Sector Field Mass Spectrometry Research Articles

Trace and Rare-earth Elements in Natural Ground Waters: Weathering Effect of Water-Rock Interaction

The distributions of Ca, Cr, Fe, Co, Zn, Ga, Se, Rb, Ba, Tl, Bi, Th, U and rare-earth elements (REEs), measured by Inductively Coupled Plasma Sector Field Mass Spectrometry (ICP-SFMS) in ground natural waters characterized by near-acidic to alkaline pH (5.7 – 9.0), were evaluated to examine the major processes of water-rock interaction. Cluster analysis of ground water quality parameters resulted in three clusters: 1) transition elements (Cr, Co and Zn); 2) REEs; and 3) geogenic elements (Rb, Ga, Ba and Th) with 55%, 60% and 75% similarity levels, respectively. Also, natural ground waters with relatively high salinity (5.3 – 6.8 g/L) were found to be significantly enriched with Ca, Cr, Co, Zn, Ga, Rb and Ba compared to lower-salinity waters (0.5 – 3.7 g/L). Negative Ce (from 0.4 to 0.9) and positive Eu (from 1.2 to 17.5) anomalies were found in the investigated waters and most of them were associated with heavy rare-earth elements (HREEs) enrichments. It was established that the relative proportion of total REE concentration (range 75 – 470 ng/L) to Ca abundance (from 1 to 180 mg/L) could be a useful indicator of weathering processes in studied ground waters. This observation is attributed to the increase in the calcite dissolution during the weathering process, as well as to REEs leaching due to the complex formation of bicarbonate. The reliability of the ICP-SFMS method was checked by using certified reference materials (SLEW-3, SLRS-4 and TMRAIN-04). The relative standard deviation (RSD) was < 10%.

Radionuclide Determination In Surface Water Samples By Inductively Coupled Plasma With Sector Field Mass Spectrometry (ICP-SFMS)

The determination of naturally occurring radionuclides in the environment by inductively coupled plasma mass spectrometry of high resolution (ICP-SFMS) has gained recognition over the last fifteen years, relative to the radiometric techniques, as the result of improvement in instrumental performance, sample introduction equipment and sample preparation. With the increase in instrumental sensitivity, it is now possible to measure ultratrace levels of many radioisotopes.The aim of this work was to determined the natural radionuclides (232Th, 234U, 235U and 238U) in surface water using Inductively Coupled Plasma-Sector Field Mass Spectrometry (ICP-SFMS). The samples were sampling from Lerma river, State of Mexico at february to april 2015. The process of treatment of sample consisted in perform an acid digestion according to the 3015A USEPA method followed of the direct measurement in ICP-SFMS. Results obtained were: a) identify the presence of 232Th, 234U, 235U and 238U isotopes in water, b) isotopic ratios were for 234U/238U=1.133 ± 0.016. ICP-SFMS has gained popularity in the field of radiochemistry, particularly as a method of detection for long lived-actinides.

Comparison of analytical methods: ICP-QMS, ICP-SFMS and FF-ET-AAS for the determination of V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb in ground natural waters

ABSTRACTThree analytical methods, namely, inductively coupled plasma sector field mass spectrometry (ICP-SFMS); inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) and filter-furnace electrothermal atomic-absorption spectroscopy (FF-ET-AAS) for the determination of V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb in ground natural water samples were compared and evaluated for their capacity to provide reliable and precise results. Two certified reference materials (SLEW-3 Estuarine Water; SLRS-4 River Water) were analysed to prove that accurate results could be obtained by using all the listed methods with properly optimised parameters. The limit of detection (LOD) for V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb provided by the ICP-MS methods ranged from 0.001 to 0.05 µg L−1. Such LOD proved sufficient for the reliable determination of the listed elements in ground natural waters. However, the LOD of the FF-ET-AAS was approximately two orders of magnitude higher than that of ICP-MS, which made it impossible to quantify V, Mn, Ni, Mo and Pb. The effects of the usage of the collision cell mode in ICP-QMS and of the desolvation system Apex for ICP-SFMS to eliminate oxide ions levels were investigated. For all three analytical methods, the influence of the matrix effect on the results of the determination of the investigated elements using matrix model solution, external calibration and standard addition methods was evaluated. A comparison using a paired Student’s t-test between the results obtained by both ICP-MS methods for V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb concentrations in ground natural waters showed that there was no significant difference on a 95% confidence level. The precision of the results for ICP-SFMS, ICP-QMS and FF-ET-AAS varied between ~0.5 and 11; 2.5 and 12.5; 3 and 13.5%, respectively. Moreover, ICP-SFMS equipped with the desolvation system APEX proved a better choice for As, Cu and Mn analysis due to its better LOD (0.008, 0.03 and 0.02 µg L−1, respectively) and precision (Sr ≤ 5.0; 7.5; 9.0%, respectively) compared to ICP-QMS and FF-ET-AAS.

U–Pb dating of zircons from PZ3–MZ igneous complexes of Transbaikalia by sector-field mass spectrometry with laser sampling: technique and comparison with SHRIMP

U–Pb zircon dating by laser ablation and sector-field mass spectrometry with inductively coupled plasma (LA–SF-ICP-MS) is an accessible local method with easy sample preparation. At the Geological Institute, Ulan-Ude, this method was applied using a Thermo Scientific Element XR single-collector SF ICP mass spectrometer and a UP-213 (New Wave Research) laser ablation system. Measurements for standard zircons showed the error of dating less than 2%. The results of U–Pb LA–SF-ICP-MS dating of zircon from Late Paleozoic granitoids of western Transbaikalia confirm the overlapping of the time intervals of formation of the Barguzin (330–290 Ma), Chivyrkui (305–285 Ma), and Zaza (305–285 Ma) intrusive complexes.

Comparison of Metal Levels between Postmortem Brain and Ventricular Fluid in Alzheimer's Disease and Nondemented Elderly Controls.

An essential metal hypothesis for neurodegenerative disease suggests an alteration in metal homeostasis contributing to the onset and progression of disease. Similar associations have been proposed for nonessential metals. To examine the relationship between metal levels in brain tissue and ventricular fluid (VF), postmortem samples of frontal cortex (FC) and VF from Alzheimer's disease (AD) cases and nondemented elderly subjects were analyzed for arsenic (As), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), manganese (Mn), mercury (Hg), nickel (Ni), tin (Sn), vanadium (V), and zinc (Zn) using inductively coupled plasma sector field mass spectrometry. All metals, with exception of equivalent Pb levels, were lower in the VF, compared to FC. Within-subject comparisons demonstrated that VF levels were not representative of levels within brain tissue. The essential metals Cu, Fe, and Zn were found highest in both compartments. Cd, Hg, and V levels in the VF were below the limit of quantification. In AD cases, FC levels of Fe were higher and As and Cd were lower than levels in controls, while levels of As in the VF were higher. Parameter estimates for FC metal levels indicated an association of Braak stage and higher Fe levels and an association of Braak stage and lower As, Mn, and Zn levels. The data showed no evidence of an accumulation of nonessential metals within the AD brain and, with the exception of As, showed no significant shift in the ratio of FC to VF levels to indicate differential clearance.

Sensitive redox speciation of iron, neptunium, and plutonium by capillary electrophoresis hyphenated to inductively coupled plasma sector field mass spectrometry.

The long-term safety assessment for nuclear waste repositories requires a detailed understanding of actinide (geo)chemistry. Advanced analytical tools are required to gain insight into actinide speciation in a given system. The geochemical conditions in the vicinity of a nuclear repository control the redox state of radionuclides, which in turn has a strong impact on their mobility. Besides the long-lived radionuclides plutonium (Pu) and neptunium (Np), which are key elements in high level nuclear waste, iron (Fe) represents a main component in natural systems controlling redox-related geochemical processes. Measuring the oxidation state distribution for redox sensitive radionuclides and other metal ions is challenging at trace concentrations below the detection limit of most available spectroscopic methods (≥10(-6) M). Consequently, ultrasensitive new analytical techniques are required. Capillary electrophoresis (CE) is a suitable separation method for metal cations. CE hyphenated to inductively coupled plasma sector field mass spectrometry (CE-ICP-SF-MS) was used to measure the redox speciation of Pu (III, IV, V, VI), Np (IV, V, VI), and Fe (II, III) at concentrations lower than 10(-7) M. CE coupling and separation parameters such as sample gas pressure, make up flow rate, capillary position, auxiliary gas flow, as well as the electrolyte system were optimized to obtain the maximum sensitivity. We obtain detection limits of 10(-12) M for Np and Pu. The various oxidation state species of Pu and Np in different samples were separated by application of an acetate-based electrolyte system. The separation of Fe (II) and Fe (III) was investigated using different organic complexing ligands, EDTA, and o-phenanthroline. For the Fe redox system, a limit of detection of 10(-8) M was calculated. By applying this analytical system to sorption studies, we were able to underline previously published results for the sorption behavior of Np in highly diluted concentrations, and we monitored the time-dependent reduction of Pu(VI) by Fe(II). This study clearly shows that CE-ICP-SF-MS is a suitable separation method for the redox states of Pu, Np, and Fe.

Mass spectrometric searches for superheavy elements in terrestrial matter

Recent searches for traces of long-lived superheavy elements (SHEs) in terrestrial materials by mass spectrometric means are reviewed. Positive evidence for long-lived neutron-deficient Th isotopes in Th and Rg isotopes in Au, and a possible A=292, Z∼122 nuclide in Th was reported from experiments with Inductively Coupled Plasma Sector Field Mass Spectrometry (ICP-SF-MS). These findings were not confirmed with Accelerator Mass Spectrometry (AMS), with abundance limits lower by several orders of magnitude. In addition, the extensive AMS searches for 42 SHE nuclides (A=288–310) around the much discussed “island of stability” (Z=114, N=184) in natural Pt, Au, Pb, Bi materials are reviewed. Due to the flatness of the mass distribution and the relatively large bandwidth of the mass acceptance in AMS searches, an effectively much larger number of SHE nuclides was scanned in the respective materials. No positive evidence for the existence of long-lived SHEs (t1/2>108 yr) with abundance limits of 10−12 to 10−16 was found.

Accelerated glacier melt on Snow Dome, Mount Olympus, Washington, USA, due to deposition of black carbon and mineral dust from wildfire

AbstractAssessing the potential for black carbon (BC) and dust deposition to reduce albedo and accelerate glacier melt is of interest in Washington because snow and glacier melt are an important source of water resources, and glaciers are retreating. In August 2012 on Snow Dome, Mount Olympus, Washington, we measured snow surface spectral albedo and collected surface snow samples and a 7 m ice core. The snow and ice samples were analyzed for iron (Fe, used as a dust proxy) via inductively coupled plasma sector field mass spectrometry, total impurity content gravimetrically, BC using a single‐particle soot photometer (SP2), and charcoal through microscopy. In the 2012 summer surface snow, BC (54 ± 50 µg/L), Fe (367±236 µg/L) and gravimetric impurity (35 ± 18 mg/L) concentrations were spatially variable, and measured broadband albedo varied between 0.67–0.74. BC and dust concentrations in the ice core 2011 summer horizon were a magnitude higher (BC = 3120 µg/L, Fe = 22000 µg/L, and gravimetric impurity = 1870 mg/L), corresponding to a modeled broadband albedo of 0.45 based on the measured BC and gravimetric impurity concentrations. The Big Hump forest fire is the likely source for the higher concentrations. Modeling constrained by measurements indicates that the all‐sky 12 h daily mean radiative forcings in summer 2012 and 2011 range between 37–53 W m−2 and 112–149 W m−2, respectively, with the greater forcings in 2011 corresponding to a 29–38 mm/d enhancement in snowmelt. The timing of the forest fire impurity deposition is coincident with an increase in observed discharge in the Hoh River, highlighting the potential for BC and dust deposition on glaciers from forest fires to accelerate melt.

Improved performance of a shielded torch using ethanol in inductively coupled plasma–sector field mass spectrometry

To improve the accuracy and precision of trace element analysis, higher analytical sensitivity and lower interference are required. In this study, we investigated the effects of the addition of ethanol in combination with a shielded torch on the signal intensities of elements from 7Li to 238U, oxide yields, doubly charged ion yields, isobaric interferences and ion distributions in inductively coupled plasma–sector field mass spectrometry (ICP–SFMS). For the 39 investigated elements in this study, using the shielded torch increases the sensitivity by a factor of 17–58. The well-known drawback of using a shielded torch is that it will increase the oxide yield. In this study, the CeO+/Ce+ ratio is increased by a factor of 3.3 in the GE-on mode compared to that in the GE-off mode at normal conditions (without ethanol). In the GE-on mode, the addition of 4% ethanol in ICP–SFMS is found not only to decrease the CeO+/Ce+ ratio by a factor of 4 but also to suppress the Ce2+/Ce+ ratio by a factor of 4.2. In large contrast, the effect of 2–6% ethanol on the oxide yield and doubly charged ratio is minimal in the GE-off mode. Except for As, Se, Sb, Te and Au, for which the signal intensities are increased by a factor of 1.4–3.7 in the presence of 2–6% ethanol, an increased concentration of ethanol suppresses intensities of other elements. In the GE-off mode, the suppression of the analyte signal due to increased ethanol concentration is more significant than that in the GE-on mode. Compared to the spatial profiles of the ion distributions in the normal mode (without ethanol), the addition of 2–4% ethanol leads to significantly wider axial and radial profiles. The significantly wider axial and radial ion distribution had a dilution effect on the ion densities, which subsequently reduced the ion signal intensities. The addition of 4% ethanol was also found to suppress the interferences of Xe by a factor of 2.8 and increase the sensitivity of Te determination in ICP–SFMS by a factor of 2.1 relative to the values obtained in conventional 2% (v/v) HNO3 solution at the corresponding optimum operating conditions in the GE-on mode. The addition of 4% ethanol in combination with the GE-on mode was successfully applied to the direct determination of nanogram levels of Te in a series of geological reference materials.

Determination of Ga, Ge, Mo, Ag, Cd, In, Sn, Sb, W, Tl and Bi in USGS Whole‐Rock Reference Materials by Standard Addition ICP‐MS

A procedure for determining a wide range of chalcophile and siderophile elements in typical crustal rocks using standard addition and ICP‐SFMS (inductively coupled plasma sector field mass spectrometry) is presented. New results for Ga, Ge, Mo, Ag, Cd, In, Sn, Sb, W, Tl and Bi abundances in USGS whole‐rock reference materials AGV‐2, BHVO‐1, BIR‐1, G‐2, GSP‐1 and W‐2 are reported using this analytical procedure. Intermediate precision of means based on multiple dissolved aliquots of each USGS reference material was 10% RSD or better for Ga, Ge, In and Sn in all, and similarly good for Ag, Cd, Sb, Tl and Bi in most reference materials. Poorer intermediate precision of Mo and W measurements in several reference materials is probably due to higher analytical blanks on these elements and powder heterogeneity due to a sulfide‐related nugget effect in the specific case of Mo in GSP‐1. Results for all elements fell within the range of available published data with the exception of Ag, which yielded systematically higher concentrations than found in the literature for five of the six reference materials, likely reflecting interference from unresolved polyatomic species.

Determination of relative rare earth element distributions in very small quantities of uranium ore concentrates using femtosecond UV laser ablation – SF-ICP-MS coupling

An alternative analytical method has been developed to determine lanthanide distribution using hundreds of nanograms of uranium ore concentrates by femtosecond ultra-violet laser ablation coupled to inductively coupled plasma sector-field mass spectrometry.

Dose-dependent clearance kinetics of intratracheally administered titanium dioxide nanoparticles in rat lung.

AEROSIL(®) P25 titanium dioxide (TiO2) nanoparticles dispersed in 0.2% disodium phosphate solution were intratracheally administered to male F344 rats at doses of 0 (control), 0.375, 0.75, 1.5, 3.0, and 6.0 mg/kg. The rats were sacrificed under anesthesia at 1 day, 3 days, 7 days, 4 weeks, 13 weeks, and 26 weeks after administration. Ti levels in various pulmonary and extrapulmonary organs were determined using sensitive inductively coupled plasma sector field mass spectrometry. One day after administration, the lungs contained 62-83% of TiO2 administered dose. Twenty-six weeks after administration, the lungs retained 6.6-8.9% of the TiO2 administered at the 0.375, 0.75, and 1.5 mg/kg doses, and 13% and 31% of the TiO2 administered at the 3.0 and 6.0 mg/kg doses, respectively. The pulmonary clearance rate constants from compartment 1, k1, were estimated using a 2-compartment model and were found to be higher for the 0.375 and 0.75 mg/kg doses of TiO2 (0.030/day for both) than for TiO2 doses of 1.5-6.0 mg/kg (0.014-0.022/day). The translocation rate constants from compartment 1 to 2, k12, were estimated to be 0.015 and 0.018/day for the 0.375 and 0.75 mg/kg doses, and 0.0025-0.0092/day for doses of 1.5-6.0mg/kg. The pulmonary clearance rate constants from compartment 2, k2, were estimated to be 0.0086 and 0.0093/day for doses of 0.375 and 0.75 mg/kg, and 0-0.00082/day for 1.5-6.0 mg/kg doses. Translocation of TiO2 from the lungs to the thoracic lymph nodes increased in a time- and dose-dependent manner, accounting for 0.10-3.4% of the administered dose at 26 weeks. The measured thoracic lymph node burdens were a much better fit to the thoracic lymph node burdens estimated assuming translocation from compartment 1 to the thoracic lymph nodes, rather than those estimated assuming translocation from compartment 2 to the thoracic lymph nodes. The translocation rate constants from the lungs to the thoracic lymph nodes, kLung→Lym, were 0.000037-0.00081/day, and these also increased with increasing doses of TiO2. Although a small amount of TiO2 had translocated to the liver by 3 days after the administration (0.0023-0.012% of the highest dose administered, 6.0 mg/kg), translocation to the other extrapulmonary organs was not detected.

Large variability of trace element mass fractions determined by ICP-SFMS in ice core samples from worldwide high altitude glaciers

We quantified leaching and mass fractions of trace elements in melted acidified ice core samples measured by Inductively Coupled Plasma Sector Field Mass Spectrometry (ICP-SFMS). This assessment was conducted using nine ice core sections retrieved from various high-altitude drilling sites in South America, Africa, Asia and Europe.Twenty trace elements (Ag, Al, As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Rb, Sb, Sn, Ti, Tl, U, V and Zn) were determined. During a 1½ month acid leaching period our assessment shows distinct increases in the concentration of various trace elements (10% for Cd; 30% for Pb; 50–80% for As, Cu, Mo, Mn, Tl and U; 80–90% for Bi, Rb, Sb, Sn and Zn; 100–160% for Al, Cr, Co, Ti and V; 200% for Fe). The exception is Ag, which shows a 50% decrease. We found that the observed relative increases in trace element concentrations are: (i) independent of the absolute trace element concentrations and micro-particle levels/size of the samples, and (ii) unlikely to affect reconstructions of the crustal/non-crustal origin of trace elements based on the use of the crustal enrichment factor.After 1½months of leaching, the measured trace element concentrations were found to be only a fraction of the estimated total concentration and that the mass fractions determined vary largely from element to element (on average 80–90% for As and Mn; 50–70% for U, Fe, Ti and Tl; 20–50% for Al, Cd, Co, Cr, Cu, Mo, Pb, Rb, V and Zn; 15% for Bi and 2% for Ag). These observations imply: (i) a significant underestimation of the mass fluxes of these trace elements to high altitude glaciers and (ii) a likely dependency of the mass fractions on the typical crystallographic position of each trace element within the micro-particles contained in the ice core samples.

Effect of the detector dead-time uncertainty on the analytical result of minor elements in low-alloy steel by isotope dilution/ICP sector field mass spectrometry.

In the present study the effects of the detector dead-time and its uncertainties on the accuracy and uncertainty of isotope dilution mass spectrometry (IDMS) were considered through an interlaboratory study on the analysis of low-alloy steel by using an ICP-sector field mass spectrometer. Also, an optimized mixing ratio of the sample and the spike to obtain highly precise results was theoretically and experimentally investigated. The detector dead-time used in the interlaboratory study showed a negative value. However, it less affected the trueness of the analytical result if the dead-time correction for the measured isotope ratio was done properly. As many researchers have pointed out, the detector dead-time showed a clear mass dependence. Therefore, it is desirable to check the dead-time in every target element by using assay standards or isotopic standards, which would lead to an accurate result even if the detector dead-time is a negative value. On the other hand, the effect of the uncertainty of the detector dead-time can be minimized when both isotope ratios and ICP-MS signals of the [sample + spike] blend in IDMS are equal to those of [spike + assay standard] in reverse IDMS. From standpoints of error magnification theory and the precision of the isotope ratio measurement, an optimized isotope ratio of the sample-spike blend would be 1.0 for an element with a large difference in ten times and more between the atomic fractions of two isotopes used for IDMS. In the case of an element with no significant difference between the atomic fractions of two isotopes, an optimized isotope ratio can be calculated by a formula expressed as a function of the atomic fractions of the sample and the spike as well as the signal of ICP-MS.

Determination of impurities in solar grade silicon by inductively coupled plasma sector field mass spectrometry (ICP-SFMS) subsequent to matrix evaporation

A method for the determination of 22 trace impurities in solar grade silicon after dissolution in a mixture of HF and HNO3 and subsequent matrix evaporation is reported. The presented method involves a simple, inexpensive, one-vessel sample preparation apparatus design. The recoveries of B, Na, Mg, Al, P, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Mo, Sb, W, and Tl at 250 μg kg−1 level are in the range of 93 to 108%. After careful selection of monitored isotopes and their respective resolutions, a sector field mass spectrometer has been used to carry out the measurements. Limits of determination down to 120 ng kg−1 have been obtained using a calibration by three-point standard addition. The method was tested on diluted NIST SRM 57b silicon powder as well as on synthetic test samples and also applied successfully on raw solar grade silicon samples in an interlaboratory comparison including NAA.

Characterization of brines and evaporites of Lake Katwe, Uganda

Lake Katwe brines and evaporites were investigated to determine their chemical, mineralogical and morphological composition. 30 brine samples and 3 solid salt samples (evaporites) were collected from different locations of the lake deposit. Several analytical techniques were used to determine the chemical composition of the samples including Inductively Coupled Plasma–Atomic Emission Spectrometry (ICP–AES), Inductively Coupled Plasma–Sector Field Mass Spectrometry (ICP–SFMS), ion chromatography, and potentiometric titration. The mineralogical composition and morphology of the evaporites was determined using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Physical parameters of the lake brines such as density, electrical conductivity, pH, and salinity were also studied. The results show that the lake brines are highly alkaline and rich in Na+, Cl−, CO32-, SO42-, and HCO3- with lesser amounts of K+, Mg2+, Ca2+, Br−, and F− ions. The brines show an intermediate transition between Na–Cl and Na–HCO3 water types. Among the trace metals, the lake brines were found to be enriched in B, I, Sr, Fe, Mo, Ba, and Mn. The solid salts are composed of halite mixed with other salts such as hanksite, burkeite and trona. It was also observed that the composition of the salts varies considerably even within the same grades.

Determination of element/Ca ratios in foraminifera and corals using cold- and hot-plasma techniques in inductively coupled plasma sector field mass spectrometry

We have developed a rapid and precise procedure for measuring multiple elements in foraminifera and corals by inductively coupled plasma sector field mass spectrometry (ICP-SF-MS) with both cold- [800W radio frequency (RF) power] and hot- (1200W RF power) plasma techniques. Our quality control program includes careful subsampling protocols, contamination-free workbench spaces, and refined plastic-ware cleaning process. Element/Ca ratios are calculated directly from ion beam intensities of 24Mg, 27Al, 43Ca, 55Mn, 57Fe, 86Sr, and 138Ba, using a standard bracketing method. A routine measurement time is 3–5min per dissolved sample. The matrix effects of nitric acid, and Ca and Sr levels, are carefully quantified and overcome. There is no significant difference between data determined by cold- and hot-plasma methods, but the techniques have different advantages. The cold-plasma technique offers a more stable plasma condition and better reproducibility for ppm-level elements. Long-term 2-sigma relative standard deviations (2-RSD) for repeat measurements of an in-house coral standard are 0.32% for Mg/Ca and 0.43% for Sr/Ca by cold-plasma ICP-SF-MS, and 0.69% for Mg/Ca and 0.51% for Sr/Ca by hot-plasma ICP-SF-MS. The higher sensitivity and enhanced measurement precision of the hot-plasma procedure yields 2-RSD precision for μmol/mol trace elements of 0.60% (Mg/Ca), 9.9% (Al/Ca), 0.68% (Mn/Ca), 2.7% (Fe/Ca), 0.50% (Sr/Ca), and 0.84% (Ba/Ca) for an in-house foraminiferal standard. Our refined ICP-SF-MS technique, which has the advantages of small sample size (2–4μg carbonate consumed) and fast sample throughput (5–8samples/hour), should open the way to the production of high precision and high resolution geochemical records for natural carbonate materials.

Sensitive quantification of gadolinium-based magnetic resonance imaging contrast agents in surface waters using hydrophilic interaction liquid chromatography and inductively coupled plasma sector field mass spectrometry

The application of gadolinium(Gd)-based contrast agents to support medical examinations by magnetic resonance imaging (MRI) results in a large input of Gd into the environment. The long-term effects of the anthropogenic Gd anomaly, especially on aqueous ecosystems, are mostly unknown. The identification and quantification of Gd-based contrast agents in the aquatic environment requires the use of powerful methods of speciation analysis. Therefore, a method employing the hyphenation of hydrophilic interaction liquid chromatography (HILIC) and inductively coupled plasma sector field mass spectrometry (ICP-SFMS) with sample introduction as dry aerosol generated by desolvation was developed. The desolvation resulted in improved limits of detection for the predominantly used contrast agents well below 0.10nmol/L. This method was subsequently used for the analysis of Gd species in surface waters. Samples from a nature reserve in the city of Münster (Germany), into which the effluent from the city's main wastewater treatment plant enters the environment, were examined. The contrast agents Gd-DTPA, Gd-DOTA and Gd-BT-DO3A were identified and quantified in constant ratios in those samples. The concentrations were found in a range from 0.59nmol/L for Gd-DOTA up to 3.55nmol/L for Gd-BT-DO3A. As a result of mass balancing, the contrast agent concentration was found to account for 74–89% of total Gd concentrations, possibly indicating the presence of further Gd species. Nevertheless, there was no direct indication of species transformation by transmetallation reactions resulting in such Gd species. The determination of REE patterns by means of ICP-MS confirmed the results of speciation analysis showing significant Gd anomalies.

Seasonal and spatial variation of trace elements and metals in quasi-ultrafine (PM0.25) particles in the Los Angeles metropolitan area and characterization of their sources

Year-long sampling campaign of quasi-ultrafine particles (PM0.25) was conducted at 10 distinct locations across the Los Angeles south coast air basin and concentrations of trace elements and metals were quantified at each site using high-resolution inductively coupled plasma sector field mass spectrometry. In order to characterize sources of trace elements and metals, principal component analysis (PCA) was applied to the dataset. The major sources were identified as road dust (influenced by vehicular emissions as well as re-suspended soil), vehicular abrasion, residual oil combustion, cadmium sources and metal plating. These sources altogether accounted for approximately 85% of the total variance of quasi-ultrafine elemental content. The concentrations of elements originating from source and urban locations generally displayed a decline as we proceeded from the coast to the inland. Occasional concentration peaks in the rural receptor sites were also observed, driven by the dominant westerly/southwesterly wind transporting the particles to the receptor areas.

A study of the extraction of plutonium from planchets by Aridus–ICP–SFMS

Two extraction processes of plutonium (Pu) on planchets from alpha spectrometry (AS) have been evaluated by inductively coupled plasma sector field mass spectrometry with a desolvator system (Aridus–ICP–SFMS). The samples were traced with known concentrations of 239Pu (1.2 × 103 fg) and 242Pu (2 × 103 fg) followed by an electrodeposition in planchets, according to the Hallstadius method. The processes of extraction were carried out with 50 mL of 0.36 mol L−1 HNO3 every 30 min up to 180 min in a glass beaker at 60 °C. The first process was on a hotplate and the second used an ultrasonic system. Finally, samples were evaporated to dryness, and resuspended in 10 mL of 0.72 mol L−1 HNO3 for evaluation. The results showed that at 120 min, a ~70 % recovery of 239Pu and a ~80 % recovery of 242Pu in both processes were obtained. The average recoveries of 239Pu and 242Pu at 180 min using the hotplate in plate were 93.4 ± 4.6 and 93.7 ± 4.2 % respectively, and with the ultrasonic system were 96.0 ± 4.3 and 98.2 ± 1.0 % respectively. In conclusion, both processes are suitable for Pu extraction, and Aridus–ICP–SFMS is an essential technique for the reassessments and quantification of Pu. In addition, procedural blanks spiked with 1 × 102 fg mL−1 U were prepared for each process, in order to study the contribution of the 238U on the background signal at m/z = 239, which was 0.5 ± 0.2 cps, indicating that the contribution of 238U on the 239Pu signal was negligible. Furthermore, this methodology can be applied to sample planchets with environmental, food, biological and nuclear origin, and thereby to avoid repetitive analysis when Pu concentration determined by AS are under minimum detectable activities.