Improved Low-Power Liquid SamplingAtmospheric Pressure Glow Discharge

CURF Reference 2011-109

Abstract
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Improved Low-Power Liquid Sampling- Atmospheric Pressure Glow Discharge

Description: This technology features a new, simple, and compact system to analyze laser ablated particulates using low-power micro plasma. Current systems require high power sources and large volume plasmas in order to function. This new method significantly reduces the power required and the necessary gas flow. The developed system simplifies the process of introducing particles to the plasma, making it beneficial for material characterization, particularly for aerosols, microparticles, and nanoparticles. Applications: Analytical chemistry Microanalysis of bulk materials Analysis of particles/aerosols Benefits: Simple method Size/portability Lower cost Ability to retrofit to existing equipment Inventors: Patent Status: Licensing Status: CURF Reference: Direct Link:

Kenneth Marcus, et al. A provisional patent has been filed This technology is available for licensing 2011-109 http://curf.technologypublisher.com/technology/13458

Figure 1: LS-APGD setup for ionization of laser ablated particles

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Femtosecond laser ablation particle introduction to a liquid sampling-atmospheric pressure glow discharge ionization source
Anthony J. Carado,a C. Derrick Quarles, Jr.,b Andrew M. Dufn,a Charles J. Barinaga,a Richard E. Russo,c R. Kenneth Marcus,b Gregory C. Eidena and David W. Koppenaal*a
Downloaded by Clemson University on 21 February 2012 Published on 09 February 2012 on http://pubs.rsc.org | doi:10.1039/C2JA10331A

Received 15th November 2011, Accepted 17th January 2012 DOI: 10.1039/c2ja10331a

This work describes the use of a compact, liquid samplingatmospheric pressure glow discharge (LS-APGD) ionization source to ionize metal particles within a laser ablation aerosol. Mass analysis was performed with a Thermo Scientic Exactive Mass Spectrometer which utilizes an orbitrap mass analyzer capable of producing mass resolution exceeding m/Dm > 160,000. The LS-APGD source generates a low-power plasma between the surface of an electrolytic solution owing at several ml min1 through a fused silica capillary and a counter electrode consisting of a stainless steel capillary employed to deliver the laser ablation particles into the plasma. Sample particles of approximately 100 nm were generated with an Applied Spectra femtosecond laser located remotely and transported through 25 meters of polyurethane tubing by means of argon carrier gas. Samples consisted of an oxygen free copper shard, a disk of solder, and a one-cent U.S. coin. Analyte signal onset was readily detectable relative to the background signal produced by the carrier gas alone. The high mass resolution capability of the orbitrap mass spectrometer was demonstrated on the solder sample with resolution exceeding 90,000 for Pb and 160,000 for Cu. In addition, results from a laser ablation depth-proling experiment of a one cent coin revealed retention of the relative locations of the 10 mm copper cladding and zinc rich bulk layers.

Introduction
Laser ablation is well established as an excellent method for direct solid sampling and introduction into conventional spectroscopic sources such as the inductively coupled plasma (ICP).15 The method allows real-time analysis without sample preparation and requires a signicantly lower quantity of mass than conventional sample dissolution procedures. Research over the years has addressed laser wavelength and pulse duration as critical parameters dening accuracy, sensitivity and precision. The femtosecond pulsed ablation process has been shown to produce a narrow, nanometre-sized, particle distribution that is ideal for consumption in the ICP.2,3,6,7
a Pacic Northwest National Laboratory, Battelle Blvd, Richland, WA 99352, USA b Department of Chemistry, Clemson University, Clemson, SC 29634, USA c Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

Recent research has provided sub-micron diameter spatial resolution for laser ablation sampling and the demonstration of nanometre particle introduction into the ICP-MS.810 As the spatial resolution is improved and the quantity of sampled mass is signicantly reduced, the conventional ICP torch becomes a rather large diluting source that is not necessary for digestion of femtograms or less material. The use of a microplasma is an attractive alternative but the question remains if their small volume and short transit time will be sufcient to atomize and ionize laser-ablated particles. The basis of this preliminary study was to demonstrate that a glow discharge microplasma has sufcient electron number density and temperature such that nanometre particles from femtosecond pulsed laser ablation can be analyzed. The liquid sampling-atmospheric pressure glow discharge was initially introduced by Marcus and Davis as a low power, small footprint optical emission source.11 These laboratories have recently reported the coupling of a LS-APGD to a high resolution Thermo Scientic Orbitrap mass analyzer.12,13 Whilst the use of the Orbitrap in the eld of atomic mass spectrometry has denite advantages, regardless of the ionization source, the LS-APGD is being developed as an alternative to the conventional ICP source used in this area. Specically, the microplasma has positive attributes in terms of design simplicity, small footprint, low operating powers (<10 W), and very low liquid ow rates (<20 mL min1) resulting in no liquid waste. Initial efforts importantly demonstrated that the LS-APGD could be easily mounted in the place of conventional electrospray ionization (ESI) sources common to organic/molecular mass spectrometer systems. Interfaced to the Orbitrap, product mass spectra could be obtained with mass resolution values of >100,000 (M/DM). Introduction of small volumes (<10 mL) of acidied, aqueous solutions resulted in readily discerned spectra for metals in the single ppm range. Injection of a 50 mL sample of 5 ng mL1 solution of Cs yielded a spectrum whose signal-to-noise ratio was greater than 1000.12 We describe here preliminary results from experiments coupling a femtosecond laser ablation apparatus to the previously described LS-APGD/Orbitrap instrument. The primary intent of this research was to assess whether or not the LS-APGD had sufcient thermal energy to vaporize/dissociate/ionize the ablated material. As in the prior experiments, use of the Orbitrap was undertaken as being representative of commercially available organic/molecular MS system, while of course offering ultrahigh mass resolution as well. It is
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believed that the results presented here provide evidence of the suitability of coupling the femtosecond LA to the microplasma, not only in terms of elemental MS, but also indicating potential as a secondary excitation source in LIBS-type systems.

Experimental
Laser ablation system Sample aerosol from the bulk solids was generated using an Applied Spectra (Fremont, CA) model J100 series femtosecond laser ablation system. The ytterbium-doped laser crystal is directly pumped by laser diodes and, after frequency tripling, delivers 343 nm wavelength light at a spot size of 80 mm. Each laser pulse is 300400 fs in duration with 110 mJ of energy. The laser repetition rate can be adjusted from 1 Hz to 10 kHz. Results obtained in this work were acquired at 100 Hz. Pb and Cu aerosols were generated while moving the sample stage at 10 mm s1, while the depth-prole of the one-cent coin required a stationary sample stage. Sample particles were transported by means of argon gas owing at 1 L min1 from a 400 cm3 ablation chamber to the ion source through 25 m of polyurethane tubing having a 6 mm o.d. and 4 mm i.d. This length of tubing was necessary to transport the laser ablation aerosol from the laser to the mass spectrometer. LS-APGD ionization source Details of the LS-APGD source as well as recent alterations to allow for lower solution ow-rates and gas consumption have been described previously.12,13 Unlike in those experiments which used a solid counter-electrode, introduction of an aerosol into the plasma required a hollow counter-electrode (1.6 mm o.d., 1.0 mm i.d.) connected to the carrier gas tubing with a series of stepped down Swagelok (Solon, OH) connections. In addition, the geometry of the electrodes relative to each other and relative to the sampling capillary of the mass spectrometer required alteration due to the change in the aerodynamic ow brought about by the carrier gas introduction. This conguration can be seen in Fig. 1. The cathode consists of a fused silica capillary (125 mm o.d., 75 mm i.d.) which delivers the electrolyte solution (5% HNO3) required to sustain the plasma, via syringe pump (Fusion 100T, Chemyx, Stafford TX) at a ow rate of 10 ml min1, surrounded by a stainless steel capillary (700 mm o.d., 500 mm i.d.) through which ows Ar cooling

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gas at a rate of 1 L min1. The plasma is generated between the grounded solution (cathode) and a counter electrode (anode) with a constant discharge current of 18 mA. Power to the counter electrode was provided by a Glassman (High Bridge, NJ) model EH, 100 mA, 1000 V power supply through a 10 kU, 225 W ballast resistor. It should be noted that both the electrolyte ow rate and discharge current were somewhat elevated relative to the values reported previously for use with the solid counter-electrode so as to provide additional vaporization/ionization power. The addition of the Ar carrier gas brought about signicantly more plasma instability which was remedied to some extent by increasing the electrolyte ow and discharge current, however the plasma instability remained an issue and will likely require additional work before full optimization is realized. The distance from the electrodes to the capillary inlet of the mass spectrometer was 0.5 cm, with the gap between the respective electrodes maintained at a distance of 1 mm. Mass analyzer Mass analysis was handled by a Thermo Scientic Exactive Orbitrap Mass Spectrometer in positive ion mode. This instrument was designed for an electrospray ionization (ESI) source, and as such, was easily adapted for use with the LS-APGD ionization source, requiring only the removal of the ESI housing. In an attempt to reduce polyatomic ions and hydrated species, the mass spectrometer was operated using in-source collision induced dissociation (CID) at an energy of 52 eV. This is a value similar to what is used with the ESI source and was utilized in these experiments because it generally produced higher ion intensities in the mass region of interest and lower intensity water clusters. Data analysis was performed with Thermo Scientic XCalibur 2.1 software. Samples Test samples were chosen to demonstrate the fundamental operation of the LS-APGD ionization source for laser ablated particles. As such, metals with simple laser ablation characteristics and relatively intense ion signals were selected. The rst sample was a square of oxygen-free hard copper from a UHV conat ange gasket. The second was a disc of lead (Pb) solder formed by melting several drops from a wire spool onto a at, cool surface. The last sample was a onecent U.S. coin. No further preparation was performed for any of the samples.

Results and discussion

In previous work, the LS-APGD ionization source was used to ionize analytes in the liquid electrolyte stream.12 The optimal electrode geometry for that application was found to be 90 between the owing electrolyte and a solid counter-electrode. The most intense ion signal occurred when directing the electrolyte/cooling gas directly at the sampling orice. Using that geometry, initial efforts to ionize the laser ablation aerosol in the argon carrier gas stream consisted of directing the tubing from the laser ablation source into the microplasma formed between the electrolyte and the solid counter electrode. Various angles were attempted including directing the ow onaxis with the sampling orice of the mass spectrometer. These efforts resulted in no detectable analyte signal. Signicantly better results were obtained by replacing the solid counter-electrode with a stainless steel capillary and owing the particles and carrier gas through the
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Fig. 1 Illustration of the LS-APGD setup for ionization of laser ablated particles.

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capillary tubing as shown in Fig. 1. It is unclear why the initial attempts to direct the aerosol into the plasma via tubing resulted in no ion signal. It had been found previously that the instrument response was sensitive to the electrolyte/cooling gas positioning,13 with greatly varying ion intensities resulting from small changes to electrode positioning (mm scale) and it is possible that the sweet spot for introducing the laser ablation aerosol simply wasnt found. In any case, combining the aerosol introduction mechanism with the counter-electrode is more simple and efcient. In order to clearly discern the response of the mass spectrometer to the sample ions relative to the background signal generated by the Ar carrier gas, data acquisition was started before or at the same time as the laser ablation. The plasma as well as the carrier gas was in continuous operation. The 25 m of tubing delivering the ablated particles to the LS-APGD ionization source resulted in a delay time of 20 s between the laser ring and mass spectrometer response. Fig. 2. shows the smoothed (15-pt. boxcar) ion chromatograms of Cu and C4H7 for the femtosecond laser ablation of the Cu target at a repetition rate of 100 Hz and a laser raster speed of 10 mm s1. The C4H7 ion at mass 55.055 amu is one of several common hydrocarbon contaminants in mass spectrometry.14 It serves, in these experiments, as the baseline mass spectrometer response to the LS-APGD/laser ablation system. In addition to the C4H7 ion, many other common hydrocarbon ions such as the tropyllium ion (m/z 95) and fragments associated with polydimethylsiloxane (PDMS) were found at m/z 73, 147, 207, 209. The LS-APGD was operated at a discharge current of 18mA, and an electrolyte ow rate of 10 ml min1. In this experiment, the laser was activated and deactivated at approximately 30 s and at 2 min. 45 s respectively. The instrument response delay is primarily a function of the particle transport tubing. Twenty-ve meters of tubing with a 4 mm inner diameter has a volume of 0.3 L. With a carrier gas ow rate of 1 L min1, the calculated transport time is 20 s, which corresponds with experimental results. The baseline Cu signal is non-zero both before and after the experiment, with the post analysis intensity slightly elevated relative to the pre-experiment value. The substantial Cu background intensity is likely due to a memory effect caused by previous experiments which resulted in residual Cu particles on the surface of the capillary counter-electrode and/or the mass spectrometer capillary interface. After laser deactivation, washout time is dependent not only on transport tubing length, but also on laser

ablation chamber volume. The sample particles that have been ablated are distributed throughout the volume and require time to enter the transport tubing resulting in washout times that exceed response times at the initiation of the experiment. Nevertheless, the response of the mass spectrometer when coupled to the LS-APGD and laser ablation particle source clearly demonstrates the efcacy of the combination of these analytical components for elemental analysis. Laser ablation techniques have been used extensively to obtain depth information from solid samples with little to no sample preparation steps required. Calibration of the amount of material removed per pulse allows for spatial information for the sample constituents to be obtained. In these experiments, the depth resolution is inversely related to the laser power used. In an initial effort to test the plausibility of using an LS-APGD ionization source for a laser ablation depth proling experiment, a 1994 one-cent U.S. coin was analyzed. Beginning in 1982, a one-cent U.S. coin consists of a 10 mm thick pure Cu shell surrounding a Zn core.15 While 10 mm is far from the lower limit of depth-resolution capability of laser ablation, it is still a useful experiment in determining if the LS-APGD source can provide adequate ionization efciency for particles generated at laser powers sufciently low to resolve the Cu cladding from the Zn core. Fig. 3 shows the results of the laser ablation depth prole of the coin using 110 mJ pulses at a frequency of 100 Hz. The LS-APGD ionization source characteristics were identical to the pure Cu shard experiment. As in the copper shard experiment, the carrier gas and source plasma were in continuous operation throughout the experiment, while the laser was activated approximately 40 s after the start of data acquisition. A minor isotope of Zn was plotted because the intensity more closely matched that of copper, demonstrating the marginally earlier arrival of the Cu particles. The background contaminant ion, C4H7, is plotted in blue. Prior to laser activation, both the Cu and hydrocarbon background intensities are signicant, and follow a similar trend, while the Zn intensity is zero. As seen with the copper shard experiment, the intensity of the Cu ion prior to laser activation indicates a signicant contamination from prior extensive experiments with pure Cu, most likely in the form of particle accumulation on the electrodes and/or sampling orice. Cu and Zn signal onset occur almost simultaneously at approximately 1 min., owing to the relatively high laser repetition rate and thin Cu cladding. The removal

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Fig. 2 Smoothed copper, m/z 62.93 (black), and a common hydrocarbon background contaminant C4H7, m/z 55.06 (red), ion intensities produced by the femtosecond laser ablation of a copper shard.

Fig. 3 Depth-prole of a U.S. one cent coin using 110 mJ femtosecond laser pulses at 100 Hz. Cu (black) and Zn (red) onset are nearly simultaneous owing to the high repetition rate of the laser. Background contaminant ion, C4H7, is shown in blue.

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rate of copper is 200 nm pulse1 which, at the 100 Hz repetition rate used, translates into complete penetration of the Cu cladding in 0.5 s. Aerosol diffusion over the extended transport tubing results in the extended Cu intensity before the signal drops to near pre-experiment levels after about 30 s, though plasma instability results in signicant uctuations of all ion intensities throughout the experiment. Attenuation of ion intensity is common in depthproling experiments as the aspect ratio (depth/diameter) increases because particles have a more difcult time escaping the crater. This effect can be seen clearly starting within 20 s of Zn reaching its peak intensity. Though the trend seems to also appear in the Cu signal, it is much more likely that this results from depletion of Cu particles, rather than crater affects given the thin nature of the cladding relative to the laser spot size (80 mm). As improvements in sensitivity are realized, lower laser repetition rates and power should produce better dened depth information (i.e. improved depth resolution and steady state analyte signal before crater effects reduce intensity). Before orbitrap technology, high mass resolution elemental analysis was only possible with FT-ICR instruments or with collision/ reaction cell techniques employing chemical resolution approaches.1618 Unfortunately, these suffer the disadvantages associated with the magnets required for their operation; size and cryogenic cooling requirement, or the need for various gas-phase reaction chemistries. One of the most important attributes of orbitrap mass analysis is the potential to provide exceedingly high mass resolution with an instrument that has a relatively small footprint; an attribute that lends itself well to the compact LS-APGD ionization source. The results presented in Fig. 4 were acquired from a disc of rosin-core solder formed by allowing drops of melted solder wire to fall onto a at surface. The composition of the solder was 60% Sn, 40% Pb and unspecic trace quantities of several other elements including Cu. The laser and LS-APGD conditions were identical to those used for the Cu shard analysis. The three major isotopes of Pb are shown, all with mass resolution exceeding 90,000, corresponding to a full width at halfmaximum value of <3 mDa for the Pb208 isotope. Given the inverse relationship between ion mass and resolving power for the orbitrap, the Pb isotope peaks exhibited somewhat lower values than the Cu isotopes, which were acquired with m/Dm > 160,000 (Fig. 4b). Given the open nature of the LS-APGD ionization source, it is expected that the oxygenated species of the analyte ions will form in signicant quantities due to the aqueous nature of the electrolyte solution and possibly the atmospheric gas entrainment around the

source and at the entrance to the mass spectrometer. Atomic ions that do form at the source must travel at least several inches, after entering the capillary inlet of the mass spectrometer, through an environment with a short mean-free path before reaching conditions more amenable for reactive metal ions. The expanded mass range spectrum of the commercial solder, Fig. 5, shows this effect clearly with extensive oxidation products of the two main constituents, Pb and Sn. In addition to the common hydroxide and water products, it appears that aluminum contamination products are also formed. The source of the contamination appears to originate from the solder, despite the fact that it is not listed as a trace metal component of the solder. None of the source components are known to contain Al. Experiments using solder wire as the cathode in conjunction with a solid stainless steel counter-electrode (i.e. no carrier gas or laser ablation particles) produced similar spectra indicating that the source of aluminum does not originate from the laser ablation or carrier gas delivery components (data not shown). The spectrum in Fig. 5 is somewhat reminiscent of the adducted elemental spectra of ESI MS.19,20 Just as there was not sufcient energy in collisions with the counter-current gas in ESI to remove all matrix adducts (e.g. MeOH, H2O, OH, etc) it appears that there is not sufcient energy in the discharge or subsequent collisions to remove all adducts in this case. However, the LS-APGD spectra are less complex than ESI spectra since there is no organic solvent present in the solution to lower the aqueous surface tension as required in ESI. These spectra are also somewhat reminiscent of the early ICP ion trap MS spectra in which case reactions with adventitious water in the three dimensional traps created similar adducts. In the ion trap case the water/oxygen adduct ions were signicantly reduced if not eliminated by cryotrapping adventitious water in the ion trap helium atmosphere.21,22 Fig. 5 illustrates both a major challenge and advantage associated with choosing the Thermo Scientic Orbitrap mass spectrometer for these experiments. The nature of the interface encourages increased spectral complexity relative to a dedicated ICP-MS instrument. However, while never desirable, the complexity added to the experimental results due to extensive oxide formation is, to an appreciable extent, offset by the resolving power offered by the orbitrap mass spectrometer. Currently, efforts are underway to create an interface chamber that can be purged with inert gas to reduce the oxygen entrainment around the plasma and also to improve stability. Initial results are encouraging and will be presented in future publications.

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Fig. 4 (a) The major isotopes of Pb generated by the laser ablation of commercial solder and ionized with the LS-APGD ionization source. The mass resolution in this mass range was greater than 90,000 m/Dm. (b) The major Cu isotope at mass resolution exceeding 160,000.

Fig. 5 The expanded mass range spectrum of solder showing its major constituents, Sn and Pb, with associated hydroxide, water and aluminum clusters.

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Conclusions
The liquid-sampling atmospheric pressure glow discharge ionization source has been shown previously to be a low cost, compact, and efcient alternative to ICP for the ionization of analytes dissolved in an electrolytic solution. Simplicity in design, low liquid and gas consumption, and no liquid waste are all positive attributes that characterize this novel method of sample ionization for elemental analysis. In this work, its been shown that this ionization source, with several simple alterations compared to its previously described operation, is indeed capable of ionizing solid sample particles on the order of 100 nm generated by femtosecond laser ablation and delivered by Ar carrier gas over 25 m of tubing. These introductory experiments utilized relatively high laser energy of 110 mJ pulse1 and a high repetition rate, 100 Hz, to generate particle streams that clearly show the instrument response to Cu particle ionization relative to the background carrier gas response when ablating a pure Cu shard sample. Despite these high uence laser operating conditions, a depth-prole experiment of a U.S. one-cent coin resolved the 10 mm Cu cladding from the Zn core. In addition, the choice of the Thermo Scientic Orbitrap mass spectrometer allowed for the ultra-high mass resolution analysis of a laser ablated solder sample resulting in resolution values of >90,000 for Pb, and 160,000 for Cu. Improvements to the interface region between the LS-APGD ionization source and the mass spectrometer inlet are currently being pursued and point toward improved plasma stability and efciency. Further work in this area should allow the potential of this microplasma ionization method for small volume laser ablation sampling to be realized.

Research (BER) program. Support for this work was provided by the DOE Ofce of Non-Proliferation Research and Engineering (NA22).

References
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Acknowledgements
This work was performed at Pacic Northwest National Laboratory, operated for the US DOE by Batelle Memorial Institute under Contract DE-AC06-76RLO-1830. The Exactive MS capability was provided by the W. R. Wiley Environmental Molecular Science Laboratory, a national scientic user facility sponsored by the U.S. Department of Energys Ofce of Biological and Environmental

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