Analyzing trace element distribution and purification of vein quartz: a case study of Qianqi Furong mine in Inner Mongolia

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Recent applications on isotope ratio measurements by ICP-MS and LA-ICP-MS on biological samples and single particles

BackgroundSafety assessment of nanoparticles (NPs) requires techniques that are suitable to quantify tissue and cellular uptake of NPs. The most commonly applied techniques for this purpose are based on inductively coupled plasma mass spectrometry (ICP-MS). Here we apply and compare three different ICP-MS methods to investigate the cellular uptake of TiO2 (diameter 7 or 20 nm, respectively) and Ag (diameter 50 or 75 nm, respectively) NPs into differentiated mouse neuroblastoma cells (Neuro-2a cells). Cells were incubated with different amounts of the NPs. Thereafter they were either directly analyzed by laser ablation ICP-MS (LA-ICP-MS) or were lysed and lysates were analyzed by ICP-MS and by single particle ICP-MS (SP-ICP-MS).ResultsAll techniques confirmed that smaller particles were taken up to a higher extent when values were converted in an NP number-based dose metric. In contrast to ICP-MS and LA-ICP-MS, this measure is already directly provided through SP-ICP-MS. Analysis of NP size distribution in cell lysates by SP-ICP-MS indicates the formation of NP agglomerates inside cells. LA-ICP-MS imaging shows that some of the 75 nm Ag NPs seemed to be adsorbed onto the cell membranes and were not penetrating into the cells, while most of the 50 nm Ag NPs were internalized. LA-ICP-MS confirms high cell-to-cell variability for NP uptake.ConclusionsBased on our data we propose to combine different ICP-MS techniques in order to reliably determine the average NP mass and number concentrations, NP sizes and size distribution patterns as well as cell-to-cell variations in NP uptake and intracellular localization.Electronic supplementary materialThe online version of this article (doi:10.1186/s12951-016-0203-z) contains supplementary material, which is available to authorized users.

Mass cytometry with antibodies labelled with stable metal isotopes enables both sensitive imaging and the quantification of protein expression in biological samples. Typically, these specimens are exposed to a panel of labelled antibodies ex vivo, after sample collection. Here, we have developed a rhodium-labelled immunoconjugate of the HER2-targeted therapeutic IgG1 antibody, trastuzumab, and evaluated its in vivo biodistribution using mass cytometry techniques. A Rh3+ complex of a macrobicyclic sarcophagine (sar, 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) chelator was appended with a dibromopyridazinedione (DBPD), to produce a novel disulfide bond labelling molecule, “Rh-sar-DBPD”. Rh-sar-DBPD was site-specifically conjugated to trastuzumab via its four native solvent-accessible disulfide bonds, to yield a near homogeneous, well-defined and stable pyridazinedione (PD) immunoconjugate, Rh-sar-PD-trastuzumab, in which four Rh-sar-PD groups were attached per molecule of trastuzumab. Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were then applied to measure 103Rh content, as a proxy for Rh-sar-PD-trastuzumab accumulation, in in vitro and in vivo studies. ICP-MS in vitro studies indicated HER2-mediated uptake of Rh-sar-PD-trastuzumab in HER2-expressing breast cancer cells, with LA-ICP-MS images showing intercellular heterogeneity in Rh-sar-PD-trastuzumab uptake. To study the in vivo biodistribution of Rh-sar-PD-trastuzumab, female NSG mice bearing orthotopic HCC1954 breast cancer tumours were administered the immunoconjugate. Quantitative ICP-MS of 103Rh signal in dissected tissues indicated receptor-specific HER2-mediated uptake in tumours, as well as accumulation in the spleen and liver. Finally, LA-ICP-MS imaging analysis of tumour and ovary tissue sections showed heterogeneous uptake in HER2-expressing HCC1954 tumour cells and follicular granulosa cells of the ovaries, which are known to express growth factor receptors. To the best of our knowledge, this is the first report in which both ICP-MS and LA-ICP-MS have been used on tissue exposed to a metal-tagged antibody in vivo, enabling quantification of the biodistribution of the novel immunoconjugate, Rh-sar-PD-trastuzumab, in a murine model of breast cancer.

Elemental analysis of white cotton fiber evidence using solution ICP-MS and laser ablation ICP-MS (LA-ICP-MS)

Актуальность исследования связана с необходимостью опробования нового эффективного способа пробоподготовки геологических образцов, подходящего для массового многоэлементного ИСП-МС анализа, снижающего общие временные затраты и обеспечивающего возможность определения широкого набора элементов в рамках одного измерительного цикла с применением лазерной абляции (ЛА-ИСП-МС). Цель исследования состоит в сравнении метрологических характеристик двух методик ИСП-МС анализа, основанных на разных способах пробоподготовки силикатных пород – переведении твердого образца в раствор после сплавления с метаборатом лития и использовании готовых боратных стекол для ЛА-ИСП-МС анализа. Объекты: международные и отечественные стандартные образцы состава естественных горных пород: базальты – BHVO-1, BHVO-2, BCR-2, граниты – СГ-1а, СГ-3, габбро СГД-1а, трапп СТ-1а. Методы: масс-спектрометрия с индуктивно-связанной плазмой (ИСП-МС), лазерная абляция с масс-спектрометрическим окончанием (ЛА-ИСП-МС). Результаты исследования показали, что разработанные методики многоэлементного ИСП-МС и ЛА-ИСП-МС анализа позволяют определять широкий набор элементов в геологических образцах в рамках одного измерительного цикла в высоком, среднем и низком разрешении при использовании для внешней градуировки стандартных образцов с аналогичной матрицей и внутреннего стандарта для учета и снижения матричного влияния и дрейфа приборных параметров. Правильность определения всех элементов в соответствии с разработанными методиками доказана сравнением результатов анализа шести стандартных геологических образцов с принятыми значениями. ЛА-ИСП-МС отличается экспрессностью за счет отсутствия стадии пробоподготовки, при этом пределы обнаружения и погрешность определения для ЛА-ИСП-МС методики выше, чем при ИСП-МС анализе растворов.

The capability of different solid-state mass spectrometric methods [spark source mass spectrometry (SSMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), radiofrequency glow discharge mass spectrometry (rf GDMS) and secondary ion mass spectrometry (SIMS)] in comparison with inductively coupled plasma mass spectrometry (ICP-MS) was investigated by the trace analysis of GaAs. For trace analysis using solid-state mass spectrometry, a semiconducting laboratory GaAs standard (using high-purity GaAs) doped with Zn, B, Si, Ge, Sn, Sb, P, S, Se and Te (in the µg g–1 concentration range) was prepared by the liquid encapsulation vertical Bridgeman technique. A selected piece of the synthetic laboratory GaAs standard was investigated directly by SIMS, SSMS, rf GDMS and LA-ICP-MS. For the quantification of SIMS measurements single element ion-implanted GaAs certified reference standards were used. After dissolution of the GaAs sample in high-purity HNO3–H2O2, the concentrations of the doped elements were measured by ICP-MS and inductively coupled plasma atomic emission spectrometry (ICP-AES). By using the results of SIMS, ICP-MS and ICP-AES for the selected piece of the synthetic laboratory GaAs standard, relative sensitivity coefficients (RSCs) of the elements in SSMS, rf GDMS and LA-ICP-MS were determined. The experimentally determined RSCs were used for correcting measured concentrations in an unknown GaAs sample.In order to reduce matrix effects in ICP-MS, a procedure for complete GaAs matrix separation in a chlorine–argon stream at 280 °C was evaluated. The recoveries of 24 elements after the chlorination of GaAs were determined to be nearly 100% (except for Sn and Ta). Ultratrace analysis of semiconducting GaAs after matrix separation was carried out by double-focusing sector field ICP-MS. The detection limits of ultratrace elements in GaAs after matrix separation (in the low ng g–1 concentration range) were better by about one order of magnitude compared with measurements without matrix separation and were comparable to those obtained by solid-state mass spectrometry.

Microthermometry, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), and Raman spectroscopy have been used to determine the temperature, apparent salinity, and composition of individual fluid inclusions in adularia-sericite Au-Ag epithermal veins from the Karangahake, Martha, Favona, and Waitekauri deposits, southern Hauraki goldfield, New Zealand. Quartz veins contain colloform to crustiform bands that alternate with coarse-grained quartz and amethyst. The ore mineralization occurs only in colloform to crustiform bands. Analyses of individual fluid inclusions by LA-ICP-MS identify Na as the most abundant cation, together with variable concentrations of K, Ca, Rb, Sr, Sb, and As. Rare inclusions have detectable Li, Al, and Ba concentrations, although recorded Al concentrations with values up to 231 ppm in Al-free quartz may reflect an accidentally captured mineral phase rather than fluid itself. The Na content ranges from ~260 to 10,200 ppm for inclusions in quartz and ~9,700 to 13,700 ppm for inclusions in amethyst. Antimony is the second most commonly detected element in both quartz- and amethyst-hosted inclusions; this element is also detected in the host mineral. Concentrations of Sb and As range from 0.3 to 988 ppm and from 3.33 to 418 ppm, respectively, and are most commonly detected in inclusions from the Karangahake and Martha deposits. The poor correlation between the Na content with either Sb or As suggests that Sb and As were transported as neutral hydroxyl complexes of Sb(OH)3 and As(OH)3. Both Au and Ag occur at concentrations that are less than their respective detection limits (ppm). Geochemical modeling of the microthermometric and LA-ICP-MS data obtained from individual fluid inclusions suggests that fluids responsible for the quartz deposition were neutral to alkaline and that adiabatic boiling is the most effective mechanism for both gold and silica precipitation. The presence of single-phase vapor-only fluid inclusions in some mineralized samples indicates that local flashing may have contributed to deposition of Au and Ag. Assuming adiabatic boiling under hydrostatic pressure, samples from the Karangahake deposit (Maria vein) were deposited from low-salinity fluids (<3.9 wt % NaCl equiv) at temperatures between 225° and 262°C and at depths of 270 to 575 m below the former water table. The average deep reservoir fluid temperature estimated from the Na/K geothermometer is 287°C, and the steam loss during boiling ranges between 8 and 17%. Fluid inclusions in quartz from the Martha deposit trapped dilute fluids with salinity less than 1.7 wt % NaCl equiv. The coexisting liquid-rich (homogenization temperature, Th = 189°–225°C) and vapor-rich inclusions (Th = 205°–243°C) suggest formation at depths of 200 to 400 m below the water table. According to the Na/K geothermometer, the deep reservoir fluid temperature was near 295°C, and the steam loss during boiling ranged between 15 and 23%. Pseudosecondary inclusions in amethyst display salinity around 4.0 wt % NaCl equiv and homogenization temperatures between 218° and 241°C. Secondary inclusions are slightly more dilute (3.2–4.2 wt % NaCl equiv), with homogenization temperatures between 213° and 242°C. Fluid inclusions in quartz from the Waitekauri deposit homogenize from 210° to 265°C and contain less than 1.2 wt % NaCl equiv. A thin quartz vein that occurs between the Jubilee and Scotia deposits contains coexisting liquid- and vapor-rich inclusions; their homogenization temperatures indicate a formation depth of 300 m below the former water table. The calculated deep reservoir fluid temperature is around 283°C and the steam loss is estimated to be between 13 and 18%. LA-ICP-MS analyses show that in some cases different fluid inclusion assemblages (FIAs) within a single sample trapped fluids with variable chemistries. These differences likely reflect modification of a single parent fluid through mineral dissolution and precipitation, water/rock interactions, boiling and vapor loss, conductive cooling, and mixing.

Recent developments in element concentration and isotope ratio analysis of individual fluid inclusions by laser ablation single and multiple collector ICP-MS

BackgroundAge, genetics, and environmental exposure are among the primary risk factors for Alzheimer's Disease (AD) and related dementias (ADRDs) [1]. Exposure to environmental toxicants is disproportionately high in disadvantaged groups, making research on this topic both a medical and social justice concern. This study (TOX‐AD: 1U01AG088683) focuses on exposure to lead (Pb), cadmium (Cd), and arsenic (As), each listed among the WHO “Top 10” chemical toxicants of public health concern [2]. We hypothesize that these neurotoxicants alter the expression of AD‐linked genes and potentiate AD pathobiology in a toxicant‐specific, neurodevelopment‐sensitive, biomarker‐responsive, and age‐dependent manner.In this project, we used laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) imaging to conduct multi‐elemental brain mapping with ultra‐trace elemental quantification and precise anatomical localization. We employed LA‐ICP‐MS imaging to investigate neurotoxicants' accumulation and regional distribution in mouse brains following chronic exposure to Pb, Cd, and As in drinking water.MethodThe study utilized MODEL‐AD mice of both sexes to establish levels of metal/metalloid retention in the brain and blood after 30‐day exposure to Pb (200 ppm), Cd (5 and 50 ppm), As (20 ppm), control (no added metal) in drinking water. Brains and blood were collected, frozen using liquid nitrogen, and stored at ‐80C. Tissue concentrations of exogenously administered neurotoxicants (Pb, Cd, As) and endogenous biometals (Zn, Cu, Fe) were evaluated by inductively coupled plasma mass spectrometry (ICP‐MS) solution analysis and LA‐ICP‐MS imaging.ResultICP‐MS results showed robust Pb, Cd, and As uptake in mouse brain and blood after 30‐day exposure to epidemiologically relevant levels of each metal/metalloid in drinking water. We also demonstrated a strong correlation between brain and blood levels of As, Cd, and Pb. LA‐ICP‐MS mapping showed that neurotoxicants have non‐homogeneous element‐specific accumulation in different brain regions and subregions, including the hippocampus and cortex.ConclusionMODEL‐AD mice exposed to Pb, Cd, or As accumulate neurotoxicants in blood and brain that can be detected, imaged, and quantified by ICP‐MS solution analysis and LA‐ICP‐MS imaging.

Evaluating LA-ICP-MS and digestion-based ICP-MS methods for trace elements determination in oil shale and its solid wastes.

Analysis of trace metals in single droplet of urine by laser ablation inductively coupled plasma mass spectrometry

Tonglushan Fe-Cu (Au) deposit is one of the largest skarn deposits in middle-lower Yangtze River metallogenic belt, which is associated with the Early Cretaceous Yangxin quartz diorite stock. Granitic pegmatites are well developed in the southeast mining area, emplaced in the Yangxin quartz diorite pluton and cut by garnet-diopside skarn. The cross-cutting relationships thus indicate that the granitic pegmatites are temporarily intermediate between the quartz diorite and skarn. Granitic pegmatites consist mainly of K-feldspar, plagioclase, and quartz, with conspicuous graphic textures marked by intergrowths of K-feldspar and quartz. K-feldspar with graphic textures from one granitic pegmatite dike has been successfully dated by the Ar/ Ar laser microprobe incremental heating technique, yielding a well-defined plateau age of 136.0±1.0 Ma (2σ), which is interpreted to be the emplacement age of the granitic pegmatite dike. The age constraints indicate that the pegmatites formed coevally with the quartz diorite stock in the mine and related skarn Cu-Au mineralization. In situ laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) provides a wealth of information on the major and trace elements of K-feldspar from granitic pegmatites and quartz diorite. The average bulk compositions of K-feldspar from the pegmatite and quartz diorite are represented by Or Ab and Or Ab , respectively. K-feldspar minerals with graphic textures have higher Si and lower Al than those without graphic texture. Textural and geochemical data indicate that graphic textures in the pegmatites resulted from alternating growth of K-feldspar and quartz due to dynamic alteration of the relative concentration of SiO and Al O in areas proximal to the outer zone of growing K-feldspar crystals. Both K-feldspars from quartz diorite and granitic pegmatite are enriched in large-ion lithophile elements (LILE), but the pegmatite contains more abundant Rb and Pb and lesser amounts of Ba, Sr, Li, and Cs. In the Rb-Ba, La-Ba, K/Ba-Ba, and Rb/Sr-Ba diagrams, samples of the pegmatite and quartz diorite display a trend predicted by the Rayleigh factional crystallization, indicating that the granitic pegmatite was generated by strong fractional crystallization of quartz dioritic magma. However, Pb, Li, and Ga deviate obviously from the trend of fractional crystallization, indicating these elements may have been complexed by a fluid phase. Abundance of melt and fluid inclusions in quartz minerals from the granitic pegmatites demonstrates that the pegmatite formed from melt and fluid coexisting system. This study provides a better understanding of the formation of pegmatites, exsolution of ore fluids from evolving magmas, and hydrothermal mineralization.

Marine resources are often shared among countries, with some fish stocks straddling multiple Exclusive Economic Zones, therefore understanding the structure of populations is important for the effective management of fish stocks. Otolith chemical analyses could discriminate among populations based on differences in the chemical composition of otoliths. We used otoliths from two deepwater snappers (flame snapper Etelis coruscans and ruby snapper Etelis boweni) to examine the evidence for population structure across six Pacific Island countries using solution‐based inductively coupled plasma mass spectrometry (ICP‐MS) for otolith core and whole otolith samples and laser ablation ICP‐MS (LA‐ICP‐MS) for core and edge areas of a cross‐sectioned otolith. The inter‐species comparison of these methods is important as the two species are often managed under the same regulations. For both species, the two methods demonstrated separation among the locations sampled with high classification accuracy. Smaller laser ablation spot size gave greater temporal resolution over the life‐history transect. Comparing the early life‐history section of the otoliths (i.e., the core), one interpretation is that young fish experienced more uniform environments in the open ocean as larvae than adults, as the elemental fingerprints had greater overlap among multiple locations. LA‐ICP‐MS methods had some advantages over solution‐based ICP‐MS and generally better discrimination for the trace elements investigated. There were substantial differences between species, but both methods suggested nonmixing populations at the regional scale. Otolith chemistry can be an effective tool in discriminating variation for deepwater marine species in multispecies fisheries, and edge measurements from LA‐ICP‐MS provided the greatest resolution. Although caution should be taken in interpreting the results from relatively small samples sizes, otolith chemical analyses could be useful at these spatial scales to investigate population structure. This information on separate or overlapping populations could be used in future regional fishery management plans.

Reproducibility of laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) measurements in mussel shells and comparison with micro-drill sampling and solution ICP–MS