A novel and simple analytical procedure has been developed for the trace-level determination of lanthanides (rare-earth elements) in uranium-bearing materials by inductively coupled plasma ...sector-field mass spectrometry (ICP-SFMS). The method involves a selective extraction chromatographic separation of lanthanides using TRU™ resin followed by ICP-SFMS analysis. The limits of detection of the method proposed is in the low pg
g
−1 range, which are approximately two orders of magnitude better than that of without chemical separation. The method was validated by the measurement of reference material and applied for the analysis of uranium ore concentrates (yellow cakes) for nuclear forensic purposes, as a potential application of the methodology.
An improved sample preparation method for the determination of americium and plutonium in sediment and soil samples by inductively coupled plasma sector field mass spectrometry (ICP-SFMS) and ...alpha-spectrometry is described. The developed procedure involves a selective CaF
co-precipitation for pre-concentration and matrix removal followed by a sequential extraction chromatographic separation. The average chemical recovery of sample preparation was between 81–94% for both americium and plutonium. The method development also focused on the elimination of possible interferences in mass spectrometric analysis caused by molecular ions (
U
,
Pb
Ar
or
Pb
) employing the suitable matrix separation prior to ICP-SFMS analysis coupled with a desolvation sample introduction system. For
Pu,
Pu,
Pu and
Am limits of detection of 15, 9.2, 14 and 23 fg g
was achieved by ICP-SFMS, respectively. The applied sample preparation and measurement can be carried out within 6 h for one batch of samples. Results of certified reference materials (IAEA-384 and IAEA-385) analysed by the two different measurement techniques agreed well with the recommended or information values.
A flow injection (FI) method was developed using electrochemical hydride generation (EcHG) as a sample introduction system, coupled to an inductively coupled plasma time-of-flight mass spectrometer ...(ICP–TOFMS) for rapid and simultaneous determination of six elements forming hydrides (As, Bi, Ge, Hg, Sb and Se). A novel low volume electrolysis cell, especially suited for FI experiments was designed and the conditions for simultaneous electrochemical hydride generation (EcHG; electrolyte concentrations and flow rates, electrolysis voltage and current) as well as the ICP–TOFMS operational parameters (carrier gas flow rate, modulation pulse width (MPW)) for the simultaneous determination of 12 isotopes were optimized. The compromise operation parameters of the electrolysis were found to be 1.4 and 3
ml
min
−1 for the anolyte and catholyte flow rates, respectively, using 2
M sulphuric acid. An optimum electrolysis current of 0.7
A (16
V) and an argon carrier gas flow rate of 0.91
l
min
−1 were chosen. A modulation pulse width of 5
μs, which influences the sensitivity through the amount of ions being collected by the MS per single analytical cycle, provided optimum results for the detection of transient signals. The achieved detection limits were compared with those obtained by using FI in combination with conventional nebulization (FI–ICP–TOFMS); values for chemical hydride generation (FI–CHG–ICP–TOFMS) were taken from the literature. By using a 200
μl sample loop absolute detection limits (3
σ) in the range of 10–160
pg for As, Bi, Ge, Hg, Sb and 1.1
ng for Se and a precision of 4–8% for seven replicate injections of 20–100
ng
ml
−1 multielemental sample solutions were achieved. The analysis of a standard reference material (SRM) 1643d (NIST, “Trace Elements in Water”) showed good agreement with the certified values for As and Sb. Se showed a drastic difference, which is probably due to the presence of hydride-inactive Se species in the sample. Recoveries better than 93% for Ge and Hg and 83.9% for Se were achieved on a spiked SRM sample. The developed method was successfully applied to the simultaneous multielemental determination of hydride forming elements in spring water samples originating from two different regions in Hungary.
This case study presents a fast and reliable method of combining strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) with a multielement pattern (Rb, Sr, Y, Zr, Mo, Cd, Ba, Pb, Th, U, Mg, Ca, Sc, Ti, Cr, Mn, Fe, ...Co, Ni, Cu, Zn, As and rare earth elements) by means of inductively coupled plasma mass spectrometry (ICP-MS) to establish a unique fingerprint of authentic Szegedi Fűszerpaprika (PDO) and classify authentic and purchased paprika from different known, declared and unknown geographical origin using multivariate statistical tools (principal component and canonical discriminant analysis). Since paprika represents a processed spice, alterations in element and Sr isotopic composition throughout the production process were investigated. The Sr source in the final product was identified to stem from bioavailable Sr sources in soil. Therefore, the ammonium nitrate extract of a soil is sufficient to establish a Sr fingerprint for agricultural products of a region. As a consequence, the spice paprika can be traced back to its geographical origin even after processing.
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► Solid sampling GFAAS was studied for Cr, Fe and Mn determination in lithium niobate. ► Solution based GFAAS, FAAS, ICP-OES and ICP-MS were elaborated for method validation. ► The ...performances of the elaborated spectrochemical methods have been compared. ► The chemical forms of the matrix produced in GFAAS cycles were studied by XANES.
Solid sampling (SS) graphite furnace atomic absorption spectrometry (GFAAS) and solution-based (SB) methods of GFAAS, flame atomic absorption spectrometry (FAAS), inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) were elaborated and/or optimized for the determination of Cr, Fe and Mn trace elements used as dopants in lithium niobate optical crystals.
The calibration of the SS-GFAAS analysis was possible with the application of the three-point-estimation standard addition method, while the SB methods were mostly calibrated against matrix-matched and/or acidic standards. Spectral and non-spectral interferences were studied in SB-GFAAS after digestion of the samples. The SS-GFAAS method required the use of less sensitive spectral lines of the analytes and a higher internal furnace gas (Ar) flow rate to decrease the sensitivity for crystal samples of higher (doped) analyte content.
The chemical forms of the matrix produced at various stages of the graphite furnace heating cycle, dispensed either as a solid sample or a solution (after digestion), were studied by means of the X-ray near-edge absorption structure (XANES). These results revealed that the solid matrix vaporized/deposited in the graphite furnace is mostly present in the metallic form, while the dry residue from the solution form mostly vaporized/deposited as the oxide of niobium.
A simultaneous multi-elemental measurement of As, Bi, Ge, Sb, Se, and Sn was performed in this study by flow injection–hydride generation–inductively coupled plasma–time-of-flight mass spectrometry ...(FI–HG–ICP–TOFMS). An off-line pre-reduction treatment using a solution of 5% (m/v) KI and ascorbic acid for 15
min at 80
°C is described by presenting its advantages and disadvantages and compared with the results achieved without pre-reduction. Using optimised conditions the following figures of merit were achieved: limits of detection in the 0.08–0.54
ng
ml
−1 range and relative standard deviations (RSD) of 1.7–6.7%, respectively. Applying the presented method, two certified reference materials (NIST 1643d freshwater and PACS-2 marine sediment) were analysed to demonstrate the suitability of the method for analysis of real samples. Results obtained from treated samples showed good agreement with certified values while the untreated ones considerably departed from them.
Application of inductively coupled plasma sector field mass spectrometry (ICP-SFMS) for the determination of americium and plutonium in environmental samples is described in comparison with alpha ...spectrometry. A sequential sample preparation method was employed using a co-precipitation step for pre-concentration and a separation step applying extraction chromatographic resins. The average recovery of sample preparation calculated from the concentration of the tracer before and after sample treatment was better than 80%. The method development focused on the elimination of possible interferences in mass spectrometric analysis caused by molecular ions (e.g.
200Hg
40Ar
+,
204Pb
36Ar
+,
208Pb
16O
2
+or
238U
1H
+) employing matrix separation and desolvation prior to ICP-SFMS analysis. The effect of N
2 gas on signal intensity and oxide ratio was investigated. A two-fold signal improvement was obtained by adding 5 ml min
−
1
N
2 to the sample gas after the desolvation system. For
239Pu,
240Pu,
241Pu and
241Am limit of detection (LOD) of 15, 9.2, 14 and 104 fg g
−
1
was achieved, respectively. Calculation of LOD was based on three times standard deviation of the method blank solution. Absolute detection limit was calculated to be 10–25 fg. For all investigated actinides the precision of the analysis was in the range 0.8–3% relative standard deviation. Results from the analysis of certified reference materials (IAEA-384 and IAEA-385) showed good agreement with recommended values and data available in the literature. The method was applied for analysis of environmental samples originated from Chernobyl and from Mayak region. The possibility of the determination of the origin and date of pollution was demonstrated using isotopic data obtained by ICP-SFMS and alpha spectrometry.
A flow injection (FI) method was developed using hydraulic high-pressure nebulization as a sample introduction system, coupled to inductively coupled plasma time-of-flight mass spectrometer ...(ICP-TOFMS) for rapid and simultaneous determination of 19 elements. The operating conditions of the system (analyte flow rate, heating and cooling temperatures of the desolvation module, carrier gas flow rate) for the simultaneous determination of 19 analytes were optimised. The optimum parameters of the sample introduction system were found to be 1.4mlmin−1 and 1.35lmin−1 for the analyte solution and nebulizer flow rates, respectively. A compromised condition for heating and cooling stage temperatures of 170 and −5°C was chosen. The detection limits were compared to those obtained by using ICP-TOFMS with alternative sample introduction techniques e.g. conventional nebulization, flow injection chemical hydride generation (FI-CHG) and the obtained results were comparable or better than those resulting from alternative sample introduction. Applying the optimised conditions the simultaneous determination of Ag, As, Ba, Cd, Co, Cu, Ga, In, Li, Mn, Mo, Pb, Sb, Se, Sn, Sr, Tl, V and Zn was carried out. Absolute detection limits (3σ) in the range of 2–750pg and precision between 0.5 and 9.6% from five replicate measurements of 10ngml−1 multielemental sample solutions were achieved by using a 200μl sample loop. The developed method was applied for the analysis of certified reference materials of biological origin (TORT-2 “Lobster Hepatopancrease”, BCR-422 “Cod Muscle” and IAEA MA-B-3/TM “Fish Homogenate”), and the results showed good agreement with the certified values.
A laboratory reference material (LRM) was prepared from Brazil nuts (Bertholletia excelsa) for quality control (QC) purposes of selenium speciation. The preparation of this LRM led through the usual ...operation steps applied during routine reference material production from biota samples-preparation of the raw material, homogenisation, storage design, checking of homogeneity, microbiological status and possible irradiation effects, and monitoring the species stability vs time at different storage temperatures. The selenium speciation studies to check species stability were carried out on a HPLC-UV-HG-AFS measurement set-up. Special attention was paid to the correct identification of selenium species by applying independent HPLC separation techniques (ion-pairing and anion-exchange chromatography). The concentration of selenomethionine (SeMet) and total Se content were quantified (79.9 microg g(-1) (calculated as Se) and 82.9 microg g(-1), respectively). The homogeneity and stability of this candidate reference material passed the relevant tests recommended by Bureau Communautaire de Référence (BCR).
Platinum originating from the excreted cancerostatic platinum compounds (CPC) cisplatin, carboplatin and oxaliplatin was monitored over a period of 28 days in the wastewater of the oncologic ward of ...the Vienna University Hospital. Concentration levels ranging from 4.7 to 145 μg L
−1 were measured by inductively coupled plasma mass spectrometry (ICP-MS). An average ratio of weekly drug emission/drug consumption of 0.27±0.12 was assessed.
Model studies were carried out for fundamental understanding of CPC interaction with the solid phases present at different stages of the water cycle. Wastewater and activated sludge were spiked with CPC at concentration levels as found in the sewer of the oncologic ward. The platinum concentration remaining in the tested solution was measured after 24 h of incubation. Depending on pH, the three substances exhibited considerably different adsorption rates in wastewater. At pH 7, cisplatin was adsorbed by 88%, whereas only 26% of carboplatin and 54% of oxaliplatin were removed from the aqueous phase. Adsorption by activated sludge was higher, less affected by pH variation and comparable for all investigated CPC (96% for cisplatin, 70% for carboplatin and 74% for oxaliplatin at pH 6.8).
In a next step, the dependence of CPC adsorption was tested for wastewater and activated sludge of different sampling sites. Strong variations were found only for wastewater, whereas activated sludge showed more consistent elimination rates (average values: cisplatin 92%, carboplatin 72%, and oxaliplatin 78%). These findings indicate that the major part of the excreted CPC is adsorbed by the solid phase in the water cycle and is thus expected to be removed from the wastewater by sewage treatment plants.
