Characterizing ablation and aerosol generation during elemental fractionation on absorption modified lithium tetraborate glasses using LA-ICP-MS

The influence of sample matrix composition, absorption behavior and laser aerosol particle size distribution on elemental fractionation in laser ablation inductively coupled plasma mass spectrometry was studied for nanosecond laser ablation at a wavelength of 266 nm. To this end, lithium tetraborate glass samples with different iron oxide contents and trace amounts of a group of 11 elements were prepared synthetically. The samples were characterized in terms of optical absorbance, melting points, trace element concentrations and homogeneity. UV/VIS spectra showed that sample absorption rises with increasing Fe₂O₃ content. Crater depths and time-dependent particle size distributions were measured, and ablated and transported sample volumes were estimated. Furthermore, the laser aerosol was filtered using a particle separation device and transient ICP-MS signals were acquired with and without filtering the aerosol. The results demonstrate that the amount of ablated sample is related to the absorption coefficient of the sample and therefore to the optical penetration depth of the laser beam into the sample. The higher energy densities resulting from the shorter penetration depths result in smaller average particle sizes for highly absorbing samples, which allows more efficient transport to and atomization and excitation of the ablated material within the ICP. The particle size distribution changes continuously with ablation time, and larger particle fractions occur mainly at the beginning of the ablation, which leads to particle-related fractionation processes at the beginning of the transient signal. Exceeding a critical depth to diameter ratio, laser-related elemental fractionation processes occur. Changes in the volatile to non-volatile element intensity ratio after the aerosol is filtered indicate that particle size-related enrichment processes contribute to elemental fractionation.     

基于大气压下介质阻挡放电抑制LA-ICP-MS分析中元素分馏效应研究

采用自制的大气压下介质阻挡放电装置串联在激光剥蚀池与ICP炬管之间, 对激光剥蚀产生的气溶胶进行预电离. 结果表明, 元素瞬时信号轮廓的平滑度得以改善, 元素分析信号精密度(RSD, n=3)可提高2.55％. 在ArF准分子激光(193 nm)和Nd∶YAG 固体激光(213 nm)两种不同波长的激光剥蚀系统中, 元素分馏因子均比常规模式下更接近于1, 表明采用介质阻挡放电对气溶胶预电离后元素分馏效应得以有效抑制. 相比两种不同波长的激光剥蚀系统, 介质阻挡放电对213 nm固体激光的元素分馏效应改善作用明显.     

Elemental composition of laser ablation aerosol particles deposited in the transport tube to an ICP

The element ratios in aerosol particles produced by laser ablation (λ=266 nm, pulse length: 5 ns) of brass and steel in Ar and He and deposited in different segments of the transport tube to an ICP have been measured by ICP-MS. The data are compared with the ratios obtained by a corresponding bulk analysis. For brass, the element compositions of the aerosol particles deposited in different parts of the tube deviated from the bulk and varied along the tube. For steel, moderate agreement of the element ratios in the aerosols and the bulk was found. It is also shown that elemental ratios measured on-line by laser ablation ICP-MS with the laser-produced aerosol should not be calibrated by elemental ratios obtained with wet aerosols from aqueous solutions of the bulk.     

Low pressure laser ablation coupled to inductively coupled plasma mass spectrometry

The particle size distribution in laser ablation inductively coupled plasma mass spectrometry is known to be a critical parameter for complete vaporization of particles. Any strategy to reduce the particle size distribution of laser generated aerosols has the potential to increase the ion signal intensity and to reduce fractionation effects. Due to the fact that vapor generation, nucleation, condensation, and agglomeration take place within an extremely short period of time, ablation under atmospheric pressure might not allow influencing these processes while under reduced pressure condition the cooling of the aerosol and therefore the condensation is expected to be slower. In this study, a low pressure laser ablation cell for the generation of laser aerosols was coupled to an ICP-MS. In contrast to the previously developed trapped ablation mode, the newly designed cell allows the adjustment of the pressure in the ablation cell between 20 and 1400 mbar prior to the ablation.Ablation experiments carried out using this configuration showed a dependence of the aerosol properties (size distribution and particle structure) on the ablation cell pressure. The intensity ratio U/Th measured as a figure of merit for complete vaporization within the ICP indicated a change in the aerosol structure at approximately 500 mbar toward smaller particle size. A significant difference between low pressure and at ambient pressure ablated aerosol was observed. The intensity ratios (U/Th) of the ablated sample moves closer to the bulk composition at lower pressures at the expense of sensitivity. Therefore the decrease in the ICP-MS signal intensity in the low pressure cell can be attributed to vapor deposition within the ablation cell walls.Moreover, scanning electron microscope images of aerosols collected on filters after the low pressure ablation cell suggest the possibility of a slower cooling velocity of the aerosol, which was observed in the condensed material on the surface of ejected spherical particles. The expansion of the laser aerosol was also investigated using polished brass substrates in the expansion path-way for particle collection.     

Emission spectroscopic monitoring of particle composition,size and transport in laser ablation inductively coupled plasma spectrometry

The spectroscopic line emissions of copper and zinc from atomized particles generated by orthogonal pre-pulse laser ablation of brass and transported from the ablation cell through tubes into an ICP have been simultaneously measured end-on with fast photomultipliers. It was shown that simultaneous line monitoring of major elements provides not only information on the aerosol transport in laser ablation ICP-spectrometry, but also on the ratios of small to single larger particles and their respective elemental compositions and, therefore, on possible elemental fractionation problems. Furthermore, the spectroscopic information can be easily exploited for proper adjustment of the laser fluence in order to minimize the production of large particles, to improve the transport efficiency and to reduce the noise of analytical signals in laser ablation ICP-spectrometry. The present particular experiment on orthogonal pre-pulse laser ablation of brass confirms the recent finding that such kind of double-pulse arrangement produces predominantly ultra-fine particles. Individual brass particles with diameters ≳ 250 nm could be analyzed. They showed large Zn depletions as expected. Finally, strong accumulations of aerosol particles were found in the ablation cell used even at low laser pulse frequencies.     

Phenomenological studies on structure and elemental composition of nanosecond and femtosecond laser-generated aerosols with implications on laser ablation inductively coupled plasma mass spectrometry

In laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), the properties of laser-generated aerosols, such as size and composition, are crucial for matrix-independent quantification. In this study, the aerosol particle morphology and elemental composition generated by two state-of-the-art laser systems (ArF excimer nanosecond-UV laser and Ti:sapphire femtosecond-IR laser) were investigated by electron microscopic techniques. Electrostatic sampling of the aerosols directly onto transmission electron microscopy (TEM) grids allowed us to study the morphology and elemental composition of the aerosols using TEM and TEM–EDX (energy dispersive X-ray spectroscopy) analyses, respectively. The results of the electron microscopic studies were finally compared to the LA-ICPMS signals of the main matrix components. The investigations were carried out for non-conducting materials (glass and zircon), metallic samples (steel and brass) and semiconductors (sulfides). The studies confirm that ns-LA-generated aerosols dominantly consist of nanoparticle agglomerates while conducting samples additionally contain larger spherical particles (diameter typically 50 to 500 nm). In contrast to ns-laser ablation, fs-LA-generated aerosols consist of a mixture of spherical particles and nanoparticle agglomerates for all investigated samples. Surprisingly, the differences in elemental composition between nanoparticle agglomerates and spherical particles produced with fs-LA were much more pronounced than in the case of ns-LA, especially for zircon (Si/Zr fractionation) and brass (Cu/Zn fractionation). These observations indicate different ablation and particle formation mechanisms for ns- and fs-LA. The particle growth mechanism for ns-LA is most likely a gas-to-particle conversion followed by agglomeration and additional hydrodynamic sputtering for conducting samples. On the other hand, phase explosion is assumed to be responsible for the mixture of large spherical particles and nanoparticle agglomerates as found for fs-LA-generated aerosols. Based on these mechanisms, the overall temporal elemental fractionation effects in ns-LA-ICPMS seem to occur mainly during the ablation. This effect was not observed for fs-LA-ICPMS despite the element separation into different particle fractions, which, on the other hand, could induce severe ICP-induced fractionation.     

Glass particles produced by laser ablation for ICP-MS measurements

Pulsed laser ablation (266 nm) was used to generate glass particles from two sets of standard reference materials using femtosecond (150 fs) and nanosecond (4 ns) laser pulses with identical fluences of 50 J cm⁻². Scanning electron microscopy (SEM) images of the collected particles revealed that there are more and larger agglomerations of particles produced by nanosecond laser ablation.In contrast to the earlier findings for metal alloy samples, no correlation between the concentration of major elements and the median particle size was found. When the current data on glass were compared with the metal alloy data, there were clear differences in terms of particle size, crater depth, heat affected zone, and ICP-MS response. For example, glass particles were larger than metal alloy particles, the craters in glass were less deep than craters in metal alloys, and damage to the sample was less pronounced in glass compared to metal alloy samples. The femtosecond laser generated more intense ICP-MS signals compared to nanosecond laser ablation for both types of samples, although glass sample behavior was more similar between ns- and fs-laser ablation than for metal alloys.     

激光剥蚀电感耦合等离子体质谱法中生物样品的元素分馏效应研究

采用213 nm-纳秒激光剥蚀系统对生物基体样品的剥蚀颗粒进行研究,优化了激光剥蚀条件.在剥蚀能量为25%,束斑直径为200 μm,剥蚀速率为20 μm/s,频率为20 Hz,载气为700 mL He + 700 mL Ar时,信号强度及稳定性最佳.以31P为内标元素,最佳剥蚀条件下,考察了56个元素的相对分馏因子.结果表明,生物基体的剥蚀颗粒相较于NIST 610 玻璃标样更大,达到3 μm;生物基体中元素分馏效应相较于玻璃基体小,大多数元素的相对分馏因子达到1.0 ±0.1.探讨了生物基体中元素分馏机理,分析了生物基体相较于玻璃基体剥蚀颗粒大,而相对分馏因子未明显增大的原因.一方面可能是粒径3 μm的颗粒进入电感耦合等离子体后能原子化;另一方面,大的剥蚀颗粒的富集效应相对较小.进一步对分馏效应的影响因素进行研究,发现分馏效应与激光剥蚀能量、激光频率和扫描速率相关,并且与元素的氧化物沸点负相关,与氧化物键能和电离能正相关.     

Investigation on elemental and isotopic fractionation during 196 nm femtosecond laser ablation multiple collector inductively coupled plasma mass spectrometry

Despite the large number of successful applications of laser ablation, elemental and isotopic fractionation coupled to inductively coupled plasma mass spectrometry (ICP-MS) remain as the main limitations for many applications of this technique in the fields of analytical chemistry and Earth Sciences. A substantial effort has been made to control such fractionations, which are well-established features of nanosecond laser ablation systems. Technological advancements made over the past decade now allow the ablation of solids by femtosecond laser pulses in the deep ultraviolet (UV) region at wavelengths less than 200 nm. Here the use of femtosecond laser ablation and its effects on elemental and isotopic fractionation is investigated. The Pb/U system is used to illustrate elemental fractionation and stable Fe isotopes are used to illustrate isotopic fractionation. No elemental fractionation is observed beyond the precision of the multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements. Without a matrix match between standard and sample, elemental fractionation is absent even when using different laser ablation protocols for standardization and samples (spot versus raster). Furthermore, we found that laser ablation-induced isotope ratio drifts, commonly observed during nanosecond laser ablation, are undetectable during ultraviolet femtosecond laser ablation. So far the precision obtained for Fe isotope ratio determinations is 0.1‰ (2 standard deviation) for the ⁵⁶Fe/⁵⁴Fe ratio. This is close to that obtainable by solution multiple-collector inductively coupled plasma mass spectrometry. The accuracy of the results appears to be independent of the matrix used for standardization. The resulting smaller particle sizes reduce fractionation processes. Femtosecond laser ablation carries the potential to solve some of the difficulties encountered during the two prior decades since the introduction of laser ablation.     

Influence of physical properties and chemical composition of sample on formation of aerosol particles generated by nanosecond laser ablation at 213 nm

The influence of sample properties and composition on the size and concentration of aerosol particles generated by nanosecond Nd:YAG laser ablation at 213 nm was investigated for three sets of different materials, each containing five specimens with a similar matrix (Co-cemented carbides with a variable content of W and Co, steel samples with minor differences in elemental content and silica glasses with various colors). The concentration of ablated particles (particle number concentration, PNC) was measured in two size ranges (10–250 nm and 0.25–17 µm) using an optical aerosol spectrometer. The shapes and volumes of the ablation craters were obtained by Scanning Electron Microscopy (SEM) and by an optical profilometer, respectively. Additionally, the structure of the laser-generated particles was studied after their collection on a filter using SEM.     

硫化物矿物LA-ICP-MS激光剥蚀元素信号响应

采用193 nm ArF准分子激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)对5种天然硫化物矿物进行激光剥蚀分析, 基于不同硫化物矿物的剥蚀形貌特征和元素瞬时信号响应, 考察了硫化物矿物的元素分馏效应及激光频率、能量和激光斑径对硫化物矿物激光剥蚀行为的影响. 结果表明, 不同硫化物矿物的激光剥蚀形貌和元素分馏效应存在明显差异, 其中黄铁矿、辉钼矿和闪锌矿的剥蚀晕约为剥蚀斑径的10倍, 而黄铜矿和磁黄铁矿的剥蚀晕约为剥蚀斑径的14倍; 黄铜矿、磁黄铁矿和闪锌矿元素分馏因子(EFI)约为1.0, 其元素分馏效应可以忽略, 而黄铁矿和辉钼矿存在明显的元素分馏效应. 在对硫化物矿物的LA-ICP-MS分析中, 选择较大的激光剥蚀斑径、较小的激光剥蚀频率与激光能量可获得理想的信号强度和准确的分析结果.     

Tungsten carbide precursors as an example for influence of a binder on the particle formation in the nanosecond laser ablation of powdered materials

A study of LA-ICP-MS analysis of pressed powdered tungsten carbide precursors was performed to show the advantages and problems of nanosecond laser ablation of matrix-unified samples. Five samples with different compositions were pressed into pellets both with silver powder as a binder serving to keep the matrix unified, and without any binder. The laser ablation was performed by nanosecond Nd:YAG laser working at 213 nm.The particle formation during ablation of both sets of pellets was studied using an optical aerosol spectrometer allowing the measurement of particle concentration in two size ranges (10-250 nm and 0.25-17 μm) and particle size distribution in the range of 0.25-17 μm. Additionally, the structure of the laser-generated particles was studied after their collection on a filter using a scanning electron microscope (SEM) and the particle chemical composition was determined by an energy dispersive X-ray spectroscope (EDS).The matrix effect was proved to be reduced using the same silver powdered binder for pellet preparation in the case of the laser ablation of powdered materials.The LA-ICP-MS signal dependence on the element content present in the material showed an improved correlation for Co, Ti, Ta and Nb of the matrix-unified samples compared to the non-matrix-unified pellets. In the case of W, the ICP-MS signal of matrix-unified pellets was influenced by the changes in the particle formation.     

First field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer for the on-line detection of particle-bound polycyclic aromatic hydrocarbons

The on-line analysis of single aerosol particles with mass spectrometrical methods is an important tool for the investigation of aerosols. Often, a single laser pulse is used for one-step laser desorption/ionisation of aerosol particles. Resulting ions are detected with time-of-flight mass spectrometry. With this method, the detection of inorganic compounds is possible. The detection of more fragile organic compounds and carbon clusters can be accomplished by separating the desorption and the ionisation in two steps, e.g. by using two laser pulses. A further method is, using a heated metal surface for thermal desorption of aerosol particles. If an ultraviolet laser is used for ionisation, a selective ionisation of polycyclic aromatic hydrocarbons (PAH) and alkylated PAH is possible via a resonance-enhanced multiphoton-ionisation process. Laser velocimetry allows individual laser triggering for single particles and additionally delivers information on aerodynamic particle diameters. It was shown that particles deriving from different combustion sources can be differentiated according to their PAH patterns. For example, retene, a C₄-alkylated phenanthrene derivative, is a marker for the combustion of coniferous wood. In this paper, the first field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer during a measurement campaign in Augsburg, Germany in winter 2010 is presented. Larger PAH-containing particles (i.e. with aerodynamic diameters larger than 1 μm), which are suspected to be originated by re-suspension processes of agglomerated material, were in the focus of the investigation. Due to the low concentration of these particles, an on-line virtual impactor enrichment system was used. The detection of particle-bound PAH in ambient particles in this larger size region was possible and in addition, retene could be detected on several particles, which allows to identify wood combustion as generic source of these particles. The observed diurnal distribution of these larger particles, however, support the origin by traffic induced re-suspension of sedimented/agglomerated material.     

Characterization of the aerosol produced by infrared femtosecond laser ablation of polyacrylamide gels for the sensitive inductively coupled plasma mass spectrometry detection of selenoproteins

A 2D high repetition rate femtosecond laser ablation strategy (2-mm wide lane) previously developed for the detection of selenoproteins in gel electrophoresis by inductively coupled plasma mass spectrometry was found to increase signal sensitivity by a factor of 40 compared to conventional nanosecond ablation (0.12-mm wide lane) [G. Ballihaut, F. Claverie, C. Pécheyran, S. Mounicou, R. Grimaud and R. Lobinski, Sensitive Detection of Selenoproteins in Gel Electrophoresis by High Repetition Rate Femtosecond Laser Ablation-Inductively Coupled Plasma Mass Spectrometry, Anal. Chem. 79 (2007) 6874–6880]. Such improvement couldn't be explained solely by the difference of amount of material ablated, and then, was attributed to the aerosol properties. In order to validate this hypothesis, the characterization of the aerosol produced by nanosecond and high repetition rate femtosecond laser ablation of polyacrylamide gels was investigated. Our 2D high repetition rate femtosecond laser ablation strategy of 2-mm wide lane was found to produce aerosols of similar particle size distribution compared to nanosecond laser ablation of 0.12-mm wide lane, with 38% mass of particles < 1 µm. However, at high repetition rate, when the ablated surface was reduced, the particle size distribution was shifted toward thinner particle diameter (up to 77% for a 0.12-mm wide lane at 285 µm depth). Meanwhile, scanning electron microscopy was employed to visualize the morphology of the aerosol. In the case of larger ablation, the fine particles ejected from the sample were found to form agglomerates due to higher ablation rate and then higher collision probability. Additionally, investigations of the plasma temperature changes during the ablation demonstrated that the introduction of such amount of polyacrylamide gel particles had very limited impact on the ICP source (ΔT~ 25 ± 5 K). This suggests that the cohesion forces between the thin particles composing these large aggregates were weak enough to have negligible impact on the ICPMS detection.     

Analyte response in laser ablation inductively coupled plasma mass spectrometry

The dependence of analyte sensitivity and vaporization efficiency on the operating parameters of an inductively coupled plasma mass spectrometer (ICPMS) was investigated for a wide range of elements in aerosols, produced by laser ablation of silicate glass. The ion signals were recorded for different carrier gas flow rates at different plasma power for two different laser ablation systems and carrier gases. Differences in atomization efficiency and analyte sensitivity are significant for the two gases and the particle size distribution of the aerosol. Vaporization of the aerosol is enhanced when helium is used, which is attributed to a better energy-transfer from the plasma to the central channel of the ICP and a higher diffusion rate of the vaporized material. This minimizes elemental fractionation caused by sequential evaporation and reduces diffusion losses in the ICP. The sensitivity change with carrier gas flow variation is dependent on m/z of the analyte ion and the chemical properties of the element. Elements with high vaporization temperatures reach a maximum at lower gas flow rates than easily vaporized elements. The sensitivity change is furthermore dependent on m/z of the analyte ion, due to the mass dependence of the ion kinetic energies. The mass response curve of the ICPMS is thus not only a result of space charge effects in the ion optics but is also affected by radial diffusion of analyte ions and the mismatch between their kinetic energy after expansion in the vacuum interface and the ion optic settings.     

The agglomeration state of nanosecond laser-generated aerosol particles entering the ICP

Fundamental understanding of aerosol formation and particle transport are important aspects of understanding and improving laser-ablation ICP–MS. To obtain more information about particles entering the ICP, laser aerosols generated under different ablation conditions were collected on membrane filters. The particles and agglomerates were then visualised using scanning electron microscope (SEM) imaging. To determine variations between different sample matrices, opaque (USGS BCR-2G) and transparent (NIST SRM 610) glass, CaF₂, and brass (MBH B26) samples were ablated using two different laser wavelengths, 193 and 266 nm. This study showed that the condensed nano-particles (∼10 nm in diameter) formed by laser ablation reach the ICP as micron-sized agglomerates; this is apparent from filters which contain only a few well-separated particles and particle agglomerates. Ablation experiments on different metals and non-metals show that the structure of the agglomerates is matrix-dependent. Laser aerosols generated from silicates and metals form linear agglomerates whereas particle-agglomerates of ablated CaF₂ have cotton-like structures. Amongst other conditions, this study shows that the absorption characteristics of the sample and the laser wavelength determine the production of micron-sized spherical particles formed by liquid droplet ejection.     

Considerations of particle vaporization and analyte diffusion in single-particle inductively coupled plasma-mass spectrometry

The intensity of individual gold nanoparticles with nominal diameters of 80, 100, 150, and 200 nm was measured using single-particle inductively coupled plasma-mass spectrometry (ICP-MS). Since the particles are not perfectly monodisperse, a distribution of ICP-MS intensity was obtained for each nominal diameter. The distribution of particle mass was determined from the transmission electron microscopy (TEM) image of the particles. The distribution of ICP-MS intensity and the distribution of particle mass for each nominal diameter were correlated to give a calibration curve. The calibration curves are linear, but the slope decreases as the nominal diameter increases. The reduced slope is probably due to a smaller degree of vaporization of the large particles.In addition to the degree of particle vaporization, the rate of analyte diffusion in the ICP is an important factor that determines the measured ICP-MS intensity. Simulated ICP-MS intensity versus particle size was calculated using a simple computer program that accounts for the vaporization rate of the gold nanoparticles and the diffusion rate and degree of ionization of the gold atoms. The curvature of the simulated calibration curves changes with sampling depth because the effects of particle vaporization and analyte diffusion on the ICP-MS intensity are dependent on the residence time of the particle in the ICP. Calibration curves of four hypothetical particles representing the four combinations of high and low boiling points (2000 and 4000 K) and high and low analyte diffusion rates (atomic masses of 10 and 200 Da) were calculated to further illustrate the relative effects of particle vaporization and analyte diffusion. The simulated calibration curves show that the sensitivity of single-particle ICP-MS is smaller than that of the ICP-MS measurement of continuous flow of standard solutions by a factor of 2 or more. Calibration using continuous flow of standard solution is semi-quantitative at best.An empirical equation is formulated for the estimation of the position of complete vaporization of a particle in the ICP. The equation takes into account the particle properties (diameter, density, boiling point, and molecular weight of the constituents of the particle) and the ICP operating parameters (ICP forward power and central channel gas flow rate). The proportional constant and exponents of the variables in the equation were solved using literature values of ICP operating conditions for single-particle inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) measurements of 6 kinds of particles in 12 studies. The calculated position is a useful guide for the selection of sampling depth or observation height for ICP-MS and ICP-AES measurements of single particles as well as discrete particles in a flow, such as laser-ablated materials and airborne particulates.     

Flicker noise spectroscopy in an analysis of the dynamics of atmospheric aerosol

Flicker noise spectroscopy was used to analyze measurements in the free atmosphere. The special features of correlations between the measured atmospheric aerosol parameters, namely, the total concentration of aerosol with particle size no larger than 3 nm, the concentration of particles whose size exceeded 150 nm, and the mean size of these particles, were determined and analyzed. These correlations could be used to create new models and reveal the rules governing the formation of new particles. Flicker noise spectroscopy was shown to offer much promise for atmospheric measurements.     

Effect of oxygen on laser-induced elemental fractionation in LA-ICP-MS analysis

Elemental fractionation poses serious difficulties in obtaining accurate concentration and isotope ratio data when using laser ablation sampling. One of the factors that control the extent of laser-induced elemental fractionation is the composition of sample carrier gas in the sample cell. This study demonstrates that the presence of small amounts of oxygen in the He carrier gas has a significant effect on elemental fractionation during the ablation of silicate (NIST 612 glass and zircon 91500) and sulphide (NiS fire assay) samples. The extent of elemental fractionation for a given amount of ablated material and concentration of oxygen in the He carrier gas was related to the volume of the plasma plume that forms above the sample surface. This indicates that an oxidation reaction takes place in the plasma plume. It has been reported that oxidation can affect the particle size distribution during laser sampling and hence change the extent of elemental fractionation. The purity of the carrier gas used in laser ablation-ICP-MS, as well as the amount of oxygen released from silicate and oxide samples during the ablation in "oxygen-free" ambient gas, is shown to contribute significantly to elemental fractionation.     

Characterisation of River Po particles by sedimentation field-flow fractionation coupled to GFAAS and ICP-MS

A procedure for elemental composition determination of water-borne river particles (Po River) on both size-fractionated and unfractionated submicron particles (0.1–1 μm) by graphite furnace atomic absorption spectroscopy (GFAAS) and inductively coupled plasma-mass spectrometry (ICP-MS) is reported. Sample fractionation was performed using sedimentation field-flow fractionation (SdFFF). The distribution of relative mass vs. particle size was determined using UV detection. Fractions were collected over a narrow size range for scanning electron microscopy. With this combination of techniques the mass, elemental composition, and shape distributions can be obtained across the size spectrum of the sample.

The size distributions of the major elements (Al, Fe) were determined by coupling both GFAAS and ICP-MS techniques to the SdFFF. The procedure was validated using a reference clay sample. Satisfactory agreement was found between both the GFAAS and ICP-MS aluminium signal and the UV detector signal. Some discrepancies were observed in the Fe/Al ratios when comparing GFAAS and ICP-MS. Thus further investigation is in order to fully assess the role of SdFFF-ICP-MS and SdFFF-GFAAS techniques for elemental characterisation of aquatic colloids. Both GFAAS and ICP-MS signals unambiguously indicate a significantly higher Fe content in the lower size range, which is consistent with previous investigations.

Trace element levels in unfractionated Po River particles, determined by both GFAAS and ICP-MS, show good agreement. The high levels of Cu, Pb, Cr and Cd found associated with the colloidal particles underlines the significance of the environmental role played by the suspended matter in rivers in both highly industrialised and intensively cultivated areas.