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Plasma-based ambient desorption/ionization (ADI) sources for mass spectrometry (MS) often use helium as the primary discharge gas due to the large reaction cross section of excited helium species with atmospheric gases, which ultimately leads to efficient reagent-ion formation. However, some studies have shown that mixed-gas plasmas provide unique advantages. For instance, our group showed that a helium‑oxygen flowing atmospheric-pressure afterglow (He:O2-FAPA) source yielded enhanced ion signals for small polar analytes, but compounds with aromatic rings underwent chemical modification to produce pyrylium species. Here, it is shown that the addition of H2 to the helium FAPA gas significantly decreased the reagent-ion signals, but analyte-ion signal was not affected to the same degree. In addition, mass spectra obtained with He:H2-FAPA were chemically cleaner with fewer ions stemming from analyte species and produced less oxidation of analytes. Addition of nitrogen increased the abundance of negative reagent ions (e.g., NO2− and NO3−) which led to enhanced ion signal for RDX. To better understand these unique advantages of a mixed-gas FAPA, the impact of molecular-gas (O2, N2, or H2) addition on the optical-emission spectra from the discharge was also measured. Spatially resolved emission was obtained from the anode- and negative-glow regions. In general, addition of small fractions (~0.1%) of molecular gases decreased helium and OH emission intensities. Atomic oxygen and hydrogen emission increased with the addition of O2 and H2, respectively. Furthermore, emission characteristics of N2, N2+, and NO with respect to molecular gas composition on He-FAPA were measured. Fundamental plasma parameters, such as OH rotational temperature (Trot), were also calculated for these mixed-gas systems.

Petroleomics, which is the characterization, separation, and quantification of the components of petroleum and crude oil, is an emerging area of study. However, the repertoire of analytical methods available to understand commercial automotive lubricant oils (ALOs) is very limited. Ambient mass spectrometry is one of the most sensitive analytical methods for real-time and in situ chemical analysis. With this technique, the chemical fingerprinting of ALOs can be performed quickly and simply using dielectric barrier discharge ionization time-of-flight mass spectrometry. In this study, the mass spectra of 35 samples were obtained without any sample preparation in positive-ion mode, and no carryover was observed. To elucidate the similarities and differences between the ALO samples, the data generated from these spectra were analyzed using four chemometric techniques: principal component analysis, multivariate curve resolution, hierarchical cluster analysis, and pattern recognition entropy. The ALO samples were readily differentiated according to their American Petroleum Institute classification and base oil types: mineral, semisynthetic, and synthetic. The development of this new methodology will aid in the semiquantitative control analysis of ALOs and offers an improved ability to identify the components therein.

The design of a miniaturized LED-based UV-absorption detector was significantly improved for on-column nanoflow LC. The detector measures approximately 27mm×24mm×10mm and weighs only 30g. Detection limits down to the nanomolar range and linearity across 3 orders of magnitude were obtained using sodium anthraquinone-2-sulfonate as a test analyte. Using two miniaturized detectors, a dual-detector system was assembled containing 255nm and 275nm LEDs with only 216nL volume between the detectors A 100μm slit was used for on-column detection with a 150μm i.d. packed capillary column. Chromatographic separation of a phenol mixture was demonstrated using the dual-detector system, with each detector producing a unique chromatogram. Less than 6% variation in the ratios of absorbances measured at the two wavelengths for specific analytes was obtained across 3 orders of magnitude concentration, which demonstrates the potential of using absorption ratio measurements for target analyte detection. The dual-detector system was used for simple, but accurate, mobile phase flow rate measurement at the exit of the column. With a flow rate range from 200 to 2000nL/min, less than 3% variation was observed.

Compartmentalization of metabolism into specific regions of the cell, tissue, and organ is critical to life for all organisms. Mass spectrometric imaging techniques have been valuable in identifying and quantifying concentrations of metabolites in specific locations of cells and tissues, but a true understanding of metabolism requires measurement of metabolite flux on a spatially resolved basis. Here, we utilize desorption ESI-MS (DESI-MS) to measure lipid turnover in the brains of mice. We show that anatomically distinct regions of the brain have distinct lipid turnover rates. These turnover measurements, in conjunction with relative concentration, will enable calculation of regiospecific synthesis rates for individual lipid species in vivo. Monitoring spatially dependent changes in metabolism has the potential to significantly facilitate research in many areas, such as brain development, cancer, and neurodegeneration.

Dielectric barrier discharge (DBD)-based analytical applications have experienced rapid development in recent years. DBD designs and parameters and the application they are used for can vary considerably. This leads to a diverse field with many apparently unique systems that are all based on the same physical principle. The most significant changes among DBDs used for chemical analysis are in how the discharge electrodes are separated from the ignited discharge gas. While the official definition of a DBD states that at least one electrode has to be covered by a dielectric to be considered a DBD, configurations with both electrodes covered by dielectric layers can also be realized. The electrode surface plays a major role in several plasma-related technical fields, surface treatment or sputtering processes, for example, and has hence been studied in great detail. Analytical DBDs are often operated at low power and atmospheric pressure, making a direct transfer of insight and know-how gained from the aforementioned well-studied fields complicated. This work focuses on comparing two DBD configurations: the low temperature plasma probe (LTP) and the dielectric barrier discharge for soft ionization (DBDI). The LTP is representative of a DBD with one covered electrode and the DBDI of a design in which both electrodes are covered. These two configurations are well suited for a systematic comparison due to their similar geometric designs based on a dielectric capillary.

Quantitative accuracy and high sensitivity in inductively coupled plasma mass spectrometry (ICP-MS) depend on consistent and efficient extraction and transport of analyte ions from an inductively coupled plasma to a mass analyzer, where they are sorted and detected. In this review we examine the fundamental physical processes that control ion sampling and transport in ICP-MS and compare the results of theory and computerized models with experimental efforts to characterize the flow of ions through plasma mass spectrometers' vacuum interfaces. We trace the flow of ions from their generation in the plasma, into the sampling cone, through the supersonic expansion in the first vacuum stage, through the skimmer, and into the ion optics that deliver the ions to the mass analyzer. At each stage we consider idealized behavior and departures from ideal behavior that affect the performance of ICP-MS as an analytical tool.

A newly developed portable capillary liquid chromatograph was investigated for the separation of various pharmaceutical and illicit drug compounds. The system consists of two high-pressure syringe pumps capable of delivering capillary-scale flow rates at pressures up to 10 000 psi. Capillary liquid chromatography columns packed with sub-2 μm particles are housed in cartridges that can be inserted into the system and easily connected through high-pressure fluidic contact points by simply applying a specific, predetermined torque rather than using standard fittings and less precise sealing protocols. Several over-the-counter analgesic drug separations are demonstrated, along with a simple online measurement of tablet dissolution. Twenty illicit drug compounds were also separated across six targeted drug panels. The results described in this study demonstrate the capability of this compact liquid chromatography instrument to address several important drug-related applications while simplifying system operation, and greatly reducing solvent usage and waste generation essential for onsite analysis.

We present a computational simulation of a helium DC glow discharge used as an ambient desorption/ionization source for mass spectrometry. Both the fluid dynamics of the flowing gases and the kinetics of the chemical reactions are modeled. The simulation incorporates measured absolute number densities of helium metastable atoms obtained using an atomic absorption spectrometer. The results indicate that the formation of protonated water cluster ions, (H2O)nH+, begins shortly downstream from the high voltage pin electrode in the active discharge region. The (H2O)nH+ ions grow in size as they flow with the helium. Several key parameters were changed to observe their effect on the formation of (H2O)nH+ ions, including the concentration of nitrogen and water impurities in the helium plasma gas, the relative humidity of the air around the discharge tube, and the air pressure. Changing impurity levels in the plasma gas had the largest effect on the formation of water clusters. Changes in ambient humidity levels affected the size of the (H2O)nH+ ions, but not the overall number of ions. Changes in air pressure did not have a significant effect.

A compact ultrahigh-pressure nanoflow liquid chromatograph (LC) was developed with the purpose in mind of creating a portable system that could be easily moved to various testing locations or placed in close proximity to other instruments for optimal coupling, such as with mass spectrometry (MS). The system utilized innovative nanoflow pumps integrated with a very low volume stop-flow injector and mixing tee. The system weighed only 5.9 kg (13 lbs) or 4.5 kg (10 lbs) without a controller and could hold up to 1100 bar (16000 psi) of pressure. The total volume pump capacity was 60 μL. In this study, the sample injection volume was determined by either a 60 nL internal sample groove machined in a high-pressure valve rotor or by a 1 μL external sample loop, although other sample grooves or loops could be selected. The gradient dwell volume was approximately 640 nL, which allowed significant reduction in sample analysis time. Gradient performance was evaluated by determining the gradient step accuracy. A low RSD (0.6%, n = 4) was obtained for day-to-day experiments. Linear gradient reproducibility was evaluated by separating a three-component polycyclic aromatic hydrocarbon mixture on a commercial 150 μm inner diameter capillary column packed with 1.7 μm particles. Good retention-time reproducibility (RSD0.17%) demonstrated that the pumping system could successfully generate ultrahigh pressures for use in capillary LC. The system was successfully coupled to an LTQ Orbitrap MS in a simple and efficient way; LC-MS of a trypsin-digested bovine serum albumin (BSA) sample provided narrow peaks, short dwell time, and good peptide coverage.

We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration. Graphical Abstract ᅟ.

Here, we report the most comprehensive characterization of nanodiamonds (NDs) yet undertaken. Five different samples from three different vendors were analyzed by a suite of analytical techniques, including X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), inductively coupled plasma mass spectrometry (ICP-MS), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Brunauer-Emmett-Teller (BET) surface area measurements, and particle size distribution (PSD) measurements. XPS revealed the elemental compositions of the ND surfaces (83-87 at.% carbon and 12-14 at.% oxygen) with varying amounts of nitrogen (0.4-1.8 at.%), silicon (0.1-0.7 at.%), and tungsten (0.3 at.% only in samples from one vendor). ToF-SIMS and ICP showed metal impurities (Al, Fe, Ni, Cr, etc. with unexpectedly high amounts of W in one vendor's samples: ca. 900 ppm). Principal component analyses were performed on the ToF-SIMS and ICP data. DRIFT showed key functional groups (-OH, C=O, C-O, and C=C). BET showed surface areas of 50-214 m(2)/g. XRD and TEM revealed PSD (bimodal distribution and a wide PSD, 5-100 nm, for one vendor's samples). XRD also provided particle sizes (2.7-27 nm) and showed the presence of graphite. EELS gave the sp(2)/sp(3) contents of the materials (37-88% sp(3)). PSD measurements were performed via differential sedimentation of the particles (mean particle size ca. 17-50 nm). This comprehensive understanding should allow for improved construction of nanodiamond-based materials.

The effects of helium gas on ablation and ICP processes were investigated. Differences in the size, shape, and abundance of aerosol particles generated in argon and helium atmosphere were studied off-line using SEM imaging of aerosol particles impacted on polycarbonate filter disks. In general, ablation in helium generated fewer large particles, and larger, more densely-packed soft agglomerates. However, corresponding changes in the ion densities in the ICP, observed in high-resolution images obtained using LIF, were not always predictable. In all cases, higher He/Ar ratios led to lower ion densities in the ICP. This effect was attributed to increased rates of off-axis diffusion at higher He/Ar ratios. Differences in the ion densities produced during ablation in argon vs helium were highly dependent on sample type, the axial position of vaporization, and the He/Ar ratio. There was evidence that vaporization efficiencies of soft agglomerates were less affected than micron-sized particles by particle acceleration at higher He/Ar ratios.

Relative contributions to ion densities in the inductively coupled plasma (ICP) of particles of various sizes produced by laser ablation (LA) were investigated. Particles generated by 266 nm, ns LA of BaF2, CaF2, and a scandium aluminum alloy, characterized using SEM, consisted of hard and soft agglomerates, spherical particles, and irregularly-shaped particles. Although soft agglomerates and spherical particles were common to aerosols generated by LA in all cases, hard agglomerates appeared to be unique to the scandium aluminum alloy, while irregularly-shaped exfoliated particles were unique to the calcium and barium fluoride windows. The spatial distributions of Ca, Ba, and Sc ions in the ICP were determined from laser-induced fluorescence images taken with filters of pore sizes from 1–8 μm added in-line to the transport tube upstream from the ICP. In all cases, a significant fraction of the ions formed in the ICP originated from micron-sized particles. Differences in the penetration depths of nanometer-sized agglomerates and micron-sized particles were about 2 mm for Ca and 1 mm for Ba. Differences in the penetration depths of nanometer and micron-sized agglomerates observed in the case of aluminum scandium were much less significant. This suggests that micron-sized hard-agglomerates and nanometer-sized soft-agglomerates experience very similar vaporization patterns. Additionally, there was evidence that flow patterns in the transport tube affect the trajectories of particles entering the plasma.

High-resolution images of the spatial distributions of Sc II, Ca II, and Ba II ion densities in the 10 mm upstream from the sampling cone in a laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) were obtained using planar laser induced fluorescence. Images were obtained for each analyte as a function of the carrier gas flow rate with laser ablation (LA) sample introduction and compared to images with solution nebulization (SN) over the same range of flow rates. Additionally, images were obtained using LA at varying fluences and with varying amounts of helium added to a constant flow of argon gas. Ion profiles in SN images followed a pattern consistent with previous work: increasing gas flow caused a downstream shift in the ion profiles. When compared to SN, LA led to ion profiles that were much narrower radially and reached a maximum near the sampling cone at higher flow rates. Increasing the fluence led to ions formed in the ICP over greater axial and radial distances. The addition of He to the carrier gas prior to the ablation cell led to an upstream shift in the position of ionization and lower overall fluorescence intensities.

The absolute number densities of helium atoms in the 2s 3S1 metastable state were determined in four plasma-based ambient desorption/ionization sources by atomic absorption spectroscopy. The plasmas included a high-frequency dielectric barrier discharge (HF-DBD), a low temperature plasma (LTP), and two atmospheric-pressure glow discharges, one with AC excitation and the other with DC excitation. Peak densities in the luminous plumes downstream from the discharge capillaries of the HF-DBD and the LTP were 1.39 × 1012 cm− 3 and 0.011 × 1012 cm− 3, respectively. Neither glow discharge produced a visible afterglow, and no metastable atoms were detected downstream from the capillary exits. However, densities of 0.58 × 1012 cm− 3 and 0.97 × 1012 cm− 3 were measured in the interelectrode regions of the AC and DC glow discharges, respectively. Time-resolved measurements of metastable atom densities revealed significant random variations in the timing of pulsed absorption signals with respect to the voltage waveforms applied to the discharges.

Pulsed laser radiation was directed at an inductively coupled plasma containing a high concentration of an alkaline earth matrix and a lower concentration of a test analyte. When the laser was tuned to an ionic resonance line of the matrix there was a universal transient enhancement of emission lines from the test analyte, irrespective of its identity. The effect was observed for Mg, Sr, Ba, Y, and Zn analytes in the presence of Mg, Sr, and Ca matrices. The enhancement is attributed to heating of the electrons in the plasma by superelastic collisions between electrons and excited matrix ions. By analogy to the laser-based experiments, a model is proposed for plasma-based matrix effects in the ICP, in which energy lost in the form of radiation from matrix ions cools the plasma, resulting in reduced emission from analyte species. The magnitudes of the radiative losses for 0.05 M Ca and Ba matrices were calculated to be 8.7 W cm−3 and 8.3 W cm−3, respectively. The model accounts for observed differences between group I and group II matrices.

We present mass spectrometric data demonstrating the effect that hydrogen has on a helium-based dielectric-barrier discharge (DBD) atmospheric-pressure plasma jet used as an ambient desorption/ionization (ADI) source. The addition of 0.9 % hydrogen to the helium support gas in a 35-W plasma jet increased signals for a range of test analytes, with enhancement factors of up to 68, without proportional increases in background levels. The changes in signal levels result from a combination of changes in the desorption kinetics from the surface and increased ion production in the gas phase. The enhancement in ADI-MS performance despite the quenching of key plasma species reported in earlier studies suggests that ionization with a H2/He plasma jet is the result of an alternate mechanism involving the direct generation of ionized hydrogen.

The effect of matrix on the formation and focusing of a Ca ion beam in the second vacuum stage of an inductively coupled plasma mass spectrometer has been evaluated with the use of planar laser induced fluorescence. A cross section of the beam was imaged near the entrance to the mass analyzer of a commercial instrument. Characteristics of the beam from a solution containing only the Ca analyte closely matched those predicted by simulation software. The individual addition of three matrix species, Mg, Cs, and Pb, had minor effect on beam shape. Cs and Pb both affected the beam trajectory. The most pronounced effect was with the Pb matrix, which caused an order-of-magnitude drop in the Ca signal intensity at the electron multiplier of the mass spectrometer. The loss in signal was due primarily to a shift in the direction and location of the Ca ion beam that caused it to miss the entrance into the mass analyzer.

Laser-induced fluorescence has been used to evaluate five commercially available skimmer cone designs from inductively coupled plasma mass spectrometers in terms of shock formation at the skimmer tip and transmission efficiency. Efficiency was measured as the ratio of analyte density downstream from the skimmer tip to analyte density upstream from the skimmer tip. The strongest shock was recorded for a skimmer with a cylindrical throat, and the weakest shock was produced by the skimmer with the largest diameter and a conical throat. Transmission efficiency increased with increasing orifice diameter. Coulombic effects, revealed in a comparison between the behaviors of neutral barium atoms and barium ions, were small. Transmission efficiencies recorded for calcium ions were lower than those recorded for barium ions by more than a factor of two.

We present a mathematical description of the signal-to-noise ratio (S/N) in a fluorescence-based protein detector for capillary electrophoresis that uses a pulsed ultraviolet (UV) laser at 266 nm as an excitation source. The model accounts for photobleaching, detector volume, laser repetition rate, and analyte flow rate. We have experimentally characterized such a system, and we present a comparison of the experimental data with the predictions of the model. Using the model, the system was optimized for test analytes tryptophan, tyrosine, bovine serum albumin (BSA), and conalbumin, producing detection limits (3σ) of 0.67 nM, 5.7 nM, 0.9 nM, and 1.5 nM, respectively. Based on the photobleaching data, a photobleaching cross-section of 1.4 × 10−18 cm2 at 266 nm was calculated for tryptophan.

Experimentally-determined flow velocities in the 6 mm upstream from the sampling cone of an inductively coupled plasma mass spectrometer were compared with velocities determined from a computer simulation of the flow and those calculated from a modified hemispherical sink model. The measured values and those from the simulation agreed within experimental error, but differed from the values calculated from the modified hemispherical sink model by as much as 30%. An empirical alternative to the modified hemispherical sink model is presented that allows for accurate calculation of flow properties upstream from the sampling cone under a range of plasma conditions.

Velocities of argon atoms and calcium ions were measured in the first vacuum stage of an inductively coupled plasma mass spectrometer using high-resolution laser-excited fluorescence spectroscopy. The calcium ions reached terminal velocities in the supersonic expansion that were consistently 5–6% higher than those of argon atoms, despite minimal differences in the masses of the two species. A computational model of the expansion was developed that shows the development of an ambipolar electric field along the expansion axis. With reasonable assumptions about electron temperatures in the expansion, the model accounts for the differences between the terminal velocities of the neutral argon atoms and the singly-charged calcium ions.

Microscopic imaging techniques were used to study sample removal from a glass surface by desorption electrospray ionization (DESI). Changes in fluorescence or absorption images of organic dyes were used to track the impact of the DESI spray on a smooth surface. Time-resolved images revealed rapid removal of the dye from an elliptical region impacted directly by the spray, followed by slower redistribution of the sample across the surface by flowing solvent and/or spray gases. The persistence of a mass spectrometric signal long after the dye was removed from the central impact region indicated that ions were being produced using processes other than impact of the spray on the surface. Placement of a barrier between the DESI spray tip and the mass spectrometer inlet provided additional evidence that ions were being produced at the ends of rivulets streaming away from the central impact region.

Planar laser-induced fluorescence was used to examine the effect of the sampling cone on analyte atom and ion distributions in the inductively coupled plasma used as an ion source for elemental mass spectrometry. Comparisons of planar laser-induced fluorescence images in the presence and absence of the sampling interface reveal that the insertion of the sampling cone into the plasma dramatically lowers singly-charged ion densities in the 1–2 mm region immediately upstream from the sampling cone, but increases densities in the region between 2 mm and 10 mm upstream from the sampling cone. Some of the drops in densities near the sampling cone can be attributed to acceleration of the plasma through the pumped sampling orifice. A shift in equilibrium between doubly and singly charged barium ions caused by cooling of the plasma is proposed to account for the increases in densities of Ba + in the upstream region.

Electric field gradient focusing (EFGF) is an equilibrium gradient focusing technique that depends on an electric field gradient and a hydrodynamic counterflow to focus, concentrate, and separate charged analytes. In this work, EFGF devices were fabricated from poly(ethylene glycol) (PEG)-functionalized acrylic plastic. The separation channel was formed in an ionically conductive and protein-resistant PEG-functionalized hydrogel, which was cast in a changing cross-sectional cavity in the plastic device. A linear electric field gradient was obtained by applying a voltage lengthwise across the shaped hydrogel. Standard proteins were used as analytes to demonstrate the performance of these EFGF devices. With an increase in counterflow rate or decrease in applied voltage, analyte bands broadened, but resolution increased in agreement with theory. To reduce analyte band dispersion and improve focusing performance, a protein-compatible PEG-functionalized monolith was incorporated in the EFGF channel. Compared with focusing in an open channel, protein bands in the monolith-filled EFGF channel were significantly narrower.

Miniaturized devices for electric field gradient focusing (EFGF) were developed that consist of a cylindrical separation channel surrounded by an acrylic-based polymer hydrogel. The ionic transport properties of the hydrogel enable the manipulation of the electric field inside the separation channel. A changing cross-section design was used in which the hydrogel is shaped such that an electric field gradient is established in the separation channel. One of the challenges with this type of EFGF device has been that experimental resolution between protein analytes is lower than theoretically predicted. In order to investigate this phenomenon, a mathematical transport model was developed using FEMLAB. Model results and experimental observations showed that the reduced performance was caused by concentration gradients formed in the EFGF channel, and that these concentration gradients were the result of an imbalance in cation transport between the open separation channel and the hydrogel. Removing acidic impurities from the monomers that form the hydrogel reduced this tendency and improved the resolution. These transport-induced concentration gradients can be used to establish electric field gradients that may be useful for sample pre-concentration. Both the results of simulation and experiments demonstrate how transport-induced concentration gradients lead to the establishment of electric field gradients.

In this work, a novel splitless nanoflow gradient generator integrated with a stop-flow injector was developed and evaluated using an on-column UV-absorption detector. The gradient pumping system consisted of two nanoflow pumps controlled by micro stepper motors, a mixer connected to a serpentine tube, and a high-pressure valve. The gradient system weighed only 4 kg (9 lbs) and could generate up to 55 MPa (8000 psi) pressure. The system could operate using a 24 V DC battery and required 1.2 A for operation. The total volume capacity of the pump was 74 μL, and a sample volume of 60 nL could be injected. The system provided accurate nanoflow rates as low as 10 nL/min without employing a splitter, making it ideal for capillary column use. The gradient dwell volume was calculated to be 1.3 μL, which created a delay of approximately 4 min with a typical flow rate of 350 nL/min. Gradient performance was evaluated for gradient step accuracy, and excellent reproducibility was obtained in day-to-day experiments (RSD1.2%, n = 4). Linear gradient reproducibility was tested by separating a three-component pesticide mixture on a poly(ethylene glycol) diacrylate (PEGDA) monolithic column. The retention time reproducibility was very good in run-to-run experiments (RSD1.42%, n = 4). Finally, excellent separation of five phenols was demonstrated using the nanoflow gradient system.

Planar laser-induced fluorescence was used to map density distributions of ground state barium atoms, ground state barium ions, and excited-state barium ions in the region between the load coil and the sampling cone of an inductively coupled plasma mass spectrometer. The effects of power, nebulizer gas flow rate, and the addition of lithium to the sample on the distributions were studied. The maps reveal that the radial distributions of atomic species across the diameter of the plasma are compressed as the plasma is drawn into the sampling orifice, and that as a result of that compression, the distribution of ions across the 1-mm diameter of the sampling orifice is non-uniform. The distribution changes as conditions in the plasma change. The skimmer cone that separates the first and second stages of the differentially-pumped vacuum interface transmits ions exclusively from the center of the distribution that exists at the sampling cone. As a result, the overall efficiency with which ions are transmitted through the vacuum interface varies as conditions in the plasma change.

The effects of collisions on the composition of the plasma passing through the first vacuum stage of an inductively coupled plasma mass spectrometer were monitored in three sets of experiments. Rates of collisional quenching of an excited state in the neutral calcium atom were estimated from changes in experimental fluorescence lifetimes. Intensities from collisionally-assisted fluorescence provided evidence of energy transfer between excited states. Changes in analyte number density along the axis of the supersonic expansion in the first vacuum stage provided evidence that ion-electron recombination occurs to a significant extent during the expansion. Together, the experiments create a picture of the first vacuum stage in which collisions play an important role in shaping the composition of the plasma that is ultimately delivered to the mass analyzer.

The supersonic expansion in the first vacuum stage of an inductively coupled plasma mass spectrometer has been characterized by laser-induced fluorescence of metastable argon atoms in the expansion. Atom velocities and temperatures were determined from Doppler shifts and linewidths, respectively, in the excitation spectra of the argon atoms. Shock structures characteristic of a supersonic expansion, the barrel shock and the Mach disk, were manifest as bimodal velocity distributions. The terminal velocities reached by the atoms were characteristic of conditions in the plasma source upstream from the entrance to the vacuum interface.

A flexible laser excited fluorescence system has been used to trace ion trajectories in the first vacuum stage of an inductively coupled plasma mass spectrometer. The system has been used to record the spatial distributions of ions immediately upstream from the sampling cone and in the 10 mm downstream from the cone for a variety of positions of the plasma with respect to the sampling cone. The data were used in turn to test the efficacy of scanning the plasma across the sampling cone to generate maps of ion distributions in the plasma. The maps generated by scanning the plasma across the cone are close approximations of the ion distribution immediately upstream from the sampling cone, but are not representative of distributions in an unperturbed plasma.

Microfabrication of ultrathin-layer chromatography (UTLC) plates via conformal deposition of silicon nitride by low-pressure chemical vapor deposition onto patterned carbon nanotube (CNT) scaffolds was demonstrated. After removal of the CNTs and hydroxylation, the resulting UTLC phase showed no expansion or distortion of their microfeatures and the absence/reduction of remaining nitrogenic species. Developing time of a mixture of lipophilic dyes on this UTLC plates was 86% shorter than on high-performance thin-layer chromatography (HPTLC) plates. A water-soluble food dye mixture was also separated resulting in low band broadening and reduced developing time compared to HPTLC. For the latter example, mobile phase optimization on a single UTLC plate consisted of 14 developments with different mobile phases, each preceded by a plate prewashing step. The same plate was again reused for additional 11 separations under varying conditions resulting in a development procedure with a mean separation efficiency of 233,000 theoretical plates/m and a reduced mobile phase consumption of only 400 μL. This repeated use proved the physical robustness of the ultrathin layer and its resistance to damage. The layer was highly suited for hyphenation to ambient mass spectrometry, including desorption electrospray ionization (DESI) mass spectrometry imaging and direct analysis in real time (DART) mass spectrometry.

A 260 nm deep UV LED-based absorption detector with low detection limits was developed and integrated with a small nanoflow pumping system. The detector is small in size (5.2 × 3.0 cm) and weighs only 85 g (without electronics). This detector was specifically designed and optimized for on-column detection to minimize extra-column band broadening. No optical reference was included due to the low drift in the signal. Two ball lenses, one of which was integrated with the LED, were used to increase light throughput through the capillary column. Stray light was minimized by the use of a band-pass filter and an adjustable slit. Signals down to the parts per billion level (nanomolar) were easily detected with a short-term noise level of 4.4 μAU, confirming a low limit of detection and low noise. The detection limit for adenosine-5'-monophosphate was 230 times lower than any previously reported values. Good linearities (3 orders of magnitude) were obtained using sodium anthraquinone-2-sulfonate, adenosine-5'-monophosphate, dl-tryptophan, and phenol. The LC system was demonstrated by performing isocratic separation of phenolic compounds using a monolithic capillary column (16.5 cm × 150 μm i.d.) synthesized from poly(ethylene glycol) diacrylate.

Laser-excited ionic fluorescence has been used to study the effects of sample matrix, operating conditions, and load coil shielding on analyte ion transport efficiency through the sampling orifice of an inductively coupled plasma mass spectrometer. Significant changes in ion transport efficiency result from changes in sample composition, RF forward power, nebulizer flow and torch shield configuration. The changes in ion transport efficiency correlate well with changes in the potential recorded on a single floating probe placed 1 mm upstream from the sampling orifice.

Two methods of characterizing the particle beam generated with a differentially pumped particle inlet are presented. Both methods are based on optical scattering of a laser beam by the particle beam. The first method images a time integrated scatter signal from the entire particle beam onto a charge coupled device (CCD), and an Abel inversion is performed on the image data to arrive at the radial particle density distribution in the beam. The second method, based on counting individual (particle) scatter pulses, yields the radial particle density directly. Initial results of the performance of the particle inlet are reported for particles with diameters between 40 and 800 nm. Under optimal working conditions, particle beams were generated with a full angle divergence on the order of 1-2 mrad. The width, measured 285 mm downstream from the exit of the particle inlet, was 250mu m, half width at half maximum (HWHM).

The effect of charge transfer reactions on analyte excitation and ionization in the inductively coupled plasma was studied by two independent techniques. In one technique, pulsed lasers were used to either deplete the ground state of neutral analyte atoms or enhance the population of selected states of the singly charged ion. In both cases the perturbed species were collision partners with argon in potential charge transfer reactions. The effects of charge transfer collisions could be detected in the form of changes in emission from product species. In the second technique, a simple correlation method was used to detect the link via charge transfer of neutral atom ground states and highly excited ionic levels. In the presence of charge transfer collisions, the populations of such linked levels show strong positive correlations. The two techniques were used to study the effects of charge transfer reactions on the third row elements Ca–Cu. With the exception of Cr and Mn, all of the elements studied showed positive evidence of excitation and ionization by charge transfer collision with argon.

Laser-induced atomic and ionic fluorescence have been used to characterize the material extracted from an inductively coupled plasma through a differentially pumped interface of the type used in inductively coupled plasma mass spectrometry. Measurements were made in the 8 mm downstream from the tip of the skimmer cone. Reference measurements were also made outside the interface at the tip of the sampling cone. Sc and Ba ions and Pb atoms were used as test analytes. Sc + densities drop more rapidly than either Ba + or Pb densities. The transmission efficiencies of both Sc + and Ba + are suppressed by the addition of either Mg or Pb to the analyte solution. The effects of the two matrix additions are approximately the same. Based on the magnitude of the fluorescence signal for Ba + , a lower limit of 0.3% for the transmission of Ba + from the plasma into the second vacuum stage has been calculated.

Velocity profiles of argon metastable atoms have been measured in the second stage of an inductively coupled plasma mass spectrometer (ICP-MS). These profiles were obtained from laser-induced fluorescence excitation spectra of the Ar I 4s[3/2]° to 4p[5/2] transition. Velocities were determined from the Doppler shift of the exciting radiation. An argon-filled hollow cathode lamp served as a stationary wavelength reference. The velocity distribution at the skimmer orifice is bimodal, indicative of a flow disturbance at or slightly upstream of the skimmer orifice.

The effects of different matrices on the analyte vertical emission profile in the inductively coupled plasma were evaluated with use of a monodisperse droplet sample introduction system in combination with a pneumatic nebulizer. The influence of matrix in the gas phase was separated from influences in the desolvation and volatilization steps. The results suggest that vertical shifts in the analyte emission profiles occur primarily during droplet desolvation and vaporization. The vertical shifts can be correlated to the size of the desolvated particles; larger particles produce emission profiles closer to the load coil. Possible effects of radiative heat transfer were also studied. Strongly absorbing species can increase the evaporation rate of the solvent and produce vertical shifts toward the load coil.

Monodisperse droplet sample introduction was used to study the ionization process in the inductively coupled plasma (ICP). The influence of the matrix on the analyte ion number density was evaluated by using laser-excited atomic fluorescence spectroscopy (LEAFS). The results suggest that the presence of 0.1 M NaCl enhances the ionization of the analyte species. With the addition of the NaCl, the spatially integrated Ba(II) signal decreases, apparently due to enhanced production of Ba2+. Added NaCl accelerates the appearance of Sc+, but does not affect the spatially integrated signal once ionization is complete. The possible effects on the fluorescence signal of quenching caused by the presence of the NaCl were evaluated by comparison of time-resolved and time-integrated detection. Quenching makes a small contribution to the fluorescence intensity change produced by the matrix but does not account for large loss in signal from singly ionized Ba.

This article is an electronic publication in Spectrochimica Acta Electronica (SAE), a section of Spectrochimica Acta Part B (SAB). The hardcopy text is accompanied by an electronic archive, stored on the SAE homepage at http://www.elsevier.nl/locate/sabe . The archive contains program, data and text files. The hardcopy text describes a program that has been developed to accept data from a compact electronic spectrograph and translate the data into a display on a computer screen. The computer display mimics the view seen through a direct vision spectroscope. Atomic spectra appear as vertical lines of the appropriate color dispersed on a black field. A conventional plot of intensity versus wavelength is simultaneously displayed. The update of the display is sufficiently rapid that the image on the screen is essentially a real-time representation of the light entering the spectrograph. The system was designed for use in conjunction with video projection equipment in demonstrations to large groups of students.

A portion of the ion beam in the second stage of an inductively coupled plasma mass spectrometer was mapped using laser induced fluorescence (LIF). With LIF relative density measurements are made in real time with minimal interference to the ion beam. We report axial measurements of Ba and Sc ion density from 22 to 45 mm behind the tip of the skimmer cone. Additionally, maps of radial ion density with and without Pb and Mg matrices are given for the same two analyte species. The results reveal that earlier ion deposition experiments dramatically underestimated the extent of the radial spread of the ion beam and the influence of matrix on the ion beam.

Doppler profiles are calculated for initial velocity distributions after charge transfer collisions. Such profiles are applied to emissions from excited Fe + following Ar + -Fe collisions, assuming an energy-independent cross section. It is shown that exoergic charge transfer processes may give significantly non-Gaussian line shapes with lines that are flatter and wider than would be expected from a Maxwellian distribution. Endoergic charge transfer processes, however, will give Gaussian line shapes with a linewidth described by a temperature only slightly below the source temperature. For exoergic reactions, our results differ slightly from results obtained using an adaptation of the method developed by Biondi and coworkers for dissociative recombination.

The optimum operating parameters of the inductively coupled plasma (ICP) with organic solvents are different from those with aqueous solutions. With organic solvents, the ICP is operated at higher power to overcome plasma cooling due to the organic solvent, and aerosol desolvation is necessary in order to reduce solvent load into the plasma. The monodisperse dried microparticulate injector (MDMI) offers the possibility of controlling solvent load by controlling the frequency with which droplets are introduced into the plasma. A test solution that contained 0.5 mg/L Ba in xylene was used to study the influence of MDMI operating parameters on the behavior of the ICP with an organic solvent. The spatial and temporal distribution of the solvent in the ICP was determined for different droplet production frequencies and MDMI oven temperatures, and the optimum operating conditions were established. The best detection limit for Ba in xylene was 1.5 ng/mL, or 0.16 pg (in 200 droplets).

A 40-MHz ICP was equipped with a novel sample introduction system capable of introducing monodisperse droplets into the plasma with 100% efficiency. The analytical performance of the system was investigated by using two different synchronous detection techniques. The detection limits determined for Ba with ensemble averaging and with boxcar averaging were 0.048 ng/mL and 0.063 ng/mL, respectively. Signal stability in time, effect of the matrix on barium ionic emission intensity, vertical emission profiles from a multicomponent solution, and washout time of the system were also studied.

A nickel mesh was placed in the ion beam in the second vacuum stage of an inductively coupled plasma mass spectrometer. Deposits on the mesh from the beam were analyzed by scanning electron microscopy combined with energy dispersive X-ray fluorescence spectroscopy in an effort to measure element-specific ion distributions in the beam. The experiments suggest that the distribution of material in the deposit depends on factors other than the spatial distributions of atomic ions in the ion beam. Neutral atoms can affect the formation of the deposit, as can either charged or neutral microparticulates. Caution is urged in the use of deposition experiments of this type to study ion beam behavior.

Supercritical fluid extraction (SFE) can greatly reduce the sample preparation time of analytes in solid matrices. The on-line coupling of SFE with high-speed gas chromatography (GC) can further reduce the total analysis time. SFE has been coupled to GC with a thermal desorption modulator (TDM) interface. A thermal energy analyzer (TEA), a chemiluminescence detector which is specific for nitro and nitroso compounds, has been coupled to the system to analyze explosives in soil samples. The use of organic modifiers to increase the solvation power of carbon dioxide was necessary for the extraction of various explosives, and did not adversely affect the performance of the system. Thermally labile compounds, however, such as the nitrate esters, were shown to decompose in the modulator before the chromatographic separation. This method allows for the rapid analysis of relatively volatile and thermally stable nitro compounds from solid matrices. The system can be used for screening small samples in short periods of time. Total analysis can be completed in less than 10 minutes and requires only 200 mg of soil. The minimum detectable quantity for the analysis of 2,4-DNT was found to be 2.6 ppb in an actual soil sample.