.9 3 103 1.9 3 103 1.8 3 103
5

RSD 0.0067 0.0020 0.0010 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008

TEST 0 0 1 1 1 1 1 1 1 1

MCR was carried out in order to obtain the phase composition proles during the reaction and determine the pure XANES spectra of each phase. The aim of the MCR method is the optimal decomposition of a data matrix into two small matrices, one of which contains as much information as possible about the pure component spectrum and the other containing its concentration proles. This algorithm allows the use of constraints in order to optimize the concentration and pure spectra proles. In this study the non-negativity constraint was used for the concentration and pure spectra proles because these values should be positive, and the closure constraint was used for the concentration proles because a mass balance for the existent species is desired.8 Phase composition proles, obtained from the XANES spectra of the catalyst by MCR, are presented in Fig. 3b. The appearance of phase 2 while phase 1 disappears can be veried. The maximum of this transformation occurs after 25 min (290 8C), after which phase 3 begins to appear while phase 2 starts to decrease. An important observation is the detection, by mass spectrometry, of water without consumption of CH4 or formation of other products while phase 2 is appearing (Fig. 3c). Starting at 350 8C, the mass spectrometry analysis reveals the formation of CO2 and H2O, which keeps up with the consumption of CH4 and O2. Above 650 8C the formation of CO and H2 in small amounts is also observed. Figure 4 shows the pure XANES spectra of each phase obtained by MCR as well as the XANES spectra of standard goethite, hematite (a-Fe2O3), and maghemite (c-Fe2O3). Phase 1 presented edge absorption at 7132 eV and post-edge absorptions at 7179, 7198, and 7279 eV. This phase was conrmed as goethite (a-FeOOH) by comparison to the standard spectra. Phases 2 and 3 also presented edge absorption at 7132 eV, indicating no alterations to the oxidation state of phases.1 Inspections in the XANES spectra of phases 2 and 3 reveal alterations with respect to phase 1. The changes can be veried mainly in the absorption increase at 7146 and 7227 eV in the spectra of phases 2 and 3, as well as the absorption decreases at 7198 and 7248 eV. These transformations make the spectra of phases 2 and 3 more similar to the spectra of hematite and maghemite. Although the hematite and magnetite spectra are similar, the material presented very slight magnetism after the reaction, which is characteristic of maghemite. Thus it can be suggested that during methane oxidation, the catalyst structure, initially goethite (phase 1), is rst converted to hematite (phase 2) and nally converted to maghemite (phase 3). Catalyst Evaluation in the Absence of Oxygen. The

FIG. 4. XANES spectra of pure species present on the catalyst during methane oxidation obtained by MCR and XANES spectra of standard a-FeOOH, aFe2O3, and c-Fe2O3.

catalyst structure was also evaluated in the presence of methane but the absence of oxygen. Methane (4% in helium) was used in the quartz tube at a total ow rate of 150 mL min1. The temperature was raised from 25 to 800 8C at a rate of 10 8C min1 and the XANES catalyst spectra were constantly recorded in situ at short time intervals. Selected XANES spectra are shown in Fig. 5. Some alteration of the spectra prole during the temperature increase can be veried. A small increase of the signal at 7227 eV and a greater change of the signal at 7146 eV is observed. In order to evaluate the number of phases present on the catalyst in the absence of O2, DRMAD and EFA were carried out. The DRMAD results (Table II) indicate the presence of four components based on the TEST output and conrmed by the stabilization of RSD after four factors. The EFA threshold (shaded area) was dened below four species (approximately 0.1) according to DRMAD indications (Fig. 6a). The EFA graph suggests that the rst species is present at the beginning of the process until around 20 min (220 8C). At this point, a new species emerges and disappears after approximately 40 min (420 8C). A short time before, another species emerges, which exists until around 70 min (700

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FIG. 5. XANES absorption spectra of the goethite-based catalyst recorded in situ in the process without O2.

8C). Finally, the fourth species becomes predominant after 60 min (650 8C) and is the only species at the end of the process. Multivariate curve resolution was also carried out in order to obtain more accurate phase composition proles as well as the pure XANES spectra of each phase. Figure 6b shows the phase composition proles obtained from the XANES spectra of the catalyst by MCR. The appearance of phase 2 while phase 1 disappears can be veried, reaching a maximum after 25 min (290 8C). Starting around 200 8C, phase 3 appears and continues until almost the end of the process. Phase 4 emerges after 40 min (400 8C) and is predominant until the end of the process. The pure XANES spectra of each previously proposed phase were also determined by MCR (Fig. 7). The main difference observed in the spectra of the phases was the shift of edge absorption to a lower energy level during the phase transition, indicating the reduction of the iron oxidation state.1 Phase 1 presented edge absorption at 7133 and was identied as goethite due to characteristic absorptions and by comparison to the standard spectrum. Phase 2 also presented edge absorption at 7133, but the spectral prole was similar to hematite. Also, water formation was detected during the formation of phase 2 (Fig. 6c), providing evidence for the formation of hematite. Phase 3 presented edge absorption at lower energy (7132 eV)
TABLE II. DEMAD results for the rst ten eigenvalues of the XANES spectra set of the goethite-based catalyst obtained in the process without O2 . n 1 2 3 4 5 6 7 8 9 10 EV 2.6 3 106 2.9 3 102 8.4 2.4 5.4 3 101 2.8 3 101 5.2 3 102 5.1 3 102 4.8 3 102 4.6 3 102 RSD 0.026 0.006 0.004 0.003 0.002 0.002 0.002 0.002 0.002 0.002 TEST 0 0 0 1 1 1 1 1 1 1

FIG. 6. (a) EFA of XANES spectra set, (b) prole concentration obtained by MCR, and (c) on-line mass spectrometry analysis recorded in the process without O2.

and was identied as magnetite (Fe3O4) by comparison to standard spectra. Finally the sample 4 with edge absorption at 7131 eV presented a spectral prole similar to the standard wustite (FeO) and was identied as such. In the absence of oxygen the catalyst presented no activity (Fig. 6c), with only the formation of water related to the hematite formation being detected, as well as methane consumption with hydrogen formation, probably related to coke production. Temperature-Programmed Reduction Analysis. The TPR proles for goethite typically present H2 consumption around 400 8C due to the reduction of Fe(III) to Fe(II,III) and H2 consumption in a large range around 750 8C, where the reduction of Fe(II,III) to Fe(0) occurs, passing through the Fe(II) metastable phase.1,4 The goethite-based catalyst was analyzed by TPR before and after methane reaction at 400, 600, and 900 8C in the absence of O2. TPR proles are presented in Fig. 8. TPR proles obtained for the catalyst before reaction and after reaction at 400 8C show the presence of Fe(III) in their structures due to the H2 consumption around 420 8C. On the other hand, the absence of Fe(III) in the materials analyzed after reaction at 600 8C and 900 8C is indicated by the

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FIG. 8. TPR proles of the goethite-based catalyst before and after methane reaction at 400, 600, and 900 8C in the absence of O2.

for obtaining the distribution of the species. MCR was also indispensable in obtaining the spectrum of each pure species. The goethite-based catalyst is shown to be active for methane oxidation, with CO2 and H2O being the main products. CO and H2 were also produced in smaller amounts at high temperatures. The catalyst presented phase transition during the reaction, from goethite to maghemite according to the XANES spectra determined by MCR. On the other hand, it was veried that the catalyst presented phase transition from goethite to wustite in the absence of the oxidant (O2).
ACKNOWLEDGMENTS The authors gratefully acknowledge the Brazilian Synchrotron Light Laboratory (LNLS) for technical and nancial support in the accomplishment of these experiments. We are also grateful to Ulf Schuchardt for reviewing the manuscript.

FIG. 7. XANES spectra of pure species present on the catalyst in the process without O2 obtained by MCR and XANES spectra of standard a-FeOOH, aFe2O3, Fe3O4, and FeO.

lack of H2 consumption centered at 420 8C. However, these samples kept the H2 consumption around 750 8C, which shows the presence of Fe(II) in these materials. Thus, this conrms the results obtained by XANES assisted by chemometric methods, which indicated the presence of Fe(III) below 550 8C, Fe(II,III) below 750 8C, and Fe(II) above 600 8C in the catalyst structure during methane reaction in the absence of oxygen.

CONCLUSIONS
Chemometric tools such as DRMAD, EFA, and MCR have been shown to be useful methods for the analysis of XANES spectroscopic data collected in situ for catalysts during catalytic reactions. DRMAD and EFA were useful in determining the number of chemical species present in the catalyst structure during reactions, while the EFA and MCR data were essential

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