Analysis of lead in tooth enamel by laser ablation-inductively coupled plasma-mass spectrometry.

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine the Pb/Ca ratios in the enamel of deciduous incisors, a biomarker of in utero Pb exposure, using pelletized bone certified reference materials (CRMs) as calibrants. The detection limit for Pb by LA-ICP-MS was 11 microg kg(-1) demonstrating an adequate sensitivity for Pb in the teeth of unexposed individuals (0.1-10 mg kg(-1)). The precision for the Pb/Ca ratios in NIST SRM 1486 Bone Meal was 3.4%. The correlation between Pb/Ca ratios obtained by LA-ICP-MS and those obtained by a digestion method was highly significant. We found one point calibration by a CRM was applicable for the quantification of Pb in tooth enamel. This method will be valuable for the assessment of in utero Pb exposure levels.     

Exploring lead exposure in ancient Chilean mummies using a single strand of hair by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

Lead exposure has received increased attention over the past few decades since it has been shown to have adverse effects on physical and intellectual development in humans. The use of biological tissues such as blood, teeth, hair, and bone for assessment of lead exposure has been previously demonstrated. While analysis of blood for trace metals provides information concerning recent exposure, hair offers insight into a period of several months, and is preferable since it is non-invasively collected and easily stored. The present study analyzed total of 49 ancient hair samples for lead (Pb_H) using LA-ICP-MS. Samples belonged to an ancient fisher hunter–gatherer culture called the “Chinchorro,” and who occupied regions of the Atacama Desert on the northern coast of Chile from approximately 5000–1500 B.C. and practiced the first-known form of artificial mummification. Several samples from a post-Chinchorro agricultural community (n = 12) ca. 1000–1400 A.D. were also analyzed. A suite of hair standards was developed using contemporary hair from the same region and was subsequently used to make linear calibration functions for lead determination in single strands of hair using LA-ICP-MS. Three linear scans ranged from 500 to 1000 μm were performed for each sample and signal intensities were normalized over ¹³C. The distribution of lead in the central medulla in a 100 μm cross-section scan of hair strand demonstrated minimal exogenous contamination. Hair lead (Pb_H) concentrations ranged between 2.2 μg/g and 12.8 μg/g could be accurately quantified with these standards. Twenty one out of 49 samples (43%) showed Pb_H concentrations higher than the average value of 5 μg/g for unexposed individuals (range 1.1–228.0 μg/g). Median hair lead concentrations by burial sites and are shown in order of decreasing concentration: Morro (13.8 μg/g) > Iquique (6.6 μg/g) > Azapa (4.5 μg/g) > Yungay (4.1 μg/g) > Camarones (2.7 μg/g). Most of the burial sites showed Pb_H concentrations greater than the normal value for unexposed individuals and outliers heavily influenced average concentrations. The results suggest that the Chinchorro and later agro-pastoral populations were not widely exposed to naturally elevated lead.     

Analysis of solids by laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS)—I. matching with a glass matrix

The possibility of quantitative elemental analysis of solids by laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS) has been investigated. The solids were mixed with a flux and fused to a glass bead so that a similar matrix composition would be obtained for the different samples (matrix matching), and an internal standard could be added. Strontium, present in the flux materials, was found to be suitable as the internal standard. Two major problems were experienced in the analysis: memory effects and interference from polyatomic ions. The memory effects were probably due to deposits of particles in the transfer tubes between the laser ablation cell and the ICP torch. At masses below 80 m/z, strong interferences from polyatomic ions caused serious problems in the quantification and, for elements studied in that mass region, detection limits were poor. The technique was further applied more specifically to the determination of rare earth elements in geological materials, for which detection limits varied from 0.02 to 3 mg/kg. Quantitative analysis, independent of the kind of sample material, proved possible.     

Modelling the temporal intensity distribution in laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) using scanning and drilling mode

Signal equations basing on dispersion functions describing the measured temporal intensity distribution for laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) used in scanning and drilling mode are developed. Variable ablation rates due to either varying focussing conditions typical for drilling mode and due to the changes of physical and chemical properties in inhomogeneous samples as typically investigated in scanning mode are considered for. The model accounts for intermixing of the sample aerosol within the sampling chamber, the influence of transport in a cylindrical transport channel and the fact that normally not the entire vapour generated and transported to the ICP can be observed. The absolute signal response is influenced by the actually ablated, transported and observed analyte mass. The dispersion functions describing the relative signal response depend on sample chamber volume, the volume of the transport channel, the laser shot frequency, the carrier gas flow rate and the part of observable cross-section at the MS interface compared to the entire cross-section filled by the vapour. All these parameters depend on the experimental set-up and the selected operating conditions only. Using the signal equation the influence of all mentioned parameters on signal course is shown both theoretically and experimentally. The signal equation can be used for calculation of optimal experimental conditions.

On this basis, an algorithm is proposed providing the relative temporal distribution of any analyte with significantly higher temporal resolution than the measured temporal intensity distribution itself. Furthermore, usage of dispersion functions for investigation of a given transport system, for explanation of typical signal deviations, for the proof of homogeneous regions in a heterogeneous sample, for examination of changes in ablation rate and for investigation of fractionation effects is shown.     

High-resolution laser ablation-inductively coupled plasma-mass spectrometry imaging of cisplatin-induced nephrotoxic side effects

Two-dimensional elemental mapping (bioimaging) via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on 5 μm thick formalin-fixed, paraffin-embedded kidney tissue sections from Cynomolgus monkeys administered with increasing pharmacological doses of cisplatin. Laterally resolved pixels of 1 μm were achieved, enabling elemental analysis on a (sub-)cellular level. Zones of high Pt response were observed in the renal cortex, where proximal tubules are present, the epithelium of which is responsible for partial reabsorption of cisplatin. Histopathological evaluation, of hematoxylin and eosin-stained serial sections, adjacent to the sections probed via LA-ICP-MS, revealed minimal to mild cisplatin-related lesions (<100 μm) in the renal cortex. Necrotic proximal tubules with sloughed epithelial cells in their lumen could be linked directly to the areas with the highest accumulation of cisplatin, indicating a direct link between cellular concentration and toxicity, thereby providing more insight into the mechanisms through which renal damage occurs.     

Study of plasma parameters influencing fractionation in laser ablation-inductively coupled plasma-mass spectrometry

Methods permitting to test the influence of the matrix as well as of its local and temporal distribution on the plasma conditions in laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) are developed. For this purpose, the MS interface is used as plasma probe allowing to investigate the average plasma condition within the ICP zone observed in terms of temporal and spatial distribution of the matrix.     

Quantification strategies for elemental imaging of biological samples using laser ablation-inductively coupled plasma-mass spectrometry

This review provides analysts with critical insights of current approaches for quantification by laser ablation-inductively coupled plasma-mass spectrometry in the field of elemental imaging. This encompasses both calibration strategies that have been used with success in imaging biological samples, as well as those with potential to improve analytical accuracy and precision if applied to imaging. Methods reviewed include the use of CRMs, laboratory prepared matrix matched standards, internal standardisation, online standard addition and a variety of novel approaches that makes elemental imaging accessible to a wider base of analysts. The importance of quantification and factors affecting its use in imaging will also be considered.     

Visualising mouse neuroanatomy and function by metal distribution using laser ablation-inductively coupled plasma-mass spectrometry imaging

Metals have a number of important roles within the brain. We used laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to map the three-dimensional concentrations and distributions of transition metals, in particular iron (Fe), copper (Cu) and zinc (Zn) within the murine brain. LA-ICP-MS is one of the leading analytical tools for measuring metals in tissue samples. Here, we present a complete data reduction protocol for measuring metals in biological samples, including the application of a pyramidal voxel registration technique to reproducibly align tissue sections. We used gold (Au) nanoparticle and ytterbium (Yb)-tagged tyrosine hydroxylase antibodies to assess the co-localisation of Fe and dopamine throughout the entire mouse brain. We also examined the natural clustering of metal concentrations within the murine brain to elucidate areas of similar composition. This clustering technique uses a mathematical approach to identify multiple ‘elemental clusters’, avoiding user bias and showing that metal composition follows a hierarchical organisation of neuroanatomical structures. This work provides new insight into the distinct compartmentalisation of metals in the brain, and presents new avenues of exploration with regard to region-specific, metal-associated neurodegeneration observed in several chronic neurodegenerative diseases.     

Comparison of laser ablation-inductively coupled plasma-mass spectrometry and micro-X-ray fluorescence spectrometry for elemental imaging in Daphnia magna

Visualization of elemental distributions in thin sections of biological tissue is gaining importance in many disciplines of biological and medical research. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and scanning micro-X-ray fluorescence spectrometry (micro-XRF) are two widely used microanalytical techniques for elemental mapping. This article compares the capabilities of the two techniques for imaging the distribution of selected elements in the model organism Daphnia magna in terms of detection power and spatial resolution. Sections with a thickness of 10 and 20 μm of the fresh water crustacean Daphnia magna were subjected to LA-ICP-MS and micro-XRF analysis. The elemental distributions obtained for Ca, P, S and Zn allow element-to-tissue correlation. LA-ICP-MS and micro-XRF offer similar limits of detection for the elements Ca and P and thus, allow a cross-validation of the imaging results. LA-ICP-MS was particularly sensitive for determining Zn (LOD 20 μg g⁻¹, 15 μm spot size) in Daphnia magna, while the detection power of micro-XRF was insufficient in this context. However, LA-ICP-MS was inadequate for the measurement of the S distributions, which could be better visualized with micro-XRF (LOD 160 μg g⁻¹, 5 s live time). Both techniques are thus complementary in providing an exhaustive chemical profiling of tissue samples.     

Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry

Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n = 3, 1σ). A good agreement between experimental results and the certified values was also observed.     

Detection of metals in proteins by means of polyacrylamide gel electrophoresis and laser ablation-inductively coupled plasma-mass spectrometry: application to selenium

The capabilities of laser ablation-inductively coupled plasma-mass spectrometry for the detection of trace elements in a gel after gel electrophoresis were systematically studied. Figures of merit, such as limit of detection, linearity, and repeatability, were evaluated for various elements (Li, V, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Pd, Ag, Cd, Pt, Tl, Pb). Two ablation strategies were followed: single hole drilling, relevant for ablation of spots after two-dimensional (2-D) separations, and ablation with translation, i.e., on a line, relevant for one-dimensional (1-D) separations. This technique was applied to the detection of selenoproteins in red blood cells extracts after a 1-D separation (sodium dodecyl sulfate-polyacrylamide gel electrophoresis) and the detection of selenium-containing proteins in yeast after 2-D electrophoresis (2-DE). The detection procedure was further improved by using the dynamic reaction cell technology, which allowed the removal of the Ar_2(+) interference and hence the use of the most abundant Se isotope, (80)Se. Reaction gases were compared (methane, carbon monoxide, ammonia, oxygen and the combination of argon (collision gas) and hydrogen (reaction gas)). In each instance, the reaction cell parameters were optimized in order to obtain the lowest detection limit for Se (as (80)Se(+), (82)Se(+) or (77)Se(+); and as (80)Se(16)O(+), (82)Se(16)O(+) or (77)Se(16)O(+) with O(2) as the reaction gas). Carbon monoxide was found to offer the best performance. The detection limit with the use of DRC and He as transport gas was 0.07 microg Se g(-1) gel with single hole drilling and 0.15 microg Se g(-1) gel for ablation with translation.     

Multi-element analysis of compost by laser ablation-inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been applied to multi-element determination in compost samples. Since compost is a heterogeneous mixture of organic and inorganic materials, the influence of sample heterogeneity on the accuracy and precision of analysis was investigated. Several parameters related to the following were studied: laser (energy, laser-beam diameter, preablation. rastering speed, carrier-gas flow rate), sample preparation (use of compacted pellets, grinding time, particle size, sample amount, length of hydraulic press treatment, position of line scan), and the ICP-MS system (quantitative versus semiquantitative analysis, matrix-matched standards and liquid standards calibration). The main causes of imprecision in sample preparation were determined to be particle size and grinding time. The effect of sample heterogeneity on precision was also evaluated by using different test samples (pellets). For Ni, Zn and Pb, the greatest contribution to the total relative standard deviation (R.S.D.) was related to analyte determination. For Mn and Cu, sample heterogeneity and analyte determination contributed equally to the total R.S.D., whereas for Cr, Co, Cd and Hg sample heterogeneity accounted for most of the total R.S.D. A comparison of semiquantitative and quantitative analysis modes showed that better precision and very good agreement with certified reference material was obtained with the latter, but semiquantitative analysis could be a practical alternative. Although accuracy of results was improved with matrix-matched standards calibration the use of standard addition calibration with aqueous standards could be another possibility.     

Feasibility of improvement in analytical performance in laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) by addition of nitrogen to the argon plasma

Addition of nitrogen to an argon ICP in LA-ICP-MS has been found to increase sensitivity and consequently reduce oxide to metal ratios (MO⁺/M⁺) for the reference elements Ce and Th. Addition of about 1% v/v N₂ to the coolant flow increased sensitivity, reducing MO⁺/M⁺ ratios from about 0.6% to about 0.2%. Addition of about 12% N₂ to the cell flow had a similar effect, being greatest at a higher forward rf plasma power (1700 W). The increased sensitivity may be useful in practical analyses; N₂ consumption is very small.     

A rapid approach for assessment of arsenic exposure by elemental analysis of single strand of hair using laser ablation-inductively coupled plasma-mass spectrometry

Application of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) as a method for identification of arsenic in a single hair strand was investigated. Using a single point ablation method detectability of ⁷⁵As and other two elements (²⁰⁸Pb and ⁶⁴Zn) were evaluated. Arsenic (⁷⁵As) signal is improved with enhanced laser ablation conditions. For the arsenic determination in hair single spots or single linear scans with enhanced laser ablation conditions described in the paper are satisfactory although  800 μm linear scans may be preferable. Arsenic levels in a single strand of hair from individuals who were chronically exposed to arsenic contaminated drinking water from a village in the Atacama Desert in northern Chile were determined by LA-ICP-MS. These results were satisfactorily correlated with total As concentration previously measured by hydride generation (HG)-ICP-MS. The sample throughput is high and it takes  3 min per each hair sample including mounting, focusing and analysis. LA-ICP-MS method can be used for the rapid identification and screening of toxic and nutritionally important elements in hair.     

Rapid survey analysis of polymeric materials by laser ablation-inductively coupled plasma spectrometry. An analytical note

An Nd-Yag laser (1064 nm) in combination with a multichannel emission spectrometer was used for rapid survey analysis of polymers and paints. A novel design feature of the ablation chamber was the incorporation of a graphite furnace to effect electrothermal pretreatments of samples. Transient emission signals were studied as a function of laser operating mode, laser duration and flashlamp energy.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Analysis and comparison of glass fragments by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and ICP-MS

The discrimination potential of Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is compared with previously reported solution ICP-MS methods using external calibration (EC) with internal standardization and a newly reported solution isotope dilution (ID) method for the analysis of two different glass populations. A total of 91 different glass samples were used for the comparison study; refractive index and elemental composition were measured by the techniques mentioned above. One set consisted of 45 headlamps taken from a variety of automobiles that represents a range of 20 years of manufacturing dates. A second set consisted of 46 automotive glasses (side windows, rear windows, and windshields) representing casework glass from different vehicle manufacturers over several years. The element menu for the LA-ICP-MS and EC-ICP-MS methods include Mg, Al, Ca, Mn, Ce, Ti, Zr, Sb, Ga, Ba, Rb, Sm, Sr, Hf, La, and Pb. The ID method was limited to the analysis of two isotopes each of Mg, Sr, Zr, Sb, Ba, Sm, Hf, and Pb. Laser ablation analyses were performed with a Q switched Nd:YAG, 266 nm, 6 mJ output energy laser. The laser was used in depth profile mode while sampling using a 50 m spot size for 50 sec at 10 Hz (500 shots). The typical bias for the analysis of NIST 612 by LA-ICP-MS was less than 5% in all cases and typically better than 5% for most isotopes. The precision for the vast majority of the element menu was determined generally less than 10% for all the methods when NIST 612 was measured (40 g g^-1). Method detection limits (MDL) for the EC and LA-ICP-MS methods were similar and generally reported as less than 1 g g^-1 for the analysis of NIST 612. While the solution sample introduction methods using EC and ID presented excellent sensitivity and precision, these methods have the disadvantages of destroying the sample, and also involve complex sample preparation. The laser ablation method was simpler, faster, and produced comparable discrimination to the EC-ICP-MS and ID-ICP-MS. LA-ICP-MS can offer an excellent alternative to solution analysis of glass in forensic casework samples.     

Evaluation of the analytical capability of NIR femtosecond laser ablation-inductively coupled plasma mass spectrometry.

A laser ablation-inductively coupled plasma-mass spectrometric (LA-ICPMS) technique utilizing a titanium-sapphire (TiS) femtosecond laser (fs-laser) has been developed for elemental and isotopic analysis. The signal intensity profile, depth of the ablation pit and level of elemental fractionation were investigated in order to evaluate the analytical capability of the present fs-laser ablation-ICPMS technique. The signal intensity profile of (57)Fe, obtained from iron sulfide (FeS(2)), demonstrated that the resulting signal intensity of (57)Fe achieved by the fs-laser ablation was almost 4-times higher than that obtained by ArF excimer laser ablation under a similar energy fluence (5 J/cm(2)). In fs-laser ablation, there is no significant difference in a depth of the ablation pit between glass and zircon material, while in ArF laser ablation, the resulting crater depth on the zircon crystal was almost half the level than that obtained for glass material. Both the thermal-induced and particle size-related elemental fractionations, which have been thought to be main sources of analytical error in the LA-ICPMS analysis, were measured on a Harvard 91500 zircon crystal. The resulting fractionation indexes on the (206)Pb/(238)U (f(Pb/U)) and (238)U/(232)Th (f(U/Th)) ratios obtained by the present fs-laser ablation system were significantly smaller than those obtained by a conventional ArF excimer laser ablation system, demonstrative of smaller elemental fractionation. Using the present fs-laser ablation technique, the time profile of the signal intensity of (56)Fe and the isotopic ratios ((57)Fe/(54)Fe and (56)Fe/(54)Fe) have been measured on a natural pyrite (FeS(2)) sample. Repeatability in signal intensity of (56)Fe achieved by the fs-laser ablation system was significantly better than that obtained by ArF excimer laser ablation. Moreover, the resulting precision in (57)Fe/(54)Fe and (56)Fe/(54)Fe ratio measurements could be improved by the fs-laser ablation system. The data obtained here clearly demonstrate that, even with the fundamental wavelength (NIR operating at 780 nm), the fs-laser ablation system has the potential to become a significant tool for in-situ elemental and isotopic analysis of geochemical samples including heavy minerals and metallic materials.     

Analysis of metal-binding proteins separated by non-denaturating gel electrophoresis using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have become established as very efficient and sensitive biopolymer and elemental mass spectrometric techniques for studying metal-binding proteins (metalloproteins) in life sciences. Protein complexes present in rat tissues (liver and kidney) were separated in their native state in the first dimension by blue native gel electrophoresis (BN-PAGE). Essential and toxic metals, such as zinc, copper, iron, nickel, chromium, cadmium and lead, were detected by scanning the gel bands using quadrupole LA-ICP-MS with and without collision cell as a microanalytical technique. Several proteins were identified by using MALDI-TOF-MS together with a database search. For example, on one protein band cut from the BN-PAGE gel and digested with the enzyme trypsin, two different proteins - protein FAM44B and cathepsin B precursor - were identified. By combining biomolecular and elemental mass spectrometry, it was possible to characterize and identify selected metal-binding rat liver and kidney tissue proteins.