# ToF-SIMS spectra of historical inorganic pigments: Natural and synthetic ultramarine blues and smalt in both polarities

Caroline Bouvier, Sebastiaan van Nuffel, Alain Brunelle

► To cite this version:

Caroline Bouvier, Sebastiaan van Nuffel, Alain Brunelle. ToF-SIMS spectra of historical inorganic pigments: Natural and synthetic ultramarine blues and smalt in both polarities. Surface Science Spectra, 2024, 31 (1), pp.015006. 10.1116/6.0003640. hal-04598771

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# ToF-SIMS spectra of historical inorganic pigments: Natural and synthetic ultramarine blues and smalt in both polarities

Caroline Bouvier, Sebastiaan van Nuffel, Alain Brunelle

► To cite this version:

Caroline Bouvier, Sebastiaan van Nuffel, Alain Brunelle. ToF-SIMS spectra of historical inorganic pigments: Natural and synthetic ultramarine blues and smalt in both polarities. Surface Science Spectra, 2024, 31 (1), pp.015006. 10.1116/6.0003640. hal-04598771

HAL Id: hal-04598771

https://hal.science/hal-04598771v1

Submitted on 3 Jun 2024

HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-
entific research documents, whether they are pub-
lished or not. The documents may come from
teaching and research institutions in France or
abroad, or from public or private research centers.

L'archive ouverte pluridisciplinaire HAL, est
destinée au dépôt et à la diffusion de documents
scientifiques de niveau recherche, publiés ou non,
émanant des établissements d'enseignement et de
recherche français ou étrangers, des laboratoires
publics ou privés.

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Distributed under a Creative Commons Attribution 4.0 International License
# ToF-SIMS spectra of historical inorganic pigments: Natural and synthetic ultramarine blues and smalt in both polarities

Special Collection: ToF-SIMS Spectra of Historical Inorganic Pigments

Caroline Bouvier ; Sebastiaan Van Nuffel ; Alain Brunelle

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Surf. Sci. Spectra 31, 015006 (2024)

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# ToF-SIMS spectra of historical inorganic pigments: Natural and synthetic ultramarine blues and smalt in both polarities

Special Collection: ToF-SIMS Spectra of Historical Inorganic Pigments

Caroline Bouvier ; Sebastiaan Van Nuffel ; Alain Brunelle

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Surf. Sci. Spectra 31, 015006 (2024)

https://doi.org/10.1116/6.0003640

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# ToF-SIMS spectra of historical inorganic pigments: Natural and synthetic ultramarine blues and smalt in both polarities

Cite as: Surf. Sci. Spectra 31, 015006 (2024); doi: 10.1116/6.0003640

Submitted: 22 March 2024 · Accepted: 13 May 2024 ·

Published Online: 31 May 2024

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Caroline Bouvier,<fnref n="1" />,<fnref n="2" /> ID Sebastiaan Van Nuffel,<fnref n="2" />,<fnref n="3" /> ID and Alain Brunelle<fnref n="1" />,ª ID

## AFFILIATIONS

**Note:** This paper is part of the 2024 Special Topic Collection on ToF-SIMS Spectra of Historical Inorganic Pigments.

ªAuthor to whom correspondence should be addressed: alain.brunelle@cnrs.fr

## ABSTRACT

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.

© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1116/6.0003640

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

## INTRODUCTION

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

<footnote n="1">¹Laboratoire d'Archéologie Moléculaire et Structurale, (LAMS), CNRS, Sorbonne Université, Paris 75005, France</footnote>

<footnote n="2">²Maastricht MultiModal Molecular Imaging Institute (M4i), Maastricht University, Maastricht 6229ER, The Netherlands</footnote>

<footnote n="3">³Faculty of Science and Engineering, Maastricht University, Maastricht 6229EN, The Netherlands</footnote>
# ToF-SIMS spectra of historical inorganic pigments: Natural and synthetic ultramarine blues and smalt in both polarities

Cite as: Surf. Sci. Spectra 31, 015006 (2024); doi: 10.1116/6.0003640

Submitted: 22 March 2024 · Accepted: 13 May 2024 ·

Published Online: 31 May 2024

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CrossMark

Caroline Bouvier,<fnref n="1" />,<fnref n="2" /> ID Sebastiaan Van Nuffel,<fnref n="2" />,<fnref n="3" /> ID and Alain Brunelle<fnref n="1" />,ª ID

## AFFILIATIONS

**Note:** This paper is part of the 2024 Special Topic Collection on ToF-SIMS Spectra of Historical Inorganic Pigments.

ªAuthor to whom correspondence should be addressed: alain.brunelle@cnrs.fr

## ABSTRACT

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.

© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1116/6.0003640

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

## INTRODUCTION

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

<footnote n="1">¹Laboratoire d'Archéologie Moléculaire et Structurale, (LAMS), CNRS, Sorbonne Université, Paris 75005, France</footnote>

<footnote n="2">²Maastricht MultiModal Molecular Imaging Institute (M4i), Maastricht University, Maastricht 6229ER, The Netherlands</footnote>

<footnote n="3">³Faculty of Science and Engineering, Maastricht University, Maastricht 6229EN, The Netherlands</footnote>
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⁺, SiO₂Na⁺, and SiO₃Na⁺. 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 DESCRIPTION (ACCESSION #01927, #01928, AND #01929)

**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,S₂,S₃,Cl,OH)₂] inclusions in dolomite, sodalite Na₈Al₆Si₆O₂₄Cl₂, pyrite FeS₂; (Accession #01929) Synthetic ultramarine, NaₓAl₆Si₆O₂₄Sᵧ (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
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⁺, SiO₂Na⁺, and SiO₃Na⁺. 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 DESCRIPTION (ACCESSION #01927, #01928, AND #01929)

**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,S₂,S₃,Cl,OH)₂] inclusions in dolomite, sodalite Na₈Al₆Si₆O₂₄Cl₂, pyrite FeS₂; (Accession #01929) Synthetic ultramarine, NaₓAl₆Si₆O₂₄Sᵧ (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 $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

**Pre-analysis Beam Exposure:** $Ar_{1500-2000}$, 20 keV, $2 \times 10^{15}$ ions/cm$^2$

## SPECIMEN DESCRIPTION (ACCESSION # 01930)

**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 $SiO_2$, $K_2O$, 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 $250 \times 250$ µm$^2$

**Ex Situ Preparation/Mounting:** Powder was deposited and pressed onto a conductive double-sided tape attached to stainless steel $1 \times 1$ cm$^2$ 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 $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

**Pre-analysis Beam Exposure:** $Ar_{1500-2000}$, 20 keV, $2 \times 10^{15}$ ions/cm$^2$

## INSTRUMENT CONFIGURATION

**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 (Θe):** 0°

## Ion Sources

### 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:** $Bi_3^+$

**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:** $250 \times 250$ µm$^2$

**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:** $Ar_n^+$ 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:** $500 \times 500$ µm$^2$

**Raster Pixel Dimensions:** N/A
**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 $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

**Pre-analysis Beam Exposure:** $Ar_{1500-2000}$, 20 keV, $2 \times 10^{15}$ ions/cm$^2$

## SPECIMEN DESCRIPTION (ACCESSION # 01930)

**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 $SiO_2$, $K_2O$, 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 $250 \times 250$ µm$^2$

**Ex Situ Preparation/Mounting:** Powder was deposited and pressed onto a conductive double-sided tape attached to stainless steel $1 \times 1$ cm$^2$ 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 $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

**Pre-analysis Beam Exposure:** $Ar_{1500-2000}$, 20 keV, $2 \times 10^{15}$ ions/cm$^2$

## INSTRUMENT CONFIGURATION

**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 (Θe):** 0°

## Ion Sources

### 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:** $Bi_3^+$

**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:** $250 \times 250$ µm$^2$

**Rotor Pixel Dimensions:** $128 \times 128$

**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:** $Ar_n^+$ 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:** $500 \times 500$ µm$^2$

**Rotor Pixel Dimensions:** N/A
**Beam Incident Angle:** 45°

**Source-to-Analyzer Angle:** 45°

## ACKNOWLEDGMENT

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.

## AUTHOR DECLARATIONS

### Conflict of Interest

The authors have no conflicts to disclose.

## Author Contributions

**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).

## DATA AVAILABILITY

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

## REFERENCES

<footnote n="1">¹Q. P. Vanbellingen, N. Elie, M. J. Eller, S. Della-Negra, D. Touboul, and A. Brunelle, *Rapid Commun. Mass Spectrom.* **29**, 1187 (2015).</footnote>

<footnote n="2">²N. Eastaugh, V. Walsh, T. Chaplin, and R. Siddall, *Pigment Compendium A Dictionary and Optical Microscopy of Historical Pigments*, 1st ed. (Routledge, London, 2008).</footnote>

<footnote n="3">³A. Roy, *Artists' Pigments: A Handbook of Their History and Characteristics* (Archetype Publications, London, 1993), Vol. 2.</footnote>

<footnote n="4">⁴J. R. Barnett, S. Miller, and E. Pearce, *Opt. Laser Technol.* **38**, 445 (2006).</footnote>
**Beam Incident Angle:** 45°

**Source-to-Analyzer Angle:** 45°

## ACKNOWLEDGMENT

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.

## AUTHOR DECLARATIONS

### Conflict of Interest

The authors have no conflicts to disclose.

## Author Contributions

**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).

## DATA AVAILABILITY

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

## REFERENCES

¹Q. P. Vanbellingen, N. Elie, M. J. Eller, S. Della-Negra, D. Touboul, and A. Brunelle, *Rapid Commun. Mass Spectrom.* **29**, 1187 (2015).

²N. Eastaugh, V. Walsh, T. Chaplin, and R. Siddall, *Pigment Compendium A Dictionary and Optical Microscopy of Historical Pigments*, 1st ed. (Routledge, London, 2008).

³A. Roy, *Artists' Pigments: A Handbook of Their History and Characteristics* (Archetype Publications, London, 1993), Vol. 2.

⁴J. R. Barnett, S. Miller, and E. Pearce, *Opt. Laser Technol.* **38**, 445 (2006).
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01927-01</td><td>26.980 (−21.0)</td><td>Al<sup>+</sup></td><td>Lazurite, sodalite</td></tr><tr><td>39.962 (−14.9)</td><td>Ca<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>55.956 (−15.8)</td><td>CaO<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>56.966 (17.4)</td><td>CaOH<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>58.959 (−26.0)</td><td>CaF<sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>82.953 (−30.9)</td><td>SiO<sub>2</sub>Na<sup>+</sup></td><td>Lazurite</td></tr><tr><td>95.921 (11.5)</td><td>Ca<sub>2</sub>O<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>98.938 (50.1)</td><td>SiONaS<sup>+</sup></td><td>Lazurite</td></tr><tr><td>111.914 (−5.73)</td><td>Ca<sub>2</sub>O<sub>2</sub></td><td>Lazurite</td></tr><tr><td>112.925 (22.0)</td><td>Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>114.919 (8.96)</td><td>Ca<sub>2</sub>OF<sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>136.918 (−11.6)</td><td>Ca<sub>2</sub>F<sub>3</sub><sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>154.897 (39.0)</td><td>CaSiNaSO<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>174.891 (−21.7)</td><td>Si<sub>2</sub>O<sub>2</sub>NaSO<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>214.863 (24.3)</td><td>Ca<sub>2</sub>OAlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>230.855 (9.91)</td><td>Ca<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>270.824 (32.8)</td><td>Ca<sub>3</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>326.783 (32.0)</td><td>Ca<sub>4</sub>O<sub>3</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr></tbody></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01927-01</td><td>26.980 (−21.0)</td><td>Al<sup>+</sup></td><td>Lazurite, sodalite</td></tr><tr><td>39.962 (−14.9)</td><td>Ca<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>55.956 (−15.8)</td><td>CaO<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>56.966 (17.4)</td><td>CaOH<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>58.959 (−26.0)</td><td>CaF<sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>82.953 (−30.9)</td><td>SiO<sub>2</sub>Na<sup>+</sup></td><td>Lazurite</td></tr><tr><td>95.921 (11.5)</td><td>Ca<sub>2</sub>O<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>98.938 (50.1)</td><td>SiONaS<sup>+</sup></td><td>Lazurite</td></tr><tr><td>111.914 (−5.73)</td><td>Ca<sub>2</sub>O<sub>2</sub></td><td>Lazurite</td></tr><tr><td>112.925 (22.0)</td><td>Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>114.919 (8.96)</td><td>Ca<sub>2</sub>OF<sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>136.918 (−11.6)</td><td>Ca<sub>2</sub>F<sub>3</sub><sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>154.897 (39.0)</td><td>CaSiNaSO<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>174.891 (−21.7)</td><td>Si<sub>2</sub>O<sub>2</sub>NaSO<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>214.863 (24.3)</td><td>Ca<sub>2</sub>OAlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>230.855 (9.91)</td><td>Ca<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>270.824 (32.8)</td><td>Ca<sub>3</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>326.783 (32.0)</td><td>Ca<sub>4</sub>O<sub>3</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr></tbody></table>
<figure><img src="image_12.png" /></figure>

<table><tr><td>Accession #:</td><td>01927-01</td></tr><tr><td>Specimen:</td><td>Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Positive polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1700 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>27 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Al<sup>+</sup> Ca<sup>+</sup> SiONa<sup>+</sup> Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup> and Ca<sub>3</sub>O<sub>3</sub>H<sup>+</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 13 nA</td></tr><tr><td>DC Beam Current:</td><td>10.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Positive</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>335 s</td></tr><tr><td>Comment:</td><td>Very large grains, mass resolution impacted. The sodium peak saturated.</td></tr></table>
<figure><img src="image_12.png" /></figure>

<table><tr><td>Accession #:</td><td>01927-01</td></tr><tr><td>■ Specimen:</td><td>Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Positive polarity</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1700 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>27 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Al<sup>+</sup> Ca<sup>+</sup> SiONa<sup>+</sup> Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup> and Ca<sub>3</sub>O<sub>3</sub>H<sup>+</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 13 nA</td></tr><tr><td>DC Beam Current:</td><td>10.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Positive</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>335 s</td></tr><tr><td>Comment:</td><td>Very large grains, mass resolution impacted. The sodium peak saturated.</td></tr></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01927-02</td><td>18.999 (−7.07)</td><td>F<sup>−</sup></td><td>Accessory mineral (ex: phlogopite)</td></tr><tr><td>31.973 (17.7)</td><td>S<sup>−</sup></td><td>Lazurite</td></tr><tr><td>34.970 (20.2)</td><td>Cl<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>42.977 (−3.48)</td><td>AlO<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>47.967 (−8.23)</td><td>SO<sup>−</sup></td><td>Lazurite</td></tr><tr><td>58.971 (−11.9)</td><td>AlO<sub>2</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>60.977 (22.6)</td><td>SiO<sub>2</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>62.971 (−2.18)</td><td>SiOF<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>63.964 (31.1)</td><td>SO<sub>2</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>76.974 (51.1)</td><td>SiO<sub>3</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>78.968 (23.9)</td><td>SiO<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>79.960 (33.5)</td><td>SO<sub>3</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>96.950 (24.6)</td><td>KNaOF<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>102.946 (22.5)</td><td>SiAlO<sub>3</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>118.937 (−17.5)</td><td>SiAlO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>134.922 (17.7)</td><td>AlSiSO<sub>3</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>136.939 (14.1)</td><td>Si<sub>2</sub>O<sub>5</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>162.917 (37.0)</td><td>Si<sub>2</sub>AlO<sub>5</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>174.898 (13.7)</td><td>K<sub>2</sub>Na<sub>2</sub>O<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>178.904 (−6.98)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>180.909 (−21.6)</td><td>Na<sub>2</sub>OAlSiO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>194.886 (18.7)</td><td>Si<sub>2</sub>AlSO<sub>5</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>196.904 (−23.1)</td><td>Na<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>204.896 (19.3)</td><td>SiAl<sub>3</sub>O<sub>6</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>212.893 (2.29)</td><td>K<sub>2</sub>Na<sub>2</sub>O<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>220.888 (7.87)</td><td>SiAl<sub>3</sub>O<sub>7</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>238.874 (6.40)</td><td>Si<sub>3</sub>AlO<sub>8</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>280.854 (4.23)</td><td>Si<sub>2</sub>Al<sub>3</sub>O<sub>9</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>298.843 (14.1)</td><td>Si<sub>4</sub>AlO<sub>10</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>322.840 (16.3)</td><td>SiAl<sub>5</sub>O<sub>10</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>336.816 (14.8)</td><td>NaSi<sub>3</sub>Al<sub>2</sub>SO<sub>9</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>340.824 (10.2)</td><td>Si<sub>3</sub>Al<sub>3</sub>O<sub>11</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>358.807 (3.43)</td><td>Si<sub>5</sub>AlO<sub>12</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>382.805 (9.45)</td><td>Si<sub>2</sub>Al<sub>5</sub>O<sub>12</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>396.762 (6.81)</td><td>NaSi<sub>4</sub>Al<sub>2</sub>S<sub>2</sub>O<sub>9</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>400.776 (−26.6)</td><td>Si<sub>4</sub>Al<sub>3</sub>O<sub>13</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr></tbody></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01927-02</td><td>18.999 (−7.07)</td><td>F<sup>−</sup></td><td>Accessory mineral (ex: phlogopite)</td></tr><tr><td>31.973 (17.7)</td><td>S<sup>−</sup></td><td>Lazurite</td></tr><tr><td>34.970 (20.2)</td><td>Cl<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>42.977 (−3.48)</td><td>AlO<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>47.967 (−8.23)</td><td>SO<sup>−</sup></td><td>Lazurite</td></tr><tr><td>58.971 (−11.9)</td><td>AlO<sub>2</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>60.977 (22.6)</td><td>SiO<sub>2</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>62.971 (−2.18)</td><td>SiOF<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>63.964 (31.1)</td><td>SO<sub>2</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>76.974 (51.1)</td><td>SiO<sub>3</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>78.968 (23.9)</td><td>SiO<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>79.960 (33.5)</td><td>SO<sub>3</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>96.950 (24.6)</td><td>KNaOF<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>102.946 (22.5)</td><td>SiAlO<sub>3</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>118.937 (−17.5)</td><td>SiAlO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>134.922 (17.7)</td><td>AlSiSO<sub>3</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>136.939 (14.1)</td><td>Si<sub>2</sub>O<sub>5</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>162.917 (37.0)</td><td>Si<sub>2</sub>AlO<sub>5</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>174.898 (13.7)</td><td>K<sub>2</sub>Na<sub>2</sub>O<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>178.904 (−6.98)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>180.909 (−21.6)</td><td>Na<sub>2</sub>OAlSiO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>194.886 (18.7)</td><td>Si<sub>2</sub>AlSO<sub>5</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>196.904 (−23.1)</td><td>Na<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>204.896 (19.3)</td><td>SiAl<sub>3</sub>O<sub>6</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>212.893 (2.29)</td><td>K<sub>2</sub>Na<sub>2</sub>O<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>220.888 (7.87)</td><td>SiAl<sub>3</sub>O<sub>7</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>238.874 (6.40)</td><td>Si<sub>3</sub>AlO<sub>8</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>280.854 (4.23)</td><td>Si<sub>2</sub>Al<sub>3</sub>O<sub>9</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>298.843 (14.1)</td><td>Si<sub>4</sub>AlO<sub>10</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>322.840 (16.3)</td><td>SiAl<sub>5</sub>O<sub>10</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>336.816 (14.8)</td><td>NaSi<sub>3</sub>Al<sub>2</sub>SO<sub>9</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>340.824 (10.2)</td><td>Si<sub>3</sub>Al<sub>3</sub>O<sub>11</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>358.807 (3.43)</td><td>Si<sub>5</sub>AlO<sub>12</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>382.805 (9.45)</td><td>Si<sub>2</sub>Al<sub>5</sub>O<sub>12</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>396.762 (6.81)</td><td>NaSi<sub>4</sub>Al<sub>2</sub>S<sub>2</sub>O<sub>9</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>400.776 (−26.6)</td><td>Si<sub>4</sub>Al<sub>3</sub>O<sub>13</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr></tbody></table>
<figure><img src="image_13.png" /></figure>

<table><tr><td>Accession #:</td><td>01927-02</td></tr><tr><td>■ Specimen:</td><td>Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Negative polarity</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1400 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 D</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Cl<sup>-</sup>, SiO<sub>2</sub>, AlSiO<sub>4</sub>, AlSi<sub>2</sub>O<sub>6</sub>, AlSi<sub>3</sub>O<sub>8</sub>, and AlSi<sub>4</sub>O<sub>10</sub></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 13 nA</td></tr><tr><td>DC Beam Current:</td><td>10.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>335 s</td></tr><tr><td>Comment:</td><td>Very large grains, mass resolution impacted. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg<sub>3</sub>(AlSi<sub>3</sub>O<sub>10</sub>)(F,OH)<sub>2</sub>]. Assignments were refined thanks to colocalization in ion images.</td></tr></table>
<figure><img src="image_13.png" /></figure>

<table><tr><td>Accession #:</td><td>01927-02</td></tr><tr><td>■ Specimen:</td><td>Lapis Lazuli from Chile—Kremer Pigmente ref. 1056038—Negative polarity</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1400 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 D</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Cl<sup>-</sup>, SiO<sub>2</sub>, AlSiO<sub>4</sub>, AlSi<sub>2</sub>O<sub>6</sub>, AlSi<sub>3</sub>O<sub>8</sub>, and AlSi<sub>4</sub>O<sub>10</sub></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 13 nA</td></tr><tr><td>DC Beam Current:</td><td>10.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>335 s</td></tr><tr><td>Comment:</td><td>Very large grains, mass resolution impacted. Fluorine content is notably high, probably from a naturally occurring accessory mineral occurring with lazurite [like phlogopite KMg<sub>3</sub>(AlSi<sub>3</sub>O<sub>10</sub>)(F,OH)<sub>2</sub>]. Assignments were refined thanks to colocalization in ion images.</td></tr></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01928-01</td><td>26.982 (38.4)</td><td>Al<sup>+</sup></td><td>Lazurite, sodalite</td></tr><tr><td>39.960 (−52.3)</td><td>Ca<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>55.954 (−50.3)</td><td>CaO<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>56.962 (−47.8)</td><td>CaOH<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>58.957 (−54.9)</td><td>CaF<sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>95.922 (29.3)</td><td>Ca<sub>2</sub>O<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>98.936 (24.6)</td><td>SiONaS<sup>+</sup></td><td>Lazurite</td></tr><tr><td>111.914 (−3.31)</td><td>Ca<sub>2</sub>O<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>112.923 (7.19)</td><td>Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>114.920 (13.1)</td><td>Ca<sub>2</sub>OF<sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>136.922 (13.8)</td><td>Ca<sub>2</sub>F<sub>3</sub><sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>151.878 (10.5)</td><td>Ca<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>154.895 (27.0)</td><td>CaSiNaSO<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>167.873 (6.75)</td><td>Ca<sub>3</sub>O<sub>3</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>174.891 (−19.4)</td><td>Si<sub>2</sub>O<sub>4</sub>NaSO<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>207.837 (11.7)</td><td>Ca<sub>4</sub>O<sub>3</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>210.858 (−19.3)</td><td>SiNaS<sub>3</sub>O<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>214.868 (47.3)</td><td>Ca<sub>2</sub>OAlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>223.832 (10.5)</td><td>Ca<sub>4</sub>O<sub>4</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>230.854 (4.70)</td><td>Ca<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>263.798 (22.3)</td><td>Ca<sub>5</sub>O<sub>4</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>270.828 (47.4)</td><td>Ca<sub>3</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>279.785 (8.04)</td><td>Ca<sub>5</sub>O<sub>5</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>319.744 (−18.1)</td><td>Ca<sub>6</sub>O<sub>5</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>326.776 (10.9)</td><td>Ca<sub>4</sub>O<sub>3</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>335.746 (4.65)</td><td>Ca<sub>6</sub>O<sub>6</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>375.709 (3.73)</td><td>Ca<sub>7</sub>O<sub>6</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>431.666 (3.96)</td><td>Ca<sub>8</sub>O<sub>7</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>487.631 (17.8)</td><td>Ca<sub>9</sub>O<sub>8</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr></tbody></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01928-01</td><td>26.982 (38.4)</td><td>Al<sup>+</sup></td><td>Lazurite, sodalite</td></tr><tr><td>39.960 (–52.3)</td><td>Ca<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>55.954 (–50.3)</td><td>CaO<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>56.962 (–47.8)</td><td>CaOH<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>58.957 (–54.9)</td><td>CaF<sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>95.922 (29.3)</td><td>Ca<sub>2</sub>O<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>98.936 (24.6)</td><td>SiONaS<sup>+</sup></td><td>Lazurite</td></tr><tr><td>111.914 (–3.31)</td><td>Ca<sub>2</sub>O<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>112.923 (7.19)</td><td>Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>114.920 (13.1)</td><td>Ca<sub>2</sub>OF<sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>136.922 (13.8)</td><td>Ca<sub>2</sub>F<sub>3</sub><sup>+</sup></td><td>F-rich mineral impurity</td></tr><tr><td>151.878 (10.5)</td><td>Ca<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>154.895 (27.0)</td><td>CaSiNaSO<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>167.873 (6.75)</td><td>Ca<sub>3</sub>O<sub>3</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>174.891 (–19.4)</td><td>Si<sub>2</sub>O<sub>4</sub>NaSO<sub>2</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>207.837 (11.7)</td><td>Ca<sub>4</sub>O<sub>3</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>210.858 (–19.3)</td><td>SiNaS<sub>3</sub>O<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>214.868 (47.3)</td><td>Ca<sub>2</sub>OAlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>223.832 (10.5)</td><td>Ca<sub>4</sub>O<sub>4</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>230.854 (4.70)</td><td>Ca<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>263.798 (22.3)</td><td>Ca<sub>5</sub>O<sub>4</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>270.828 (47.4)</td><td>Ca<sub>3</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>279.785 (8.04)</td><td>Ca<sub>5</sub>O<sub>5</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>319.744 (–18.1)</td><td>Ca<sub>6</sub>O<sub>5</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>326.776 (10.9)</td><td>Ca<sub>4</sub>O<sub>3</sub>AlSiO<sub>4</sub><sup>+</sup></td><td>Lazurite</td></tr><tr><td>335.746 (4.65)</td><td>Ca<sub>6</sub>O<sub>6</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>375.709 (3.73)</td><td>Ca<sub>7</sub>O<sub>6</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>431.666 (3.96)</td><td>Ca<sub>8</sub>O<sub>7</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr><tr><td>487.631 (17.8)</td><td>Ca<sub>9</sub>O<sub>8</sub><sup>+</sup></td><td>Lazurite, dolomite</td></tr></tbody></table>
<figure><img src="image_14.png" /></figure>

<table><tr><td>Accession #:</td><td>01928-01</td></tr><tr><td>Specimen:</td><td>Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Positive polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight (with delayed extraction)</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>3400 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>39 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Na<sup>+</sup>, Ca<sup>+</sup>, Na<sub>2</sub><sup>+</sup>, SiONa<sup>+</sup>, Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup>, Ca<sub>3</sub>O<sub>3</sub>H<sup>+</sup>, and Ca<sub>4</sub>O<sub>4</sub>H<sup>+</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>3.28 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>~100 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>6.7 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 09 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 nA</td></tr><tr><td>Beam Diameter:</td><td>400 μm</td></tr><tr><td>Beam Raster Size:</td><td>150 × 150 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Positive</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>2010 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>197 s</td></tr><tr><td>Comment:</td><td>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<sup>-</sup> in the corresponding negative polarity dataset obtained on the same area.</td></tr></table>
<figure><img src="image_14.png" /></figure>

<table><tr><td>Accession #:</td><td>01928-01</td></tr><tr><td>Specimen:</td><td>Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Positive polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight (with delayed extraction)</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>3400 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>39 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Na<sup>+</sup>, Ca<sup>+</sup>, Na<sub>2</sub><sup>+</sup>, SiONa<sup>+</sup>, Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup>, Ca<sub>3</sub>O<sub>3</sub>H<sup>+</sup>, and Ca<sub>4</sub>O<sub>4</sub>H<sup>+</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>3.28 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>~100 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>6.7 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 09 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 nA</td></tr><tr><td>Beam Diameter:</td><td>400 μm</td></tr><tr><td>Beam Raster Size:</td><td>150 × 150 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Positive</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>2010 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>197 s</td></tr><tr><td>Comment:</td><td>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<sup>-</sup> in the corresponding negative polarity dataset obtained on the same area.</td></tr></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01928-02</td><td>19.008 (−)</td><td>F<sup>−</sup></td><td>Accessory mineral (ex: phlogopite)</td></tr><tr><td>31.974 (38.7)</td><td>S<sup>−</sup></td><td>Lazurite</td></tr><tr><td>34.971 (31.1)</td><td>Cl<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>42.976 (−18.9)</td><td>AlO<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>47.965 (−60.1)</td><td>SO<sup>−</sup></td><td>Lazurite</td></tr><tr><td>58.970 (−27.8)</td><td>AlO<sub>2</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>60.972 (−51.4)</td><td>SiO<sub>2</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>63.960 (−45.6)</td><td>SO<sub>2</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>76.970 (−4.17)</td><td>SiO<sub>3</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>78.966 (−3.00)</td><td>SiO<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>79.957 (−10.5)</td><td>SO<sub>3</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>95.956 (33.1)</td><td>SO<sub>4</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>96.966 (−24.9)</td><td>Na<sub>2</sub>O<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>102.947 (27.4)</td><td>SiAlO<sub>3</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>118.941 (19.1)</td><td>SiAlO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>134.922 (44.2)</td><td>AlSiSO<sub>3</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>136.939 (16.4)</td><td>Si<sub>2</sub>O<sub>5</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>147.895 (12.3)</td><td>Si<sub>3</sub>SO<sub>2</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>152.916 (22.3)</td><td>Al<sub>2</sub>O<sub>4</sub>Cl<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>161.918 (16.2)</td><td>SiAl<sub>2</sub>O<sub>5</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>162.914 (21.6)</td><td>Si<sub>2</sub>AlO<sub>5</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>174.912 (−28.0)</td><td>KNa<sub>3</sub>O<sub>3</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>178.903 (−11.2)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>180.910 (−15.2)</td><td>Na<sub>2</sub>OAlSiO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>194.885 (13.5)</td><td>Si<sub>2</sub>AlSO<sub>5</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>196.901 (−37.5)</td><td>Na<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>220.884 (−11.6)</td><td>SiAl<sub>3</sub>O<sub>7</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>234.852 (31.7)</td><td>NaSi<sub>3</sub>S<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>238.865 (−29.2)</td><td>Si<sub>3</sub>AlO<sub>8</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>280.846 (−25.9)</td><td>Si<sub>2</sub>Al<sub>3</sub>O<sub>9</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>298.838 (−4.47)</td><td>Si<sub>4</sub>AlO<sub>10</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>322.832 (−7.14)</td><td>SiAl<sub>5</sub>O<sub>10</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>336.804 (−18.9)</td><td>NaSi<sub>3</sub>Al<sub>2</sub>SO<sub>9</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>340.818 (−5.18)</td><td>Si<sub>3</sub>Al<sub>3</sub>O<sub>11</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>358.807 (3.36)</td><td>Si<sub>5</sub>AlO<sub>12</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>382.797 (−11.0)</td><td>Si<sub>2</sub>Al<sub>5</sub>O<sub>12</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>396.771 (28.0)</td><td>NaSi<sub>4</sub>Al<sub>2</sub>S<sub>2</sub>O<sub>9</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>400.777 (−24.8)</td><td>Si<sub>4</sub>Al<sub>3</sub>O<sub>13</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>424.780 (−6.23)</td><td>SiAl<sub>7</sub>O<sub>13</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>442.746 (29.9)</td><td>Si<sub>3</sub>Al<sub>5</sub>S<sub>2</sub>O<sub>10</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>456.719 (−14.9)</td><td>NaSi<sub>5</sub>Al<sub>2</sub>S<sub>2</sub>O<sub>11</sub><sup>−</sup></td><td>Lazurite</td></tr></tbody></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01928-02</td><td>19.008 (−)</td><td>F<sup>−</sup></td><td>Accessory mineral (ex: phlogopite)</td></tr><tr><td>31.974 (38.7)</td><td>S<sup>−</sup></td><td>Lazurite</td></tr><tr><td>34.971 (31.1)</td><td>Cl<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>42.976 (−18.9)</td><td>AlO<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>47.965 (−60.1)</td><td>SO<sup>−</sup></td><td>Lazurite</td></tr><tr><td>58.970 (−27.8)</td><td>AlO<sub>2</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>60.972 (−51.4)</td><td>SiO<sub>2</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>63.960 (−45.6)</td><td>SO<sub>2</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>76.970 (−4.17)</td><td>SiO<sub>3</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>78.966 (−3.00)</td><td>SiO<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>79.957 (−10.5)</td><td>SO<sub>3</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>95.956 (33.1)</td><td>SO<sub>4</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>96.966 (−24.9)</td><td>Na<sub>2</sub>O<sub>2</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>102.947 (27.4)</td><td>SiAlO<sub>3</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>118.941 (19.1)</td><td>SiAlO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>134.922 (44.2)</td><td>AlSiSO<sub>3</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>136.939 (16.4)</td><td>Si<sub>2</sub>O<sub>5</sub>H<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>147.895 (12.3)</td><td>Si<sub>3</sub>SO<sub>2</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>152.916 (22.3)</td><td>Al<sub>2</sub>O<sub>4</sub>Cl<sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>161.918 (16.2)</td><td>SiAl<sub>2</sub>O<sub>5</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>162.914 (21.6)</td><td>Si<sub>2</sub>AlO<sub>5</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>174.912 (−28.0)</td><td>KNa<sub>3</sub>O<sub>3</sub>F<sup>−</sup></td><td>Phlogopite</td></tr><tr><td>178.903 (−11.2)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>180.910 (−15.2)</td><td>Na<sub>2</sub>OAlSiO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>194.885 (13.5)</td><td>Si<sub>2</sub>AlSO<sub>5</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>196.901 (−37.5)</td><td>Na<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>220.884 (−11.6)</td><td>SiAl<sub>3</sub>O<sub>7</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>234.852 (31.7)</td><td>NaSi<sub>3</sub>S<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>238.865 (−29.2)</td><td>Si<sub>3</sub>AlO<sub>8</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>280.846 (−25.9)</td><td>Si<sub>2</sub>Al<sub>3</sub>O<sub>9</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>298.838 (−4.47)</td><td>Si<sub>4</sub>AlO<sub>10</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>322.832 (−7.14)</td><td>SiAl<sub>5</sub>O<sub>10</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>336.804 (−18.9)</td><td>NaSi<sub>3</sub>Al<sub>2</sub>SO<sub>9</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>340.818 (−5.18)</td><td>Si<sub>3</sub>Al<sub>3</sub>O<sub>11</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>358.807 (3.36)</td><td>Si<sub>5</sub>AlO<sub>12</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>382.797 (−11.0)</td><td>Si<sub>2</sub>Al<sub>5</sub>O<sub>12</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>396.771 (28.0)</td><td>NaSi<sub>4</sub>Al<sub>2</sub>S<sub>2</sub>O<sub>9</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>400.777 (−24.8)</td><td>Si<sub>4</sub>Al<sub>3</sub>O<sub>13</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>424.780 (−6.23)</td><td>SiAl<sub>7</sub>O<sub>13</sub><sup>−</sup></td><td>Lazurite, sodalite, phlogopite</td></tr><tr><td>442.746 (29.9)</td><td>Si<sub>3</sub>Al<sub>5</sub>S<sub>2</sub>O<sub>10</sub><sup>−</sup></td><td>Lazurite</td></tr><tr><td>456.719 (−14.9)</td><td>NaSi<sub>5</sub>Al<sub>2</sub>S<sub>2</sub>O<sub>11</sub><sup>−</sup></td><td>Lazurite</td></tr></tbody></table>
<figure><img src="image_15.png" /></figure>

<table><tr><td>Accession #:</td><td>01928-02</td></tr><tr><td>Specimen:</td><td>Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Negative polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV (with delayed extraction)</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>3300 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>49 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>SiO<sub>2</sub>, AlSiO<sub>4</sub>, AlSi<sub>2</sub>O<sub>6</sub>, AlSi<sub>3</sub>O<sub>8</sub>, and AlSi<sub>4</sub>O<sub>10</sub></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>3.28 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>~100 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>6.7 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 09 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 nA</td></tr><tr><td>Beam Diameter:</td><td>400 μm</td></tr><tr><td>Beam Raster Size:</td><td>150 × 150 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>2022 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>197 s</td></tr><tr><td>Comment:</td><td>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 KMg<sub>3</sub>(AlSi<sub>3</sub>O<sub>10</sub>)(F,OH)<sub>2</sub>]. Assignments were refined thanks to colocalization in ion images.</td></tr></table>
<figure><img src="image_15.png" /></figure>

<table><tr><td>Accession #:</td><td>01928-02</td></tr><tr><td>■ Specimen:</td><td>Lapis Lazuli, sky blue—Kremer Pigmente ref. 10562—Negative polarity</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV (with delayed extraction)</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>3300 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>49 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>SiO<sub>2</sub>, AlSiO<sub>4</sub>, AlSi<sub>2</sub>O<sub>6</sub>, AlSi<sub>3</sub>O<sub>8</sub>, and AlSi<sub>4</sub>O<sub>10</sub></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>3.28 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>~100 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>6.7 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 09 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 nA</td></tr><tr><td>Beam Diameter:</td><td>400 μm</td></tr><tr><td>Beam Raster Size:</td><td>150 × 150 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>2022 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>197 s</td></tr><tr><td>Comment:</td><td>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 KMg<sub>3</sub>(AlSi<sub>3</sub>O<sub>10</sub>)(F,OH)<sub>2</sub>]. Assignments were refined thanks to colocalization in ion images.</td></tr></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01929-01</td><td>26.982 (20.4)</td><td>Al<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>45.979 (−3.68)</td><td>Na<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>61.973 (−10.1)</td><td>Na<sub>2</sub>O<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>77.960 (−3.47)</td><td>Al<sub>2</sub>HNa<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>91.055 (−7.92)</td><td>C<sub>7</sub>H<sub>7</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>93.942 (−7.25)</td><td>SiONaAl<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>94.936 (−16.6)</td><td>Si<sub>2</sub>ONa<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>100.941 (31.2)</td><td>SiAlNa<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>104.949 (−17.7)</td><td>Na<sub>2</sub>O<sub>2</sub>Al<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>105.071 (10.7)</td><td>C<sub>8</sub>H<sub>9</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>105.945 (−7.18)</td><td>Na<sub>2</sub>O<sub>2</sub>Si<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>109.926 (28.5)</td><td>Na<sub>2</sub>S<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>115.052 (−21.6)</td><td>C<sub>9</sub>H<sub>7</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>121.923 (23.1)</td><td>NaKSiO<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>128.059 (−23.7)</td><td>C<sub>10</sub>H<sub>8</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>128.936 (4.33)</td><td>SiNa<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>132.910 (−24.4)</td><td>Na<sub>3</sub>H<sub>2</sub><sup>+</sup></td><td>-/Sodium aluminum sulfosilicate/-</td></tr><tr><td>141.066 (−30.8)</td><td>C<sub>11</sub>H<sub>9</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>144.933 (14.9)</td><td>SiNa<sub>3</sub>O<sub>3</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>148.926 (25.7)</td><td>SiNa<sub>2</sub>AlO<sub>3</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>160.907 (18.2)</td><td>Si<sub>2</sub>Na<sub>2</sub>AlO<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>164.918 (5.34)</td><td>SiNa<sub>2</sub>AlO<sub>4</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>165.066 (−23.3)</td><td>C<sub>13</sub>H<sub>9</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>176.884 (14.2)</td><td>Si<sub>2</sub>Na<sub>2</sub>AlSO<sub>3</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>204.882 (30.1)</td><td>Si<sub>2</sub>Na<sub>2</sub>AlSiO<sub>3</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>227.174 (−25.0)</td><td>C<sub>17</sub>H<sub>23</sub></td><td>Abietic acid fragment (M—C<sub>3</sub>H<sub>7</sub>O<sub>2</sub>)</td></tr><tr><td>246.842 (10.0)</td><td>Si<sub>2</sub>Na<sub>2</sub>Al<sub>3</sub>SO<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>255.187 (49.0)</td><td>C<sub>18</sub>H<sub>23</sub>O<sup>+</sup></td><td>Abietic acid fragment (M—C<sub>2</sub>H<sub>7</sub>O)</td></tr><tr><td>271.213 (26.0)</td><td>C<sub>19</sub>H<sub>27</sub>O<sup>+</sup></td><td>Abietic acid fragment (M—CH<sub>2</sub>O)</td></tr><tr><td>311.229 (−16.6)</td><td>C<sub>20</sub>H<sub>31</sub>ONaH<sup>+</sup></td><td>Resin acid soap</td></tr><tr><td>327.229 (−7.99)</td><td>C<sub>22</sub>H<sub>31</sub>O<sub>2</sub><sup>+</sup></td><td>Abietic-type ester</td></tr><tr><td>348.784 (−8.34)</td><td>Si<sub>2</sub>Al<sub>5</sub>Na<sub>2</sub>SO<sub>5</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>366.266 (28.9)</td><td>C<sub>25</sub>H<sub>34</sub>O<sub>2</sub><sup>+</sup></td><td>Abietic-type ester</td></tr><tr><td>413.274 (13.1)</td><td>C<sub>26</sub>H<sub>37</sub>O<sub>4</sub><sup>+</sup></td><td>Abietic-type ester</td></tr><tr><td>450.733 (34.5)</td><td>Si<sub>2</sub>Al<sub>7</sub>Na<sub>2</sub>S<sub>2</sub>O<sub>6</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr></tbody></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01929-01</td><td>26.982 (20.4)</td><td>Al<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>45.979 (−3.68)</td><td>Na<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>61.973 (−10.1)</td><td>Na<sub>2</sub>O<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>77.960 (−3.47)</td><td>Al<sub>2</sub>HNa<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>91.055 (−7.92)</td><td>C<sub>7</sub>H<sub>7</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>93.942 (−7.25)</td><td>SiONaAl<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>94.936 (−16.6)</td><td>Si<sub>2</sub>ONa<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>100.941 (31.2)</td><td>SiAlNa<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>104.949 (−17.7)</td><td>Na<sub>2</sub>O<sub>2</sub>Al<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>105.071 (10.7)</td><td>C<sub>8</sub>H<sub>9</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>105.945 (−7.18)</td><td>Na<sub>2</sub>O<sub>2</sub>Si<sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>109.926 (28.5)</td><td>Na<sub>2</sub>S<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>115.052 (−21.6)</td><td>C<sub>9</sub>H<sub>7</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>121.923 (23.1)</td><td>NaKSiO<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>128.059 (−23.7)</td><td>C<sub>10</sub>H<sub>8</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>128.936 (4.33)</td><td>SiNa<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>132.910 (−24.4)</td><td>Na<sub>3</sub>H<sub>2</sub><sup>+</sup></td><td>-/Sodium aluminum sulfosilicate/-</td></tr><tr><td>141.066 (−30.8)</td><td>C<sub>11</sub>H<sub>9</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>144.933 (14.9)</td><td>SiNa<sub>3</sub>O<sub>3</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>148.926 (25.7)</td><td>SiNa<sub>2</sub>AlO<sub>3</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>160.907 (18.2)</td><td>Si<sub>2</sub>Na<sub>2</sub>AlO<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>164.918 (5.34)</td><td>SiNa<sub>2</sub>AlO<sub>4</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>165.066 (−23.3)</td><td>C<sub>13</sub>H<sub>9</sub><sup>+</sup></td><td>Abietic-type acid from colophony</td></tr><tr><td>176.884 (14.2)</td><td>Si<sub>2</sub>Na<sub>2</sub>AlSO<sub>3</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>204.882 (30.1)</td><td>Si<sub>2</sub>Na<sub>2</sub>AlSiO<sub>3</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>227.174 (−25.0)</td><td>C<sub>17</sub>H<sub>23</sub></td><td>Abietic acid fragment (M-C<sub>3</sub>H<sub>7</sub>O<sub>2</sub>)</td></tr><tr><td>246.842 (10.0)</td><td>Si<sub>2</sub>Na<sub>2</sub>Al<sub>3</sub>SO<sub>2</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>255.187 (49.0)</td><td>C<sub>18</sub>H<sub>23</sub>O<sup>+</sup></td><td>Abietic acid fragment (M-C<sub>2</sub>H<sub>7</sub>O)</td></tr><tr><td>271.213 (26.0)</td><td>C<sub>19</sub>H<sub>27</sub>O<sup>+</sup></td><td>Abietic acid fragment (M-CH<sub>2</sub>O)</td></tr><tr><td>311.229 (−16.6)</td><td>C<sub>20</sub>H<sub>31</sub>ONaH<sup>+</sup></td><td>Resin acid soap</td></tr><tr><td>327.229 (−7.99)</td><td>C<sub>22</sub>H<sub>31</sub>O<sub>2</sub><sup>+</sup></td><td>Abietic-type ester</td></tr><tr><td>348.784 (−8.34)</td><td>Si<sub>2</sub>Al<sub>5</sub>Na<sub>2</sub>SO<sub>5</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>366.266 (28.9)</td><td>C<sub>25</sub>H<sub>34</sub>O<sub>2</sub><sup>+</sup></td><td>Abietic-type ester</td></tr><tr><td>413.274 (13.1)</td><td>C<sub>26</sub>H<sub>37</sub>O<sub>4</sub><sup>+</sup></td><td>Abietic-type ester</td></tr><tr><td>450.733 (34.5)</td><td>Si<sub>2</sub>Al<sub>7</sub>Na<sub>2</sub>S<sub>2</sub>O<sub>6</sub><sup>+</sup></td><td>Sodium aluminum sulfosilicate</td></tr></tbody></table>
<figure><img src="image_16.png" /></figure>

<table><tr><td>Accession #:</td><td>01929-01</td></tr><tr><td>■ Specimen:</td><td>Ultramarine Blue—Kremer Pigmente ref. 45000—Positive polarity</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>3000 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>27 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Al<sup>+</sup> Ca<sup>+</sup> SiONa<sup>+</sup> SiO<sub>2</sub>Na<sub>2</sub><sup>+</sup> and SiO<sub>3</sub>Na<sub>3</sub><sup>+</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>400 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Positive</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>293 s</td></tr><tr><td>Comment:</td><td>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.<sup>3</sup></td></tr></table>
<figure><img src="image_16.png" /></figure>

<table><tr><td>Accession #:</td><td>01929-01</td></tr><tr><td>Specimen:</td><td>Ultramarine Blue—Kremer Pigmente ref. 45000—Positive polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>3000 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>27 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Al<sup>+</sup>, Ca<sup>+</sup>, SiONa<sup>+</sup>, SiO<sub>2</sub>Na<sub>2</sub><sup>+</sup> and SiO<sub>3</sub>Na<sub>3</sub><sup>+</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>400 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Positive</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>293 s</td></tr><tr><td>Comment:</td><td>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.<sup>3</sup></td></tr></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01929-02</td><td>31.972 (−18.9)</td><td>S<sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>42.976 (−26.1)</td><td>AlO<sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>47.966 (−22.7)</td><td>SO<sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>58.971 (−15.0)</td><td>AlO<sub>2</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>60.974 (−13.3)</td><td>SiO<sub>2</sub>H<sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>63.946 (19.5)</td><td>S<sub>2</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>63.962 (−6.30)</td><td>SO<sub>2</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>76.974 (48.1)</td><td>SiO<sub>3</sub>H<sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>79.943 (37.5)</td><td>S<sub>2</sub>O<sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>91.938 (−15.6)</td><td>SiSO<sub>2</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>101.946 (−20.6)</td><td>Al<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>102.943 (−10.9)</td><td>SiAlO<sub>3</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>118.938 (−9.51)</td><td>SiAlO<sub>4</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>134.916 (4.25)</td><td>AlSiSO<sub>3</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>136.935 (−11.9)</td><td>Si<sub>2</sub>O<sub>5</sub>H<sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>162.910 (−5.94)</td><td>Si<sub>2</sub>AlO<sub>5</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>178.907 (6.72)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>194.886 (19.0)</td><td>Si<sub>2</sub>AlSO<sub>5</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>204.886 (−25.0)</td><td>SiAl<sub>3</sub>O<sub>6</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>220.881 (−26.2)</td><td>SiAl<sub>3</sub>O<sub>7</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>238.876 (15.1)</td><td>Si<sub>3</sub>AlO<sub>8</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>280.849 (−15.9)</td><td>Si<sub>2</sub>Al<sub>3</sub>O<sub>9</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>298.843 (14.3)</td><td>Si<sub>4</sub>AlO<sub>10</sub></td><td>Aluminosilicate</td></tr><tr><td>322.826 (−26.3)</td><td>SiAl<sub>5</sub>O<sub>10</sub></td><td>Aluminosilicate</td></tr><tr><td>340.814 (−17.7)</td><td>Si<sub>3</sub>Al<sub>3</sub>O<sub>11</sub></td><td>Aluminosilicate</td></tr><tr><td>358.802 (−11.6)</td><td>Si<sub>5</sub>AlO<sub>12</sub></td><td>Aluminosilicate</td></tr><tr><td>364.790 (18.3)</td><td>Si<sub>2</sub>Al<sub>5</sub>Na<sub>2</sub>SO<sub>6</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>382.793 (−24.5)</td><td>Si<sub>2</sub>Al<sub>5</sub>O<sub>12</sub></td><td>Aluminosilicate</td></tr><tr><td>400.779 (−20.3)</td><td>Si<sub>4</sub>Al<sub>3</sub>O<sub>13</sub></td><td>Aluminosilicate</td></tr><tr><td>424.763 (−44.3)</td><td>SiAl<sub>7</sub>O<sub>13</sub></td><td>Aluminosilicate</td></tr><tr><td>442.727 (−12.6)</td><td>Si<sub>3</sub>Al<sub>5</sub>S<sub>2</sub>O<sub>10</sub></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>460.724 (13.5)</td><td>Al<sub>3</sub>Si<sub>5</sub>S<sub>2</sub>O<sub>11</sub></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>466.718 (10.6)</td><td>Si<sub>2</sub>Al<sub>7</sub>Na<sub>2</sub>S<sub>2</sub>O<sub>7</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>484.707 (−12.5)</td><td>Al<sub>7</sub>Si<sub>2</sub>S<sub>2</sub>O<sub>11</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr></tbody></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01929-02</td><td>31.972 (−18.9)</td><td>S<sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>42.976 (−26.1)</td><td>AlO<sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>47.966 (−22.7)</td><td>SO<sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>58.971 (−15.0)</td><td>AlO<sub>2</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>60.974 (−13.3)</td><td>SiO<sub>2</sub>H<sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>63.946 (19.5)</td><td>S<sub>2</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>63.962 (−6.30)</td><td>SO<sub>2</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>76.974 (48.1)</td><td>SiO<sub>3</sub>H<sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>79.943 (37.5)</td><td>S<sub>2</sub>O<sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>91.938 (−15.6)</td><td>SiSO<sub>2</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>101.946 (−20.6)</td><td>Al<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>102.943 (−10.9)</td><td>SiAlO<sub>3</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>118.938 (−9.51)</td><td>SiAlO<sub>4</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>134.916 (4.25)</td><td>AlSiSO<sub>3</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>136.935 (−11.9)</td><td>Si<sub>2</sub>O<sub>5</sub>H<sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>162.910 (−5.94)</td><td>Si<sub>2</sub>AlO<sub>5</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>178.907 (6.72)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>194.886 (19.0)</td><td>Si<sub>2</sub>AlSO<sub>5</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>204.886 (−25.0)</td><td>SiAl<sub>3</sub>O<sub>6</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>220.881 (−26.2)</td><td>SiAl<sub>3</sub>O<sub>7</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>238.876 (15.1)</td><td>Si<sub>3</sub>AlO<sub>8</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>280.849 (−15.9)</td><td>Si<sub>2</sub>Al<sub>3</sub>O<sub>9</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>298.843 (14.3)</td><td>Si<sub>4</sub>AlO<sub>10</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>322.826 (−26.3)</td><td>SiAl<sub>5</sub>O<sub>10</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>340.814 (−17.7)</td><td>Si<sub>3</sub>Al<sub>3</sub>O<sub>11</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>358.802 (−11.6)</td><td>Si<sub>5</sub>AlO<sub>12</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>364.790 (18.3)</td><td>Si<sub>2</sub>Al<sub>5</sub>Na<sub>2</sub>SO<sub>6</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>382.793 (−24.5)</td><td>Si<sub>2</sub>Al<sub>5</sub>O<sub>12</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>400.779 (−20.3)</td><td>Si<sub>4</sub>Al<sub>3</sub>O<sub>13</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>424.763 (−44.3)</td><td>SiAl<sub>7</sub>O<sub>13</sub><sup>−</sup></td><td>Aluminosilicate</td></tr><tr><td>442.727 (−12.6)</td><td>Si<sub>3</sub>Al<sub>5</sub>S<sub>2</sub>O<sub>10</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>460.724 (13.5)</td><td>Al<sub>3</sub>Si<sub>5</sub>S<sub>2</sub>O<sub>11</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>466.718 (10.6)</td><td>Si<sub>2</sub>Al<sub>7</sub>Na<sub>2</sub>S<sub>2</sub>O<sub>7</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr><tr><td>484.707 (−12.5)</td><td>Al<sub>7</sub>Si<sub>2</sub>S<sub>2</sub>O<sub>11</sub><sup>−</sup></td><td>Sodium aluminum sulfosilicate</td></tr></tbody></table>
<figure><img src="image_17.png" /></figure>

<table><tr><td>Accession #:</td><td>01929-02</td></tr><tr><td>Specimen:</td><td>Ultramarine Blue—Kremer Pigmente ref. 45000—Negative polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>2700 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>SiO<sub>2</sub>, AlSiO<sub>4</sub>, AlSi<sub>2</sub>O<sub>6</sub>, AlSi<sub>3</sub>O<sub>8</sub>, AlSi<sub>4</sub>O<sub>10</sub>, and AlSi<sub>5</sub>O<sub>12</sub></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>400 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>293 s</td></tr><tr><td>Comment:</td><td>Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode.</td></tr></table>
<figure><img src="image_17.png" /></figure>

<table><tr><td>Accession #:</td><td>01929-02</td></tr><tr><td>Specimen:</td><td>Ultramarine Blue—Kremer Pigmente ref. 45000—Negative polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>2700 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>SiO<sub>2</sub>, AlSiO<sub>4</sub>, AlSi<sub>2</sub>O<sub>6</sub>, AlSi<sub>3</sub>O<sub>8</sub>, AlSi<sub>4</sub>O<sub>10</sub>, and AlSi<sub>5</sub>O<sub>12</sub></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>400 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>293 s</td></tr><tr><td>Comment:</td><td>Delayed extraction mode used in addition to refine peak assignment. Data shown are standard mode.</td></tr></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01930-01</td><td>43.971 (−4.75)</td><td>SiO<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>44.979 (−8.83)</td><td>SiOH<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>45.978 (−0.44)</td><td>Na<sub>2</sub><sup>+</sup></td><td>—</td></tr><tr><td>58.932 (−6.22)</td><td>Co<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>61.952 (−11.8)</td><td>Na<sub>2</sub>O<sup>+</sup></td><td>—</td></tr><tr><td>62.982 (3.14)</td><td>Na<sub>2</sub>OH<sup>+</sup></td><td>—</td></tr><tr><td>77.951 (35.6)</td><td>KNaO<sup>+</sup></td><td>—</td></tr><tr><td>82.937 (18.5)</td><td>SiOK<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>84.965 (14.3)</td><td>Na<sub>3</sub>O<sup>+</sup></td><td>—</td></tr><tr><td>93.921 (−10.8)</td><td>K<sub>2</sub>O<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>94.915 (−20.6)</td><td>Si<sub>2</sub>K<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>94.937 (−8.95)</td><td>Si<sub>2</sub>ONa<sup>+</sup></td><td>—</td></tr><tr><td>128.948 (35.9)</td><td>(SiOH)<sub>2</sub>NaO<sup>+</sup></td><td>—</td></tr><tr><td>144.923 (38.9)</td><td>(SiOH)<sub>2</sub>KO<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>160.908 (−25.1)</td><td>(SiOH)<sub>2</sub>KO<sub>2</sub><sup>+</sup></td><td>CoOKSi</td></tr><tr><td>206.902 (10.6)</td><td>(SiOH)<sub>3</sub>KO<sub>2</sub>H<sup>+</sup></td><td>CoOKSi</td></tr></tbody></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="16">01930-01</td><td>43.971 (−4.75)</td><td>SiO<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>44.979 (−8.83)</td><td>SiOH<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>45.978 (−0.44)</td><td>Na<sub>2</sub><sup>+</sup></td><td>—</td></tr><tr><td>58.932 (−6.22)</td><td>Co<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>61.952 (−11.8)</td><td>Na<sub>2</sub>O<sup>+</sup></td><td>—</td></tr><tr><td>62.982 (3.14)</td><td>Na<sub>2</sub>OH<sup>+</sup></td><td>—</td></tr><tr><td>77.951 (35.6)</td><td>KNaO<sup>+</sup></td><td>—</td></tr><tr><td>82.937 (18.5)</td><td>SiOK<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>84.965 (14.3)</td><td>Na<sub>3</sub>O<sup>+</sup></td><td>—</td></tr><tr><td>93.921 (−10.8)</td><td>K<sub>2</sub>O<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>94.915 (−20.6)</td><td>Si<sub>2</sub>K<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>94.937 (−8.95)</td><td>Si<sub>2</sub>ONa<sup>+</sup></td><td>—</td></tr><tr><td>128.948 (35.9)</td><td>(SiOH)<sub>2</sub>NaO<sup>+</sup></td><td>—</td></tr><tr><td>144.923 (38.9)</td><td>(SiOH)<sub>2</sub>KO<sup>+</sup></td><td>CoOKSi</td></tr><tr><td>160.908 (−25.1)</td><td>(SiOH)<sub>2</sub>KO<sub>2</sub><sup>+</sup></td><td>CoOKSi</td></tr><tr><td>206.902 (10.6)</td><td>(SiOH)<sub>3</sub>KO<sub>2</sub>H<sup>+</sup></td><td>CoOKSi</td></tr></tbody></table>
<figure><img src="image_18.png" /></figure>

<table><tr><td>Accession #:</td><td>01930-01</td></tr><tr><td>Specimen:</td><td>Smalt—Kremer Pigmente ref. 10000—Positive polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1700 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>27 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Al<sup>+</sup>, <sup>41</sup>K<sup>+</sup>, Na<sub>2</sub><sup>+</sup>, SiONa<sup>+</sup>, SiO<sub>2</sub>Na<sub>2</sub><sup>+</sup> and SiO<sub>3</sub>Na<sub>3</sub><sup>+</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Positive</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>293 s</td></tr><tr><td>Comment:</td><td>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.</td></tr></table>
<figure><img src="image_18.png" /></figure>

<table><tr><td>Accession #:</td><td>01930-01</td></tr><tr><td>Specimen:</td><td>Smalt—Kremer Pigmente ref. 10000—Positive polarity</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1700 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>27 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Al<sup>+</sup>, <sup>41</sup>K<sup>+</sup>, Na<sub>2</sub><sup>+</sup>, SiONa<sup>+</sup>, SiO<sub>2</sub>Na<sub>2</sub><sup>+</sup> and SiO<sub>3</sub>Na<sub>3</sub><sup>+</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Positive</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>293 s</td></tr><tr><td>Comment:</td><td>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.</td></tr></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01930-02</td><td>58.935 (26.1)</td><td>Co<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>74.929 (7.03)</td><td>CoO<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>90.923 (−9.67)</td><td>CoO<sub>2</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>98.951 (6.97)</td><td>NaOSiO<sub>2</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>106.920 (16.6)</td><td>CoO<sub>3</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>134.898 (12.0)</td><td>CoSiO<sub>3</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>150.888 (−16.3)</td><td>CoSiO<sub>4</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>158.915 (−26.2)</td><td>NaSi<sub>2</sub>O<sub>5</sub><sup>-</sup></td><td>—</td></tr><tr><td>178.878 (58.5)</td><td>CoSi<sub>2</sub>O<sub>4</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>188.924 (43.5)</td><td>KNa<sub>3</sub>O<sub>5</sub>H<sup>-</sup></td><td>—</td></tr><tr><td>195.892 (−20.1)</td><td>Si<sub>3</sub>O<sub>7</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>210.855 (−11.8)</td><td>CoSi<sub>2</sub>O<sub>6</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>218.869 (19.8)</td><td>Si<sub>3</sub>O<sub>6</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>234.867 (31.1)</td><td>Si<sub>3</sub>O<sub>7</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>238.877 (19.7)</td><td>Si<sub>2</sub>O<sub>9</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>255.860 (−10.1)</td><td>Si<sub>4</sub>O<sub>9</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>266.846 (−12.1)</td><td>KSi<sub>3</sub>O<sub>9</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>270.821 (−9.66)</td><td>CoSi<sub>3</sub>O<sub>8</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>278.837 (20.2)</td><td>Si<sub>4</sub>O<sub>8</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>294.830 (14.0)</td><td>Si<sub>4</sub>O<sub>9</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>316.834 (−9.30)</td><td>Si<sub>5</sub>O<sub>11</sub>H<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>330.782 (−25.8)</td><td>CoSi<sub>4</sub>O<sub>10</sub></td><td>CoOKSi</td></tr><tr><td>338.802 (10.7)</td><td>KSi<sub>5</sub>O<sub>10</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>354.787 (−12.3)</td><td>KSi<sub>5</sub>O<sub>11</sub><sup>-</sup></td><td>CoOKSi</td></tr></tbody></table>
SPECTRAL FEATURES TABLE

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="25">01930-02</td><td>58.935 (26.1)</td><td>Co<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>74.929 (7.03)</td><td>CoO<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>90.923 (−9.67)</td><td>CoO<sub>2</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>98.951 (6.97)</td><td>NaOSiO<sub>2</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>106.920 (16.6)</td><td>CoO<sub>3</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>134.898 (12.0)</td><td>CoSiO<sub>3</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>150.888 (−16.3)</td><td>CoSiO<sub>4</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>158.915 (−26.2)</td><td>NaSi<sub>2</sub>O<sub>5</sub><sup>-</sup></td><td>—</td></tr><tr><td>178.878 (58.5)</td><td>CoSi<sub>2</sub>O<sub>4</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>188.924 (43.5)</td><td>KNa<sub>3</sub>O<sub>5</sub>H<sup>-</sup></td><td>—</td></tr><tr><td>195.892 (−20.1)</td><td>Si<sub>3</sub>O<sub>7</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>210.855 (−11.8)</td><td>CoSi<sub>2</sub>O<sub>6</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>218.869 (19.8)</td><td>Si<sub>3</sub>O<sub>6</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>234.867 (31.1)</td><td>Si<sub>3</sub>O<sub>7</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>238.877 (19.7)</td><td>Si<sub>2</sub>O<sub>9</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>255.860 (−10.1)</td><td>Si<sub>4</sub>O<sub>9</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>266.846 (−12.1)</td><td>KSi<sub>3</sub>O<sub>9</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>270.821 (−9.66)</td><td>CoSi<sub>3</sub>O<sub>8</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>278.837 (20.2)</td><td>Si<sub>4</sub>O<sub>8</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>294.830 (14.0)</td><td>Si<sub>4</sub>O<sub>9</sub>K<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>316.834 (−9.30)</td><td>Si<sub>5</sub>O<sub>11</sub>H<sup>-</sup></td><td>CoOKSi</td></tr><tr><td>330.782 (−25.8)</td><td>CoSi<sub>4</sub>O<sub>10</sub></td><td>CoOKSi</td></tr><tr><td>338.802 (10.7)</td><td>KSi<sub>5</sub>O<sub>10</sub><sup>-</sup></td><td>CoOKSi</td></tr><tr><td>354.787 (−12.3)</td><td>KSi<sub>5</sub>O<sub>11</sub><sup>-</sup></td><td>CoOKSi</td></tr></tbody></table>
<figure><img src="image_19.png" /></figure>

<table><tr><td>Accession #:</td><td>01930-02</td></tr><tr><td>■ Specimen:</td><td>Smalt—Kremer Pigmente ref. 10000—Negative polarity</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1500 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Cl<sup>-</sup>, SiO<sub>2</sub><sup>-</sup>, Si<sub>2</sub>O<sub>5</sub>H<sup>-</sup>, Si<sub>3</sub>O<sub>7</sub>H<sup>-</sup>, Si<sub>4</sub>O<sub>9</sub>H<sup>-</sup>, and Si<sub>5</sub>O<sub>11</sub>H<sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3540 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>308 s</td></tr><tr><td>Comment:</td><td>Very large grains, mass resolution impacted. Co containing ions were identified thanks to the images, with colocalization with the Co<sup>+</sup> and Co<sup>-</sup> ions. The absence of aluminum oxide is notable, and this avoids to misattribute some peaks to aluminosilicate compounds.</td></tr></table>
<figure><img src="image_19.png" /></figure>

<table><tr><td>Accession #:</td><td>01930-02</td></tr><tr><td>■ Specimen:</td><td>Smalt—Kremer Pigmente ref. 10000—Negative polarity</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time-of-flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1500 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Cl<sup>-</sup>, SiO<sub>2</sub>, Si<sub>2</sub>O<sub>5</sub>H<sup>-</sup>, Si<sub>3</sub>O<sub>7</sub>H<sup>-</sup>, Si<sub>4</sub>O<sub>9</sub>H<sup>-</sup>, and Si<sub>5</sub>O<sub>11</sub>H<sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3540 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>308 s</td></tr><tr><td>Comment:</td><td>Very large grains, mass resolution impacted. Co containing ions were identified thanks to the images, with colocalization with the Co<sup>+</sup> and Co<sup>-</sup> ions. The absence of aluminum oxide is notable, and this avoids to misattribute some peaks to aluminosilicate compounds.</td></tr></table>
<table><caption>SPECTRAL FEATURES TABLE (peaks appearing in all spectra—Positive Polarity)</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td>All</td><td>22.99 (–)</td><td>Na<sup>+</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>27.98 (27.4)</td><td>Si<sup>+</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>38.96 (29.9)</td><td>K<sup>+</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>66.96 (7.03)</td><td>SiONa<sup>+</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr></tbody></table>

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

<table><caption>SPECTRAL FEATURES TABLE (peaks appearing in all spectra—Negative Polarity)</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td>All</td><td>59.97 (15.8)</td><td>SiO<sub>2</sub><sup>–</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>75.97 (34.3)</td><td>SiO<sub>3</sub><sup>–</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>119.94 (8.45)</td><td>Si<sub>2</sub>O<sub>4</sub><sup>–</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>135.93 (14.0)</td><td>Si<sub>2</sub>O<sub>5</sub><sup>–</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr></tbody></table>

(Mean absolute deviation values are given for the mass deviations.)
SPECTRAL FEATURES TABLE (peaks appearing in all spectra—Positive Polarity)

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td>All</td><td>22.99 (–)</td><td>Na<sup>+</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>27.98 (27.4)</td><td>Si<sup>+</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>38.96 (29.9)</td><td>K<sup>+</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>66.96 (7.03)</td><td>SiONa<sup>+</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr></tbody></table>

(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)

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td>All</td><td>59.97 (15.8)</td><td>SiO<sub>2</sub><sup>–</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>75.97 (34.3)</td><td>SiO<sub>3</sub><sup>–</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>119.94 (8.45)</td><td>Si<sub>2</sub>O<sub>4</sub><sup>–</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr><tr><td>...</td><td>135.93 (14.0)</td><td>Si<sub>2</sub>O<sub>5</sub><sup>–</sup></td><td>Lapis Iazuli, Synthetic ultramarine, Smalt</td></tr></tbody></table>

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