Panoply - Elemental

Periodic table - elemental analysis

2015-05-04T10:31:00+00:00

Analyzes of major cations and metallic elements concentrations in water and sediments or rocks

2015-12-15T08:32:01+00:00

Agilent Technologies AAS 240 FS and GTA 120

Flame or Graphite Furnace Atomic Absorption Spectrometer to analyze cation concentrations (Al, As, Ba, Ca, Cr, Co, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Pt, Sb, Sn, Sr, Zn)

Description of the instrument

The Atomic Absorption Spectrometer (Agilent Technologies AAS 240 FS and GTA 120) can measure the concentrations of many elements. Depending on the concentrations of the solutions, it can be used in flame mode or in graphite furnace mode. It is equipped with automatic diluters (flame/oven) and autosamplers (flame/oven).

Principle of analysis

A liquid sample is injected as a mist into a flame (in flame mode) or a drop is placed in a graphite furnace (in graphite furnace mode). The heat vaporizes the elements contained in the sample and excites their atoms. These disrupt a light signal by reducing its intensity (absorption) or by emitting photons (emission). The light emitted by a hollow cathode lamp(s) or by the electrons of the excited atoms is sent via a set of mirrors and a crystal lattice to a detector which performs an optical measurement of the signal compared to a signal of undisturbed reference. The difference in light intensity is proportional to the concentration of the element in the solution. Calibration is done by injecting a standard solution to obtain the appropriate range. See principle of measurement here: http://spin.mines-stetienne.fr/sites/default/files/specatom.pdf

Analyzes carried out on the instrument

Major cations (Ca, Mg, Na and K) between 0.05 and 100 ppm in flame with an accuracy of +/- 5%;
Metals (Al, As, Ba, Cr, Co, Cu, Fe, Li, Mn, Mo, Ni, Pb, Pt, Sb, Sn, Sr, Zn) between 0.01 and 1000 ppm in flame depending on the elements and a few tens of ppt to a few tens of ppb in graphite furnace mode for some elements with an accuracy of +/- 5%;
Only liquid solutions (filtered and acidified) are analyzed but it is possible to measure solutions of acid attack on rocks, sediments or other solid samples.

Contacts

Gaël Monvoisin : + 33 (0)1.69.15.71.74 / gael.monvoisin@universite-paris-saclay.fr

Fundings

CNRS – INSU / University Paris-Sud : AAS flame Year 2010 – AAS graphite furnace Year 2012

Analyzes of the concentration of major anions in solution

2015-12-15T08:35:49+00:00

Dionex ICS 1000

Ionic Chromatography for anion concentrations analysis (F^-, Cl^-, NO₂^-, Br^-, NO₃^-, PO₄^3-, SO₄^2-)

Description of instrument:

Ionic chromatography (Dionex ICS 1000) measures the anion concentrations of solutions. The separation of anions can be done on different columns depending on the matrix and ions of interest.

Principle of analysis:

A liquid sample (filtered) is introduced, from the autosampler, into an injection loop, then through a column separating the ions which arrive, one after the other, separated by the column, on a detection cell (here conductimetry). The concentration of the anions is determined in relation to a previously established calibration range.

See measurement principle here :

http://tools.thermofisher.com/content/sfs/manuals/Man-031879-ICS-1000-Ion-Chromatography-Man031879-EN.pdf

Analyzes carried out on the instrument:

Major anions (F^-, Cl^-, NO₂^-, Br^-, NO₃^-, PO₄^3-, SO₄^2-) between 0.05 and 100 ppm depending on the elements with an accuracy of +/- 5%, only on liquid solutions (filtered).

Contacts:

Gaël Monvoisin : +33 (0)1.69.15.71.74 / gael.monvoisin[a}universite-paris-saclay.fr

Fundings:

University Paris-Sud: Year 2005

Quantitative analysis of major and trace elements in various materials (waters, carbonates, sediments, rocks, etc). Pb isotope measurements and U / Th dating (carbonates-apatites)

2015-12-07T08:50:24+00:00

Inductively Coupled Plasma – Quadrupole Mass Spectrometer - ICP-QMS X-series^II CCT

Characteristics of Instrumentation:

The Inductively Coupled Plasma – Quadrupole Mass Spectrometer (ICP-QMS) X-series II CCT Thermo Fisher Scientific is dedicated to quantitative multi-element analysis. This instrument allows rapid (~ minute), precise (~ percent) and quasi-simultaneous determination of the content of many chemical elements of the Periodic Table from the majors to those present in trace amounts in natural samples (freshwater, seawater, plants, soils, carbonates, apatites, rocks, etc.) or for any other type of materials or solutions. In its basic configuration, this mass spectrometer offers detection limits lower than μg / L (ppb) for many elements in solution and can reach several 100 pg / L (ppq) for heavy elements such as Rare Earth Elements or Uranium. Two options improve its performance: i- the CCT collision cell eliminates polyatomic interferences, typically for elementary analysis with atomic mass between 40 and 80 (transition metals, metalloids such as As, Se) ; ii- an additional pumping called “option S” at the interface lowering the detection limit for some heavy elements (uranium) to a few pg / L.

Three major application domains are currently being developed at the LSCE: i- elementary or isotopic (Pb) characterization of samples dissolved in solution to trace erosion processes, study of particle mobility as well as determine their origins, and quantitatively monitor the dissemination of some heavy or toxic metals in the environment, particularly in urban environments ; ii- elementary characterization of marine or continental carbonates/apatite archives (corals, foraminifera, speleothems, teeth, etc.) for paleoceanography, climatology or archeological studies (marine geochemistry, ocean temperature, carbon cycle and ocean acidification, precipitation, etc.) ; and iii- U-series Geochronology and U-Th dating of carbonates (corals) or apatites (teeth).

Principle of Measurement:

The principle is based on dissociation of molecules, atomization and ionization of the elements present in a solution and injected into a "Plasma" source of argon at 6000-8000 °K and atmospheric pressure. After the formation of an ion beam via the interface (sampler and skimmer cones) during a progressive transition to a secondary vacuum, a Quadrupole separates the isotopes or ions at low resolution according the m/z ratio. The ions/isotopes are then detected by a discrete-dynode electron multiplier. The precise quantification of the contents of major and / or trace elements is obtained after calibration of the instrumentation (standard solutions known or certified). Depending on the matrix or nature of the samples analyzed, the elements studied and the degree of precision sought, different calibration methods are used (standard calibration curves, standard addition or matrix recomposition methods, “bracketing” approach).

Other informations

Nebulizers : PFA 20, 50 or 100 µL/min ; quartz 1 mL/mn (solutions);
Quartz micro-cyclonic spray chamber or conic chamber with impact bead (solutions);
Desolvating systems APEX HF (2 à 10-fold more sensitive, solutions) ;
Ablation laser Excimer ESI – NWR 193 nm (in-situ analysis, aerosols from solid materials).

Measurements performed by ICP-QMS:

Quantification of major and/or trace elements in waters, soils, rocks, carbonates (erosion / transfer of particles) ;
Relative measurement of Pb isotopes (source tracing) ;
Quantification of majors (Sr/Ca, Mg/Ca) and trace elements (Li/Mg; B/Ca; Ba/Ca, U/Ca, REE, etc.) present in carbonates like corals or speleothems (paleoceanography / climatology / carbon cycle) ;
Quantification of rare earths and other elements present as ultra-traces in seawater or sediments (characterization of materials or processes) ;
Relative measurement of U and Th isotopes for U-Th dating of corals, speleothems, teeth.

Contacts:

Delphine Thomas : delphine.thomas[a]lsce.ipsl.fr 01 69 08 33 77

Sophie Ayrault : sophie.ayrault[a]lsce.ipsl.fr 01 69 08 40 71

Eric Douville : eric.douville[a]lsce.ipsl.fr 01 69 08 22 57

Isotopic (δ13C) and elementary (C, N) analysis of the organic matter

2015-12-10T15:15:24+00:00

Mass spectrometer IRMS ThermoFinnigan Delta Plus XP connected to an elemental analyzer Flash EA 1112 series

Flash EA 1112 Series Delta Plus XP

Characteristics of Instrumentation:

Isotope Ratio Mass Spectrometer (IRMS) Delta Plus XP (ThermoFinnigan), installed at LSCE in 2001, coupled to an Elemental Analyzer Flash EA 1112 Series installed in 2008. This spectrometer is a Continuous Flow type spectrometer. It is dedicated to the analysis of organic matter contained in different types of samples (sediments, bones, tissues, particles in suspension, etc.). The measurement accuracy of carbon isotopes is about 0.05 ‰. The amount of carbon required for a measurement is from 20 to 40 μg for isotopic measurements and an amount of 10 to 15 mg of samples is required for elemental analysis.

Principle of Measurement:

http://en.wikipedia.org/wiki/Isotope-ratio_mass_spectrometry

Measurements performed by instrumentation:

Carbon and nitrogen elementary quantification and carbon isotope (δ¹³C) analysis of organic matter. Developing in progress of isotopic measurements of nitrogen.

Contacts:

Caroline Gauthier : caroline.gauthier[a]lsce.ipsl.fr

Christine Hatté : christine.hatte[a]lsce.ipsl.fr

Jérémy Jacob : jeremy.jacob[a]lsce.ipsl.fr

Major to ultra-trace elemental and isotopic analysis in solution and by laser ablation

2015-12-10T08:18:31+00:00

High-resolution inductively coupled plasma-mass spectrometer Thermo element XR coupled to the last generation of excimer Laser ablation (LA-ICPMS-HR).

Description:

This magnetic sector mass spectrometer is dedicated to the elemental and isotopic analysis of major to ultra-trace ions, allowing to precisely separate ions at different levels (300, 4000 et 10000, at a highly better resolution than an ICP-QMS for instance), and thus to correct isobaric interferences. This instrument is characterized by a very low background noise and a very low detection level at 1 ppq (i.e., 10^-15g of element/g of sample) with a very stable signal (2% RSD per day). Protocols are very esay to adapt for the different kinds of use, allwing to measure major elements and isotopes (at about 1% RSD). The introduction system can be by a fast sample system for solutions, or by laser ablation of solid samples (Excimer 193 nm CETAC).

Analysis:

Different kinds of elements, isotopes and samples can be measured:

- Solutions et soils : dissolved metals from 0,1 µg/l to thousands of µg/l (Cu, Zn, Fe, As) and some isotope ratios (e.g., Pb). Analysis of micrometric particles.

- Seawater: Rare Earth Elements REE by direct injection.

- Biogenic carbonates (corals, foraminifers, sediments, calcite, dolomite…): minor and trace elements (ng/g : U, µg/g : B, Li, Cd, mg/g : Mg, Sr) in corals and very small samples (e.g., planktonic foraminifers: 100 µm, 10 µg ; benthic foraminifers: 100 µm, 50 µg) for elemental ratios (e.g., Li/Mg, B/Ca…), and Mg, Sr, Ba, U, Mn, REE concentrations at a percision level of about 0,5 %. U, Th and Pa isotopic ratios for U/Th dating of corals and ocean ventilation rates with a reproducibility of about 0,5 ‰.

- Minerals (apatite, zircon, diagenetic cements): major, minor and trace elements concentrations in solution and solids (laser), from very low concentrations (U, Th, REE in ppm, ppb for micrometric samples). Isopic ratios of U/Pb by laser ablation (ppm, 100 µm)

Contacts:

ICPMS : Sophie Sepulcre sophie.sepulcre@universite-paris-saclay.fr

Laser and ICPMS : Cécile Gautheron cecile.gautheron@universite-paris-saclay.fr

Laser: Guillaume Delpech guillaume.delpech@universite-paris-saclay.fr

Semi-quantitative analyses of major and minor elemental contents (Mg to Ba) in sediments (using X-ray Fluorescence)

2021-12-10T11:18:25+00:00

X-ray Fluorescence (XRF) core scanner

Instrument description
The 4th generation Avaatech XRF core scanner (bought in 2019) provides high-resolution (down to 100 µm) measurements of the chemical composition of marine and continental sediments. This semi-quantitative analysis gives access to the contents of major and minor elements (Mg to Ba), in an ultra-rapid and non-destructive manner, and with a very limited preparation of sediment cores. The measurement of one meter of sediment core (at 10, 30 and 50 kV) with a 1-cm step size takes about 2.5 hours.

Principle of analysis
Elemental contents are measured by X-ray Fluorescence directly at the sediment surface of split cores, which has been previously smoothed and covered with a thin transparent foil. Primary X-radiation emitted by a tube of varying intensity and voltage induces the ionisation of atoms of the sediment and the reorganisation of electrons between inner and outer shells of atoms. This results in the emission of fluorescent X-radiation, whose energy is characteristic of a particular atom. The energy-dispersive detector measures the energy distribution of the fluorescent X-radiation, from which the bAxil® software deduces the number of counts for each element.

Analyses performed with the instrument
Contents of major and minor elements (Mg to Ba) measured at the sediment surface of split cores.

Contacts
Aline Govin : aline.govin[a]lsce.ipsl.fr

Camille Wandres : camille.wandres[a]lsce.ipsl.fr

Quantitative analysis of major and minor elemental concentrations (Mg to Ba) in sediments (using X-ray Fluorescence)

2021-12-13T11:16:19+00:00

Benchtop Energy-Dispersive X-ray Fluorescence (ED-XRF) spectrometer

Instrument description
The benchtop PANalytical Epsilon 3XLE ED-XRF spectrometer (bought in 2018) provides quantitative measurements of the chemical composition of ground samples of marine and continental sediments. Thus, it gives access to the concentrations of 19 major and minor elements (Mg to Ba) of sediment samples, in a rapid, non-destructive and cheap manner, and with a limited preparation of sediment samples. The measurement of one sample takes about 10 minutes.

Principle of analysis
Elemental concentrations are measured by X-ray Fluorescence directly at the surface of ground sediment samples (protected by a thin transparent foil). Primary X-radiation emitted by a tube of varying intensity and voltage induces the ionisation of atoms of the sediment and the reorganisation of electrons between inner and outer shells of atoms. This results in the emission of fluorescent X-radiation, whose energy is characteristic of a particular atom. The energy-dispersive detector measures the energy distribution of the fluorescent X-radiation, from which the number of counts is deduced for each element. The calibration established using 39 certified sediment standards of various compositions converts, for each element, the number of counts into concentrations (in ppm).

Analyses performed with the instrument
Concentrations of 19 major and minor elements (Al, As, Ca, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Rb, Si, Sr, Ti, Zn, Zr) measured at the surface of dry and ground sediment samples.

Contacts
Aline Govin: aline.govin[a]lsce.ipsl.fr
Aurélie Van Toer: aurelie.vantoer[a]lsce.ipsl.fr

Analysis of trace elements in small calcite samples (20µg CaCO3) by ICP MS

2023-10-02T13:59:40+00:00

ICP-MS Analytic Jena Model PlasmaQuant Elite

Instrument description

The ICP-MS Analytic Jena Model PlasmaQuant Elite can measure several elements in the same sequence (up to 75 elements). The High Definition quadrupole can measure the elemental composition of calcite (from ppm to ppt).

Principle of analysis

The analysis of a series of trace elements in small samples of calcite is carried out in an acid matrix (after cleaning and dissolution of the calcite) using a low-flow nebuliser (50µL/min). The sample solution is then injected into a cyclonic chamber where the temperature is controlled by the Peltier effect, then injected into a plasma at 7000K. This ionises the sample. The quadrupole mass spectrometer separates the ions according to their mass-tocharge ratio. The ions strike a succession of dynodes, releasing electrons that are accelerated to produce an electrical pulse. This is measured using a digital detector.

Analyses performed with the instrument

Li, B, Na, Mg, Al, Ca, Mn, Sr, Cd, Ba, Nd, U

Contacts

William Gray : william.gray[a]lsce.ipsl.fr

Helene Rebaubier : helene.rebaubier[a]lsce.ipsl.fr

Scanning electron microscopy ESEM with EDS/µ-XRF

2023-10-03T14:19:32+00:00

QUATTRO S environmental scanning electron microscope (FEG-ESEM) is equipped with a Dual EDS (60 m m2) / µ-XRF coupling

Special features

Modes: High Vacuum (<6*10-4 Pa), Gradient Vacuum (10 Pa to 130 Pa), ESEM (10Pa to 4000 Pa).
5-axis motorized stage
NavCam: 6 megapixels with digital zoom, co-located with the stage.
Field emission cannon: voltages 200V-30 keV, current up to 200 nA.
Resolution: 1.0 nm (high vacuum) to 1.3 nm (ESEM) in SE at 30 keV; 3.0 nm at 1 keV.
Magnifications: x6 - x1,000,000
Conventional Everhardt-Thornley high-vacuum secondary electron detector
High-field gradient vacuum gas secondary electron detector.
4-segment diode backscattered electron detector
IR camera
2x QUANTAX 200 EDS detector (60 mm2) in symmetry (Bruker)
Canon X XTrace 400i (Bruker) with <35 µm capillary for µ-XRF
RapidStage piezoelectric stage for µ-XRF mapping
Licenses MAPS (correlative microscopy), TOPOMAPS (3D reconstructions), ESPRIT2 (EDS and XRF acquisition and processing)

Variable pressure

In gradient vacuum or ESEM mode, samples can be observed without any preparation, whether they be insulating, hydrated or oily, at the cost of a slight compromise in spatial resolution in SE, BSE and EDS (there is no consequence for µ-XRF).
Nominal resolutions are achieved in high-vacuum mode, but they require the deposition of a conductive layer on the surface of insulating samples. The laboratory has AU/Pd and C metallizers for this purpose.

Electron imaging

Secondary electron (SE) detectors provide topography contrast, enabling surface details to be imaged, even at very low accelerating voltages. The segmented diode backscattered electron (BSE) detector is primarily sensitive to atomic weight contrast, and can thus reconstruct a chemical contrast image of the sample at 2 keV and above.

The segmented BSE detector is compatible with TopoMaps Advanced software, and enables 3D reconstruction based on the three outer segments acquired in angular configuration (ABS), making it possible to restitute surfaces in 3D, calculate distances and slopes, extract object contours, etc.

Bivalve shell fragment (3D reconstruction)

Energy dispersive X-ray spectroscopy

The QUANTAX microanalysis system (Bruker) comprises two XFlash detectors with an active area of 60 mm2, and achieves an output count rate of 600 kcps per detector (at 66% dead time), i.e. 1.2 Mcps for both detectors. This system is therefore particularly well-suited to fast, quantitative elemental analysis, including mapping, with detection thresholds > 1000 ppm and spot sizes of the order of 1-2 µm at 15 keV.

EDS qualitative map (2,5 min)

X-ray micro-fluorescence

The Quantax µ-XRF system consists of an X-ray gun (50 keV), and uses both XFlash detectors, benefitting from its fast acquisition times. Easy to set up (i.e. for insulating samples), it is suitable for precise quantification, including trace elements (detection thresholds ~50ppm for many elements), but with less spatial resolution than EDS (of the order of 40 µm). The RapideStage stage can be used to acquire µ-XRF maps.

Funding

This instrument has been co-financed by the Ile-de-France Region as part of the "ACAV+" major area of interest.

Contacts

Julius NOUET – 01 69 15 61 21 – julius.nouet[a]universite-paris-saclay.fr

Amélie PLAUTRE – 01 69 15 61 27 – amelie.plautre[a]universite-paris-saclay.fr

Panoply - Elemental

Periodic table - elemental analysis

Analyzes of major cations and metallic elements concentrations in water and sediments or rocks

Agilent Technologies AAS 240 FS and GTA 120

Description of the instrument

Principle of analysis

Analyzes carried out on the instrument

Contacts

Fundings

Analyzes of the concentration of major anions in solution

Dionex ICS 1000

Description of instrument:

Principle of analysis:

Analyzes carried out on the instrument:

Contacts:

Fundings:

Quantitative analysis of major and trace elements in various materials (waters, carbonates, sediments, rocks, etc). Pb isotope measurements and U / Th dating (carbonates-apatites)

Inductively Coupled Plasma – Quadrupole Mass Spectrometer - ICP-QMS X-seriesII CCT

Characteristics of Instrumentation:

Principle of Measurement:

Measurements performed by ICP-QMS:

Contacts:

Isotopic (δ13C) and elementary (C, N) analysis of the organic matter

Principle of Measurement:

Measurements performed by instrumentation:

Contacts:

Major to ultra-trace elemental and isotopic analysis in solution and by laser ablation

Description:

Analysis:

Contacts:

Semi-quantitative analyses of major and minor elemental contents (Mg to Ba) in sediments (using X-ray Fluorescence)

Quantitative analysis of major and minor elemental concentrations (Mg to Ba) in sediments (using X-ray Fluorescence)

Analysis of trace elements in small calcite samples (20µg CaCO3) by ICP MS

ICP-MS Analytic Jena Model PlasmaQuant Elite

Instrument description

Principle of analysis

Analyses performed with the instrument

Contacts

Scanning electron microscopy ESEM with EDS/µ-XRF

QUATTRO S environmental scanning electron microscope (FEG-ESEM) is equipped with a Dual EDS (60 m m2) / µ-XRF coupling

Special features

Variable pressure

Electron imaging

Energy dispersive X-ray spectroscopy

X-ray micro-fluorescence

Funding

Contacts

Inductively Coupled Plasma – Quadrupole Mass Spectrometer - ICP-QMS X-series^II CCT