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# Tof-SIMS spectra of historical inorganic pigments: Calcium white pigments 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: Calcium white pigments in both polarities. Surface Science Spectra, 2024, 31 (1), 10.1116/6.0003592. hal-04604818

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HAL
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# Tof-SIMS spectra of historical inorganic pigments: Calcium white pigments 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: Calcium white pigments in both polarities. Surface Science Spectra, 2024, 31 (1), pp.015007. 10.1116/6.0003592. hal-04604818

HAL Id: hal-04604818

https://hal.science/hal-04604818v1

Submitted on 7 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: Calcium white pigments 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, 015007 (2024)

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RESEARCH ARTICLE | JUNE 06 2024

# Tof-SIMS spectra of historical inorganic pigments: Calcium white pigments 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, 015007 (2024)

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# Tof-SIMS spectra of historical inorganic pigments: Calcium white pigments in both polarities

Cite as: Surf. Sci. Spectra 31, 015007 (2024); doi: 10.1116/6.0003592

Submitted: 4 March 2024 · Accepted: 23 May 2024 ·

Published Online: 6 June 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.

a) Author 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 database focuses on six white pigments made from calcium-rich natural or synthetized materials, prepared following traditional processes. Such pigments are frequently found in the preparation layers, namely, "ground," separating the support from the observable paint layers, and providing a smooth surface to hold the paint on while preventing its absorption by the substrate. Differentiating between these pigments is helpful to better describe the painting practice. Here, ToF-SIMS reference spectra using a Bi₃⁺ primary ion species are presented for both polarities.

© 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/10.1116/6.0003592

Accession #: 01931, 01932, 01933, 01934, 01935, 01936

Technique: SIMS

Specimen: Alba Albula, Bianco San Giovanni, Eggshell white, Dolomite, Anhydrite plaster, Natural alabaster

Instrument: IONTOF, TOF SIMS IV

Major Species in Spectra: O, H, Si, S, Al, C, Ca, Na, Mg, K, P, Cl

Minor Species in Spectra: Hydrocarbon contamination

Published Spectra: 12

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 six white pigments made of calcium-rich materials. Such materials are likely to be present in historical paintings and painted objects, especially in the deeper layers, commonly referred to as "ground" or "preparation" layers. Their structure and composition depends on the time and place in art history.

The reference materials were supplied by specialized manufacturers selling pigments reproducing historical recipes as closely as

possible, such as Kremer Pigmente GmbH, Masters Pigments, Laverdure, and Sennelier. Pigments were available as finely ground powder of variable particle size (between one and a few tens of 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 mm<fnref n="2" /> piece of conductive double-sided tape (3M Electrically Conductive Adhesive Transfer

<footnote n="1">¹Sorbonne Université, CNRS, Laboratoire d'Archéologie Moléculaire et Structurale (LAMS), 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 6229ER, The Netherlands</footnote>
# Tof-SIMS spectra of historical inorganic pigments: Calcium white pigments in both polarities

Cite as: Surf. Sci. Spectra 31, 015007 (2024); doi: 10.1116/6.0003592

Submitted: 4 March 2024 · Accepted: 23 May 2024 ·

Published Online: 6 June 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.

a) Author 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 database focuses on six white pigments made from calcium-rich natural or synthetized materials, prepared following traditional processes. Such pigments are frequently found in the preparation layers, namely, "ground," separating the support from the observable paint layers, and providing a smooth surface to hold the paint on while preventing its absorption by the substrate. Differentiating between these pigments is helpful to better describe the painting practice. Here, ToF-SIMS reference spectra using a Bi₃⁺ primary ion species are presented for both polarities.

© 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/10.1116/6.0003592

Accession #: 01931, 01932, 01933, 01934, 01935, 01936

Technique: SIMS

Specimen: Alba Albula, Bianco San Giovanni, Eggshell white, Dolomite, Anhydrite plaster, Natural alabaster

Instrument: IONTOF, TOF SIMS IV

Major Species in Spectra: O, H, Si, S, Al, C, Ca, Na, Mg, K, P, Cl

Minor Species in Spectra: Hydrocarbon contamination

Published Spectra: 12

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 six white pigments made of calcium-rich materials. Such materials are likely to be present in historical paintings and painted objects, especially in the deeper layers, commonly referred to as "ground" or "preparation" layers. Their structure and composition depends on the time and place in art history.

The reference materials were supplied by specialized manufacturers selling pigments reproducing historical recipes as closely as

possible, such as Kremer Pigmente GmbH, Masters Pigments, Laverdure, and Sennelier. Pigments were available as finely ground powder of variable particle size (between one and a few tens of 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 mm<fnref n="2" /> piece of conductive double-sided tape (3M Electrically Conductive Adhesive Transfer

<footnote n="1">¹Sorbonne Université, CNRS, Laboratoire d'Archéologie Moléculaire et Structurale (LAMS), 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 6229ER, The Netherlands</footnote>
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 (10⁻⁸–10⁻⁹ 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 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 the low-energetic 20 eV electrons of the flood gun.

All positive polarity data were calibrated using the same set of peaks appearing in all spectra, namely, Na⁺ at m/z 22.99, Ca⁺ at m/z 39.96, Ca₂O⁺ at m/z 95.92, Ca₃O₂⁺ at m/z 151.88, Ca₄O₃⁺ at m/z 207.83, Ca₅O₄⁻ at m/z 263.79, and Ca₆O₇⁻ at m/z 319.75. All negative polarity data were calibrated using combinations of the following ions: Cl⁻ at m/z 34.97, CaO⁻ at m/z 55.96, CaO₂H⁻ at m/z 72.96, Ca₂O₃H⁻ at m/z 128.92, and Ca₃O₄H⁻ at m/z 184.88. These calibration lists allowed for an adequate coverage of the mass range of interest, and the calcium containing calibration ions could be verified using their isotopic pattern. The actual calibration set for each individual dataset can be found in the associated table.

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 the current literature.¹⁻⁵ The Spectrum ID# refers to that number, added with “-01” for positive spectra and with “-02” for negative spectra.

## SPECIMEN DESCRIPTION (ACCESSION # 01931)

**Specimen:** Alba Albula, warm white chalk from Albula, Switzerland (Kremer Pigmente ref. 11283)

**CAS Registry #:** 471-34-1

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** Calcium carbonate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** CaCO₃

**Form:** Ground pigment powder

**History and Significance:** White earths derived directly from calcite-rich clay sediments are one of the oldest pigments. They are often found in the preparation layer applied to the substrate of a painting. This white pigment with a beige hue is made by ground stones naturally found in the Albula mountain pass (Switzerland). It is likely to contain other minerals than calcite.

**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 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 2.35A. Residual surface potential was compensated before analysis.

**Temp. During Analysis:** 300 K

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

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

## SPECIMEN DESCRIPTION (ACCESSION # 01932)

**Specimen:** Bianco San Giovanni (Kremer Pigmente ref. 11415)

**CAS Registry #:** 471-34-1 and 1305-62-0-1

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** Calcium carbonate with calcium hydroxide

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** CaCO₃ + Ca(OH)₂

**Form:** Ground pigment powder

**History and Significance:** White pigment prepared according to Cennino Cenninis recipe. Mainly composed of hydrated lime that was slowly dried and very finely ground (well below 150 µm for instance).

**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 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 2.35 A. Residual surface potential was compensated before analysis.

**Temp. During Analysis:** 300 K

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

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

## SPECIMEN DESCRIPTION (ACCESSION # 01933)

**Specimen:** Eggshell White (Kremer Pigmente ref. 11410)

**CAS Registry #:** Unknown

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** Ground eggshell

**Source:** Kremer Pigmente GmbH
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 (10⁻⁸–10⁻⁹ 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 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 the low-energetic 20 eV electrons of the flood gun.

All positive polarity data were calibrated using the same set of peaks appearing in all spectra, namely, Na⁺ at m/z 22.99, Ca⁺ at m/z 39.96, Ca₂O⁺ at m/z 95.92, Ca₃O₂⁺ at m/z 151.88, Ca₄O₃⁺ at m/z 207.83, Ca₅O₄⁻ at m/z 263.79, and Ca₆O₇⁻ at m/z 319.75. All negative polarity data were calibrated using combinations of the following ions: Cl⁻ at m/z 34.97, CaO⁻ at m/z 55.96, CaO₂H⁻ at m/z 72.96, Ca₂O₃H⁻ at m/z 128.92, and Ca₃O₄H⁻ at m/z 184.88. These calibration lists allowed for an adequate coverage of the mass range of interest, and the calcium containing calibration ions could be verified using their isotopic pattern. The actual calibration set for each individual dataset can be found in the associated table.

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 the current literature.¹⁻⁵ The Spectrum ID# refers to that number, added with “-01” for positive spectra and with “-02” for negative spectra.

## SPECIMEN DESCRIPTION (ACCESSION # 01931)

**Specimen:** Alba Albula, warm white chalk from Albula, Switzerland (Kremer Pigmente ref. 11283)

**CAS Registry #:** 471-34-1

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** Calcium carbonate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** CaCO₃

**Form:** Ground pigment powder

**History and Significance:** White earths derived directly from calcite-rich clay sediments are one of the oldest pigments. They are often found in the preparation layer applied to the substrate of a painting. This white pigment with a beige hue is made by ground stones naturally found in the Albula mountain pass (Switzerland). It is likely to contain other minerals than calcite.

**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 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 2.35A. Residual surface potential was compensated before analysis.

**Temp. During Analysis:** 300 K

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

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

## SPECIMEN DESCRIPTION (ACCESSION # 01932)

**Specimen:** Bianco San Giovanni (Kremer Pigmente ref. 11415)

**CAS Registry #:** 471-34-1 and 1305-62-0-1

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** Calcium carbonate with calcium hydroxide

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** CaCO₃ + Ca(OH)₂

**Form:** Ground pigment powder

**History and Significance:** White pigment prepared according to Cennino Cenninis recipe. Mainly composed of hydrated lime that was slowly dried and very finely ground (well below 150 µm for instance).

**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 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 2.35 A. Residual surface potential was compensated before analysis.

**Temp. During Analysis:** 300 K

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

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

## SPECIMEN DESCRIPTION (ACCESSION # 01933)

**Specimen:** Eggshell White (Kremer Pigmente ref. 11410)

**CAS Registry #:** Unknown

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** Ground eggshell

**Source:** Kremer Pigmente GmbH
**Specimen Composition:** CaCO₃, MgCO₃, Ca₃(PO₄)₂, proteins from the shell

**Form:** Ground pigment powder

**History and Significance:** Finely ground eggshell is an easily accessible source of white pigment in a workshop and is frequently mentioned in preparations. The material has been classified as an inorganic pigment in this paper, as it mainly consists of calcium and magnesium carbonates. It is, however, worth noticing that some fragments originating from the peptide backbone of proteins, naturally found in the eggshell structure, can be detected using ToF-SIMS in this pigment.

**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 $250 \times 250 \ \mu m^2$

**Ex Situ Preparation/Mounting:** Powder was deposited and pressed onto 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 2.35 A. Residual surface potential was compensated before analysis.

**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 # 01934)

**Specimen:** Dolomite $10 \ \mu m$ (Kremer Pigmente ref. 58740)

**CAS Registry #:** 16389-88-1

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** Natural calcium-magnesium carbonate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** CaMg(CO₃)₂

**Form:** Ground pigment powder

**History and Significance:** White CaMg(CO₃)₂-rich white sediments or minerals are often found in the preparation layer applied to the substrate of a painting.

**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 $250 \times 250 \ \mu m^2$

**Ex Situ Preparation/Mounting:** Powder was deposited and pressed onto 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 2.35 A. Residual surface potential was compensated before analysis.

**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 # 01935, 01936)

**Specimen:** (Accession #01935) Anhydrite plaster, burnt gypsum (Kremer Pigmente ref. 58320), (Accession #01936) Natural alabaster plaster (Kremer Pigmente ref. 58340).

**CAS Registry #:** 7778-18-9

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** (Accession #01935) Calcium sulfate anhydrite, (Accession #01936) Calcium sulfate dihydrate + calcium sulfate alpha hemihydrate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** (Accession #01935) CaSO₄, (Accession #01936) CaSO₄·1/2H₂O (n = 1/2, 2)

**Form:** Ground pigment powder

**History and Significance:** Natural plasters are found in many paint mixtures as a filler to lighten a color or as a preparation material. Characterizing gypsum is important to understand the structure of a painted artwork. Natural gypsum contains strontium inclusions.

**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 $250 \times 250 \ \mu m^2$

**Ex Situ Preparation/Mounting:** Powder was deposited and pressed onto 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 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:** None

**Energy Acceptance Window:** 20 eV
**Specimen Composition:** CaCO₃, MgCO₃, Ca₃(PO₄)₂, proteins from the shell

**Form:** Ground pigment powder

**History and Significance:** Finely ground eggshell is an easily accessible source of white pigment in a workshop and is frequently mentioned in preparations. The material has been classified as an inorganic pigment in this paper, as it mainly consists of calcium and magnesium carbonates. It is, however, worth noticing that some fragments originating from the peptide backbone of proteins, naturally found in the eggshell structure, can be detected using ToF-SIMS in this pigment.

**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 $250 \times 250 \ \mu m^2$

**Ex Situ Preparation/Mounting:** Powder was deposited and pressed onto 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 2.35 A. Residual surface potential was compensated before analysis.

**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 # 01934)

**Specimen:** Dolomite $10 \ \mu m$ (Kremer Pigmente ref. 58740)

**CAS Registry #:** 16389-88-1

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** Natural calcium-magnesium carbonate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** CaMg(CO$_3$)$_2$

**Form:** Ground pigment powder

**History and Significance:** White CaMg(CO$_3$)$_2$-rich white sediments or minerals are often found in the preparation layer applied to the substrate of a painting.

**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 $250 \times 250 \ \mu m^2$

**Ex Situ Preparation/Mounting:** Powder was deposited and pressed onto 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 2.35 A. Residual surface potential was compensated before analysis.

**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 # 01935, 01936)

**Specimen:** (Accession #01935) Anhydrite plaster, burnt gypsum (Kremer Pigmente ref. 58320), (Accession #01936) Natural alabaster plaster (Kremer Pigmente ref. 58340).

**CAS Registry #:** 7778-18-9

**Specimen Characteristics:** Unknown homogeneity; solid; unknown crystallinity; dielectric; inorganic compound; powder

**Chemical Name:** (Accession #01935) Calcium sulfate anhydrite, (Accession #01936) Calcium sulfate dihydrate + calcium sulfate alpha hemihydrate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** (Accession #01935) CaSO$_4$, (Accession #01936) CaSO$_4$·1/2H$_2$O (n = 1/2, 2)

**Form:** Ground pigment powder

**History and Significance:** Natural plasters are found in many paint mixtures as a filler to lighten a color or as a preparation material. Characterizing gypsum is important to understand the structure of a painted artwork. Natural gypsum contains strontium inclusions.

**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 $250 \times 250 \ \mu m^2$

**Ex Situ Preparation/Mounting:** Powder was deposited and pressed onto 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 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:** None

**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 × 250 µm²

**Rotor 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:** 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 ns

**Ion Pulse Rate:** N/A

**DC Beam Current:** ~10 nA

**Pulsed Beam Current:** N/A

**Current Measurement Method:** Faraday cup

**Beam Diameter:** ~50 µm

**Beam Raster Size:** 500 × 500 µm²

**Rotor Pixel Dimensions:** N/A

**Beam Incident Angle:** 45°

**Source-to-Analyzer Angle:** 45°

## ACKNOWLEDGMENTS

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 the 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 (lead). **Sebastiaan Van Nuffel:** Investigation (equal); Writing – review & editing (lead). **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

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

²E. Robert and L. Feller, *Artists' Pigments: A Handbook of Their History and Characteristics, Vol. 1* (Archetype Publications, London, 1986).

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

⁴E. W. FitzHugh, *Artists' Pigments: A Handbook of Their History and Characteristics, Vol. 3* (Archetype Publications, London, 1997).

⁵J. R. Barnett, S. Miller, and E. Pearce, *Opt. Laser Technol.* **38**, 445 (2006).

⁶E. Franceschi and F. Locardi, *J. Cult. Herit.* **15**, 522 (2014).
**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 × 250 µm<fnref n="2" />

**Rotor 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:** 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 ns

**Ion Pulse Rate:** N/A

**DC Beam Current:** ~10 nA

**Pulsed Beam Current:** N/A

**Current Measurement Method:** Faraday cup

**Beam Diameter:** ~50 µm

**Beam Raster Size:** 500 × 500 µm<fnref n="2" />

**Rotor Pixel Dimensions:** N/A

**Beam Incident Angle:** 45°

**Source-to-Analyzer Angle:** 45°

ACKNOWLEDGMENTS

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 the 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 (lead). **Sebastiaan Van Nuffel:** Investigation (equal); Writing – review & editing (lead). **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">¹N. 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="2">²E. Robert and L. Feller, *Artists' Pigments: A Handbook of Their History and Characteristics, Vol. 1* (Archetype Publications, London, 1986).</footnote>

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

<footnote n="4">⁴E. W. FitzHugh, *Artists' Pigments: A Handbook of Their History and Characteristics, Vol. 3* (Archetype Publications, London, 1997).</footnote>

<footnote n="5">⁵J. R. Barnett, S. Miller, and E. Pearce, *Opt. Laser Technol.* **38**, 445 (2006).</footnote>

<footnote n="6">⁶E. Franceschi and F. Locardi, *J. Cult. Herit.* **15**, 522 (2014).</footnote>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="12">01931-01</td><td>23.984 (–42.8)</td><td>Mg<sup>+</sup></td><td>–</td></tr><tr><td>26.980 (–30.0)</td><td>Al<sup>+</sup></td><td>Clay</td></tr><tr><td>27.975 (–33.7)</td><td>Si<sup>+</sup></td><td>Clay</td></tr><tr><td>38.965 (52.6)</td><td>K<sup>+</sup></td><td>–</td></tr><tr><td>79.945 (38.0)</td><td>CaMgO<sup>+</sup></td><td>–</td></tr><tr><td>135.900 (3.30)</td><td>Ca<sub>2</sub>MgO<sub>2</sub><sup>+</sup></td><td>–</td></tr><tr><td>191.858 (4.51)</td><td>Ca<sub>3</sub>O<sub>2</sub>MgO<sup>+</sup></td><td>–</td></tr><tr><td>231.833 (–17.0)</td><td>Ca<sub>3</sub>O<sub>2</sub>(MgO)<sub>2</sub><sup>+</sup></td><td>–</td></tr><tr><td>247.816 (5.49)</td><td>Ca<sub>4</sub>O<sub>3</sub>MgO<sup>+</sup></td><td>–</td></tr><tr><td>287.796 (5.88)</td><td>Ca<sub>4</sub>O<sub>3</sub>(MgO)<sub>2</sub><sup>+</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>303.773 (3.81)</td><td>Ca<sub>5</sub>O<sub>4</sub>MgO<sup>+</sup></td><td>CaCO<sub>3</sub></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="15">01931-01</td><td>23.984 (–42.8)</td><td>Mg<sup>+</sup></td><td>–</td></tr><tr><td>26.980 (–30.0)</td><td>Al<sup>+</sup></td><td>Clay</td></tr><tr><td>27.975 (–33.7)</td><td>Si<sup>+</sup></td><td>Clay</td></tr><tr><td>38.965 (52.6)</td><td>K<sup>+</sup></td><td>–</td></tr><tr><td>79.945 (38.0)</td><td>CaMgO<sup>+</sup></td><td>–</td></tr><tr><td>135.900 (3.30)</td><td>Ca<sub>2</sub>MgO<sub>2</sub><sup>+</sup></td><td>–</td></tr><tr><td>191.858 (4.51)</td><td>Ca<sub>3</sub>O<sub>2</sub>MgO<sup>+</sup></td><td>–</td></tr><tr><td>231.833 (–17.0)</td><td>Ca<sub>3</sub>O<sub>2</sub>(MgO)<sub>2</sub><sup>+</sup></td><td>–</td></tr><tr><td>247.816 (5.49)</td><td>Ca<sub>4</sub>O<sub>3</sub>MgO<sup>+</sup></td><td>–</td></tr><tr><td>287.796 (5.88)</td><td>Ca<sub>4</sub>O<sub>3</sub>(MgO)<sub>2</sub><sup>+</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>303.773 (3.81)</td><td>Ca<sub>5</sub>O<sub>4</sub>MgO<sup>+</sup></td><td>CaCO<sub>3</sub></td></tr></tbody></table>
<figure><img src="image_13.png" /></figure>

<table><tr><td>Accession #:</td><td>01931-01</td></tr><tr><td>■ Specimen:</td><td>Alba Albula - Kremer Pigmente ref. 11283 - 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>2500 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr></table>
<figure><img src="image_13.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01931-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Alba Albula - Kremer Pigmente ref. 11283 - 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>2500 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="10">01931-02</td><td>15.995 (−8.90)</td><td>O<sup>−</sup></td><td>–</td></tr><tr><td>63.961 (−16.7)</td><td>SO<sub>2</sub><sup>−</sup></td><td>–</td></tr><tr><td>75.966 (43.5)</td><td>SiO<sub>3</sub><sup>−</sup></td><td>Clay</td></tr><tr><td>79.959 (16.3)</td><td>SO<sub>3</sub><sup>−</sup></td><td>–</td></tr><tr><td>99.946 (−14.8)</td><td>CaCO<sub>3</sub><sup>−</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>116.948 (−17.9)</td><td>CaOHCO<sub>3</sub><sup>−</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>118.938 (−1.81)</td><td>AlSiO<sub>4</sub><sup>−</sup></td><td>Clay</td></tr><tr><td>178.907 (6.51)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>−</sup></td><td>Clay</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="10">01931-02</td><td>15.995 (–8.90)</td><td>O<sup>–</sup></td><td>–</td></tr><tr><td>63.961 (–16.7)</td><td>SO<sub>2</sub><sup>–</sup></td><td>–</td></tr><tr><td>75.966 (43.5)</td><td>SiO<sub>3</sub><sup>–</sup></td><td>Clay</td></tr><tr><td>79.959 (16.3)</td><td>SO<sub>3</sub><sup>–</sup></td><td>–</td></tr><tr><td>99.946 (–14.8)</td><td>CaCO<sub>3</sub><sup>–</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>116.948 (–17.9)</td><td>CaOHCO<sub>3</sub><sup>–</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>118.938 (–1.81)</td><td>AlSiO<sub>4</sub><sup>–</sup></td><td>Clay</td></tr><tr><td>178.907 (6.51)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>–</sup></td><td>Clay</td></tr></tbody></table>
<figure><img src="image_14.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01931-02</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Alba Albula - Kremer Pigmente ref. 11283 - 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>2400 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>, CaO<sup>-</sup>, Ca<sub>2</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>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>The peak at m/z 59.98 could be attributed to CO<sub>3</sub><sup>-</sup> along with a near isobaric interference from SiO<sub>2</sub>, thanks to the ion images.</td></tr></tbody></table>
<figure><img src="image_14.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01931-02</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Alba Albula - Kremer Pigmente ref. 11283 - 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>2400 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>, CaO<sup>-</sup>, Ca<sub>2</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>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>The peak at m/z 59.98 could be attributed to CO<sub>3</sub><sup>-</sup> along with a near isobaric interference from SiO<sub>2</sub>, thanks to the ion images.</td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><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">01932-01</td><td>39.962 (4.34)</td><td>Ca<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>56.965 (3.08)</td><td>CaOH<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>95.920 (6.66)</td><td>Ca<sub>2</sub>O<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>111.916 (16.7)</td><td>Ca<sub>2</sub>O<sub>2</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>112.925 (24.1)</td><td>Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>151.878 (3.21)</td><td>Ca<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>167.873 (4.08)</td><td>Ca<sub>3</sub>O<sub>3</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>168.881 (6.44)</td><td>Ca<sub>3</sub>O<sub>3</sub>H<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>207.833 (−6.07)</td><td>Ca<sub>4</sub>O<sub>3</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>223.829 (−1.46)</td><td>Ca<sub>4</sub>O<sub>4</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>224.838 (1.07)</td><td>Ca<sub>4</sub>O<sub>4</sub>H<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>263.789 (−10.4)</td><td>Ca<sub>5</sub>O<sub>4</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>279.784 (−10.1)</td><td>Ca<sub>5</sub>O<sub>5</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>280.794 (−2.46)</td><td>Ca<sub>5</sub>O<sub>5</sub>H<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>319.744 (−18.9)</td><td>Ca<sub>6</sub>O<sub>5</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><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">01932-01</td><td>39.962 (4.34)</td><td>Ca<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>56.965 (3.08)</td><td>CaOH<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>95.920 (6.66)</td><td>Ca<sub>2</sub>O<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>111.916 (16.7)</td><td>Ca<sub>2</sub>O<sub>2</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>112.925 (24.1)</td><td>Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>151.878 (3.21)</td><td>Ca<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>167.873 (4.08)</td><td>Ca<sub>3</sub>O<sub>3</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>168.881 (6.44)</td><td>Ca<sub>3</sub>O<sub>3</sub>H<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>207.833 (–6.07)</td><td>Ca<sub>4</sub>O<sub>3</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>223.829 (–1.46)</td><td>Ca<sub>4</sub>O<sub>4</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>224.838 (1.07)</td><td>Ca<sub>4</sub>O<sub>4</sub>H<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>263.789 (–10.4)</td><td>Ca<sub>5</sub>O<sub>4</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>279.784 (–10.1)</td><td>Ca<sub>5</sub>O<sub>5</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>280.794 (–2.46)</td><td>Ca<sub>5</sub>O<sub>5</sub>H<sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>319.744 (–18.9)</td><td>Ca<sub>6</sub>O<sub>5</sub><sup>+</sup></td><td>Ca(OH)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_15.png" /></figure>

<table><tr><td>Accession #:</td><td>01932-01</td></tr><tr><td>■ Specimen:</td><td>Bianco San Giovanni - Kremer Pigmente ref. 11415 - 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>2900 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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<sup>3+</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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>250 s</td></tr></table>
<figure><img src="image_15.png" /></figure>

<table><tr><td>Accession #:</td><td>01932-01</td></tr><tr><td>■ Specimen:</td><td>Bianco San Giovanni - Kremer Pigmente ref. 11415 - 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>2900 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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<sup>3+</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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>250 s</td></tr></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><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">01932-02</td><td>44.999 (8.89)</td><td>CO<sub>2</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>56.966 (3.55)</td><td>CaOH<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>59.986 (17.2)</td><td>CO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>72.964 (40.0)</td><td>(CaO)OH<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>89.965 (13.5)</td><td>(CaO)(OH)<sub>2</sub><sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>90.974 (23.7)</td><td>(CaOH)(OH)<sub>2</sub><sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>99.949 (6.77)</td><td>CaCO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>115.940 (-27.8)</td><td>(CaO)CO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>116.951 (-1.12)</td><td>(CaOH)CO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>128.921 (17.1)</td><td>(CaO)<sub>2</sub>(OH)<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>136.928 (30.0)</td><td>Ca<sub>2</sub>H(CO)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>146.929 (2.06)</td><td>H(CaO)<sub>2</sub>(OH)<sub>2</sub><sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>152.921 (16.3)</td><td>Ca<sub>2</sub>OH(CO)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>168.888 (43.6)</td><td>Ca<sub>3</sub>O<sub>3</sub>H<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>172.911 (15.0)</td><td>(CaO)<sub>2</sub>CO<sub>3</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>184.878 (11.3)</td><td>(CaO)<sub>3</sub>(OH)<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>202.885 (-4.64)</td><td>H(CaO)<sub>3</sub>(OH)<sub>2</sub><sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>240.832 (-6.09)</td><td>(CaO)<sub>4</sub>(OH)<sup>-</sup></td><td>Ca(OH)<sub>2</sub></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">01932-02</td><td>44.999 (8.89)</td><td>CO<sub>2</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>56.966 (3.55)</td><td>CaOH<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>59.986 (17.2)</td><td>CO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>72.964 (40.0)</td><td>(CaO)OH<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>89.965 (13.5)</td><td>(CaO)(OH)<sub>2</sub><sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>90.974 (23.7)</td><td>(CaOH)(OH)<sub>2</sub><sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>99.949 (6.77)</td><td>CaCO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>115.940 (-27.8)</td><td>(CaO)CO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>116.951 (-1.12)</td><td>(CaOH)CO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>128.921 (17.1)</td><td>(CaO)<sub>2</sub>(OH)<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>136.928 (30.0)</td><td>Ca<sub>2</sub>H(CO)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>146.929 (2.06)</td><td>H(CaO)<sub>2</sub>(OH)<sub>2</sub><sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>152.921 (16.3)</td><td>Ca<sub>2</sub>OH(CO)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>168.888 (43.6)</td><td>Ca<sub>3</sub>O<sub>3</sub>H<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>172.911 (15.0)</td><td>(CaO)<sub>2</sub>CO<sub>3</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>184.878 (11.3)</td><td>(CaO)<sub>3</sub>(OH)<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>202.885 (-4.64)</td><td>H(CaO)<sub>3</sub>(OH)<sub>2</sub><sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr><tr><td>240.832 (-6.09)</td><td>(CaO)<sub>4</sub>(OH)<sup>-</sup></td><td>Ca(OH)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_16.png" /></figure>

<table><tr><td>Accession #:</td><td>01932-02</td></tr><tr><td>■ Specimen:</td><td>Bianco San Giovanni - Kremer Pigmente ref. 11415 - 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>2500 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>, CaO<sup>-</sup>, Ca<sub>2</sub>O<sub>3</sub>H<sup>-</sup>, Ca<sub>3</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>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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>250 s</td></tr></table>
<figure><img src="image_16.png" /></figure>

<table><tr><td>Accession #:</td><td>01932-02</td></tr><tr><td>■ Specimen:</td><td>Bianco San Giovanni - Kremer Pigmente ref. 11415 - 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>2500 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>, CaO<sup>-</sup>, Ca<sub>2</sub>O<sub>3</sub>H<sup>-</sup>, Ca<sub>3</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>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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>250 s</td></tr></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="15">01933-01</td><td>64.970 (64.6)</td><td>(CN)K<sup>+</sup></td><td>Eggshell proteins</td></tr><tr><td>65.967 (28.2)</td><td>(CN)Ca<sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>78.958 (27.7)</td><td>KNaOH<sup>+</sup></td><td>Eggshell materials</td></tr><tr><td>121.927 (32.1)</td><td>(CN)Ca<sub>2</sub>O<sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>137.922 (28.8)</td><td>(CNO)Ca<sub>2</sub>O<sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>177.888 (46.0)</td><td>(CN)Ca<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>193.881 (32.2)</td><td>(CNO)Ca<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>233.846 (36.2)</td><td>(CN)Ca<sub>4</sub>O<sub>3</sub><sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>249.842 (38.2)</td><td>(CNO)Ca<sub>4</sub>O<sub>3</sub><sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>289.807 (39.6)</td><td>(CN)Ca<sub>5</sub>O<sub>4</sub><sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>305.799 (29.6)</td><td>(CNO)Ca<sub>5</sub>O<sub>4</sub><sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>345.762 (28.3)</td><td>(CN)Ca<sub>6</sub>O<sub>5</sub><sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>361.755 (21.6)</td><td>(CNO)Ca<sub>6</sub>O<sub>5</sub><sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="15">01933-01</td><td>64.970 (64.6)</td><td>(CN)K<sup>+</sup></td><td>Eggshell proteins</td></tr><tr><td>65.967 (28.2)</td><td>(CN)Ca<sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>78.958 (27.7)</td><td>KNaOH<sup>+</sup></td><td>Eggshell materials</td></tr><tr><td>121.927 (32.1)</td><td>(CN)Ca<sub>2</sub>O<sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>137.922 (28.8)</td><td>(CNO)Ca<sub>2</sub>O<sup>+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>177.888 (46.0)</td><td>(CN)Ca<sub>3</sub>O<sup>2+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>193.881 (32.2)</td><td>(CNO)Ca<sub>3</sub>O<sup>2+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>233.846 (36.2)</td><td>(CN)Ca<sub>4</sub>O<sup>3+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>249.842 (38.2)</td><td>(CNO)Ca<sub>4</sub>O<sup>3+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>289.807 (39.6)</td><td>(CN)Ca<sub>5</sub>O<sup>4+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>305.799 (29.6)</td><td>(CNO)Ca<sub>5</sub>O<sup>4+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>345.762 (28.3)</td><td>(CN)Ca<sub>6</sub>O<sup>5+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>361.755 (21.6)</td><td>(CNO)Ca<sub>6</sub>O<sup>5+</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr></tbody></table>
<figure><img src="image_17.png" /></figure>

<table><tr><td>Accession #:</td><td>01933-01</td></tr><tr><td>Specimen:</td><td>Eggshell White - Kremer Pigmente ref. 11410 - 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>2100 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>250 s</td></tr><tr><td>Comment:</td><td>Peaks attributed to (CNO)Ca<sub>x</sub>O<sub>y</sub><sup>+</sup> are detected for this material. Additional series of peaks are detected, with lower intensity. They can be attributed to PO<sub>2</sub>(CaO)<sub>n</sub><sup>+</sup> and CNNa(CaO)<sub>n</sub><sup>+</sup> with n = 2–6 and are likely from the eggshell materials.</td></tr></table>
<figure><img src="image_17.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01933-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Eggshell White - Kremer Pigmente ref. 11410 - 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>2100 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>250 s</td></tr><tr><td>Comment:</td><td>Peaks attributed to (CNO)Ca<sub>x</sub>O<sub>y</sub><sup>+</sup> are detected for this material. Additional series of peaks are detected, with lower intensity. They can be attributed to PO<sub>2</sub>(CaO)<sub>n</sub> and CNNa(CaO)<sub>n</sub><sup>+</sup> with n = 2–6 and are likely from the eggshell materials.</td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><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">01933-02</td><td>26.005 (56.4)</td><td>CN<sup>-</sup></td><td>Eggshell proteins</td></tr><tr><td>42.001 (48.5)</td><td>CNO<sup>-</sup></td><td>Eggshell proteins</td></tr><tr><td>44.999 (26.2)</td><td>CO<sub>2</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub>/Eggshell materials</td></tr><tr><td>56.965 (–7.63)</td><td>CaOH<sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>59.987 (27.8)</td><td>CO<sub>3</sub><sup>-</sup></td><td>Eggshell materials</td></tr><tr><td>62.966 (28.1)</td><td>PO<sub>2</sub><sup>-</sup></td><td>Eggshell materials/Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>66.002 (51.4)</td><td>C<sub>3</sub>N<sup>-</sup></td><td>Eggshell proteins</td></tr><tr><td>72.964 (45.1)</td><td>CaO<sub>2</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>78.963 (52.2)</td><td>PO<sub>3</sub><sup>-</sup></td><td>Eggshell materials/Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>89.966 (24.8)</td><td>(CaO)(OH)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>90.974 (23.8)</td><td>(CaOH)(OH)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>99.953 (46.2)</td><td>CaCO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>108.974 (14.3)</td><td>CaOH(CN)<sub>2</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>115.946 (23.2)</td><td>CaOCO<sub>3</sub></td><td>CaCO<sub>3</sub></td></tr><tr><td>116.953 (19.7)</td><td>CaOHCO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>117.974 (9.87)</td><td>Ca(CN)<sub>3</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>124.970 (20.6)</td><td>CaO<sub>2</sub>H(CN)<sub>2</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>128.920 (9.25)</td><td>(CaO)<sub>2</sub>(OH)<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>133.970 (14.9)</td><td>CaOC<sub>3</sub>N<sub>3</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>146.931 (14.2)</td><td>H(CaO)<sub>2</sub>(OH)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>149.968 (35.4)</td><td>CaO<sub>2</sub>C<sub>3</sub>N<sub>3</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>173.938 (43.7)</td><td>Ca<sub>2</sub>OC<sub>3</sub>N<sub>3</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>184.881 (25.6)</td><td>Ca<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>202.889 (–2.97)</td><td>H(CaO)<sub>3</sub>(OH)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>240.832 (–6.39)</td><td>Ca<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub></td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><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">01933-02</td><td>26.005 (56.4)</td><td>CN<sup>-</sup></td><td>Eggshell proteins</td></tr><tr><td>42.001 (48.5)</td><td>CNO<sup>-</sup></td><td>Eggshell proteins</td></tr><tr><td>44.999 (26.2)</td><td>CO<sub>2</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub>/Eggshell materials</td></tr><tr><td>56.965 (–7.63)</td><td>CaOH<sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>59.987 (27.8)</td><td>CO<sub>3</sub><sup>-</sup></td><td>Eggshell materials</td></tr><tr><td>62.966 (28.1)</td><td>PO<sub>2</sub><sup>-</sup></td><td>Eggshell materials/Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>66.002 (51.4)</td><td>C<sub>3</sub>N<sup>-</sup></td><td>Eggshell proteins</td></tr><tr><td>72.964 (45.1)</td><td>CaO<sub>2</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>78.963 (52.2)</td><td>PO<sub>3</sub><sup>-</sup></td><td>Eggshell materials/Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>89.966 (24.8)</td><td>(CaO)(OH)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>90.974 (23.8)</td><td>(CaOH)(OH)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>99.953 (46.2)</td><td>CaCO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>108.974 (14.3)</td><td>CaOH(CN)<sub>2</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>115.946 (23.2)</td><td>CaOCO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>116.953 (19.7)</td><td>CaOHCO<sub>3</sub><sup>-</sup></td><td>CaCO<sub>3</sub></td></tr><tr><td>117.974 (9.87)</td><td>Ca(CN)<sub>3</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>124.970 (20.6)</td><td>CaO<sub>2</sub>H(CN)<sub>2</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>128.920 (9.25)</td><td>(CaO)<sub>2</sub>(OH)<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>133.970 (14.9)</td><td>CaOC<sub>3</sub>N<sub>3</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>146.931 (14.2)</td><td>H(CaO)<sub>2</sub>(OH)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>149.968 (35.4)</td><td>CaO<sub>2</sub>C<sub>3</sub>N<sub>3</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>173.938 (43.7)</td><td>Ca<sub>2</sub>OC<sub>3</sub>N<sub>3</sub><sup>-</sup></td><td>Eggshell proteins/CaCO<sub>3</sub></td></tr><tr><td>184.881 (25.6)</td><td>Ca<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>202.889 (–2.97)</td><td>H(CaO)<sub>3</sub>(OH)<sub>2</sub><sup>-</sup></td><td>CaCO<sub>3</sub>/Ca(OH)<sub>2</sub></td></tr><tr><td>240.832 (–6.39)</td><td>Ca<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>CaCO<sub>3</sub></td></tr></tbody></table>
<figure><img src="image_18.png" /></figure>

<table><tr><td>Accession #:</td><td>01933-02</td></tr><tr><td>Specimen:</td><td>Eggshell White - Kremer Pigmente ref. 11410 - 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>2000 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>, CaO<sup>-</sup>, Ca<sub>2</sub>O<sub>3</sub>H<sup>-</sup>, Ca<sub>3</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<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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>250 s</td></tr></table>
<figure><img src="image_18.png" /></figure>

<table><tr><td>Accession #:</td><td>01933-02</td></tr><tr><td>Specimen:</td><td>Eggshell White - Kremer Pigmente ref. 11410 - 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>2000 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>, CaO<sup>-</sup>, Ca<sub>2</sub>O<sub>3</sub>H<sup>-</sup>, Ca<sub>3</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>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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>250 s</td></tr></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="10">01934-01</td><td>23.983 (−51.8)</td><td>Mg<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>64.973 (11.2)</td><td>Mg<sub>2</sub>OH<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>79.946 (52.6)</td><td>CaMgO<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>119.922 (3.37)</td><td>CaMg<sub>2</sub>O<sub>2</sub><sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>135.902 (16.8)</td><td>Ca<sub>2</sub>MgO<sub>2</sub><sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>175.880 (−1.49)</td><td>Ca<sub>2</sub>Mg<sub>2</sub>O<sub>3</sub></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>191.860 (16.7)</td><td>Ca<sub>3</sub>O<sub>2</sub>MgO<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>231.838 (4.73)</td><td>Ca<sub>3</sub>O<sub>2</sub>(MgO)<sub>2</sub><sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>247.818 (12.9)</td><td>Ca<sub>4</sub>O<sub>3</sub>MgO<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="10">01934-01</td><td>23.983 (−51.8)</td><td>Mg<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>64.973 (11.2)</td><td>Mg<sub>2</sub>OH<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>79.946 (52.6)</td><td>CaMgO<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>119.922 (3.37)</td><td>CaMg<sub>2</sub>O<sub>2</sub><sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>135.902 (16.8)</td><td>Ca<sub>2</sub>MgO<sub>2</sub><sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>175.880 (−1.49)</td><td>Ca<sub>2</sub>Mg<sub>2</sub>O<sub>3</sub></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>191.860 (16.7)</td><td>Ca<sub>3</sub>O<sub>2</sub>MgO<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>231.838 (4.73)</td><td>Ca<sub>3</sub>O<sub>2</sub>(MgO)<sub>2</sub><sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>247.818 (12.9)</td><td>Ca<sub>4</sub>O<sub>3</sub>MgO<sup>+</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_19.png" /></figure>

<table><tr><td>Accession #:</td><td>01934-01</td></tr><tr><td>Specimen:</td><td>Dolomite 10 μ – Kremer Pigmente ref. 58740 – 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>2500 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>283 s</td></tr></table>
<figure><img src="image_19.png" /></figure>

<table><tr><td>Accession #:</td><td>01934-01</td></tr><tr><td>Specimen:</td><td>Dolomite 10 μ – Kremer Pigmente ref. 58740 – 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>2500 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>283 s</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="10">01934-02</td><td>59.983 (−31.5)</td><td>CO<sub>3</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>90.974 (28.0)</td><td>(CaOH)(OH)<sub>2</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>99.944 (−35.3)</td><td>CaCO<sub>3</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>116.947 (−31.3)</td><td>CaHCO<sub>4</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>128.914 (−30.0)</td><td>(CaO)<sub>2</sub>(OH)<sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>136.921 (−15.0)</td><td>Ca<sub>2</sub>H(CO)<sub>2</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>152.911 (−47.2)</td><td>Ca<sub>2</sub>OH(CO)<sub>2</sub></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></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="10">01934-02</td><td>59.983 (−31.5)</td><td>CO<sub>3</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>90.974 (28.0)</td><td>(CaOH)(OH)<sub>2</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>99.944 (−35.3)</td><td>CaCO<sub>3</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>116.947 (−31.3)</td><td>CaHCO<sub>4</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>128.914 (−30.0)</td><td>(CaO)<sub>2</sub>(OH)<sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>136.921 (−15.0)</td><td>Ca<sub>2</sub>H(CO)<sub>2</sub><sup>−</sup></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr><tr><td>152.911 (−47.2)</td><td>Ca<sub>2</sub>OH(CO)<sub>2</sub></td><td>CaMg(CO<sub>3</sub>)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_20.png" /></figure>

<table><tr><td>Accession #:</td><td>01934-02</td></tr><tr><td>■ Specimen:</td><td>Dolomite 10 μ – Kremer Pigmente ref. 58740 – 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>2000 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>, CaO<sup>-</sup>, Ca<sub>2</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<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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>283 s</td></tr></table>
<figure><img src="image_20.png" /></figure>

<table><tr><td>Accession #:</td><td>01934-02</td></tr><tr><td>■ Specimen:</td><td>Dolomite 10 μ – Kremer Pigmente ref. 58740 – 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>2000 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>, CaO<sup>-</sup>, Ca<sub>2</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<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 16 nA</td></tr><tr><td>DC Beam Current:</td><td>15.7 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>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>283 s</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="15">01935-01</td><td>64.971 (20.3)</td><td>SO<sub>2</sub>H<sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>71.935 (15.5)</td><td>CaS<sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>87.904 (−8.75)</td><td>Sr<sup>+</sup></td><td>Natural impurities</td></tr><tr><td>87.929 (3.63)</td><td>CaSO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>103.924 (3.64)</td><td>CaSO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>104.909 (7.02)</td><td>SrOH<sup>+</sup></td><td>Natural impurities</td></tr><tr><td>127.895 (29.5)</td><td>Ca<sub>2</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>143.887 (2.22)</td><td>Ca<sub>2</sub>SO<sub>3</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>159.882 (9.09)</td><td>Ca<sub>2</sub>SO<sub>3</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>183.853 (21.2)</td><td>Ca<sub>3</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>239.813 (26.4)</td><td>Ca<sub>4</sub>SO<sub>3</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>255.801 (−2.38)</td><td>Ca<sub>4</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>295.770 (20.1)</td><td>Ca<sub>5</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></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="15">01935-01</td><td>64.971 (20.3)</td><td>SO<sub>2</sub>H<sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>71.935 (15.5)</td><td>CaS<sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>87.904 (−8.75)</td><td>Sr<sup>+</sup></td><td>Natural impurities</td></tr><tr><td>87.929 (3.63)</td><td>CaSO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>103.924 (3.64)</td><td>CaSO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>104.909 (7.02)</td><td>SrOH<sup>+</sup></td><td>Natural impurities</td></tr><tr><td>127.895 (29.5)</td><td>Ca<sub>2</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>143.887 (2.22)</td><td>Ca<sub>2</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>159.882 (9.09)</td><td>Ca<sub>2</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>183.853 (21.2)</td><td>Ca<sub>3</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>239.813 (26.4)</td><td>Ca<sub>4</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>255.801 (−2.38)</td><td>Ca<sub>4</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>295.770 (20.1)</td><td>Ca<sub>5</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr></tbody></table>
<figure><img src="image_21.png" /></figure>

<table><tr><td>Accession #:</td><td>01935-01</td></tr><tr><td>Specimen:</td><td>Anhydrite plaster, burnt gypsum – Kremer Pigmente ref. 58320 – 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>2600 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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><br/>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>The detection of strontium in both gypsum samples is noteworthy, as it is an element found in natural gypsum.⁶ Anhydrite and gypsum share almost identical ToF-SIMS spectra.</td></tr></table>
<figure><img src="image_21.png" /></figure>

<table><tr><td>Accession #:</td><td>01935-01</td></tr><tr><td>Specimen:</td><td>Anhydrite plaster, burnt gypsum – Kremer Pigmente ref. 58320 – 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>2600 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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><br/>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>The detection of strontium in both gypsum samples is noteworthy, as it is an element found in natural gypsum.<sup>6</sup> Anhydrite and gypsum share almost identical ToF-SIMS spectra.</td></tr></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><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">01935-02</td><td>15.995 (−14.9)</td><td>O<sup>−</sup></td><td>–</td></tr><tr><td>31.972 (−6.76)</td><td>S<sup>−</sup></td><td>–</td></tr><tr><td>34.968 (−34.1)</td><td>Cl<sup>−</sup></td><td>Natural impurities</td></tr><tr><td>47.965 (−45.3)</td><td>SO<sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>59.965 (−32.2)</td><td>SiO<sub>2</sub><sup>−</sup></td><td>Natural impurities</td></tr><tr><td>63.964 (31.0)</td><td>SO<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>75.965 (42.2)</td><td>SiO<sub>3</sub><sup>−</sup></td><td>Natural impurities</td></tr><tr><td>79.956 (−11.7)</td><td>SO<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>90.967 (−38.5)</td><td>CaO<sub>3</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>95.948 (−39.7)</td><td>SO<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>103.926 (9.26)</td><td>CaSO<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>119.917 (−21.2)</td><td>CaSO<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>128.919 (3.63)</td><td>Ca<sub>2</sub>O<sub>3</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>135.910 (−33.0)</td><td>CaSO<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>144.898 (15.9)</td><td>SO<sub>2</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>152.915 (−16.9)</td><td>CaSO<sub>5</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>160.896 (32.2)</td><td>SO<sub>3</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>167.882 (−27.5)</td><td>CaS<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>176.891 (32.2)</td><td>SO<sub>4</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>183.876 (−30.1)</td><td>CaS<sub>2</sub>O<sub>5</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>192.875 (−25.2)</td><td>SO<sub>5</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>199.870 (−31.6)</td><td>CaS<sub>2</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>208.865 (34.6)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>4</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>216.859 (−11.1)</td><td>CaHS<sub>3</sub>O<sub>5</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>224.848 (−16.8)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>5</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>232.851 (−24.9)</td><td>CaHS<sub>3</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>240.837 (−41.3)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>6</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>264.821 (−28.9)</td><td>CaHS<sub>4</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>280.820 (−14.4)</td><td>CaOHS<sub>4</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="28">01935-02</td><td>15.995 (−14.9)</td><td>O<sup>−</sup></td><td>–</td></tr><tr><td>31.972 (−6.76)</td><td>S<sup>−</sup></td><td>–</td></tr><tr><td>34.968 (−34.1)</td><td>Cl<sup>−</sup></td><td>Natural impurities</td></tr><tr><td>47.965 (−45.3)</td><td>SO<sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>59.965 (−32.2)</td><td>SiO<sub>2</sub><sup>−</sup></td><td>Natural impurities</td></tr><tr><td>63.964 (31.0)</td><td>SO<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>75.965 (42.2)</td><td>SiO<sub>3</sub><sup>−</sup></td><td>Natural impurities</td></tr><tr><td>79.956 (−11.7)</td><td>SO<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>90.967 (−38.5)</td><td>CaO<sub>3</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>95.948 (−39.7)</td><td>SO<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>103.926 (9.26)</td><td>CaSO<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>119.917 (−21.2)</td><td>CaSO<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>128.919 (3.63)</td><td>Ca<sub>2</sub>O<sub>3</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>135.910 (−33.0)</td><td>CaSO<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>144.898 (15.9)</td><td>SO<sub>2</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>152.915 (−16.9)</td><td>CaSO<sub>5</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>160.896 (32.2)</td><td>SO<sub>3</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>167.882 (−27.5)</td><td>CaS<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>176.891 (32.2)</td><td>SO<sub>4</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>183.876 (−30.1)</td><td>CaS<sub>2</sub>O<sub>5</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>192.875 (−25.2)</td><td>SO<sub>5</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>199.870 (−31.6)</td><td>CaS<sub>2</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>208.865 (34.6)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>4</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>216.859 (−11.1)</td><td>CaHS<sub>3</sub>O<sub>5</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>224.848 (−16.8)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>5</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>232.851 (−24.9)</td><td>CaHS<sub>3</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>240.837 (−41.3)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>6</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>264.821 (−28.9)</td><td>CaHS<sub>4</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>280.820 (−14.4)</td><td>CaOHS<sub>4</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr></tbody></table>
<figure><img src="image_22.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01935-02</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Anhydrite plaster, burnt gypsum – Kremer Pigmente ref. 58320 – 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>2400 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>, CaO<sub>2</sub>H<sup>-</sup>, Ca<sub>2</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>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>Anhydrite and gypsum share almost identical ToF-SIMS spectra.</td></tr></tbody></table>
<figure><img src="image_22.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01935-02</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Anhydrite plaster, burnt gypsum – Kremer Pigmente ref. 58320 – 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>2400 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>, CaO<sub>2</sub>H<sup>-</sup>, Ca<sub>2</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>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>Anhydrite and gypsum share almost identical ToF-SIMS spectra.</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="14">01936-01</td><td>64.970 (14.3)</td><td>SO<sub>2</sub>H<sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>71.935 (12.3)</td><td>CaS<sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>87.906 (12.5)</td><td>Sr<sup>+</sup></td><td>Natural impurities</td></tr><tr><td>87.929 (−3.64)</td><td>CaSO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>103.923 (−11.6)</td><td>CaSO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>104.910 (20.7)</td><td>SrOH<sup>+</sup></td><td>Natural impurities</td></tr><tr><td>127.895 (25.8)</td><td>Ca<sub>2</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>143.887 (13.7)</td><td>Ca<sub>2</sub>SO<sub>3</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>159.884 (13.4)</td><td>Ca<sub>2</sub>SO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>183.853 (20.5)</td><td>Ca<sub>3</sub>SO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>239.812 (20.2)</td><td>Ca<sub>4</sub>SO<sub>3</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>255.806 (16.8)</td><td>Ca<sub>4</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>295.772 (26.6)</td><td>Ca<sub>5</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></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="15">01936-01</td><td>64.970 (14.3)</td><td>SO<sub>2</sub>H<sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>71.935 (12.3)</td><td>CaS<sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>87.906 (12.5)</td><td>Sr<sup>+</sup></td><td>Natural impurities</td></tr><tr><td>87.929 (−3.64)</td><td>CaSO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>103.923 (−11.6)</td><td>CaSO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>104.910 (20.7)</td><td>SrOH<sup>+</sup></td><td>Natural impurities</td></tr><tr><td>127.895 (25.8)</td><td>Ca<sub>2</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>143.887 (13.7)</td><td>Ca<sub>2</sub>SO<sub>3</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>159.884 (13.4)</td><td>Ca<sub>2</sub>SO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>183.853 (20.5)</td><td>Ca<sub>3</sub>SO<sub>2</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>239.812 (20.2)</td><td>Ca<sub>4</sub>SO<sub>3</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>255.806 (16.8)</td><td>Ca<sub>4</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>295.772 (26.6)</td><td>Ca<sub>5</sub>SO<sub>4</sub><sup>+</sup></td><td>CaSO<sub>4</sub></td></tr></tbody></table>
<figure><img src="image_23.png" /></figure>

<table><tr><td>Accession #:</td><td>01936-01</td></tr><tr><td>Specimen:</td><td>Natural alabaster plaster – Kremer Pigmente ref. 58340 – 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>2700 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>The detection of strontium in both gypsum samples is noteworthy, as it is an element found in natural gypsum.<sup>6</sup> Anhydrite and gypsum share almost identical TOF-SIMS spectra.</td></tr></table>
<figure><img src="image_23.png" /></figure>

<table><tr><td>Accession #:</td><td>01936-01</td></tr><tr><td>Specimen:</td><td>Natural alabaster plaster – Kremer Pigmente ref. 58340 – 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>2700 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>Na<sup>+</sup>, Ca<sup>+</sup>, CaO<sup>+</sup>, Ca<sub>2</sub>O<sup>+</sup>, Ca<sub>3</sub>O<sub>2</sub><sup>+</sup>, Ca<sub>4</sub>O<sub>3</sub><sup>+</sup>, Ca<sub>5</sub>O<sub>4</sub><sup>+</sup>, Ca<sub>6</sub>O<sub>5</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>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>The detection of strontium in both gypsum samples is noteworthy, as it is an element found in natural gypsum.<sup>6</sup> Anhydrite and gypsum share almost identical TOF-SIMS spectra.</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="28">01936-02</td><td>15.995 (–7.16)</td><td>O<sup>−</sup></td><td>–</td></tr><tr><td>31.972 (–25.2)</td><td>S<sup>−</sup></td><td>–</td></tr><tr><td>34.968 (–44.1)</td><td>Cl<sup>−</sup></td><td>Natural impurities</td></tr><tr><td>47.965 (–47.8)</td><td>SO<sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>59.966 (–27.1)</td><td>SiO<sub>2</sub><sup>−</sup></td><td>Natural impurities</td></tr><tr><td>63.963 (15.6)</td><td>SO<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>75.965 (30.0)</td><td>SiO<sub>3</sub><sup>−</sup></td><td>Natural impurities</td></tr><tr><td>79.955 (–25.7)</td><td>SO<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>90.968 (–33.0)</td><td>CaO<sub>3</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>95.948 (–41.0)</td><td>SO<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>103.923 (–19.5)</td><td>CaSO<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>119.916 (–29.8)</td><td>CaSO<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>128.918 (–1.46)</td><td>Ca<sub>2</sub>O<sub>3</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>135.909 (–39.0)</td><td>CaSO<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>144.896 (5.45)</td><td>SO<sub>2</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>152.915 (–15.2)</td><td>CaSO<sub>5</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>160.896 (35.5)</td><td>SO<sub>3</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>167.880 (–38.4)</td><td>CaS<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>176.888 (13.6)</td><td>SO<sub>4</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>183.874 (–38.3)</td><td>CaS<sub>2</sub>O<sub>5</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>192.875 (–21.5)</td><td>SO<sub>5</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>199.871 (–24.0)</td><td>CaS<sub>2</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>208.862 (22.0)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>4</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>216.858 (–15.6)</td><td>CaHS<sub>3</sub>O<sub>5</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>224.853 (1.88)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>5</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>232.851 (–18.6)</td><td>CaHS<sub>3</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>240.841 (–22.0)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>6</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>264.822 (–24.7)</td><td>CaHS<sub>4</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>280.820 (3.40)</td><td>CaOHS<sub>4</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></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="28">01936-02</td><td>15.995 (−7.16)</td><td>O<sup>−</sup></td><td>–</td></tr><tr><td>31.972 (−25.2)</td><td>S<sup>−</sup></td><td>–</td></tr><tr><td>34.968 (−44.1)</td><td>Cl<sup>−</sup></td><td>Natural impurities</td></tr><tr><td>47.965 (−47.8)</td><td>SO<sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>59.966 (−27.1)</td><td>SiO<sub>2</sub><sup>−</sup></td><td>Natural impurities</td></tr><tr><td>63.963 (15.6)</td><td>SO<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>75.965 (30.0)</td><td>SiO<sub>3</sub><sup>−</sup></td><td>Natural impurities</td></tr><tr><td>79.955 (−25.7)</td><td>SO<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>90.968 (−33.0)</td><td>CaO<sub>3</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>95.948 (−41.0)</td><td>SO<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>103.923 (−19.5)</td><td>CaSO<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>119.916 (−29.8)</td><td>CaSO<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>128.918 (−1.46)</td><td>Ca<sub>2</sub>O<sub>3</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>135.909 (−39.0)</td><td>CaSO<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>144.896 (5.45)</td><td>SO<sub>2</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>152.915 (−15.2)</td><td>CaSO<sub>5</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>160.896 (35.5)</td><td>SO<sub>3</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>167.880 (−38.4)</td><td>CaS<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>176.888 (13.6)</td><td>SO<sub>4</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>183.874 (−38.3)</td><td>CaS<sub>2</sub>O<sub>5</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>192.875 (−21.5)</td><td>SO<sub>5</sub>HCa<sub>2</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>199.871 (−24.0)</td><td>CaS<sub>2</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>208.862 (22.0)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>4</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>216.858 (−15.6)</td><td>CaHS<sub>3</sub>O<sub>5</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>224.853 (1.88)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>5</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>232.851 (−18.6)</td><td>CaHS<sub>3</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>240.841 (−22.0)</td><td>Ca<sub>2</sub>S<sub>2</sub>O<sub>6</sub>H<sub>3</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>264.822 (−24.7)</td><td>CaHS<sub>4</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr><tr><td>280.820 (3.40)</td><td>CaOHS<sub>4</sub>O<sub>6</sub><sup>−</sup></td><td>CaSO<sub>4</sub></td></tr></tbody></table>
<figure><img src="image_24.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01936-02</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Natural alabaster plaster - Kremer Pigmente ref. 58340 - 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>2400 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>, CaO<sub>2</sub>H<sup>-</sup>, Ca<sub>2</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<sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>Anhydrite and gypsum share almost identical ToF-SIMS spectra.</td></tr></tbody></table>
<figure><img src="image_24.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01936-02</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Natural alabaster plaster - Kremer Pigmente ref. 58340 - 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>2400 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>, CaO<sub>2</sub>H<sup>-</sup>, Ca<sub>2</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<sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.34 × 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 21 nA</td></tr><tr><td>DC Beam Current:</td><td>14.6 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>210 s</td></tr><tr><td>Comment:</td><td>Anhydrite and gypsum share almost identical ToF-SIMS spectra.</td></tr></tbody></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 rowspan="15">All</td><td>39.96 (13.4)</td><td>Ca<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>56.94 (8.77)</td><td>CaOH<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>95.92 (11.0)</td><td>Ca<sub>2</sub>O<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>111.92 (13.4)</td><td>Ca<sub>2</sub>O<sub>2</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>112.93 (13.4)</td><td>Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>151.879 (13.1)</td><td>Ca<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>167.874 (7.62)</td><td>Ca<sub>3</sub>O<sub>3</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>168.882 (11.1)</td><td>Ca<sub>3</sub>O<sub>3</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>207.836 (7.75)</td><td>Ca<sub>4</sub>O<sub>3</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>223.831 (11.3)</td><td>Ca<sub>4</sub>O<sub>4</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>224.84 (11.7)</td><td>Ca<sub>4</sub>O<sub>4</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>263.79 (11.3)</td><td>Ca<sub>5</sub>O<sub>4</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>279.79 (9.29)</td><td>Ca<sub>5</sub>O<sub>5</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>280.79 (12.0)</td><td>Ca<sub>5</sub>O<sub>5</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>319.75 (6.54)</td><td>Ca<sub>6</sub>O<sub>5</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>335.74 (13.3)</td><td>Ca<sub>6</sub>O<sub>6</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>336.75 (12.1)</td><td>Ca<sub>6</sub>O<sub>6</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>375.71 (5.43)</td><td>Ca<sub>7</sub>O<sub>6</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>391.73 (2.18)</td><td>Ca<sub>7</sub>O<sub>7</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>392.72 (21.1)</td><td>Ca<sub>7</sub>O<sub>7</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr></tbody></table>

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

<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 rowspan="2">All</td><td>55.96 (11.0)</td><td>CaO<sup>-</sup></td><td>All white pigments containing calcium</td></tr><tr><td>71.96 (20.9)</td><td>CaO<sub>2</sub><sup>-</sup></td><td>All white pigments containing calcium</td></tr></tbody></table>

(Mean absolute deviation values are given for the mass deviations.)
<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 rowspan="15">All</td><td>39.96 (13.4)</td><td>Ca<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>56.94 (8.77)</td><td>CaOH<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>95.92 (11.0)</td><td>Ca<sub>2</sub>O<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>111.92 (13.4)</td><td>Ca<sub>2</sub>O<sub>2</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>112.93 (13.4)</td><td>Ca<sub>2</sub>O<sub>2</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>151.879 (13.1)</td><td>Ca<sub>3</sub>O<sub>2</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>167.874 (7.62)</td><td>Ca<sub>3</sub>O<sub>3</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>168.882 (11.1)</td><td>Ca<sub>3</sub>O<sub>3</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>207.836 (7.75)</td><td>Ca<sub>4</sub>O<sub>3</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>223.831 (11.3)</td><td>Ca<sub>4</sub>O<sub>4</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>224.84 (11.7)</td><td>Ca<sub>4</sub>O<sub>4</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>263.79 (11.3)</td><td>Ca<sub>5</sub>O<sub>4</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>279.79 (9.29)</td><td>Ca<sub>5</sub>O<sub>5</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>280.79 (12.0)</td><td>Ca<sub>5</sub>O<sub>5</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>319.75 (6.54)</td><td>Ca<sub>6</sub>O<sub>5</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>335.74 (13.3)</td><td>Ca<sub>6</sub>O<sub>6</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>336.75 (12.1)</td><td>Ca<sub>6</sub>O<sub>6</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>375.71 (5.43)</td><td>Ca<sub>7</sub>O<sub>6</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>391.73 (2.18)</td><td>Ca<sub>7</sub>O<sub>7</sub><sup>+</sup></td><td>All white pigments containing calcium</td></tr><tr><td>392.72 (21.1)</td><td>Ca<sub>7</sub>O<sub>7</sub>H<sup>+</sup></td><td>All white pigments containing calcium</td></tr></tbody></table>

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

<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 rowspan="2">All</td><td>55.96 (11.0)</td><td>CaO<sup>-</sup></td><td>All white pigments containing calcium</td></tr><tr><td>71.96 (20.9)</td><td>CaO<sub>2</sub><sup>-</sup></td><td>All white pigments containing calcium</td></tr></tbody></table>

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