Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is increasingly used to analyze cultural heritage materials because it can simultaneously detect organic and inorganic materials while mapping them on a surface. The precise identification of a pigment in a specific layer of a painting or of remaining color on a statue can inform about the technique used or the time of manufacture as well as expose possible forgeries when anachronistic ingredients are identified. Reference spectra are required to confidently identify a given pigment using ToF-SIMS. This paper focuses on four blue pigments manufactured following historical recipes: two natural ground and processed lapis lazuli pigments, one synthetic ultramarine pigment, and the blue-colored ground cobalt glass pigment smalt. The positive and negative polarity ToF-SIMS reference spectra using a Bi3+ primary ion species are presented. Differentiating these family of pigments is of interest as they have similar compositions but are used in very different contexts. It is particularly noteworthy that the two natural lapis lazuli pigments can be distinguished from the synthetic counterpart ultramarine using ToF-SIMS.

  • Accession#: 01927, 01928, 01929, and 01930

  • Technique: SIMS

  • Specimen: Lapis Lazuli from Chile, Lapis Lazuli sky-blue, Ultramarine blue, and Smalt

  • Instrument: IONTOF, TOF SIMS IV

  • Major Species in Spectra: O, H, Al, Si, Na, Ca, K, Co, S, Cl, Fe, and C

  • Minor Species in Spectra: Hydrocarbon contamination

  • Published Spectra: 8

  • Spectral Category: Reference

ToF-SIMS imaging can detect a wide range of elements, so colored minerals can be identified and mapped, given that reference spectra are available for reliable assignment. Here, we provide a ToF-SIMS spectral database for four historical blue inorganic pigments of similar composition, as they all contain some proportion of silicon oxide. As the definite chemical composition of the pigments made from ground natural lapis lazuli is subjected to the variable mineral content of the stone, two pigments from distinct geographical origin and color shade (namely #01927 and #01928) are compared. A synthetic equivalent, commonly referred to as “ultramarine” and existing since the 19th century, is presented in comparison (#01929) as well as a blue-colored ground cobalt glass, known as smalt (#01930). For each, a list of their secondary ions is given in both polarities.

The reference materials were supplied by specialized manufacturers selling pigments reproducing historical recipes as closely as possible, such as Kremer Pigmente GmbH. Pigments were available as ground powder of variable particle size (a few tens of μm to 100 μm) conditioned in glass sealed vials. In paintings, pigment particles are dispersed and not dissolved, so all references were analyzed without any preparation treatment. Natural and synthetic pigments may contain impurities, and specimen compositions described below are the major components as found on the material data sheets provided by the suppliers.

A stainless-steel spatula was cleaned with propan-2-ol, and the powder was directly deposited on a 1 × 1 mm2 piece of a conductive double-sided tape (3M Electrically Conductive Adhesive Transfer Tape 9703) already fixed to a 1 cm × 1 cm × 0.125 mm stainless steel plate (17-7PH, Goodfellow Cambridge Limited, UK) fitting the dimensions of the sample holder. A hand press covered with clean aluminum foil was applied onto the powder to fix it to the tape. This allowed us to minimize the risk of dust formation when operating in the analysis chamber under ultrahigh vacuum (10−8 to 10−9 hPa) while ensuring a flat surface.

All spectra were obtained on an IONTOF TOF SIMS IV equipped with a 25 keV bismuth liquid metal ion gun and an argon gas cluster ion beam (GCIB). Before all analyses, a 500 × 500 μm2 surface was cleaned using 1500–2000 Ar clusters with a kinetic energy of 20 keV (sputter ion dose of 2 × 1015 ions/cm2). Analyses were then performed on a 250 × 250 μm2 area centered in this larger cleaned area, rastered over 128 × 128 pixels using the high current bunched mode. Primary ion dose (25 keV Bi3+) was 4.35 × 1011 ions/cm2. Surface potential was compensated and charging of the sample was compensated with low-energetic 20 eV electrons of the flood gun.

In cases where the grain size and shape prevented a large enough flat surface accessible for the analysis, delayed extraction mode included on the ToF analyzer was used since this reduces the variation in time of flight due to surface topography.1 This was necessary for lapis lazuli sky-blue (Accession #01928), as the data obtained using bunched mode were limited in mass resolution due to topography. The imaging capabilities of the ToF-SIMS instrument were also especially useful in attributing peaks by referring to their co-localization.

Data were calibrated using sets of peaks as similar as possible for all spectra, using peaks that could be confidently identified while taking into account the mass interferences involving Al, Si, Na, K, and Ca. The lists were designed so that meaningful comparisons between datasets are possible. Calcium has a distinctive isotopic pattern ensuring confident attribution of the peaks; hence, #01927 and #01928 positive polarity data were calibrated using lists including Ca+, SiONa+, Ca2O2H+, and Ca3O3H+ ions. #01929 and #01930 positive polarity data were calibrated, which included Al+, SiONa+, SiO2Na2+, and SiO3Na3+. The negative polarity data were calibrated for #01927, #01928, and #01929 using SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10, while the non-Al containing smalt #01930 was calibrated using SiO2, Si2O5H, Si3O7H, Si4O9H, and Si5O11H. The calibration lists allowed for a good coverage of the mass range of interest for each specimen, and they are reported in the corresponding tables below. The mass calibration in the range below m/z 30 in the datasets #01928 is impacted by the low count and peak asymmetry due to the use of delayed extraction.

Figures and tables presented below contain the major peaks for both polarities. Each pigment is uniquely identified thanks to an accession number, and they are grouped according to their composition and described in the following section. Their historical relevance is briefly described based on current literature.2–4 The spectrum ID# refer to that number, added with “−01” for positive spectra and with “−02” for negative spectra.

Specimen: (Accession #01927) Lapis Lazuli from Chile (Kremer Pigmente ref. 1056038), (Accession #01928) Lapis Lazuli, sky-blue (Kremer Pigmente ref. 10562), and (Accession #01929) Ultramarine Blue (Kremer Pigmente ref. 45000)

CAS Registry #: (Accession #01927 and #01928) 57455-35-5; (Accession #01929) 101357-30-6 (57455-37-5), 1332-58-7

Specimen Characteristics: Inhomogeneous; solid; unknown crystallinity; dielectric; inorganic compound; powder

Chemical Name: (Accession #01927 and #01928) Sodium aluminum silicate sulfurized; (Accession #01929) Silicic acid, aluminum sodium salt, sulfurized, and kaolin

Source: Kremer Pigmente GmbH

Specimen Composition: (Accession #01927 and #01928) Lazurite [Na6Ca2(AlSiO4)6 (SO4,S,S2,S3,Cl,OH)2] inclusions in dolomite, sodalite Na8Al6Si6O24Cl2, pyrite FeS2; (Accession #01929) Synthetic ultramarine, NaxAl6Si6O24Sy (x = 6−10 and y = 2−4 depending on manufacturing process)

Form: Ground pigment powder

History and Significance: A rare, semiprecious, dark-blue stone found as inclusions in dolomite/calcite marble. Its main mineral is sulfur aluminosilicate lazurite, combined with various minerals like sodalite and pyrite. The pigment is produced from stone by grinding, sieving, and washing. It is blue to blue gray, with large irregular particles and variable quantities of colorless crystalline impurities. The rarity and complexity of the process led to ultramarine being more expensive than gold for centuries. A synthetic form has been available since the 19th century, recognizable by the distinctive shape of the particles, which are smaller. Its chemical structure is very close to lazurite, but not fully known, as discussed in the literature.2 TOF-SIMS informs about the synthetic or natural origin by both the particle morphology and the spectral differences. The spectra of both natural lapis lazuli pigments are similar, while that of synthetic ultramarine are distinctive. Natural organic resins can be used in the manufacturing process, and they can be detected simultaneously as the inorganic compounds (see #01929). The sensitivity of ToF-SIMS for fluorine also proved to be of interest, as F-rich mineral can be found in natural lapis lazuli.

As Received Condition: Ground pigment powders were stored in a sealed glass vial in a wooden box, protected from daylight. Stored at room temperature.

Analyzed Region: Areas of 250 × 250 μm2

Ex Situ Preparation/Mounting: Powder was deposited and pressed onto a conductive double-sided tape attached to stainless steel 1 × 1 cm2 plates. The resulting deposit of powder had a flat surface and was fixed in a suitable way for the vacuum chamber. The plate was directly mounted on a “backmount” sample holder (IONTOF).

In Situ Preparation: None

Charge Control Conditions and Procedures: A low-energy electron flood gun was used. Bias voltage between 20 and −30 V. Flood gun filament current of 2.35 A. Surface potential was corrected (sample dependent).

Temp. During Analysis: 300 K

Pressure During Analysis: Between 1 × 10−5 and 1 × 10−6 Pa

Pre-analysis Beam Exposure: Ar1500–2000, 20 keV, 2 × 1015ions/cm2

Specimen: Smalt (Kremer Pigmente ref. 10000)

CAS Registry #: 14808-60-7, 1308-06-1,1307-96-6

Specimen Characteristics: Inhomogeneous; solid; amorphous; dielectric; inorganic compound; powder

Chemical Name: Cobalt potassium silicate glass (quartz, tricobalt tetraoxide, and cobalt monoxide)

Source: Kremer Pigmente GmbH

Specimen Composition: CoOKSi (various wt. % of SiO2, K2O, and CoO)2 

Form: Ground pigment powder

History and Significance: It is the oldest synthetic cobalt pigment, obtained by grinding blue glass colored by cobalt oxides, in turn obtained by heating quartz in the presence of potassium carbonate and cobalt chloride. Used from the 16th to 18th centuries as a cheap alternative to lapis and azurite. It tends to turn gray in oil paints over time. Possible traces of nickel and arsenic can be present. This pigment does not contain aluminum.

As Received Condition: Ground pigment powders were stored in a sealed glass vial in a wooden box, protected from daylight. Stored at room temperature.

Analyzed Region: Areas of 250 × 250 μm2

Ex Situ Preparation/Mounting: Powder was deposited and pressed onto a conductive double-sided tape attached to stainless steel 1 × 1 cm2 plates. The resulting deposit of powder had a flat surface and was fixed in a suitable way for the vacuum chamber. The plate was directly mounted on a “backmount” sample holder (IONTOF).

In Situ Preparation: None

Charge Control Conditions and Procedures: A low-energy electron flood gun was used. Bias voltage between 20 and −30 V. Flood gun filament current of 2.35 A. Surface potential was corrected (sample dependent).

Temp. During Analysis: 300 K

Pressure During Analysis: Between 1 × 10−5 and 1 × 10−6 Pa

Pre-analysis Beam Exposure: Ar1500–2000, 20 keV, 2 × 1015ions/cm2

Manufacturer and Model: IONTOF, TOF SIMS IV

Analyzer Type: Time-of-flight

Sample Rotation: No

Rotation Rate: 0 rpm

Oxygen Flood Source: None

Oxygen Flood Pressure: N/A

Other Flood Source: None

Other Flood Pressure: N/A

Unique Instrument Features Used: The analyzer was equipped with delayed extraction mode. It was used when the topography of the pigment's grains impacted the signal quality (e.g., grains of several tens of micrometers with sharp edges). The delayed extraction mode allows for an attenuation of the relative delays between secondary ions due to height differences on the surface.

Energy Acceptance Window: 20 eV

Post-acceleration Voltage: 10 000 eV

Sample Bias: 10–20 eV

Specimen Normal-to-analyzer ( Θ e ):

Ion Source 1 of 2

Purpose of This Ion Source: Analysis beam

Ion Source Manufacturer: IONTOF GmbH

Ion Source Model: Liquid metal ion gun (LMIG) with bismuth cluster (25 keV)

Beam Mass Filter: Yes

Beam Species and Charge State: Bi3+

Beam Gating Used: Double pulsed + bunched

Additional Beam Comments: None

Beam Voltage: 25 000 eV

Net Beam Voltage (impact voltage): 25 000 eV

Ion Pulse Width: 0.8–1.2 ns

Ion Pulse Rate: 5–10 kHz

DC Beam Current: ∼10 nA

Pulsed Beam Current: ∼0.0004 nA

Current Measurement Method: Faraday cup

Beam Diameter: ∼2 μm

Beam Raster Size: 250 × 250 μm2

Raster Pixel Dimensions: 128 × 128

Beam Incident Angle: 45°

Source-to-Analyzer Angle: 45°

Ion Source 2 of 2

Purpose of This Ion Source: Sputtering beam

Ion Source Manufacturer: IONTOF GmbH

Ion Source Model: Argon gas cluster ion beam (GCIB)

Beam Mass Filter: Yes

Beam Species and Charge State: Arn+ with n = 1500–2000

Beam Gating Used: Wien filter

Additional Beam Comments: Used as sputter gun, not analysis mode

Beam Voltage: 20 000 eV

Net Beam Voltage (impact voltage): 20 000 eV

Ion Pulse Width: N/A

Ion Pulse Rate: N/A

DC Beam Current: ∼10 nA

Pulsed Beam Current: N/A

Current Measurement Method: Faraday cup

Beam Diameter: ∼50 μm

Beam Raster Size: 500 × 500 μm2

Raster Pixel Dimensions: N/A

Beam Incident Angle: 45°

Source-to-Analyzer Angle: 45°

SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01927-01 26.980 (−21.0) Al+ Lazurite, sodalite 
39.962 (−14.9) Ca+ Lazurite, dolomite 
55.956 (−15.8) CaO+ Lazurite, dolomite 
56.966 (17.4) CaOH+ Lazurite, dolomite 
58.959 (−26.0) CaF+ F-rich mineral impurity 
82.953 (−30.9) SiO2Na+ Lazurite 
95.921 (11.5) Ca2O+ Lazurite, dolomite 
98.938 (50.1) SiONaS+ Lazurite 
111.914 (−5.73) Ca2O2+ Lazurite 
112.925 (22.0) Ca2O2H+ Lazurite, dolomite 
114.919 (8.96) Ca2OF+ F-rich mineral impurity 
136.918 (−11.6) Ca2F3+ F-rich mineral impurity 
154.897 (39.0) CaSiNaSO2+ Lazurite 
174.891 (−21.7) Si2O2NaSO2+ Lazurite 
214.863 (24.3) Ca2OAlSiO4+ Lazurite 
230.855 (9.91) Ca2O2AlSiO4+ Lazurite 
270.824 (32.8) Ca3O2AlSiO4+ Lazurite 
326.783 (32.0) Ca4O3AlSiO4+ Lazurite 
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01927-01 26.980 (−21.0) Al+ Lazurite, sodalite 
39.962 (−14.9) Ca+ Lazurite, dolomite 
55.956 (−15.8) CaO+ Lazurite, dolomite 
56.966 (17.4) CaOH+ Lazurite, dolomite 
58.959 (−26.0) CaF+ F-rich mineral impurity 
82.953 (−30.9) SiO2Na+ Lazurite 
95.921 (11.5) Ca2O+ Lazurite, dolomite 
98.938 (50.1) SiONaS+ Lazurite 
111.914 (−5.73) Ca2O2+ Lazurite 
112.925 (22.0) Ca2O2H+ Lazurite, dolomite 
114.919 (8.96) Ca2OF+ F-rich mineral impurity 
136.918 (−11.6) Ca2F3+ F-rich mineral impurity 
154.897 (39.0) CaSiNaSO2+ Lazurite 
174.891 (−21.7) Si2O2NaSO2+ Lazurite 
214.863 (24.3) Ca2OAlSiO4+ Lazurite 
230.855 (9.91) Ca2O2AlSiO4+ Lazurite 
270.824 (32.8) Ca3O2AlSiO4+ Lazurite 
326.783 (32.0) Ca4O3AlSiO4+ Lazurite 

Accession #: 01927-01 
■ Specimen: Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1700 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, Ca+, SiONa+, Ca2O2H+, and Ca3O3H+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.35 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 13 nA 
DC Beam Current: 10.4 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 335 s 
Comment: Very large grains, mass resolution impacted. The sodium peak saturated. 
Accession #: 01927-01 
■ Specimen: Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1700 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, Ca+, SiONa+, Ca2O2H+, and Ca3O3H+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.35 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 13 nA 
DC Beam Current: 10.4 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 335 s 
Comment: Very large grains, mass resolution impacted. The sodium peak saturated. 

Accession #: 01927-01 
■ Specimen: Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1700 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, Ca+, SiONa+, Ca2O2H+, and Ca3O3H+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.35 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 13 nA 
DC Beam Current: 10.4 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 335 s 
Comment: Very large grains, mass resolution impacted. The sodium peak saturated. 
Accession #: 01927-01 
■ Specimen: Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1700 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, Ca+, SiONa+, Ca2O2H+, and Ca3O3H+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.35 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 13 nA 
DC Beam Current: 10.4 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 335 s 
Comment: Very large grains, mass resolution impacted. The sodium peak saturated. 

Close modal
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01927-02 18.999 (−7.07) F Accessory mineral (ex: phlogopite) 
31.973 (17.7) S Lazurite 
34.970 (20.2) Cl Lazurite, sodalite, phlogopite 
42.977 (−3.48) AlO Lazurite, sodalite, phlogopite 
47.967 (−8.23) SO Lazurite 
58.971 (−11.9) AlO2 Lazurite, sodalite, phlogopite 
60.977 (22.6) SiO2H Lazurite, sodalite, phlogopite 
62.971 (−2.18) SiOF Phlogopite 
63.964 (31.1) SO2 Lazurite 
76.974 (51.1) SiO3H Lazurite, sodalite, phlogopite 
78.968 (23.9) SiO2F Phlogopite 
79.960 (33.5) SO3 Lazurite 
96.950 (24.6) KNaOF Phlogopite 
102.946 (22.5) SiAlO3 Lazurite, sodalite, phlogopite 
118.937 (−17.5) SiAlO4 Lazurite, sodalite, phlogopite 
134.922 (17.7) AlSiSO3 Lazurite 
136.939 (14.1) Si2O5H Lazurite, sodalite, phlogopite 
162.917 (37.0) Si2AlO5 Lazurite, sodalite, phlogopite 
174.898 (13.7) K2Na2O2F Phlogopite 
178.904 (−6.98) Si2AlO6 Lazurite, sodalite, phlogopite 
180.909 (−21.6) Na2OAlSiO4 Lazurite, sodalite, phlogopite 
194.886 (18.7) Si2AlSO5 Lazurite 
196.904 (−23.1) Na2O2AlSiO4 Lazurite, sodalite, phlogopite 
204.896 (19.3) SiAl3O6 Lazurite, sodalite, phlogopite 
212.893 (2.29) K2Na2O2F3 Phlogopite 
220.888 (7.87) SiAl3O7 Lazurite, sodalite, phlogopite 
238.874 (6.40) Si3AlO8 Lazurite, sodalite, phlogopite 
280.854 (4.23) Si2Al3O9 Lazurite, sodalite, phlogopite 
298.843 (14.1) Si4AlO10 Lazurite, sodalite, phlogopite 
322.840 (16.3) SiAl5O10 Lazurite, sodalite, phlogopite 
336.816 (14.8) NaSi3Al2SO9 Lazurite 
340.824 (10.2) Si3Al3O11 Lazurite, sodalite, phlogopite 
358.807 (3.43) Si5AlO12 Lazurite, sodalite, phlogopite 
382.805 (9.45) Si2Al5O12 Lazurite, sodalite, phlogopite 
396.762 (6.81) NaSi4Al2S2O9 Lazurite 
400.776 (−26.6) Si4Al3O13 Lazurite, sodalite, phlogopite 
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01927-02 18.999 (−7.07) F Accessory mineral (ex: phlogopite) 
31.973 (17.7) S Lazurite 
34.970 (20.2) Cl Lazurite, sodalite, phlogopite 
42.977 (−3.48) AlO Lazurite, sodalite, phlogopite 
47.967 (−8.23) SO Lazurite 
58.971 (−11.9) AlO2 Lazurite, sodalite, phlogopite 
60.977 (22.6) SiO2H Lazurite, sodalite, phlogopite 
62.971 (−2.18) SiOF Phlogopite 
63.964 (31.1) SO2 Lazurite 
76.974 (51.1) SiO3H Lazurite, sodalite, phlogopite 
78.968 (23.9) SiO2F Phlogopite 
79.960 (33.5) SO3 Lazurite 
96.950 (24.6) KNaOF Phlogopite 
102.946 (22.5) SiAlO3 Lazurite, sodalite, phlogopite 
118.937 (−17.5) SiAlO4 Lazurite, sodalite, phlogopite 
134.922 (17.7) AlSiSO3 Lazurite 
136.939 (14.1) Si2O5H Lazurite, sodalite, phlogopite 
162.917 (37.0) Si2AlO5 Lazurite, sodalite, phlogopite 
174.898 (13.7) K2Na2O2F Phlogopite 
178.904 (−6.98) Si2AlO6 Lazurite, sodalite, phlogopite 
180.909 (−21.6) Na2OAlSiO4 Lazurite, sodalite, phlogopite 
194.886 (18.7) Si2AlSO5 Lazurite 
196.904 (−23.1) Na2O2AlSiO4 Lazurite, sodalite, phlogopite 
204.896 (19.3) SiAl3O6 Lazurite, sodalite, phlogopite 
212.893 (2.29) K2Na2O2F3 Phlogopite 
220.888 (7.87) SiAl3O7 Lazurite, sodalite, phlogopite 
238.874 (6.40) Si3AlO8 Lazurite, sodalite, phlogopite 
280.854 (4.23) Si2Al3O9 Lazurite, sodalite, phlogopite 
298.843 (14.1) Si4AlO10 Lazurite, sodalite, phlogopite 
322.840 (16.3) SiAl5O10 Lazurite, sodalite, phlogopite 
336.816 (14.8) NaSi3Al2SO9 Lazurite 
340.824 (10.2) Si3Al3O11 Lazurite, sodalite, phlogopite 
358.807 (3.43) Si5AlO12 Lazurite, sodalite, phlogopite 
382.805 (9.45) Si2Al5O12 Lazurite, sodalite, phlogopite 
396.762 (6.81) NaSi4Al2S2O9 Lazurite 
400.776 (−26.6) Si4Al3O13 Lazurite, sodalite, phlogopite 

Accession #: 01927-02 
■ Specimen: Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1400 m/Δm 
Mass Resolving Power Determined at: 25 D 
Species Used for Mass Calibration: Cl, SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.35 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 13 nA 
DC Beam Current: 10.4 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 335 s 
Comment: Very large grains, mass resolution impacted. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg3(AlSi3O10)(F,OH)2]. Assignments were refined thanks to colocalization in ion images. 
Accession #: 01927-02 
■ Specimen: Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1400 m/Δm 
Mass Resolving Power Determined at: 25 D 
Species Used for Mass Calibration: Cl, SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.35 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 13 nA 
DC Beam Current: 10.4 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 335 s 
Comment: Very large grains, mass resolution impacted. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg3(AlSi3O10)(F,OH)2]. Assignments were refined thanks to colocalization in ion images. 

Accession #: 01927-02 
■ Specimen: Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1400 m/Δm 
Mass Resolving Power Determined at: 25 D 
Species Used for Mass Calibration: Cl, SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.35 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 13 nA 
DC Beam Current: 10.4 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 335 s 
Comment: Very large grains, mass resolution impacted. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg3(AlSi3O10)(F,OH)2]. Assignments were refined thanks to colocalization in ion images. 
Accession #: 01927-02 
■ Specimen: Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1400 m/Δm 
Mass Resolving Power Determined at: 25 D 
Species Used for Mass Calibration: Cl, SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.35 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 13 nA 
DC Beam Current: 10.4 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 335 s 
Comment: Very large grains, mass resolution impacted. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg3(AlSi3O10)(F,OH)2]. Assignments were refined thanks to colocalization in ion images. 

Close modal
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01928-01 26.982 (38.4) Al+ Lazurite, sodalite 
39.960 (−52.3) Ca+ Lazurite, dolomite 
55.954 (−50.3) CaO+ Lazurite, dolomite 
56.962 (−47.8) CaOH+ Lazurite, dolomite 
58.957 (−54.9) CaF+ F-rich mineral impurity 
95.922 (29.3) Ca2O+ Lazurite, dolomite 
98.936 (24.6) SiONaS+ Lazurite 
111.914 (−3.31) Ca2O2+ Lazurite 
112.923 (7.19) Ca2O2H+ Lazurite, dolomite 
114.920 (13.1) Ca2OF+ F-rich mineral impurity 
136.922 (13.8) Ca2F3+ F-rich mineral impurity 
151.878 (10.5) Ca3O2+ Lazurite, dolomite 
154.895 (27.0) CaSiNaSO2+ Lazurite 
167.873 (6.75) Ca3O3+ Lazurite, dolomite 
174.891 (−19.4) Si2O2NaSO2+ Lazurite 
207.837 (11.7) Ca4O3+ Lazurite, dolomite 
210.858 (−19.3) SiNaS3O4+ Lazurite 
214.868 (47.3) Ca2OAlSiO4+ Lazurite 
223.832 (10.5) Ca4O4+ Lazurite, dolomite 
230.854 (4.70) Ca2O2AlSiO4+ Lazurite 
263.798 (22.3) Ca5O4+ Lazurite, dolomite 
270.828 (47.4) Ca3O2AlSiO4+ Lazurite 
279.785 (8.04) Ca5O5+ Lazurite, dolomite 
319.744 (−18.1) Ca6O5+ Lazurite, dolomite 
326.776 (10.9) Ca4O3AlSiO4+ Lazurite 
335.746 (4.65) Ca6O6+ Lazurite, dolomite 
375.709 (3.73) Ca7O6+ Lazurite, dolomite 
431.666 (3.96) Ca8O7+ Lazurite, dolomite 
487.631 (17.8) Ca9O8+ Lazurite, dolomite 
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01928-01 26.982 (38.4) Al+ Lazurite, sodalite 
39.960 (−52.3) Ca+ Lazurite, dolomite 
55.954 (−50.3) CaO+ Lazurite, dolomite 
56.962 (−47.8) CaOH+ Lazurite, dolomite 
58.957 (−54.9) CaF+ F-rich mineral impurity 
95.922 (29.3) Ca2O+ Lazurite, dolomite 
98.936 (24.6) SiONaS+ Lazurite 
111.914 (−3.31) Ca2O2+ Lazurite 
112.923 (7.19) Ca2O2H+ Lazurite, dolomite 
114.920 (13.1) Ca2OF+ F-rich mineral impurity 
136.922 (13.8) Ca2F3+ F-rich mineral impurity 
151.878 (10.5) Ca3O2+ Lazurite, dolomite 
154.895 (27.0) CaSiNaSO2+ Lazurite 
167.873 (6.75) Ca3O3+ Lazurite, dolomite 
174.891 (−19.4) Si2O2NaSO2+ Lazurite 
207.837 (11.7) Ca4O3+ Lazurite, dolomite 
210.858 (−19.3) SiNaS3O4+ Lazurite 
214.868 (47.3) Ca2OAlSiO4+ Lazurite 
223.832 (10.5) Ca4O4+ Lazurite, dolomite 
230.854 (4.70) Ca2O2AlSiO4+ Lazurite 
263.798 (22.3) Ca5O4+ Lazurite, dolomite 
270.828 (47.4) Ca3O2AlSiO4+ Lazurite 
279.785 (8.04) Ca5O5+ Lazurite, dolomite 
319.744 (−18.1) Ca6O5+ Lazurite, dolomite 
326.776 (10.9) Ca4O3AlSiO4+ Lazurite 
335.746 (4.65) Ca6O6+ Lazurite, dolomite 
375.709 (3.73) Ca7O6+ Lazurite, dolomite 
431.666 (3.96) Ca8O7+ Lazurite, dolomite 
487.631 (17.8) Ca9O8+ Lazurite, dolomite 

Accession #: 01928-01 
■ Specimen: Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight (with delayed extraction) 
Analyzer Mass Resolving Power: 3400 m/Δm 
Mass Resolving Power Determined at: 39 Da 
Species Used for Mass Calibration: Na+, Ca+, Na2+, SiONa+, Ca2O2H+, Ca3O3H+, and Ca4O4H+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 3.28 × 1011 ion/cm2 
Primary Ion Pulse Width: ∼100 ns 
Primary Ion Pulse Rate: 6.7 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 09 nA 
DC Beam Current: 14.6 nA 
Beam Diameter: 400 μ
Beam Raster Size: 150 × 150 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 2010 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 197 s 
Comment: Very large grains, delayed extraction mode had to be used. The lighter the hue of lapis lazuli is, the higher is the proportion of other minerals such as dolomite. Fluorine-containing ions were identified thanks to imaging capabilities, as they were colocalized with F in the corresponding negative polarity dataset obtained on the same area. 
Accession #: 01928-01 
■ Specimen: Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight (with delayed extraction) 
Analyzer Mass Resolving Power: 3400 m/Δm 
Mass Resolving Power Determined at: 39 Da 
Species Used for Mass Calibration: Na+, Ca+, Na2+, SiONa+, Ca2O2H+, Ca3O3H+, and Ca4O4H+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 3.28 × 1011 ion/cm2 
Primary Ion Pulse Width: ∼100 ns 
Primary Ion Pulse Rate: 6.7 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 09 nA 
DC Beam Current: 14.6 nA 
Beam Diameter: 400 μ
Beam Raster Size: 150 × 150 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 2010 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 197 s 
Comment: Very large grains, delayed extraction mode had to be used. The lighter the hue of lapis lazuli is, the higher is the proportion of other minerals such as dolomite. Fluorine-containing ions were identified thanks to imaging capabilities, as they were colocalized with F in the corresponding negative polarity dataset obtained on the same area. 

Accession #: 01928-01 
■ Specimen: Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight (with delayed extraction) 
Analyzer Mass Resolving Power: 3400 m/Δm 
Mass Resolving Power Determined at: 39 Da 
Species Used for Mass Calibration: Na+, Ca+, Na2+, SiONa+, Ca2O2H+, Ca3O3H+, and Ca4O4H+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 3.28 × 1011 ion/cm2 
Primary Ion Pulse Width: ∼100 ns 
Primary Ion Pulse Rate: 6.7 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 09 nA 
DC Beam Current: 14.6 nA 
Beam Diameter: 400 μ
Beam Raster Size: 150 × 150 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 2010 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 197 s 
Comment: Very large grains, delayed extraction mode had to be used. The lighter the hue of lapis lazuli is, the higher is the proportion of other minerals such as dolomite. Fluorine-containing ions were identified thanks to imaging capabilities, as they were colocalized with F in the corresponding negative polarity dataset obtained on the same area. 
Accession #: 01928-01 
■ Specimen: Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight (with delayed extraction) 
Analyzer Mass Resolving Power: 3400 m/Δm 
Mass Resolving Power Determined at: 39 Da 
Species Used for Mass Calibration: Na+, Ca+, Na2+, SiONa+, Ca2O2H+, Ca3O3H+, and Ca4O4H+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 3.28 × 1011 ion/cm2 
Primary Ion Pulse Width: ∼100 ns 
Primary Ion Pulse Rate: 6.7 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 09 nA 
DC Beam Current: 14.6 nA 
Beam Diameter: 400 μ
Beam Raster Size: 150 × 150 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 2010 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 197 s 
Comment: Very large grains, delayed extraction mode had to be used. The lighter the hue of lapis lazuli is, the higher is the proportion of other minerals such as dolomite. Fluorine-containing ions were identified thanks to imaging capabilities, as they were colocalized with F in the corresponding negative polarity dataset obtained on the same area. 

Close modal
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01928-02 19.008 (−) F Accessory mineral (ex: phlogopite) 
31.974 (38.7) S Lazurite 
34.971 (31.1) Cl Lazurite, sodalite, phlogopite 
42.976 (−18.9) AlO Lazurite, sodalite, phlogopite 
47.965 (−60.1) SO Lazurite 
58.970 (−27.8) AlO2 Lazurite, sodalite, phlogopite 
60.972 (−51.4) SiO2H Lazurite, sodalite, phlogopite 
63.960 (−45.6) SO2 Lazurite 
76.970 (−4.17) SiO3H Lazurite, sodalite, phlogopite 
78.966 (−3.00) SiO2F Phlogopite 
79.957 (−10.5) SO3 Lazurite 
95.956 (33.1) SO4 Lazurite 
96.966 (−24.9) Na2O2F Phlogopite 
102.947 (27.4) SiAlO3 Lazurite, sodalite, phlogopite 
118.941 (19.1) SiAlO4 Lazurite, sodalite, phlogopite 
134.922 (44.2) AlSiSO3 Lazurite 
136.939 (16.4) Si2O5H Lazurite, sodalite, phlogopite 
147.895 (12.3) Si3SO2 Lazurite 
152.916 (22.3) Al2O4Cl Lazurite, sodalite, phlogopite 
161.918 (16.2) SiAl2O5 Lazurite, sodalite, phlogopite 
162.914 (21.6) Si2AlO5 Lazurite, sodalite, phlogopite 
174.912 (−28.0) KNa3O3F Phlogopite 
178.903 (−11.2) Si2AlO6 Lazurite, sodalite, phlogopite 
180.910 (−15.2) Na2OAlSiO4 Lazurite, sodalite, phlogopite 
194.885 (13.5) Si2AlSO5 Lazurite 
196.901 (−37.5) Na2O2AlSiO4 Lazurite, sodalite, phlogopite 
220.884 (−11.6) SiAl3O7 Lazurite, sodalite, phlogopite 
234.852 (31.7) NaSi3S2O4 Lazurite 
238.865 (−29.2) Si3AlO8 Lazurite, sodalite, phlogopite 
280.846 (−25.9) Si2Al3O9 Lazurite, sodalite, phlogopite 
298.838 (−4.47) Si4AlO10 Lazurite, sodalite, phlogopite 
322.832 (−7.14) SiAl5O10 Lazurite, sodalite, phlogopite 
336.804 (−18.9) NaSi3Al2SO9 Lazurite 
340.818 (−5.18) Si3Al3O11 Lazurite, sodalite, phlogopite 
358.807 (3.36) Si5AlO12 Lazurite, sodalite, phlogopite 
382.797 (−11.0) Si2Al5O12 Lazurite, sodalite, phlogopite 
396.771 (28.0) NaSi4Al2S2O9 Lazurite 
400.777 (−24.8) Si4Al3O13 Lazurite, sodalite, phlogopite 
424.780 (−6.23) SiAl7O13 Lazurite, sodalite, phlogopite 
442.746 (29.9) Si3Al5S2O10 Lazurite 
456.719 (−14.9) NaSi5Al2S2O11 Lazurite 
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01928-02 19.008 (−) F Accessory mineral (ex: phlogopite) 
31.974 (38.7) S Lazurite 
34.971 (31.1) Cl Lazurite, sodalite, phlogopite 
42.976 (−18.9) AlO Lazurite, sodalite, phlogopite 
47.965 (−60.1) SO Lazurite 
58.970 (−27.8) AlO2 Lazurite, sodalite, phlogopite 
60.972 (−51.4) SiO2H Lazurite, sodalite, phlogopite 
63.960 (−45.6) SO2 Lazurite 
76.970 (−4.17) SiO3H Lazurite, sodalite, phlogopite 
78.966 (−3.00) SiO2F Phlogopite 
79.957 (−10.5) SO3 Lazurite 
95.956 (33.1) SO4 Lazurite 
96.966 (−24.9) Na2O2F Phlogopite 
102.947 (27.4) SiAlO3 Lazurite, sodalite, phlogopite 
118.941 (19.1) SiAlO4 Lazurite, sodalite, phlogopite 
134.922 (44.2) AlSiSO3 Lazurite 
136.939 (16.4) Si2O5H Lazurite, sodalite, phlogopite 
147.895 (12.3) Si3SO2 Lazurite 
152.916 (22.3) Al2O4Cl Lazurite, sodalite, phlogopite 
161.918 (16.2) SiAl2O5 Lazurite, sodalite, phlogopite 
162.914 (21.6) Si2AlO5 Lazurite, sodalite, phlogopite 
174.912 (−28.0) KNa3O3F Phlogopite 
178.903 (−11.2) Si2AlO6 Lazurite, sodalite, phlogopite 
180.910 (−15.2) Na2OAlSiO4 Lazurite, sodalite, phlogopite 
194.885 (13.5) Si2AlSO5 Lazurite 
196.901 (−37.5) Na2O2AlSiO4 Lazurite, sodalite, phlogopite 
220.884 (−11.6) SiAl3O7 Lazurite, sodalite, phlogopite 
234.852 (31.7) NaSi3S2O4 Lazurite 
238.865 (−29.2) Si3AlO8 Lazurite, sodalite, phlogopite 
280.846 (−25.9) Si2Al3O9 Lazurite, sodalite, phlogopite 
298.838 (−4.47) Si4AlO10 Lazurite, sodalite, phlogopite 
322.832 (−7.14) SiAl5O10 Lazurite, sodalite, phlogopite 
336.804 (−18.9) NaSi3Al2SO9 Lazurite 
340.818 (−5.18) Si3Al3O11 Lazurite, sodalite, phlogopite 
358.807 (3.36) Si5AlO12 Lazurite, sodalite, phlogopite 
382.797 (−11.0) Si2Al5O12 Lazurite, sodalite, phlogopite 
396.771 (28.0) NaSi4Al2S2O9 Lazurite 
400.777 (−24.8) Si4Al3O13 Lazurite, sodalite, phlogopite 
424.780 (−6.23) SiAl7O13 Lazurite, sodalite, phlogopite 
442.746 (29.9) Si3Al5S2O10 Lazurite 
456.719 (−14.9) NaSi5Al2S2O11 Lazurite 

Accession #: 01928-02 
■ Specimen: Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV (with delayed extraction) 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 3300 m/Δm 
Mass Resolving Power Determined at: 49 Da 
Species Used for Mass Calibration: SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 3.28 × 1011 ion/cm2 
Primary Ion Pulse Width: ∼100 ns 
Primary Ion Pulse Rate: 6.7 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 09 nA 
DC Beam Current: 14.6 nA 
Beam Diameter: 400 μ
Beam Raster Size: 150 × 150 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 2022 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 197 s 
Comment: Very large grains, delayed extraction mode had to be used. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg3(AlSi3O10)(F,OH)2]. Assignments were refined thanks to colocalization in ion images. 
Accession #: 01928-02 
■ Specimen: Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV (with delayed extraction) 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 3300 m/Δm 
Mass Resolving Power Determined at: 49 Da 
Species Used for Mass Calibration: SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 3.28 × 1011 ion/cm2 
Primary Ion Pulse Width: ∼100 ns 
Primary Ion Pulse Rate: 6.7 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 09 nA 
DC Beam Current: 14.6 nA 
Beam Diameter: 400 μ
Beam Raster Size: 150 × 150 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 2022 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 197 s 
Comment: Very large grains, delayed extraction mode had to be used. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg3(AlSi3O10)(F,OH)2]. Assignments were refined thanks to colocalization in ion images. 

Accession #: 01928-02 
■ Specimen: Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV (with delayed extraction) 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 3300 m/Δm 
Mass Resolving Power Determined at: 49 Da 
Species Used for Mass Calibration: SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 3.28 × 1011 ion/cm2 
Primary Ion Pulse Width: ∼100 ns 
Primary Ion Pulse Rate: 6.7 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 09 nA 
DC Beam Current: 14.6 nA 
Beam Diameter: 400 μ
Beam Raster Size: 150 × 150 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 2022 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 197 s 
Comment: Very large grains, delayed extraction mode had to be used. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg3(AlSi3O10)(F,OH)2]. Assignments were refined thanks to colocalization in ion images. 
Accession #: 01928-02 
■ Specimen: Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV (with delayed extraction) 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 3300 m/Δm 
Mass Resolving Power Determined at: 49 Da 
Species Used for Mass Calibration: SiO2, AlSiO4, AlSi2O6, AlSi3O8, and AlSi4O10 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 3.28 × 1011 ion/cm2 
Primary Ion Pulse Width: ∼100 ns 
Primary Ion Pulse Rate: 6.7 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 09 nA 
DC Beam Current: 14.6 nA 
Beam Diameter: 400 μ
Beam Raster Size: 150 × 150 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 2022 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 197 s 
Comment: Very large grains, delayed extraction mode had to be used. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg3(AlSi3O10)(F,OH)2]. Assignments were refined thanks to colocalization in ion images. 

Close modal
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01929-01 26.982 (20.4) Al+ Sodium aluminum sulfosilicate 
45.979 (−3.68) Na2+ Sodium aluminum sulfosilicate 
61.973 (−10.1) Na2O+ Sodium aluminum sulfosilicate 
77.960 (−3.47) Al2HNa+ Sodium aluminum sulfosilicate 
91.055 (−7.92) C7H7+ Abietic-type acid from colophony 
93.942 (−7.25) SiONaAl+ Sodium aluminum sulfosilicate 
94.936 (−16.6) Si2ONa+ Sodium aluminum sulfosilicate 
100.941 (31.2) SiAlNa2+ Sodium aluminum sulfosilicate 
104.949 (−17.7) Na2O2Al+ Sodium aluminum sulfosilicate 
105.071 (10.7) C8H9+ Abietic-type acid from colophony 
105.945 (−7.18) Na2O2Si+ Sodium aluminum sulfosilicate 
109.926 (28.5) Na2S2+ Sodium aluminum sulfosilicate 
115.052 (−21.6) C9H7+ Abietic-type acid from colophony 
121.923 (23.1) NaKSiO2+ Sodium aluminum sulfosilicate 
128.059 (−23.7) C10H8+ Abietic-type acid from colophony 
128.936 (4.33) SiNa3O2+ Sodium aluminum sulfosilicate 
132.910 (−24.4) Na3S2+ -/Sodium aluminum sulfosilicate/- 
141.066 (−30.8) C11H9+ Abietic-type acid from colophony 
144.933 (14.9) SiNa3O3+ Sodium aluminum sulfosilicate 
148.926 (25.7) SiNa2AlO3+ Sodium aluminum sulfosilicate 
160.907 (18.2) Si2Na2AlO2+ Sodium aluminum sulfosilicate 
164.918 (5.34) SiNa2AlO4+ Sodium aluminum sulfosilicate 
165.066 (−23.3) C13H9+ Abietic-type acid from colophony 
176.884 (14.2) Si2Na2AlSO+ Sodium aluminum sulfosilicate 
204.882 (30.1) Si2Na2AlSiO3+ Sodium aluminum sulfosilicate 
227.174 (−25.0) C17H23+ Abietic acid fragment (M—C3H7O2
246.842 (10.0) Si2Na2Al3SO2+ Sodium aluminum sulfosilicate 
255.187 (49.0) C18H23O+ Abietic acid fragment (M—C2H7O
271.213 (26.0) C19H27O+ Abietic acid fragment (M—CH2O
311.229 (−16.6) C20H31ONaH+ Resin acid soap 
327.229 (−7.99) C22H31O2+ Abietic-type ester 
348.784 (−8.34) Si2Al5Na2SO5+ Sodium aluminum sulfosilicate 
366.266 (28.9) C25H34O2+ Abietic-type ester 
413.274 (13.1) C26H37O4+ Abietic-type ester 
450.733 (34.5) Si2Al7Na2S2O6+ Sodium aluminum sulfosilicate 
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01929-01 26.982 (20.4) Al+ Sodium aluminum sulfosilicate 
45.979 (−3.68) Na2+ Sodium aluminum sulfosilicate 
61.973 (−10.1) Na2O+ Sodium aluminum sulfosilicate 
77.960 (−3.47) Al2HNa+ Sodium aluminum sulfosilicate 
91.055 (−7.92) C7H7+ Abietic-type acid from colophony 
93.942 (−7.25) SiONaAl+ Sodium aluminum sulfosilicate 
94.936 (−16.6) Si2ONa+ Sodium aluminum sulfosilicate 
100.941 (31.2) SiAlNa2+ Sodium aluminum sulfosilicate 
104.949 (−17.7) Na2O2Al+ Sodium aluminum sulfosilicate 
105.071 (10.7) C8H9+ Abietic-type acid from colophony 
105.945 (−7.18) Na2O2Si+ Sodium aluminum sulfosilicate 
109.926 (28.5) Na2S2+ Sodium aluminum sulfosilicate 
115.052 (−21.6) C9H7+ Abietic-type acid from colophony 
121.923 (23.1) NaKSiO2+ Sodium aluminum sulfosilicate 
128.059 (−23.7) C10H8+ Abietic-type acid from colophony 
128.936 (4.33) SiNa3O2+ Sodium aluminum sulfosilicate 
132.910 (−24.4) Na3S2+ -/Sodium aluminum sulfosilicate/- 
141.066 (−30.8) C11H9+ Abietic-type acid from colophony 
144.933 (14.9) SiNa3O3+ Sodium aluminum sulfosilicate 
148.926 (25.7) SiNa2AlO3+ Sodium aluminum sulfosilicate 
160.907 (18.2) Si2Na2AlO2+ Sodium aluminum sulfosilicate 
164.918 (5.34) SiNa2AlO4+ Sodium aluminum sulfosilicate 
165.066 (−23.3) C13H9+ Abietic-type acid from colophony 
176.884 (14.2) Si2Na2AlSO+ Sodium aluminum sulfosilicate 
204.882 (30.1) Si2Na2AlSiO3+ Sodium aluminum sulfosilicate 
227.174 (−25.0) C17H23+ Abietic acid fragment (M—C3H7O2
246.842 (10.0) Si2Na2Al3SO2+ Sodium aluminum sulfosilicate 
255.187 (49.0) C18H23O+ Abietic acid fragment (M—C2H7O
271.213 (26.0) C19H27O+ Abietic acid fragment (M—CH2O
311.229 (−16.6) C20H31ONaH+ Resin acid soap 
327.229 (−7.99) C22H31O2+ Abietic-type ester 
348.784 (−8.34) Si2Al5Na2SO5+ Sodium aluminum sulfosilicate 
366.266 (28.9) C25H34O2+ Abietic-type ester 
413.274 (13.1) C26H37O4+ Abietic-type ester 
450.733 (34.5) Si2Al7Na2S2O6+ Sodium aluminum sulfosilicate 

Accession #: 01929-01 
■ Specimen: Ultramarine Blue—Kremer Pigmente ref. 45000—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 3000 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, Ca+, SiONa+, SiO2Na2+, and SiO3Na3+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: 400 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode. The assignment given here are those with smallest mass deviation and isotopic pattern. Organic compounds are detected, likely colophony resin, mentioned in the manufacturing process.3  
Accession #: 01929-01 
■ Specimen: Ultramarine Blue—Kremer Pigmente ref. 45000—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 3000 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, Ca+, SiONa+, SiO2Na2+, and SiO3Na3+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: 400 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode. The assignment given here are those with smallest mass deviation and isotopic pattern. Organic compounds are detected, likely colophony resin, mentioned in the manufacturing process.3  

Accession #: 01929-01 
■ Specimen: Ultramarine Blue—Kremer Pigmente ref. 45000—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 3000 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, Ca+, SiONa+, SiO2Na2+, and SiO3Na3+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: 400 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode. The assignment given here are those with smallest mass deviation and isotopic pattern. Organic compounds are detected, likely colophony resin, mentioned in the manufacturing process.3  
Accession #: 01929-01 
■ Specimen: Ultramarine Blue—Kremer Pigmente ref. 45000—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 3000 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, Ca+, SiONa+, SiO2Na2+, and SiO3Na3+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: 400 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode. The assignment given here are those with smallest mass deviation and isotopic pattern. Organic compounds are detected, likely colophony resin, mentioned in the manufacturing process.3  

Close modal
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01929-02 31.972 (−18.9) S Sodium aluminum sulfosilicate 
42.976 (−26.1) AlO Aluminosilicate 
47.966 (−22.7) SO Sodium aluminum sulfosilicate 
58.971 (−15.0) AlO2 Aluminosilicate 
60.974 (−13.3) SiO2H Aluminosilicate 
63.946 (19.5) S2 Sodium aluminum sulfosilicate 
63.962 (−6.30) SO2 Sodium aluminum sulfosilicate 
76.974 (48.1) SiO3H Aluminosilicate 
79.943 (37.5) S2O Sodium aluminum sulfosilicate 
91.938 (−15.6) SiSO2 Sodium aluminum sulfosilicate 
101.946 (−20.6) Al2O3 Aluminosilicate 
102.943 (−10.9) SiAlO3 Aluminosilicate 
118.938 (−9.51) SiAlO4 Aluminosilicate 
134.916 (4.25) AlSiSO3 Sodium aluminum sulfosilicate 
136.935 (−11.9) Si2O5H Aluminosilicate 
162.910 (−5.94) Si2AlO5 Aluminosilicate 
178.907 (6.72) Si2AlO6 Aluminosilicate 
194.886 (19.0) Si2AlSO5 Sodium aluminum sulfosilicate 
204.886 (−25.0) SiAl3O6 Aluminosilicate 
220.881 (−26.2) SiAl3O7 Aluminosilicate 
238.876 (15.1) Si3AlO8 Aluminosilicate 
280.849 (−15.9) Si2Al3O9 Aluminosilicate 
298.843 (14.3) Si4AlO10 Aluminosilicate 
322.826 (−26.3) SiAl5O10 Aluminosilicate 
340.814 (−17.7) Si3Al3O11 Aluminosilicate 
358.802 (−11.6) Si5AlO12 Aluminosilicate 
364.790 (18.3) Si2Al5Na2SO6 Sodium aluminum sulfosilicate 
382.793 (−24.5) Si2Al5O12 Aluminosilicate 
400.779 (−20.3) Si4Al3O13 Aluminosilicate 
424.763 (−44.3) SiAl7O13 Aluminosilicate 
442.727 (−12.6) Si3Al5S2O10 Sodium aluminum sulfosilicate 
460.724 (13.5) Al3Si5S2O11 Sodium aluminum sulfosilicate 
466.718 (10.6) Si2Al7Na2S2O7 Sodium aluminum sulfosilicate 
484.707 (−12.5) Al7Si2S2O11 Sodium aluminum sulfosilicate 
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01929-02 31.972 (−18.9) S Sodium aluminum sulfosilicate 
42.976 (−26.1) AlO Aluminosilicate 
47.966 (−22.7) SO Sodium aluminum sulfosilicate 
58.971 (−15.0) AlO2 Aluminosilicate 
60.974 (−13.3) SiO2H Aluminosilicate 
63.946 (19.5) S2 Sodium aluminum sulfosilicate 
63.962 (−6.30) SO2 Sodium aluminum sulfosilicate 
76.974 (48.1) SiO3H Aluminosilicate 
79.943 (37.5) S2O Sodium aluminum sulfosilicate 
91.938 (−15.6) SiSO2 Sodium aluminum sulfosilicate 
101.946 (−20.6) Al2O3 Aluminosilicate 
102.943 (−10.9) SiAlO3 Aluminosilicate 
118.938 (−9.51) SiAlO4 Aluminosilicate 
134.916 (4.25) AlSiSO3 Sodium aluminum sulfosilicate 
136.935 (−11.9) Si2O5H Aluminosilicate 
162.910 (−5.94) Si2AlO5 Aluminosilicate 
178.907 (6.72) Si2AlO6 Aluminosilicate 
194.886 (19.0) Si2AlSO5 Sodium aluminum sulfosilicate 
204.886 (−25.0) SiAl3O6 Aluminosilicate 
220.881 (−26.2) SiAl3O7 Aluminosilicate 
238.876 (15.1) Si3AlO8 Aluminosilicate 
280.849 (−15.9) Si2Al3O9 Aluminosilicate 
298.843 (14.3) Si4AlO10 Aluminosilicate 
322.826 (−26.3) SiAl5O10 Aluminosilicate 
340.814 (−17.7) Si3Al3O11 Aluminosilicate 
358.802 (−11.6) Si5AlO12 Aluminosilicate 
364.790 (18.3) Si2Al5Na2SO6 Sodium aluminum sulfosilicate 
382.793 (−24.5) Si2Al5O12 Aluminosilicate 
400.779 (−20.3) Si4Al3O13 Aluminosilicate 
424.763 (−44.3) SiAl7O13 Aluminosilicate 
442.727 (−12.6) Si3Al5S2O10 Sodium aluminum sulfosilicate 
460.724 (13.5) Al3Si5S2O11 Sodium aluminum sulfosilicate 
466.718 (10.6) Si2Al7Na2S2O7 Sodium aluminum sulfosilicate 
484.707 (−12.5) Al7Si2S2O11 Sodium aluminum sulfosilicate 

Accession #: 01929-02 
■ Specimen: Ultramarine Blue—Kremer Pigmente ref. 45000—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 2700 m/Δm 
Mass Resolving Power Determined at: 25 Da 
Species Used for Mass Calibration: SiO2, AlSiO4, AlSi2O6, AlSi3O8, AlSi4O10, and AlSi5O12 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: 400 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode. 
Accession #: 01929-02 
■ Specimen: Ultramarine Blue—Kremer Pigmente ref. 45000—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 2700 m/Δm 
Mass Resolving Power Determined at: 25 Da 
Species Used for Mass Calibration: SiO2, AlSiO4, AlSi2O6, AlSi3O8, AlSi4O10, and AlSi5O12 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: 400 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode. 

Accession #: 01929-02 
■ Specimen: Ultramarine Blue—Kremer Pigmente ref. 45000—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 2700 m/Δm 
Mass Resolving Power Determined at: 25 Da 
Species Used for Mass Calibration: SiO2, AlSiO4, AlSi2O6, AlSi3O8, AlSi4O10, and AlSi5O12 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: 400 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode. 
Accession #: 01929-02 
■ Specimen: Ultramarine Blue—Kremer Pigmente ref. 45000—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 2700 m/Δm 
Mass Resolving Power Determined at: 25 Da 
Species Used for Mass Calibration: SiO2, AlSiO4, AlSi2O6, AlSi3O8, AlSi4O10, and AlSi5O12 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: 400 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode. 

Close modal
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01930-01 43.971 (−4.75) SiO+ CoOKSi 
44.979 (−8.83) SiOH+ CoOKSi 
45.978 (−0.44) Na2+ — 
58.932 (−6.22) Co+ CoOKSi 
61.952 (−11.8) Na2O+ — 
62.982 (3.14) Na2OH+ — 
77.951 (35.6) KNaO+ — 
82.937 (18.5) SiOK+ CoOKSi 
84.965 (14.3) Na3O+ — 
93.921 (−10.8) K2O+ CoOKSi 
94.915 (−20.6) Si2K+ CoOKSi 
94.937 (−8.95) Si2ONa+ — 
128.948 (35.9) (SiOH)2NaO+ — 
144.923 (38.9) (SiOH)2KO+ CoOKSi 
160.908 (−25.1) (SiOH)2KO2+ CoOKSi 
206.902 (10.6) (SiOH)3KO2H+ CoOKSi 
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01930-01 43.971 (−4.75) SiO+ CoOKSi 
44.979 (−8.83) SiOH+ CoOKSi 
45.978 (−0.44) Na2+ — 
58.932 (−6.22) Co+ CoOKSi 
61.952 (−11.8) Na2O+ — 
62.982 (3.14) Na2OH+ — 
77.951 (35.6) KNaO+ — 
82.937 (18.5) SiOK+ CoOKSi 
84.965 (14.3) Na3O+ — 
93.921 (−10.8) K2O+ CoOKSi 
94.915 (−20.6) Si2K+ CoOKSi 
94.937 (−8.95) Si2ONa+ — 
128.948 (35.9) (SiOH)2NaO+ — 
144.923 (38.9) (SiOH)2KO+ CoOKSi 
160.908 (−25.1) (SiOH)2KO2+ CoOKSi 
206.902 (10.6) (SiOH)3KO2H+ CoOKSi 

Accession #: 01930-01 
■ Specimen: Smalt—Kremer Pigmente ref. 10000—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1700 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, 41K+, Na2+, SiONa+, SiO2Na2+, and SiO3Na3+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Large grains, mass resolution impacted. High sodium content, likely from the glass. Above m/z 200 attribution is not given, as many possibilities exist due to the mass interferences between K and NaO. 
Accession #: 01930-01 
■ Specimen: Smalt—Kremer Pigmente ref. 10000—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1700 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, 41K+, Na2+, SiONa+, SiO2Na2+, and SiO3Na3+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Large grains, mass resolution impacted. High sodium content, likely from the glass. Above m/z 200 attribution is not given, as many possibilities exist due to the mass interferences between K and NaO. 

Accession #: 01930-01 
■ Specimen: Smalt—Kremer Pigmente ref. 10000—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1700 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, 41K+, Na2+, SiONa+, SiO2Na2+, and SiO3Na3+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Large grains, mass resolution impacted. High sodium content, likely from the glass. Above m/z 200 attribution is not given, as many possibilities exist due to the mass interferences between K and NaO. 
Accession #: 01930-01 
■ Specimen: Smalt—Kremer Pigmente ref. 10000—Positive polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1700 m/Δm 
Mass Resolving Power Determined at: 27 Da 
Species Used for Mass Calibration: Al+, 41K+, Na2+, SiONa+, SiO2Na2+, and SiO3Na3+ 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Positive 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3545 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 293 s 
Comment: Large grains, mass resolution impacted. High sodium content, likely from the glass. Above m/z 200 attribution is not given, as many possibilities exist due to the mass interferences between K and NaO. 

Close modal
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01930-02 58.935 (26.1) Co CoOKSi 
74.929 (7.03) CoO CoOKSi 
90.923 (−9.67) CoO2 CoOKSi 
98.951 (6.97) NaOSiO2 CoOKSi 
106.920 (16.6) CoO3 CoOKSi 
134.898 (12.0) CoSiO3 CoOKSi 
150.888 (−16.3) CoSiO4 CoOKSi 
158.915 (−26.2) NaSi2O5 — 
178.878 (58.5) CoSi2O4 CoOKSi 
188.924 (43.5) KNa3O5H — 
195.892 (−20.1) Si3O7 CoOKSi 
210.855 (−11.8) CoSi2O6 CoOKSi 
218.869 (19.8) Si3O6K CoOKSi 
234.867 (31.1) Si3O7K CoOKSi 
238.877 (19.7) Si2O9K CoOKSi 
255.860 (−10.1) Si4O9 CoOKSi 
266.846 (−12.1) KSi3O9 CoOKSi 
270.821 (−9.66) CoSi3O8 CoOKSi 
278.837 (20.2) Si4O8K CoOKSi 
294.830 (14.0) Si4O9K CoOKSi 
316.834 (−9.30) Si5O11H CoOKSi 
330.782 (−25.8) CoSi4O10 CoOKSi 
338.802 (10.7) KSi5O10 CoOKSi 
354.787 (−12.3) KSi5O11 CoOKSi 
SPECTRAL FEATURES TABLE
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
01930-02 58.935 (26.1) Co CoOKSi 
74.929 (7.03) CoO CoOKSi 
90.923 (−9.67) CoO2 CoOKSi 
98.951 (6.97) NaOSiO2 CoOKSi 
106.920 (16.6) CoO3 CoOKSi 
134.898 (12.0) CoSiO3 CoOKSi 
150.888 (−16.3) CoSiO4 CoOKSi 
158.915 (−26.2) NaSi2O5 — 
178.878 (58.5) CoSi2O4 CoOKSi 
188.924 (43.5) KNa3O5H — 
195.892 (−20.1) Si3O7 CoOKSi 
210.855 (−11.8) CoSi2O6 CoOKSi 
218.869 (19.8) Si3O6K CoOKSi 
234.867 (31.1) Si3O7K CoOKSi 
238.877 (19.7) Si2O9K CoOKSi 
255.860 (−10.1) Si4O9 CoOKSi 
266.846 (−12.1) KSi3O9 CoOKSi 
270.821 (−9.66) CoSi3O8 CoOKSi 
278.837 (20.2) Si4O8K CoOKSi 
294.830 (14.0) Si4O9K CoOKSi 
316.834 (−9.30) Si5O11H CoOKSi 
330.782 (−25.8) CoSi4O10 CoOKSi 
338.802 (10.7) KSi5O10 CoOKSi 
354.787 (−12.3) KSi5O11 CoOKSi 

Accession #: 01930-02 
■ Specimen: Smalt—Kremer Pigmente ref. 10000—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1500 m/Δm 
Mass Resolving Power Determined at: 25 Da 
Species Used for Mass Calibration: Cl, SiO2, Si2O5H, Si3O7H, Si4O9H, and Si5O11H 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3540 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 308 s 
Comment: Very large grains, mass resolution impacted. Co containing ions were identified thanks to the images, with colocalization with the Co+ and Co ions. The absence of aluminum oxide is notable, and this avoids to misattribute some peaks to aluminosilicate compounds. 
Accession #: 01930-02 
■ Specimen: Smalt—Kremer Pigmente ref. 10000—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1500 m/Δm 
Mass Resolving Power Determined at: 25 Da 
Species Used for Mass Calibration: Cl, SiO2, Si2O5H, Si3O7H, Si4O9H, and Si5O11H 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3540 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 308 s 
Comment: Very large grains, mass resolution impacted. Co containing ions were identified thanks to the images, with colocalization with the Co+ and Co ions. The absence of aluminum oxide is notable, and this avoids to misattribute some peaks to aluminosilicate compounds. 

Accession #: 01930-02 
■ Specimen: Smalt—Kremer Pigmente ref. 10000—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1500 m/Δm 
Mass Resolving Power Determined at: 25 Da 
Species Used for Mass Calibration: Cl, SiO2, Si2O5H, Si3O7H, Si4O9H, and Si5O11H 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3540 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 308 s 
Comment: Very large grains, mass resolution impacted. Co containing ions were identified thanks to the images, with colocalization with the Co+ and Co ions. The absence of aluminum oxide is notable, and this avoids to misattribute some peaks to aluminosilicate compounds. 
Accession #: 01930-02 
■ Specimen: Smalt—Kremer Pigmente ref. 10000—Negative polarity 
■ Technique: SIMS 
Instrument: IONTOF, TOF SIMS IV 
Analyzer Type: Time-of-flight 
Analyzer Mass Resolving Power: 1500 m/Δm 
Mass Resolving Power Determined at: 25 Da 
Species Used for Mass Calibration: Cl, SiO2, Si2O5H, Si3O7H, Si4O9H, and Si5O11H 
Specimen Normal-to-Analyzer: 0° 
Source-to-Analyzer Angle: 45° 
Primary Beam Ion Gun: LMIG 
Primary Ion Species: Bi3+ 
Primary Ion Dose: 4.37 × 1011 ion/cm2 
Primary Ion Pulse Width: 0.8–1.2 ns 
Primary Ion Pulse Rate: 5 kHz 
Net Beam Voltage: 25 000 eV 
Pulsed Beam Current: 0.000 15 nA 
DC Beam Current: 14.7 nA 
Beam Diameter: ∼2 μ
Beam Raster Size: 250 × 250 μm2 
Beam Incident Angle: 45° 
Secondary Source Polarity: Negative 
Mass Range Minimum: 0 Da 
Mass Range Maximum: 3540 Da 
Spectrum Dead Time Corrected: Yes 
Total Spectral Acquisition Time: 308 s 
Comment: Very large grains, mass resolution impacted. Co containing ions were identified thanks to the images, with colocalization with the Co+ and Co ions. The absence of aluminum oxide is notable, and this avoids to misattribute some peaks to aluminosilicate compounds. 

Close modal
SPECTRAL FEATURES TABLE (peaks appearing in all spectra—Positive Polarity)
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
All 22.99 (−) Na+ Lapis lazuli, Synthetic ultramarine, Smalt 
… 27.98 (27.4) Si+ Lapis lazuli, Synthetic ultramarine, Smalt 
… 38.96 (29.9) K+ Lapis lazuli, Synthetic ultramarine, Smalt 
… 66.96 (7.03) SiONa+ Lapis lazuli, Synthetic ultramarine, Smalt 
SPECTRAL FEATURES TABLE (peaks appearing in all spectra—Positive Polarity)
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
All 22.99 (−) Na+ Lapis lazuli, Synthetic ultramarine, Smalt 
… 27.98 (27.4) Si+ Lapis lazuli, Synthetic ultramarine, Smalt 
… 38.96 (29.9) K+ Lapis lazuli, Synthetic ultramarine, Smalt 
… 66.96 (7.03) SiONa+ Lapis lazuli, Synthetic ultramarine, Smalt 

(Mean absolute deviation values are given for the mass deviations, except for sodium as the peaks were saturated).

SPECTRAL FEATURES TABLE (peaks appearing in all spectra—Negative Polarity)
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
All 59.97 (15.8) SiO2 Lapis lazuli, Synthetic ultramarine, Smalt 
… 75.97 (34.3) SiO3 Lapis lazuli, Synthetic ultramarine, Smalt 
… 119.94 (8.45) Si2O4 Lapis lazuli, Synthetic ultramarine, Smalt 
… 135.93 (14.0) Si2O5 Lapis lazuli, Synthetic ultramarine, Smalt 
SPECTRAL FEATURES TABLE (peaks appearing in all spectra—Negative Polarity)
Spectrum ID #Mass (Δm), DaSpeciesPeak Assignment
All 59.97 (15.8) SiO2 Lapis lazuli, Synthetic ultramarine, Smalt 
… 75.97 (34.3) SiO3 Lapis lazuli, Synthetic ultramarine, Smalt 
… 119.94 (8.45) Si2O4 Lapis lazuli, Synthetic ultramarine, Smalt 
… 135.93 (14.0) Si2O5 Lapis lazuli, Synthetic ultramarine, Smalt 

(Mean absolute deviation values are given for the mass deviations.)

This work was financially supported by the Agence Nationale de la Recherche (Grant No. ANR-2015-CE29-0007 DEFIMAGE). C.B. has received funding from the European Union’s Horizon Europe Research and Innovation Programme under the Marie Skłodowska-Curie Grant Agreement No. 101108506. The authors thank Sven Kayser and Matthias Kleine-Boymann (IONTOF GmbH) for providing extended access to software SurfaceLab 7.3 that allowed thorough processing of the data.

The authors have no conflicts to disclose.

Caroline Bouvier: Investigation (lead); Writing – original draft (equal). Sebastiaan Van Nuffel: Investigation (equal); Writing – review & editing (equal). Alain Brunelle: Conceptualization (lead); Supervision (equal); Writing – review & editing (equal).

The data that support the findings of this study are available within the article and its supplementary material.

1.
Q. P.
Vanbellingen
,
N.
Elie
,
M. J.
Eller
,
S.
Della-Negra
,
D.
Touboul
, and
A.
Brunelle
,
Rapid Commun. Mass Spectrom.
29
,
1187
(
2015
).
2.
N.
Eastaugh
,
V.
Walsh
,
T.
Chaplin
, and
R.
Siddall
,
Pigment Compendium A Dictionary and Optical Microscopy of Historical Pigments
, 1st ed. (
Routledge
,
London
,
2008
).
3.
A.
Roy
,
Artists’ Pigments: A Handbook of Their History and Characteristics
(
Archetype Publications
,
London
,
1993
), Vol. 2.
4.
J. R.
Barnett
,
S.
Miller
, and
E.
Pearce
,
Opt. Laser Technol.
38
,
445
(
2006
).

Supplementary Material