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Compositional data for Bengal delta sediment collected from boreholes at Srirampur, Kachua, Bangladesh

Processes active within sediment of the Bengal delta have attracted world concern because of the locally high content of arsenic dissolved in ground water drawn from that sediment. Sediment samples were collected from two boreholes in Srirampur village, Kachua upazila, Chandphur district, Bangladesh, to investigate the processes contributing to arsenic contamination. The samples were mineralogically and chemically analyzed to determine compositional variations related to the arsenic content of the sediment. Mineralogy of the sediments was determined using powder X-ray diffraction. Bulk chemical composition was measured by Combustion, Inductively Coupled Plasma Atomic Emission Spectroscopy, Energy Dispersive X-ray Fluorescence, and Hydride Generation Atomic Absorption Spectrophotometry. Solutions produced by four chemical extractions-0.1 molar strontium chloride, 0.5 normal hydrochloric acid, titanium(III)-EDTA, and a solution of hydrogen peroxide and hydrochloric acid-were analyzed to evaluate the chemical reactivity of the sediment with an emphasis on arsenic residence. Acid-volatile sulfide, acid-soluble sulfate, and reducible sulfide were also measured. Sediment sampled at Srirampur is typically unlithified, gray, micaceous, feldspathic, arenaceous silt and sand. Arsenic content of the sediment ranges from <1 to 210 ppm, with the highest contents measured in sediment collected at a depth of 320 meters. Samples with high arsenic contents typically contain high concentrations of sulfur. The greatest amount of arsenic was extracted using the oxidative hydrogen peroxide and hydrochloric acid extraction solution. The extraction results are consistent with the apparent association of arsenic in sulfur in the bulk chemical analyses. Pyrite is typically the most abundant form of sulfur in the sediment and is dissolved by the oxidative extraction.

Open-File Report

Compositional Data for Bengal Delta Sediment Collected from a Borehole at Rajoir, Bangladesh

Processes active within sediment of the Bengal basin have attracted world concern because of the locally high content of arsenic dissolved in ground water drawn from that sediment. Sediment samples were collected from a borehole in the town of Rajoir, Rajoir upazila, Madaripur district, Bangladesh, to investigate the processes contributing to arsenic contamination. The samples were mineralogically and chemically analyzed to determine compositional variations related to the arsenic content of the sediment. Mineralogy of the sediment was determined using powder X-ray diffraction. Bulk chemical composition was measured by Combustion; Inductively Coupled Plasma Atomic Emission Spectroscopy; Energy Dispersive X-ray Fluorescence; and Hydride Generation Atomic Absorption Spectrophotometry. Sediment was treated with 0.5 N HCl and resulting solutions were analyzed, primarily to evaluate the abundance and oxidation state of acid-soluble iron. Acid-volatile sulfide, acid-soluble sulfate, and reducible sulfide were also measured on a few samples. Sediment sampled at Rajoir is typically unlithified, gray, micaceous, feldspathic arenaceous sand with a few silt and clay layers. Arsenic content of the sediment ranges from 0.6 to 21 ppm with a median of 1.2 ppm.

Open-File Report

Geochemical analysis of soils and sediments, Coeur d'Alene drainage basin, Idaho: sampling, analytical methods, and results

This report presents the locations, descriptions, analytical procedures used, and an inter-lab comparison of over 1100 geochemical analyses of samples of soil and sediment in and downstream of a major lead-zinc-silver mining district in the Coeur d'Alene (CdA) drainage basin of northern Idaho. The samples fall in 3 broad categories: (1) samples from vertical profiles of floodplain soils in the valley of the main stem of the CdA River (767 samples) and of the South Fork of the CdA River (38 samples), (2) size fractionated surficial samples of sediment bedload within the channel of the South Fork of the CdA River (68 samples), and (3) samples from vertical profiles of sediment bedload within the channel of the main stem of the CdA River (260 samples). Five different laboratories contributed geochemical data for this report. Four of the five laboratories employed analytical methods that require sample dissolution prior to analysis; one laboratory (US Geological Survey) used analytical instrumentation (energy dispersive x-ray fluorescence [EDXRF]) that is applied to pulverized samples. Some dissolution procedures use four acids (hydrochloric, nitric, perchloric, and hydrofluoric; Eastern Washington University [EWU] Geochemical Laboratory and XRAL Laboratories, Inc.), others use two acids (nitric acid and aqua regia; CHEMEX Labs, Inc.), and some use only concentrated nitric acid (ACZ Laboratories, Inc.). Most analyses of dissolved samples were done by Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES) or by ICP - MS (Mass Spectroscopy). Some analyses for Ag and K were done by Flame Atomic Absorption (FAA). Inter-laboratory comparisons are made for 6 elements: lead (Pb), zinc (Zn), iron (Fe), manganese (Mn), arsenic (As), and cadmium (Cd). In general inter-laboratory correlations are better for samples within the compositional range of the Standard Reference Materials (SRMs) from the National Institute of Standards and Technology (NIST). Analyses by EWU are the most accurate relative to the NIST standards (mean recoveries within 1% for Pb, Fe, Mn, and As, 3% for Zn and 5% for Cd) and are the most precise (within 7% of the mean at the 95% confidence interval). USGS-EDXRF is similarly accurate for Pb and Zn. XRAL and ACZ are relatively accurate for Pb (within 5-8% of certified NIST values), but were considerably less accurate for the other 5 elements of concern (10-25% of NIST values). However, analyses of sample splits by more than one laboratory reveal that, for some elements, XRAL (Pb, Mn, Cd) and ACZ (Pb, Mn, Zn, Fe) analyses were comparable to EWU analyses of the same samples (when values are within the range of NIST SRMs). These results suggest that, for some elements, XRAL and ACZ dissolutions are more effective on the matrix of the CdA samples than on the matrix of the NIST samples (obtained from soils around Butte, Montana). Splits of CdA samples analyzed by CHEMEX were the least accurate, yielding values 10-25% less than those of EWU.

Idaho

A comparison of geochemical exploration techniques and sample media within accretionary continental margins: an example from the Pacific Border Ranges, Southern Alaska, U.S.A.

The Pacific Border Ranges of the southern Alaskan Cordillera are composed of a number of allochthonous tectonostratigraphic terranes. Within these terranes are widespread volcanogenic, massive sulfide deposits in and adjacent to portions of accreted ophiolite complexes, bands and disseminations of chromite in accreted island-arc ultramafic rocks, and epigenetic, gold-bearing quartz veins in metamorphosed turbidite sequences. A geochemical pilot study was undertaken to determine the most efficient exploration strategy for locating these types of mineral deposits within the Pacific Border Ranges and other typical convergent continental margin environments. High-density sediment sampling was carried out in first- and second-order stream channels surrounding typical gold, chromite and massive sulfide occurrences. At each site, a stream-sediment and a panned-concentrate sample were collected. In the laboratory, the stream sediments were sieved into coarse-sand, fine- to medium-sand, and silt- to clay-size fractions prior to analysis. One split of the panned concentrates was retained for analysis; a second split was further concentrated by gravity separation in heavy liquids and then divided into magnetic, weakly magnetic and nonmagnetic fractions for analysis. A number of different techniques including atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry and semi-quantitative emission spectrography were used to analyze the various sample media. Comparison of the various types of sample media shows that in this tectonic environment it is most efficient to include a silt- to clay-size sediment fraction and a panned-concentrate sample. Even with the relatively low detection limits for many elements by plasma spectrometry and atomic absorption spectrometry, anomalies reflecting the presence of gold veins could not be identified in any of the stream-sediment fractions. Unseparated panned-concentrate samples should be analyzed by emission spectroscopy and atomic absorption spectrometry for Ag and Au. If, however, magnetic and nonmagnetic concentrate fractions are used in a reconnaissance program, semiquantitative emission spectrography is adequate for all analytical work.

Journal of Geochemical Exploration

Chemical composition of the hydrothermal fluids responsible for the lead-zinc deposits at Providencia, Zacatecas, Mexico

The chemical composition of 22 samples of primary fluid inclusions in quartz, calcite, and sphalerite from Providencia, Mexico, has been determined. Samples were prepared, crushed, and leached as described by Roedder et al. (1963). Cation analyses of leachates were made by atomic absorption spectroscopy, and the anions were analyzed by a special X-ray fluorescence technique. The Na, K, Ca, and C1 concentrations show a considerable range that reflects the widespread salinity variations in the hydrothermal fluids observed by Sawkins (1964). The K/Na atomic ratios of most samples range from 0.18 to 0.43 and the ratios tend to increase with the salinity of the inclusions. The temperatures indicated by the K/Na ratios from the published curves of K/Na ratios vs. temperature are mostly at least 100 ø C greater than corresponding filling temperatures. The Ca/Na atomic ratios of inclusions in sphalerite range from 0.12 to 0.61. The K/Na and Ca/Na data agree well with previous δO¹⁸ data (Rye, 1966; Rye and O'Neil. 1968) which indicate that the hydrothermal fluids were derived from the magma related to the Providencia granodiorite stock and that the fluids reacted only slightly with the crystalline stock during the late phases of ore deposition. The data also indicate that the salinity variations in the hydrothermal fluids probably occurred at the source of the fluids and may have resulted from boiling in the magma chamber. Mg concentrations are generally no more than a few hundred parts per million. Most of the Mg in the hydrothermal fluids was evidently removed during the formation of calcium-magnesium silicates in the lower levels of the ore pipes. Mg/Ca atomic ratios are generally less than 0.08 and are consistent with the paucity of dolomite in the area. Zn and Cu concentrations in water leaches of inclusions in calcite are generally less than 50 ppm. Maximum base-metal concentrations from water leaches of two samples of inclusions in quartz are 890 ppm Zn and 530 ppm Cu. Chloride is the major anion in the fluids, and C1 concentrations vary with corresponding cation concentrations. With two exceptions, sulfur concentrations of the inclusions in calcite and quartz, analyzed as SO₄, are below the level of detection

Zacatecas

Improving ChemCam LIBS long-distance elemental compositions using empirical abundance trends

The ChemCam instrument on the Curiosity rover provides chemical compositions of Martian rocks and soils using remote laser-induced breakdown spectroscopy (LIBS). The elemental calibration is stable as a function of distance for Ti, Fe, Mg, and Ca. The calibration shows small, systematically increasing abundance trends as a function of distance for Al, Na, K, and to some extent, Si. The distance effect is known to be due to a dependence with distance on the relative strengths of atomic transition lines. Emission lines representing transitions from relatively low energy levels remain intense at longer distances while emission lines representing transitions from higher energy levels decrease in intensity more rapidly as a function of distance. The multivariate algorithms used to determine elemental compositions rely on a large number of emission lines in many cases, so rather than trying to correct all emission lines, a study was made of the predicted compositions as a function of distance, in order to determine an empirical correction. Abundance trends can be well approximated by a linear trend with distance within the ranges of abundances and distances observed up to ~6 m. Data from 11 distinct geological members and data groups of the Murray formation in Gale crater, Mars, were used to form the model, selecting the members and data groups yielding the best statistics. The model was tested using data from several targets observed from two different distances, and using data from the Kimberley formation, the composition of which is significantly different from the Murray formation, showing that the model works on other compositions beyond those used to build the model. For long-distance observations up to ~6 m, corrections can be made back to an equivalent composition at the median distance of ChemCam observations (2.6 m). The model has been validated up to 6.2 m, although ChemCam is able to observe bedrock targets to >7 m, and iron meteorites to distances of >9 m.

Spectrochimica Acta Part B: Atomic Spectroscopy

Finalization of the Confocal Laser Scanning Microscopy (CLSM) working group

A working group in Commission II to investigate applications of confocal laser scanning microscopy (CLSM) for organic petrology investigations has finalized with publication of the manuscript “Characterization of bituminite in Kimmeridge Clay by confocal laser scanning and atomic force microscopy” in the International Journal of Coal Geology. The manuscript is available via Open Access from https://doi.org/10.1016/j.coal.2022.103927 and also from the Commission II working group (WG) webpage https://www.iccop.org/workinggroup/confocal-laser-scanning-microscopy-clsm/. A report detailing the full history and results from the WG also is available from the Commission II WG webpage. The working group investigated the application of CLSM to an organic-rich (44 wt.% TOC), thermally immature sample (VRo 0.42%) of the Kimmeridge Clay Formation. CLSM imaging and spectroscopy and atomic force microscopy (AFM) were used to characterize bituminite.

ICCP News

Improved accuracy in quantitative laser-induced breakdown spectroscopy using sub-models

Accurate quantitative analysis of diverse geologic materials is one of the primary challenges faced by the Laser-Induced Breakdown Spectroscopy (LIBS)-based ChemCam instrument on the Mars Science Laboratory (MSL) rover. The SuperCam instrument on the Mars 2020 rover, as well as other LIBS instruments developed for geochemical analysis on Earth or other planets, will face the same challenge. Consequently, part of the ChemCam science team has focused on the development of improved multivariate analysis calibrations methods. Developing a single regression model capable of accurately determining the composition of very different target materials is difficult because the response of an element’s emission lines in LIBS spectra can vary with the concentration of other elements. We demonstrate a conceptually simple “sub-model” method for improving the accuracy of quantitative LIBS analysis of diverse target materials. The method is based on training several regression models on sets of targets with limited composition ranges and then “blending” these “sub-models” into a single final result. Tests of the sub-model method show improvement in test set root mean squared error of prediction (RMSEP) for almost all cases. The sub-model method, using partial least squares regression (PLS), is being used as part of the current ChemCam quantitative calibration, but the sub-model method is applicable to any multivariate regression method and may yield similar improvements.

Spectrochimica Acta Part B: Atomic Spectroscopy

Recalibration of the Mars Science Laboratory ChemCam instrument with an expanded geochemical database

The ChemCam Laser-Induced Breakdown Spectroscopy (LIBS) instrument onboard the Mars Science Laboratory (MSL) rover Curiosity has obtained > 300,000 spectra of rock and soil analysis targets since landing at Gale Crater in 2012, and the spectra represent perhaps the largest publicly-available LIBS datasets. The compositions of the major elements, reported as oxides (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O), have been re-calibrated using a laboratory LIBS instrument, Mars-like atmospheric conditions, and a much larger set of standards (408) that span a wider compositional range than previously employed. The new calibration uses a combination of partial least squares (PLS1) and Independent Component Analysis (ICA) algorithms, together with a calibration transfer matrix to minimize differences between the conditions under which the standards were analyzed in the laboratory and the conditions on Mars. While the previous model provided good results in the compositional range near the average Mars surface composition, the new model fits the extreme compositions far better. Examples are given for plagioclase feldspars, where silicon was significantly over-estimated by the previous model, and for calcium-sulfate veins, where silicon compositions near zero were inaccurate. The uncertainties of major element abundances are described as a function of the abundances, and are overall significantly lower than the previous model, enabling important new geochemical interpretations of the data.

Spectrochimica Acta Part B: Atomic Spectroscopy

Pre-flight calibration and initial data processing for the ChemCam laser-induced breakdown spectroscopy instrument on the Mars Science Laboratory rover

The ChemCam instrument package on the Mars Science Laboratory rover, Curiosity, is the first planetary science instrument to employ laser-induced breakdown spectroscopy (LIBS) to determine the compositions of geological samples on another planet. Pre-processing of the spectra involves subtracting the ambient light background, removing noise, removing the electron continuum, calibrating for the wavelength, correcting for the variable distance to the target, and applying a wavelength-dependent correction for the instrument response. Further processing of the data uses multivariate and univariate comparisons with a LIBS spectral library developed prior to launch as well as comparisons with several on-board standards post-landing. The level-2 data products include semi-quantitative abundances derived from partial least squares regression. A LIBS spectral library was developed using 69 rock standards in the form of pressed powder disks, glasses, and ceramics to minimize heterogeneity on the scale of the observation (350–550 μm dia.). The standards covered typical compositional ranges of igneous materials and also included sulfates, carbonates, and phyllosilicates. The provenance and elemental and mineralogical compositions of these standards are described. Spectral characteristics of this data set are presented, including the size distribution and integrated irradiances of the plasmas, and a proxy for plasma temperature as a function of distance from the instrument. Two laboratory-based clones of ChemCam reside in Los Alamos and Toulouse for the purpose of adding new spectra to the database as the need arises. Sensitivity to differences in wavelength correlation to spectral channels and spectral resolution has been investigated, indicating that spectral registration needs to be within half a pixel and resolution needs to match within 1.5 to 2.6 pixels. Absolute errors are tabulated for derived compositions of each major element in each standard using PLS regression. Sources of errors are investigated and discussed, and methods for improving the analytical accuracy of compositions derived from ChemCam spectra are discussed.

Spectrochimica Acta Part B: Atomic Spectroscopy

Chemical and textural controls on phosphorus mobility in drylands of southeastern Utah

We investigated several forms of phosphorus (P) in dryland soils to examine the chemical and textural controls on P stabilization on a diverse set of substrates. We examined three P fractions including labile, moderately labile, and occluded as determined by a modified Hedley fractionation technique. The P fractions were compared to texture measurements and total elemental concentrations determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Labile P related to the absence of materials involved in P sorption. Moderately labile P was most strongly associated with high total Al & Fe content that we interpret to represent oxides and 1:1 clay minerals. The occluded P fraction was strongly associated with low total Al & Fe environments and interpreted to represent 2:1 clay minerals where ligand exchange tightly sequesters P. The results indicate that the controls on P fraction distribution are initially closely tied to the chemical and physical properties of the bedrock units that contribute to soil formation. Further, these results suggest that the progression of stabilized P forms in dryland areas differs from the progression observed in mesic environments. Soil development in dryland settings, such as the formation of pedogenic carbonates, may lead to differing controls on P availability and the proportional size of the moderately labile fraction.

Utah

The group separation of the rare-earth elements and yttrium from geologic materials by cation-exchange chromatography

Demand is increasing for the determination of the rare-earth elements (REE) and yttrium in geologic materials. Due to their low natural abundance in many materials and the interferences that occur in many methods of determination, a separation procedure utilizing gradient strong-acid cation-exchange chromatography is often used to preconcentrate and isolate these elements from the host-rock matrix. Two separate gradient strong-acid cation-exchange procedures were characterized and the major elements as well as those elements thought to provide the greatest interference for the determination of the REE in geologic materials were tested for separation from the REE. Simultaneous inductively coupled argon plasma-atomic emission spectroscopy (ICAP-AES) measurements were used to construct the chromatograms for the elution studies, allowing the elution patterns of all the elements of interest to be determined in a single fraction of eluent. As a rock matrix, U.S. Geological Survey standard reference BCR-1 basalt was digested using both an acid decomposition procedure and a lithium metaborate fusion. Hydrochloric and nitric acids were tested as eluents and chromatograms were plotted using the ICAP-AES data; and we observed substantial differences in the elution patterns of the REE and as well as in the solution patterns of Ba, Ca, Fe and Sr. The nitric acid elution required substantially less eluent to elute the REE and Y as a group when compared to the hydrochloric acid elution, and provided a clearer separation of the REE from interfering and matrix elements. ?? 1984.

Chemical Geology

Separation and preconcentration of the rare-earth elements and yttrium from geological materials by ion-exchange and sequential acid elution

The abundance of rare-earth elements (REE) and yttrium in geological materials is generally low, and most samples contain elements that interfere in the determination of the REE and Y, so a separation and/or preconcentration step is often necessary. This is often achieved by ion-exchange chromatography with either nitric or hydrochloric acid. It is advantageous, however, to use both acids sequentially. The final solution thus obtained contains only the REE and Y, with minor amounts of Al, Ba, Ca, Sc, Sr and Ti. Elements that potentially interfere, such as Be, Co, Cr, Fe, Mn, Th, U, V and Zr, are virtually eliminated. Inductively-coupled argon plasma atomic-emission spectroscopy can then be used for a final precise and accurate measurement. The method can also be used with other instrumental methods of analysis.

Talanta

Mineralogical basis for the interpretation of multi-element (ICP-AES), oxalic acid, and aqua regia partial digestions of stream sediments for reconnaissance exploration geochemistry

We have applied partial digestion procedures, primarily oxalic acid and aqua regia leaches, to several regional geochemical reconnaissance studies carried out using Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) analytical methods. We have chosen to use these two acids because the oxalic acid primarily attacks those compounds formed during secondary geochemical processes, whereas aqua regia will digest the primary sulfide phases as well as secondary phases. Application of the partial digestion technique has proven superior to total digestion because the concentration of metals in hydromorphic compounds and the sulfides is enhanced relative to the metals bound in the unattacked silicate phases. The aqua regia digestion attacks and leaches metals from the mafic chain silicates and the phyllosilicates (coordination number of VI or more), yielding a characteristic geochemical signature, but does not leach appreciable metal from many other silicates. In order to interpret the results from these leach studies, we have initiated an investigation of a large suite of hand-picked mineral separates. The study includes analyses of about two hundred minerals representing the common rock-forming minerals as well as end-member compositions of various silicates, oxides, sulfides, carbonates, sulfates, and some vanadates, molybdates, tungstates, and phosphates. The objective of this study is to evaluate the effect of leaching by acids of particular lattice sites in specific mineral structures.

Journal of Geochemical Exploration

An analytical method for hydrogeochemical surveys: Inductively coupled plasma-atomic emission spectrometry after using enrichment coprecipitation with cobalt and ammonium pyrrolidine dithiocarbamate

Trace metals that are commonly associated with mineralization were concentrated and separated from natural water by coprecipitation with ammonium pyrollidine dithiocarbamate (APDC) and cobalt and determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The method is useful in hydrogeochemical surveys because it permits preconcentration near the sample sites, and selected metals are preserved shortly after the samples are collected. The procedure is relatively simple: (1) a liter of water is filtered; (2) the pH is adjusted; (3) Co chloride and APDC are added to coprecipitate the trace metals; and (4) later, the precipitate is filtered, dissolved, and diluted to 10 ml for a 100-fold concentration enrichment of the separated metals. Sb(III), As(III), Cd, Cr, Cu, Fe, Pb, Mo, Ni, Ag, V, and Zn can then be determined simultaneously by ICP-AES. In an experiment designed to measure the coprecipitation efficiency, Sb(III), Cd and Ag were recovered at 70 to 75% of their original concentration. The remaining metals were recovered at 85 to 100% of their original concentrations, however. The range for the lower limits of determination for the metals after preconcentration is 0.1 to 3.0 μg/l.

Journal of Geochemical Exploration

Sets of spectral lines for spectrographic thermometry and manometry in d.c. arcs of geologic materials

Sets of 5 Fe(I) lines and 3 Ti(I) Ti(II) line pairs have been characterized for precise spectrographic thermometry and manometry, respectively, in d.c. arcs of geologic materials. The recommended lines are free of spectral interferences, exhibit minimal self absorption within defined concentration intervals, and are useful for chemically-unaltered silicate rocks, arced in an argon—oxygen stream. The functional character of these lines in thermometry and manometry of d.c. arcs for evaluations of electrical parameter effects, for temporal studies, and for matrix-effect investigations on real samples is illustrated.

Spectrochimica Acta Part B: Atomic Spectroscopy

Reduction of matrix interferences in furnace atomic absorption with the L'vov Platform

Use of a modified L'vov Platform and ammonium phosphate as a matrix modifier greatly reduced matrix interferences in a commercial Massmann-type atomic absorption furnace. Platforms were readily fabricated from furnace tubes and, once positioned in the furnace, caused no inconvenience in operation. Two volatile elements (Pb, Cd), two of intermediate volatility (Co, Cr) and two which form stable oxides (Al, Sn) were tested in natural water and selected synthetic matrices. In every case for which there was a significant matrix effect during atomization from the tube wall, the platform and platform plus modifier gave improved performance. With lead, for example, an average ratio of 0.48 ± 0.11 was found when the slope of the standard additions plot for six different natural water samples was compared to the slope of the standard working curve in dilute acid. The average slope ratio between the natural water matrices and the dilute acid matrix was 0.94 ± 0.03 with the L'vov Platform and 0.96 ± 0.03 with the platform and matrix modifier. In none of the cases studied did the use of the platform or platform plus modifier cause an interference problem where none existed while atomizing from the tube wall. An additional benefit of the platform was a factor of about two improvement in peak height precision.

Spectrochimica Acta Part B: Atomic Spectroscopy

Heating rates in furnace atomic absorption using the L'vov platform

Heating rate profiles for the furnace tube wall, the furnace atmosphere, and a L'vov platform were established for a range of conditions in a cyclically heated graphite atomizer. The tube wall profile was made by direct observation with a recording optical pyrometer. The sodium line reversal method was used to establish the heating rate of the furnace atmosphere, and appearance temperatures for a series metals of differing volatility was used to establish platform profiles. The tube wall heating rate was nearly linear at 2240°C s − until the desired temperature was reached after which the temperature remained constant. The furnace atmosphere reached a given temperature 0.2–0.4 s later than the tube wall through most of the atomize cycle. The platform lagged the tube wall 0.5–0.8 s. Under typical operating conditions the furnace atmosphere was 100–200°C cooler than the tube wall and at nearly constant temperature when the analyte vaporized from the platform. The L'vov platform causes the cyclically heated commercial furnace to approximate the behavior of a constant temperature furnace during atomization.

Spectrochimica Acta Part B: Atomic Spectroscopy