# ToF-SIMS spectra of historical inorganic pigments: Lead-based pigments in negative polarity

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: Lead-based pigments in negative polarity. Surface Science Spectra, 2024, 31 (1), pp.015005. 10.1116/6.0003507. hal-04595993

HAL Id: hal-04595993

https://hal.science/hal-04595993

Submitted on 31 May 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.

<figure><img src="image_1.png" /></figure>

Distributed under a Creative Commons Attribution 4.0 International License
RESEARCH ARTICLE | MAY 30 2024

# ToF-SIMS spectra of historical inorganic pigments: Lead-based pigments in negative polarity

Special Collection: ToF-SIMS Spectra of Historical Inorganic Pigments

Caroline Bouvier ; Sebastiaan Van Nuffel ; Alain Brunelle

<figure><img src="image_1.png" /></figure>

Check for updates

Surf. Sci. Spectra 31, 015005 (2024)

https://doi.org/10.1116/6.0003560

<figure><img src="image_2.png" /></figure>

View
Online

<figure><img src="image_3.png" /></figure>

Export
Citation

<figure><img src="image_4.png" /></figure>

<figure><img src="image_5.png" /></figure>

<figure><img src="image_6.png" /></figure>

<figure><img src="image_7.png" /></figure>
# ToF-SIMS spectra of historical inorganic pigments: Lead-based pigments in negative polarity

Special Collection: ToF-SIMS Spectra of Historical Inorganic Pigments

Caroline Bouvier ; Sebastiaan Van Nuffel ; Alain Brunelle

<figure><img src="image_2.png" /></figure>

Check for updates

Surf. Sci. Spectra 31, 015005 (2024)

https://doi.org/10.1116/6.0003560

<figure><img src="image_3.png" /></figure>

View
Online

<figure><img src="image_4.png" /></figure>

Export
Citation

<figure><img src="image_5.png" /></figure>

<figure><img src="image_6.png" /></figure>

<figure><img src="image_7.png" /></figure>

<figure><img src="image_8.png" /></figure>
# ToF-SIMS spectra of historical inorganic pigments: Lead-based pigments in negative polarity

Cite as: Surf. Sci. Spectra 31, 015005 (2024); doi: 10.1116/6.0003560

Submitted: 20 February 2024 · Accepted: 13 May 2024 ·

Published Online: 30 May 2024

<figure><img src="image_8.png" /></figure>

View Online

<figure><img src="image_9.png" /></figure>

Export Citation

<figure><img src="image_10.png" /></figure>

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

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 eight lead-based historical inorganic pigments, manufactured following traditional recipes. Lead pigments have been widely used in painting until the late 19th century. Here, the negative polarity ToF-SIMS reference spectra using a Bi₃⁺ primary ion species are presented.

© 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/10.1116/6.0003560

**Accession #:** 01919, 01920, 01921, 01922, 01923, 01924, 01925, 01926

**Technique:** SIMS

**Specimen:** Lead tin yellow I, Naples yellow, Lead white, Flake white 10 µm, Flake white, Cerussite, Minium, Litharge

**Instrument:** IONTOF, TOF SIMS IV

**Major Species in Spectra:** O, H, Si, S, Al, C, Na, Pb, K, Cl, Sb, Sn

**Minor Species in Spectra:** Hydrocarbon contamination

**Published Spectra:** 8

**Spectral Category:** Reference

## INTRODUCTION

ToF-SIMS imaging can detect a wide range of elements, so colored minerals can be identified and mapped, given that reference spectra are available for reliable assignment. Here, we provide a ToF-SIMS spectral database for eight lead-based inorganic pigments. Lead-based pigments have been commonly used in all painting techniques until the late 19th century and, therefore, are very likely to be found when analyzing a historical painting sample. In particular, the pigment generally referred to as “lead white” can have various compositions depending on the manufacturing process, and this paper compares a selection of them (namely, #01921, #01922, #01923, and #01924). For each, a list of their fragmentation products is given.

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

possible, such as Kremer Pigmente GmbH, Master 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) 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

<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 6229EN, The Netherlands</footnote>
# ToF-SIMS spectra of historical inorganic pigments: Lead-based pigments in negative polarity

Cite as: Surf. Sci. Spectra 31, 015005 (2024); doi: 10.1116/6.0003560

Submitted: 20 February 2024 · Accepted: 13 May 2024 ·

Published Online: 30 May 2024

<figure><img src="image_9.png" /></figure>

View Online

<figure><img src="image_10.png" /></figure>

Export Citation

<figure><img src="image_11.png" /></figure>

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

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 eight lead-based historical inorganic pigments, manufactured following traditional recipes. Lead pigments have been widely used in painting until the late 19th century. Here, the negative polarity ToF-SIMS reference spectra using a Bi₃⁺ primary ion species are presented.

© 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/10.1116/6.0003560

**Accession #:** 01919, 01920, 01921, 01922, 01923, 01924, 01925, 01926

**Technique:** SIMS

**Specimen:** Lead tin yellow I, Naples yellow, Lead white, Flake white 10 µm, Flake white, Cerussite, Minium, Litharge

**Instrument:** IONTOF, TOF SIMS IV

**Major Species in Spectra:** O, H, Si, S, Al, C, Na, Pb, K, Cl, Sb, Sn

**Minor Species in Spectra:** Hydrocarbon contamination

**Published Spectra:** 8

**Spectral Category:** Reference

## INTRODUCTION

ToF-SIMS imaging can detect a wide range of elements, so colored minerals can be identified and mapped, given that reference spectra are available for reliable assignment. Here, we provide a ToF-SIMS spectral database for eight lead-based inorganic pigments. Lead-based pigments have been commonly used in all painting techniques until the late 19th century and, therefore, are very likely to be found when analyzing a historical painting sample. In particular, the pigment generally referred to as “lead white” can have various compositions depending on the manufacturing process, and this paper compares a selection of them (namely, #01921, #01922, #01923, and #01924). For each, a list of their fragmentation products is given.

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

possible, such as Kremer Pigmente GmbH, Master 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) 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

<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 6229EN, The Netherlands</footnote>
with clean aluminum foil was applied onto the powder to fix it to the tape. This allowed us to minimize the risk of dust formation when operating in the analysis chamber under ultrahigh vacuum ($10^{-8}$ to $10^{-9}$ hPa) while ensuring a flat surface.

All spectra were obtained on an IONTOF TOF SIMS IV equipped with a 25 keV bismuth liquid metal ion gun (LMIG) and an Argon gas cluster ion beam (GCIB). Before all analyses, a $500 \times 500 \ \mu m^2$ surface was cleaned using 1500-2000 Ar clusters with a kinetic energy of 20 keV (sputter ion dose $2 \times 10^{15}$ ions/cm²). Analyses were then performed on a $250 \times 250 \ \mu m^2$ area rastered over $128 \times 128$ pixels using the high current bunched mode. Primary ion dose (25 keV $Bi_3^+$) was $4.35 \times 10^{11}$ ions/cm². Surface potential was compensated.

Data were calibrated using a set of peaks appearing in all spectra, namely, the peaks $O_2^-$ at m/z 31.99, $Cl^-$ at m/z 34.97, $PbO_2H^-$ at m/z 241.98, and $^{206}\text{PbPbO}_3H^-$ at m/z 462.94, as well as $^{206}\text{PbPb}_2\text{O}_4H^-$ at m/z 686.94 for all data except #01919. This calibration list allowed for a complete coverage of the mass range of interest, and the lead-containing calibration ions could easily be verified using their isotopic pattern.

Figures and tables presented below contain the major monoisotopic peaks for negative polarity. Sn, Sb, and Pb clusters have isotopic patterns with often more than 5-10 peaks and all of them should be present for accurate identification. Full data are available within the supplementary material. 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# refer to that number.

## SPECIMEN DESCRIPTION (ACCESSION # 01919)

**Specimen:** Lead Tin Yellow I (Kremer Pigmente ref. 10100)

**CAS Registry #:** 12143-43-0

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

**Chemical Name:** Lead stannate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Pb_2SnO_4$

**Form:** Ground pigment powder

**History and Significance:** A light-yellow pigment that was widely used in oil painting from the Middle Ages to the dawn of the 19th century. Prohibited today because of its lead content.

**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/cm²

## SPECIMEN DESCRIPTION (ACCESSION # 01920)

**Specimen:** Naples Yellow (Kremer Pigmente ref. 43130)

**CAS Registry #:** 13510-89-9

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

**Chemical Name:** Lead antimonate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Pb_2Sb_2O_7$ [and $Pb_3(SbO_4)_2$]

**Form:** Ground pigment powder

**History and Significance:** A yellow pigment used on Renaissance palettes, which is synthesized by heating a lead compound (oxide or nitrate) with an antimony compound (oxide, sulfide, or potassium antimonate). Particle size is in the micrometer range.

**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/cm²

## SPECIMEN DESCRIPTION (ACCESSION # 01921, 01922, 01923, 01924)

**Specimen:** (Accession #01921) Lead white (Kremer Pigmente ref. 46000), (Accession #01922) Flake white $10 \ \mu m$ (Masters Pigments ref. 901010), (Accession #01923) Flake white (Sennelier PW no.108), (Accession #01924) Cerussite (Masters Pigments ref. 951010)

**CAS Registry #:** (Accession #01921, #01924) 598-63-0, (Accession #01922, #01923) 1319-46-6

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

**Chemical Name:** (Accession #01921, #01924) Lead (II) carbonate, synth., (Accession #01922, #01923) Lead (II) carbonate, basic

**Source:** (Accession #01921) Kremer Pigmente GmbH, (Accession #01922, #01924) Masters Pigments, USA, (Accession #01923) Sennelier, France

**Specimen Composition:** (Accession #01921, #01924) $PbCO_3$, (Accession #01922, #01923) $2PbCO_3 \cdot Pb(OH)_2$

**Form:** Ground pigment powder
with clean aluminum foil was applied onto the powder to fix it to the tape. This allowed us to minimize the risk of dust formation when operating in the analysis chamber under ultrahigh vacuum ($10^{-8}$ to $10^{-9}$ hPa) while ensuring a flat surface.

All spectra were obtained on an IONTOF TOF SIMS IV equipped with a 25 keV bismuth liquid metal ion gun (LMIG) and an Argon gas cluster ion beam (GCIB). Before all analyses, a $500 \times 500 \ \mu m^2$ surface was cleaned using 1500–2000 Ar clusters with a kinetic energy of 20 keV (sputter ion dose $2 \times 10^{15}$ ions/cm²). Analyses were then performed on a $250 \times 250 \ \mu m^2$ area rastered over $128 \times 128$ pixels using the high current bunched mode. Primary ion dose (25 keV $Bi_3^+$) was $4.35 \times 10^{11}$ ions/cm². Surface potential was compensated.

Data were calibrated using a set of peaks appearing in all spectra, namely, the peaks $O_2^-$ at m/z 31.99, $Cl^-$ at m/z 34.97, $PbO_2H^-$ at m/z 241.98, and $^{206}\text{PbPbO}_3H^-$ at m/z 462.94, as well as $^{206}\text{PbPb}_2\text{O}_4H^-$ at m/z 686.94 for all data except #01919. This calibration list allowed for a complete coverage of the mass range of interest, and the lead-containing calibration ions could easily be verified using their isotopic pattern.

Figures and tables presented below contain the major monoisotopic peaks for negative polarity. Sn, Sb, and Pb clusters have isotopic patterns with often more than 5–10 peaks and all of them should be present for accurate identification. Full data are available within the supplementary material. 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# refer to that number.

## SPECIMEN DESCRIPTION (ACCESSION # 01919)

**Specimen:** Lead Tin Yellow I (Kremer Pigmente ref. 10100)

**CAS Registry #:** 12143-43-0

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

**Chemical Name:** Lead stannate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Pb_2SnO_4$

**Form:** Ground pigment powder

**History and Significance:** A light-yellow pigment that was widely used in oil painting from the Middle Ages to the dawn of the 19th century. Prohibited today because of its lead content.

**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/cm²

## SPECIMEN DESCRIPTION (ACCESSION # 01920)

**Specimen:** Naples Yellow (Kremer Pigmente ref. 43130)

**CAS Registry #:** 13510-89-9

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

**Chemical Name:** Lead antimonate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Pb_2Sb_2O_7$ [and $Pb_3(SbO_4)_2$]

**Form:** Ground pigment powder

**History and Significance:** A yellow pigment used on Renaissance palettes, which is synthesized by heating a lead compound (oxide or nitrate) with an antimony compound (oxide, sulfide, or potassium antimonate). Particle size is in the micrometer range.

**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/cm²

## SPECIMEN DESCRIPTION (ACCESSION # 01921, 01922, 01923, 01924)

**Specimen:** (Accession #01921) Lead white (Kremer Pigmente ref. 46000), (Accession #01922) Flake white $10 \ \mu m$ (Masters Pigments ref. 901010), (Accession #01923) Flake white (Sennelier PW no.108), (Accession #01924) Cerussite (Masters Pigments ref. 951010)

**CAS Registry #:** (Accession #01921, #01924) 598-63-0, (Accession #01922, #01923) 1319-46-6

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

**Chemical Name:** (Accession #01921, #01924) Lead (II) carbonate, synth., (Accession #01922, #01923) Lead (II) carbonate, basic

**Source:** (Accession #01921) Kremer Pigmente GmbH, (Accession #01922, #01924) Masters Pigments, USA, (Accession #01923) Sennelier, France

**Specimen Composition:** (Accession #01921, #01924) $PbCO_3$, (Accession #01922, #01923) $2PbCO_3 \cdot Pb(OH)_2$

**Form:** Ground pigment powder
**History and Significance:** The most widely used white pigment was progressively replaced during the beginning of the 20th century with newly available less toxic alternatives. A mixture of cerussite (lead carbonate) and hydrocerussite (basic lead carbonate) with proportions varying according to the manufacturing process can inform about the origin of the pigment. It is synthesized using lead strips, vinegar, CO₂, and heat. The latter two are usually provided by a fermenting material. In the presence of acetic acid vapors, the lead surface corrodes to lead acetate, which is then converted to basic lead carbonate in the presence of CO₂. This stable process has been used over centuries, and its origins date back to Ancient Greece and China. It was also used as a cosmetic since ancient times.

**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/cm²

## SPECIMEN DESCRIPTION (ACCESSION # 01925)

**Specimen:** Minium/Red Lead (Kremer Pigmente ref. 42500)

**CAS Registry #:** 1314-41-6

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

**Chemical Name:** Lead tetraoxide

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Pb_3O_4$

**Form:** Ground pigment powder

**History and Significance:** This naturally occurring lead oxide has been synthesized since early times by heating lead carbonates. Its color approaches that of cinnabar, providing a cheaper alternative. Used since ancient Greek times as a rust inhibitor for metals, it remained its main use in the 20th century until it was banned in the 1990s.

**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/cm²

## SPECIMEN DESCRIPTION (ACCESSION # 01926)

**Specimen:** Massicot, Litharge (Kremer Pigmente ref. 43010)

**CAS Registry #:** 1317-36-8

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

**Chemical Name:** Lead (II) oxide

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** PbO

**Form:** Ground pigment powder

**History and Significance:** Litharge and massicot are lead monoxide polymorphs with the formula PbO, respectively, red and yellow orange in appearance. They are both formed by heating lead or lead white. Litharge plays a key role in the preparation of drying oil for painting: when mixed, it accelerates polymerization of the film.

**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/cm²

## 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
**History and Significance:** The most widely used white pigment was progressively replaced during the beginning of the 20th century with newly available less toxic alternatives. A mixture of cerussite (lead carbonate) and hydrocerussite (basic lead carbonate) with proportions varying according to the manufacturing process can inform about the origin of the pigment. It is synthesized using lead strips, vinegar, CO₂, and heat. The latter two are usually provided by a fermenting material. In the presence of acetic acid vapors, the lead surface corrodes to lead acetate, which is then converted to basic lead carbonate in the presence of CO₂. This stable process has been used over centuries, and its origins date back to Ancient Greece and China. It was also used as a cosmetic since ancient times.

**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/cm²

## SPECIMEN DESCRIPTION (ACCESSION # 01925)

**Specimen:** Minium/Red Lead (Kremer Pigmente ref. 42500)

**CAS Registry #:** 1314-41-6

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

**Chemical Name:** Lead tetraoxide

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Pb_3O_4$

**Form:** Ground pigment powder

**History and Significance:** This naturally occurring lead oxide has been synthesized since early times by heating lead carbonates. Its color approaches that of cinnabar, providing a cheaper alternative. Used since ancient Greek times as a rust inhibitor for metals, it remained its main use in the 20th century until it was banned in the 1990s.

**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/cm²

## SPECIMEN DESCRIPTION (ACCESSION # 01926)

**Specimen:** Massicot, Litharge (Kremer Pigmente ref. 43010)

**CAS Registry #:** 1317-36-8

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

**Chemical Name:** Lead (II) oxide

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** PbO

**Form:** Ground pigment powder

**History and Significance:** Litharge and massicot are lead monoxide polymorphs with the formula PbO, respectively, red and yellow orange in appearance. They are both formed by heating lead or lead white. Litharge plays a key role in the preparation of drying oil for painting: when mixed, it accelerates polymerization of the film.

**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/cm²

## 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): 0̂

■ Ion Sources

Ion Source 1 of 2

Purpose of This Ion Source: Analysis beam

Ion Source Manufacturer: IONTOF GmbH

Ion Source Model: LMIG with bismuth cluster (25 keV)

Beam Mass Filter: Yes

Beam Species and Charge State: Bi<fnref n="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: Argon GCIB

Beam Mass Filter: Yes

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

Beam Gating Used: Wien filter

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

Beam Voltage: 20 000 eV

Net Beam Voltage (impact voltage): 20 000 eV

Ion Pulse Width: N/A

Ion Pulse Rate: N/A

DC Beam Current: ~10 nA

Pulsed Beam Current: N/A

Current Measurement Method: Faraday cup

Beam Diameter: ~50 µm

Beam Raster Size: 500 × 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 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* (Archetype Publications, London, 1986), Vol. 1.</footnote>

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

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

<footnote n="5">⁵J. R. Barnett, S. Miller, and E. Pearce, *Opt. Laser Technol.* **38**, 445 (2006).</footnote>
Specimen Normal-to-Analyzer (Θe): 0̂

■ Ion Sources

Ion Source 1 of 2

Purpose of This Ion Source: Analysis beam

Ion Source Manufacturer: IONTOF GmbH

Ion Source Model: LMIG with bismuth cluster (25 keV)

Beam Mass Filter: Yes

Beam Species and Charge State: Bi<fnref n="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: Argon GCIB

Beam Mass Filter: Yes

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

Beam Gating Used: Wien filter

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

Beam Voltage: 20 000 eV

Net Beam Voltage (impact voltage): 20 000 eV

Ion Pulse Width: N/A

Ion Pulse Rate: N/A

DC Beam Current: ~10 nA

Pulsed Beam Current: N/A

Current Measurement Method: Faraday cup

Beam Diameter: ~50 µm

Beam Raster Size: 500 × 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 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* (Archetype Publications, London, 1986), Vol. 1.</footnote>

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

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

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

Lead Tin Yellow I—Kremer Pigmente ref. 10100—Negative polarity

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01919-01</td><td>119.900 (−25.6)</td><td>Sn<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>135.898 (5.42)</td><td>SnO<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>151.896 (22.0)</td><td>SnO<sub>2</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>167.890 (14.0)</td><td>SnO<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>168.899 (21.6)</td><td>SnO<sub>3</sub>H<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>223.974 (9.20)</td><td>PbO<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>239.966 (6.39)</td><td>PbO<sub>2</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>255.956 (−23.7)</td><td>PbO<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>271.801 (22.0)</td><td>Sn<sub>2</sub>O<sub>2</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>287.798 (29.4)</td><td>Sn<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>303.792 (22.9)</td><td>Sn<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>359.877 (21.6)</td><td>PbO<sub>2</sub>Sn<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>375.875 (28.5)</td><td>PbO<sub>3</sub>Sn<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>423.702 (35.7)</td><td>Sn<sub>3</sub>O<sub>4</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>439.688 (14.6)</td><td>Sn<sub>3</sub>O<sub>5</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>463.940 (3.85)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>511.783 (41.8)</td><td>PbOSn<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>527.777 (40.3)</td><td>PbOSn<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>583.860 (32.4)</td><td>Pb<sub>2</sub>OSnO<sub>2</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>599.853 (29.6)</td><td>Pb<sub>2</sub>OSnO<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr></tbody></table>
SPECTRAL FEATURES TABLE

Lead Tin Yellow I—Kremer Pigmente ref. 10100—Negative polarity

<table><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01919-01</td><td>119.900 (−25.6)</td><td>Sn<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>135.898 (5.42)</td><td>SnO<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>151.896 (22.0)</td><td>SnO<sub>2</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>167.890 (14.0)</td><td>SnO<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>168.899 (21.6)</td><td>SnO<sub>3</sub>H<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>223.974 (9.20)</td><td>PbO<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>239.966 (6.39)</td><td>PbO<sub>2</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>255.956 (−23.7)</td><td>PbO<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>271.801 (22.0)</td><td>Sn<sub>2</sub>O<sub>2</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>287.798 (29.4)</td><td>Sn<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>303.792 (22.9)</td><td>Sn<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>359.877 (21.6)</td><td>PbO<sub>2</sub>Sn<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>375.875 (28.5)</td><td>PbO<sub>3</sub>Sn<sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>423.702 (35.7)</td><td>Sn<sub>3</sub>O<sub>4</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>439.688 (14.6)</td><td>Sn<sub>3</sub>O<sub>5</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>463.940 (3.85)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>511.783 (41.8)</td><td>PbOSn<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>527.777 (40.3)</td><td>PbOSn<sub>2</sub>O<sub>4</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>583.860 (32.4)</td><td>Pb<sub>2</sub>OSnO<sub>2</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr><tr><td>599.853 (29.6)</td><td>Pb<sub>2</sub>OSnO<sub>3</sub><sup>−</sup></td><td>Pb<sub>2</sub>SnO<sub>4</sub></td></tr></tbody></table>
<figure><img src="image_11.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01919-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Lead Tin Yellow I—Kremer Pigmente ref. 10100</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>2800 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<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>14.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>207 s</td></tr><tr><td>Comment:</td><td>Distinctive isotopic pattern for Sn-containing ions</td></tr></tbody></table>
<figure><img src="image_12.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01919-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Lead Tin Yellow I—Kremer Pigmente ref. 10100</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>2800 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<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>14.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>207 s</td></tr><tr><td>Comment:</td><td>Distinctive isotopic pattern for Sn-containing ions</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">01920-01</td><td>58.972 (8.57)</td><td>AlO<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>59.970 (40.5)</td><td>SiO<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>75.975 (−2.10)</td><td>AlO<sub>3</sub>H<sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>76.983 (9.38)</td><td>AlO<sub>3</sub>H<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>79.960 (36.9)</td><td>SO<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>118.943 (37.9)</td><td>AlSiO<sub>4</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>136.898 (−12.6)</td><td>SbO<sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>152.899 (29.0)</td><td>SbO<sub>2</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>168.890 (6.46)</td><td>SbO<sub>3</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>178.918 (0.95)</td><td>AlSiO<sub>4</sub>AlO<sub>2</sub>H<sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>195.876 (27.6)</td><td>SbAlO<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>212.869 (36.5)</td><td>SbOSiO<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>223.970 (−10.9)</td><td>PbO<sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>239.965 (−18.9)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>254.846 (13.9)</td><td>SbAl<sub>2</sub>O<sub>5</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>272.859 (21.8)</td><td>SbAl<sub>2</sub>O<sub>6</sub>H<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>283.947 (28.4)</td><td>PbSiO<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>289.800 (23.4)</td><td>Sb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>305.794 (18.5)</td><td>Sb<sub>2</sub>O<sub>4</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>328.890 (26.3)</td><td>PbSb<sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>342.921 (31.5)</td><td>PbAlSiO<sub>5</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>348.771 (20.1)</td><td>Sb<sub>2</sub>O<sub>5</sub>Al<sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>376.874 (21.1)</td><td>PbSbO<sub>3</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>436.845 (28.7)</td><td>PbSbO<sub>3</sub>SiO<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>463.933 (−12.6)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>600.860 (38.0)</td><td>Pb<sub>2</sub>SbO<sub>4</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</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="24">01920-01</td><td>58.972 (8.57)</td><td>AlO<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>59.970 (40.5)</td><td>SiO<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>75.975 (−2.10)</td><td>AlO<sub>3</sub>H<sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>76.983 (9.38)</td><td>AlO<sub>3</sub>H<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>79.960 (36.9)</td><td>SO<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>118.943 (37.9)</td><td>AlSiO<sub>4</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>136.898 (−12.6)</td><td>SbO<sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>152.899 (29.0)</td><td>SbO<sub>2</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>168.890 (6.46)</td><td>SbO<sub>3</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>178.918 (0.95)</td><td>AlSiO<sub>4</sub>AlO<sub>2</sub>H<sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>195.876 (27.6)</td><td>SbAlO<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>212.869 (36.5)</td><td>SbOSiO<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>223.970 (−10.9)</td><td>PbO<sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>239.965 (−18.9)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>254.846 (13.9)</td><td>SbAl<sub>2</sub>O<sub>5</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>272.859 (21.8)</td><td>SbAl<sub>2</sub>O<sub>6</sub>H<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>283.947 (28.4)</td><td>PbSiO<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>289.800 (23.4)</td><td>Sb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>305.794 (18.5)</td><td>Sb<sub>2</sub>O<sub>4</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>328.890 (26.3)</td><td>PbSb<sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>342.921 (31.5)</td><td>PbAlSiO<sub>5</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>348.771 (20.1)</td><td>Sb<sub>2</sub>O<sub>5</sub>Al<sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>376.874 (21.1)</td><td>PbSbO<sub>3</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>436.845 (28.7)</td><td>PbSbO<sub>3</sub>SiO<sub>2</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>463.933 (−12.6)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>600.860 (38.0)</td><td>Pb<sub>2</sub>SbO<sub>4</sub><sup>-</sup></td><td>Pb<sub>2</sub>Sb<sub>2</sub>O<sub>7</sub>/Pb<sub>3</sub>(SbO<sub>4</sub>)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_12.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01920-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Naples Yellow—Kremer Pigmente ref. 43130</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>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>O<sub>2</sub>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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>4.34 × 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>Distinctive isotopic pattern for Sb-containing ions</td></tr></tbody></table>
<figure><img src="image_13.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01920-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Naples Yellow—Kremer Pigmente ref. 43130</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>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>O<sub>2</sub>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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>4.34 × 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>Distinctive isotopic pattern for Sb-containing ions</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="13">01921-01</td><td>34.970 (17.5)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>58.008 (36.5)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.986 (5.70)</td><td>CO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>63.965 (38.9)</td><td>SO<sub>2</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>79.962 (51.3)</td><td>SO<sub>3</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>95.954 (16.7)</td><td>SO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>121.035 (42.9)</td><td>C<sub>6</sub>H<sub>4</sub>CO<sub>2</sub>H<sup>-</sup></td><td>Phthalate contamination</td></tr><tr><td>207.973 (−21.0)</td><td>Pb<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>223.969 (−15.9)</td><td>PbO<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>239.964 (−11.6)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>258.943 (8.45)</td><td>PbOCl<sup>-</sup></td><td>—</td></tr><tr><td>267.957 (−19.6)</td><td>PbCO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>279.959 (−9.12)</td><td>PbOC<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>283.962 (18.4)</td><td>PbCO<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>303.944 (49.6)</td><td>PbSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>320.951 (60.1)</td><td>PbOHSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>328.007 (26.4)</td><td>PbC<sub>7</sub>H<sub>4</sub>O<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>415.955 (3.08)</td><td>Pb<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>431.941 (−18.8)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>447.936 (−16.6)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>463.931 (−16.8)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>464.937 (−20.6)</td><td>Pb<sub>2</sub>O<sub>2</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>482.913 (0.10)</td><td>Pb<sub>2</sub>O<sub>2</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>503.939 (11.6)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>523.931 (15.4)</td><td>Pb<sub>2</sub>O<sub>3</sub>CO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>544.911 (14.6)</td><td>Pb<sub>2</sub>O<sub>2</sub>HSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>623.952 (33.7)</td><td>Pb<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>639.939 (20.8)</td><td>Pb<sub>3</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>655.933 (18.9)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>671.933 (26.1)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>687.932 (31.3)</td><td>Pb<sub>3</sub>O<sub>3</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>688.933 (22.3)</td><td>Pb<sub>3</sub>O<sub>3</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>706.907 (31.8)</td><td>Pb<sub>3</sub>O<sub>3</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>727.926 (28.5)</td><td>Pb<sub>3</sub>C<sub>2</sub>O<sub>5</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>743.915 (19.5)</td><td>Pb<sub>3</sub>C<sub>2</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>744.917 (12.0)</td><td>Pb<sub>3</sub>C<sub>2</sub>O<sub>6</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>831.920 (15.2)</td><td>Pb<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>911.901 (21.5)</td><td>Pb<sub>4</sub>O<sub>4</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>912.902 (13.1)</td><td>Pb<sub>4</sub>O<sub>4</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1039.907 (22.8)</td><td>Pb<sub>5</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1119.906 (42.2)</td><td>Pb<sub>5</sub>O<sub>5</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1135.879 (23.1)</td><td>Pb<sub>5</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1136.888 (23.8)</td><td>Pb<sub>5</sub>O<sub>5</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1247.875 (11.7)</td><td>Pb<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1343.865 (25.8)</td><td>Pb<sub>6</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1359.860 (25.8)</td><td>Pb<sub>6</sub>O<sub>6</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1360.853 (15.2)</td><td>Pb<sub>6</sub>O<sub>6</sub>OH<sup>-</sup></td><td>PbCO<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">01921-01</td><td>34.970 (17.5)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>58.008 (36.5)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.986 (5.70)</td><td>CO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>63.965 (38.9)</td><td>SO<sub>2</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>79.962 (51.3)</td><td>SO<sub>3</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>95.954 (16.7)</td><td>SO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>121.035 (42.9)</td><td>C<sub>6</sub>H<sub>4</sub>CO<sub>2</sub>H<sup>-</sup></td><td>Phthalate contamination</td></tr><tr><td>207.973 (−21.0)</td><td>Pb<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>223.969 (−15.9)</td><td>PbO<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>239.964 (−11.6)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>258.943 (8.45)</td><td>PbOCl<sup>-</sup></td><td>—</td></tr><tr><td>267.957 (−19.6)</td><td>PbCO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>279.959 (−9.12)</td><td>PbOC<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>283.962 (18.4)</td><td>PbCO<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>303.944 (49.6)</td><td>PbSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>320.951 (60.1)</td><td>PbOHSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>328.007 (26.4)</td><td>PbC<sub>7</sub>H<sub>4</sub>O<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>415.955 (3.08)</td><td>Pb<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>431.941 (−18.8)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>447.936 (−16.6)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>463.931 (−16.8)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>464.937 (−20.6)</td><td>Pb<sub>2</sub>O<sub>2</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>482.913 (0.10)</td><td>Pb<sub>2</sub>O<sub>2</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>503.939 (11.6)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>523.931 (15.4)</td><td>Pb<sub>2</sub>O<sub>3</sub>CO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>544.911 (14.6)</td><td>Pb<sub>2</sub>O<sub>2</sub>HSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>623.952 (33.7)</td><td>Pb<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>639.939 (20.8)</td><td>Pb<sub>3</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>655.933 (18.9)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>671.933 (26.1)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>687.932 (31.3)</td><td>Pb<sub>3</sub>O<sub>3</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>688.933 (22.3)</td><td>Pb<sub>3</sub>O<sub>3</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>706.907 (31.8)</td><td>Pb<sub>3</sub>O<sub>3</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>727.926 (28.5)</td><td>Pb<sub>3</sub>C<sub>2</sub>O<sub>5</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>743.915 (19.5)</td><td>Pb<sub>3</sub>C<sub>2</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>744.917 (12.0)</td><td>Pb<sub>3</sub>C<sub>2</sub>O<sub>6</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>831.920 (15.2)</td><td>Pb<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>911.901 (21.5)</td><td>Pb<sub>4</sub>O<sub>4</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>912.902 (13.1)</td><td>Pb<sub>4</sub>O<sub>4</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1039.907 (22.8)</td><td>Pb<sub>5</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1119.906 (42.2)</td><td>Pb<sub>5</sub>O<sub>5</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1135.879 (23.1)</td><td>Pb<sub>5</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1136.888 (23.8)</td><td>Pb<sub>5</sub>O<sub>5</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1247.875 (11.7)</td><td>Pb<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1343.865 (25.8)</td><td>Pb<sub>6</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1359.860 (25.8)</td><td>Pb<sub>6</sub>O<sub>6</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>1360.853 (15.2)</td><td>Pb<sub>6</sub>O<sub>6</sub>OH<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr></tbody></table>
<figure><img src="image_13.png" /></figure>

<table><tr><td>Accession #:</td><td>01921-01</td></tr><tr><td>Specimen:</td><td>Lead white—Kremer Pigmente ref. 46000</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>3500 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>O<sub>2</sub>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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><tr><td>Comment:</td><td>None</td></tr></table>
<figure><img src="image_14.png" /></figure>

<table><tr><td>Accession #:</td><td>01921-01</td></tr><tr><td>Specimen:</td><td>Lead white—Kremer Pigmente ref. 46000</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>3500 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>O<sub>2</sub>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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><tr><td>Comment:</td><td>None</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="21">01922-01</td><td>34.971 (33.8)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>44.998 (5.24)</td><td>CHO<sub>2</sub><sup>-</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>58.008 (33.3)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.016 (31.1)</td><td>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.987 (27.9)</td><td>CO<sub>3</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>79.962 (53.3)</td><td>SO<sub>3</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>95.954 (14.5)</td><td>SO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>114.971 (53.4)</td><td>NaO<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>121.036 (49.9)</td><td>C<sub>7</sub>H<sub>5</sub>O<sub>2</sub><sup>-</sup></td><td>Phthalate contamination</td></tr><tr><td>156.986 (32.9)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub>SO<sub>4</sub>H<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>223.970 (−10.1)</td><td>PbO<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>239.965 (−8.51)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>258.928 (−50.2)</td><td>PbOCl<sup>-</sup></td><td>—</td></tr><tr><td>267.946 (−59.3)</td><td>PbCO<sub>3</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>282.981 (−17.1)</td><td>PbOC<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>283.955 (−6.83)</td><td>PbCO<sub>4</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>296.930 (9.08)</td><td>PbO<sub>2</sub>CaOH<sup>-</sup></td><td>—</td></tr><tr><td>303.934 (15.9)</td><td>PbSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>320.942 (31.3)</td><td>PbOHSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>338.943 (19.7)</td><td>PbCO<sub>3</sub>NaO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>362.968 (21.0)</td><td>PbO<sub>2</sub>H(HCO<sub>3</sub>)<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>422.891 (7.38)</td><td>PbO<sub>3</sub>NaO<sub>3</sub>SO<sub>4</sub><sup>-</sup></td><td>—</td></tr><tr><td>431.947 (−3.27)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>447.946 (5.95)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>463.947 (17.7)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>464.949 (5.13)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>482.916 (7.54)</td><td>Pb<sub>2</sub>O<sub>2</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>506.970 (25.1)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>520.902 (−3.07)</td><td>Pb<sub>2</sub>O<sub>3</sub>CaOH<sup>-</sup></td><td>—</td></tr><tr><td>527.912 (21.9)</td><td>Pb<sub>2</sub>OSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>544.898 (−9.24)</td><td>Pb<sub>2</sub>O<sub>2</sub>HSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>562.891 (−30.3)</td><td>Pb<sub>2</sub>OCO<sub>3</sub>NaO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>586.951 (32.7)</td><td>Pb<sub>2</sub>O<sub>3</sub>H(HCO<sub>3</sub>)<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>671.913 (−3.39)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>687.912 (2.40)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>688.918 (−0.38)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>706.887 (4.16)</td><td>Pb<sub>3</sub>O<sub>3</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>710.909 (13.2)</td><td>NaPb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>—</td></tr><tr><td>730.937 (10.9)</td><td>Pb<sub>3</sub>O<sub>3</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>744.880 (5.46)</td><td>Pb<sub>3</sub>O<sub>4</sub>CaOH<sup>-</sup></td><td>—</td></tr><tr><td>768.888 (17.2)</td><td>HSO<sub>4</sub>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>786.891 (13.9)</td><td>Pb<sub>3</sub>O<sub>2</sub>CO<sub>3</sub>NaO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>911.888 (7.90)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>912.895 (6.11)</td><td>Pb<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(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="21">01922-01</td><td>34.971 (33.8)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>44.998 (5.24)</td><td>CHO<sub>2</sub><sup>-</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>58.008 (33.3)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.016 (31.1)</td><td>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.987 (27.9)</td><td>CO<sub>3</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>79.962 (53.3)</td><td>SO<sub>3</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>95.954 (14.5)</td><td>SO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>114.971 (53.4)</td><td>NaO<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>121.036 (49.9)</td><td>C<sub>7</sub>H<sub>5</sub>O<sub>2</sub><sup>-</sup></td><td>Phthalate contamination</td></tr><tr><td>156.986 (32.9)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub>SO<sub>4</sub>H<sub>3</sub><sup>-</sup></td><td>From manufacturing process</td></tr><tr><td>223.970 (−10.1)</td><td>PbO<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>239.965 (−8.51)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>258.928 (−50.2)</td><td>PbOCl<sup>-</sup></td><td>—</td></tr><tr><td>267.946 (−59.3)</td><td>PbCO<sub>3</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>282.981 (−17.1)</td><td>PbOC<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>283.955 (−6.83)</td><td>PbCO<sub>4</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>296.930 (9.08)</td><td>PbO<sub>2</sub>CaOH<sup>-</sup></td><td>—</td></tr><tr><td>303.934 (15.9)</td><td>PbSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>320.942 (31.3)</td><td>PbOHSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>338.943 (19.7)</td><td>PbCO<sub>3</sub>NaO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>362.968 (21.0)</td><td>PbO<sub>2</sub>H(HCO<sub>3</sub>)<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>422.891 (7.38)</td><td>PbO<sub>3</sub>NaO<sub>3</sub>SO<sub>4</sub><sup>-</sup></td><td>—</td></tr><tr><td>431.947 (−3.27)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>447.946 (5.95)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>463.947 (17.7)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>464.949 (5.13)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>482.916 (7.54)</td><td>Pb<sub>2</sub>O<sub>2</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>506.970 (25.1)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>520.902 (−3.07)</td><td>Pb<sub>2</sub>O<sub>3</sub>CaOH<sup>-</sup></td><td>—</td></tr><tr><td>527.912 (21.9)</td><td>Pb<sub>2</sub>OSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>544.898 (−9.24)</td><td>Pb<sub>2</sub>O<sub>2</sub>HSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>562.891 (−30.3)</td><td>Pb<sub>2</sub>OCO<sub>3</sub>NaO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>586.951 (32.7)</td><td>Pb<sub>2</sub>O<sub>3</sub>H(HCO<sub>3</sub>)<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>671.913 (−3.39)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>687.912 (2.40)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>688.918 (−0.38)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>706.887 (4.16)</td><td>Pb<sub>3</sub>O<sub>3</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>710.909 (13.2)</td><td>NaPb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>—</td></tr><tr><td>730.937 (10.9)</td><td>Pb<sub>3</sub>O<sub>3</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>744.880 (5.46)</td><td>Pb<sub>3</sub>O<sub>4</sub>CaOH<sup>-</sup></td><td>—</td></tr><tr><td>768.888 (17.2)</td><td>HSO<sub>4</sub>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>786.891 (13.9)</td><td>Pb<sub>3</sub>O<sub>2</sub>CO<sub>3</sub>NaO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>911.888 (7.90)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>912.895 (6.11)</td><td>Pb<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_14.png" /></figure>

<table><tr><td>Accession #:</td><td>01922-01</td></tr><tr><td>■ Specimen:</td><td>Flake White 10 μm—Masters Pigments ref. 901010</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>3600 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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>8.3 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 38 nA</td></tr><tr><td>DC Beam Current:</td><td>1.9 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 μm</td></tr><tr><td>Beam Raster Size:</td><td>200 × 200 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>1994 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>161 s</td></tr><tr><td>Comment:</td><td>None</td></tr></table>
<figure><img src="image_15.png" /></figure>

<table><tr><td>Accession #:</td><td>01922-01</td></tr><tr><td>■ Specimen:</td><td>Flake White 10 µm—Masters Pigments ref. 901010</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>3600 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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>8.3 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 38 nA</td></tr><tr><td>DC Beam Current:</td><td>1.9 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>200 × 200 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>1994 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>161 s</td></tr><tr><td>Comment:</td><td>None</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="11">01923-01</td><td>17.003 (−21.5)</td><td>OH<sup>−</sup></td><td>—</td></tr><tr><td>34.970 (18.0)</td><td>Cl<sup>−</sup></td><td>—</td></tr><tr><td>41.004 (21.1)</td><td>C<sub>2</sub>HO<sup>−</sup></td><td>—</td></tr><tr><td>44.998 (−9.10)</td><td>CHO<sub>2</sub><sup>−</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>58.008 (26.0)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>−</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.017 (48.7)</td><td>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>−</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.986 (5.88)</td><td>CO<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>121.038 (67.5)</td><td>C<sub>7</sub>H<sub>5</sub>O<sub>2</sub><sup>−</sup></td><td>Phthalate contamination</td></tr><tr><td>207.974 (−13.8)</td><td>Pb<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>223.968 (−19.8)</td><td>PbO<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>239.966 (−6.10)</td><td>PbO<sub>2</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>240.973 (−8.00)</td><td>PbO<sub>2</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>255.238 (18.9)</td><td>C<sub>16</sub>H<sub>31</sub>O<sub>2</sub><sup>−</sup></td><td>Fatty acid from contamination</td></tr><tr><td>267.945 (−64.6)</td><td>PbCO<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>283.269 (15.3)</td><td>C<sub>18</sub>H<sub>35</sub>O<sub>2</sub><sup>−</sup></td><td>Fatty acid from contamination</td></tr><tr><td>296.930 (−8.05)</td><td>PbO<sub>2</sub>CaOH<sup>−</sup></td><td>—</td></tr><tr><td>303.939 (33.6)</td><td>PbSO<sub>4</sub><sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>320.942 (31.5)</td><td>PbOHSO<sub>4</sub><sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>328.001 (34.0)</td><td>PbC<sub>7</sub>H<sub>4</sub>O<sub>2</sub><sup>−</sup></td><td>—</td></tr><tr><td>345.019 (53.3)</td><td>PbC<sub>7</sub>H<sub>5</sub>O<sub>3</sub><sup>−</sup></td><td>—</td></tr><tr><td>415.950 (−10.0)</td><td>Pb<sub>2</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>431.945 (−9.12)</td><td>Pb<sub>2</sub>O<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>447.940 (−7.74)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>463.942 (9.16)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>464.950 (6.75)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>482.914 (3.43)</td><td>Pb<sub>2</sub>O<sub>2</sub>Cl<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>504.933 (−17.5)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>O<sub>2</sub>H<sup>−</sup></td><td>—</td></tr><tr><td>506.950 (−13.6)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>−</sup></td><td>—</td></tr><tr><td>520.896 (−14.6)</td><td>Pb<sub>2</sub>O<sub>3</sub>CaOH<sup>−</sup></td><td>—</td></tr><tr><td>544.887 (−30.1)</td><td>Pb<sub>2</sub>O<sub>2</sub>HSO<sub>4</sub><sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>560.865 (4.97)</td><td>Pb<sub>2</sub>S<sub>3</sub>O<sub>3</sub>H<sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>623.930 (−0.47)</td><td>Pb<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>639.916 (−14.5)</td><td>Pb<sub>3</sub>O<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>655.905 (−23.4)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>671.905 (−15.4)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>687.911 (0.54)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>688.915 (−4.55)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>706.876 (−11.8)</td><td>Pb<sub>3</sub>O<sub>3</sub>Cl<sup>−</sup></td><td>—</td></tr><tr><td>728.898 (−20.4)</td><td>Pb<sub>3</sub>O<sub>3</sub>C<sub>2</sub>O<sub>2</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>744.875 (0.01)</td><td>Pb<sub>3</sub>O<sub>4</sub>CaOH<sup>−</sup></td><td>—</td></tr><tr><td>768.879 (5.91)</td><td>HSO<sub>4</sub>Pb<sub>3</sub>O<sub>3</sub><sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>784.858 (30.0)</td><td>Pb<sub>3</sub>S<sub>3</sub>O<sub>4</sub>H<sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>911.881 (−1.02)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>912.879 (−11.5)</td><td>Pb<sub>4</sub>O<sub>5</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(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">01923-01</td><td>17.003 (−21.5)</td><td>OH<sup>−</sup></td><td>—</td></tr><tr><td>34.970 (18.0)</td><td>Cl<sup>−</sup></td><td>—</td></tr><tr><td>41.004 (21.1)</td><td>C<sub>2</sub>HO<sup>−</sup></td><td>—</td></tr><tr><td>44.998 (−9.10)</td><td>CHO<sub>2</sub><sup>−</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>58.008 (26.0)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>−</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.017 (48.7)</td><td>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>−</sup></td><td>Acetate from manufacturing process</td></tr><tr><td>59.986 (5.88)</td><td>CO<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>121.038 (67.5)</td><td>C<sub>7</sub>H<sub>5</sub>O<sub>2</sub><sup>−</sup></td><td>Phthalate contamination</td></tr><tr><td>207.974 (−13.8)</td><td>Pb<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>223.968 (−19.8)</td><td>PbO<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>239.966 (−6.10)</td><td>PbO<sub>2</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>240.973 (−8.00)</td><td>PbO<sub>2</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>255.238 (18.9)</td><td>C<sub>16</sub>H<sub>31</sub>O<sub>2</sub><sup>−</sup></td><td>Fatty acid from contamination</td></tr><tr><td>267.945 (−64.6)</td><td>PbCO<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>283.269 (15.3)</td><td>C<sub>18</sub>H<sub>35</sub>O<sub>2</sub><sup>−</sup></td><td>Fatty acid from contamination</td></tr><tr><td>296.930 (−8.05)</td><td>PbO<sub>2</sub>CaOH<sup>−</sup></td><td>—</td></tr><tr><td>303.939 (33.6)</td><td>PbSO<sub>4</sub><sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>320.942 (31.5)</td><td>PbOHSO<sub>4</sub><sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>328.001 (34.0)</td><td>PbC<sub>7</sub>H<sub>4</sub>O<sub>2</sub><sup>−</sup></td><td>—</td></tr><tr><td>345.019 (53.3)</td><td>PbC<sub>7</sub>H<sub>5</sub>O<sub>3</sub><sup>−</sup></td><td>—</td></tr><tr><td>415.950 (−10.0)</td><td>Pb<sub>2</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>431.945 (−9.12)</td><td>Pb<sub>2</sub>O<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>447.940 (−7.74)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>463.942 (9.16)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>464.950 (6.75)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>482.914 (3.43)</td><td>Pb<sub>2</sub>O<sub>2</sub>Cl<sup>−</sup></td><td>—</td></tr><tr><td>504.933 (−17.5)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>O<sub>2</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>506.950 (−13.6)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>−</sup></td><td>—</td></tr><tr><td>520.896 (−14.6)</td><td>Pb<sub>2</sub>O<sub>3</sub>CaOH<sup>−</sup></td><td>—</td></tr><tr><td>544.887 (−30.1)</td><td>Pb<sub>2</sub>O<sub>2</sub>HSO<sub>4</sub><sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>560.865 (4.97)</td><td>Pb<sub>2</sub>S<sub>3</sub>O<sub>3</sub>H<sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>623.930 (−0.47)</td><td>Pb<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>639.916 (−14.5)</td><td>Pb<sub>3</sub>O<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>655.905 (−23.4)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>671.905 (−15.4)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>687.911 (0.54)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>688.915 (−4.55)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>706.876 (−11.8)</td><td>Pb<sub>3</sub>O<sub>3</sub>Cl<sup>−</sup></td><td>—</td></tr><tr><td>728.898 (−20.4)</td><td>Pb<sub>3</sub>O<sub>3</sub>C<sub>2</sub>O<sub>2</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>744.875 (0.01)</td><td>Pb<sub>3</sub>O<sub>4</sub>CaOH<sup>−</sup></td><td>—</td></tr><tr><td>768.879 (5.91)</td><td>HSO<sub>4</sub>Pb<sub>3</sub>O<sub>3</sub><sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>784.858 (30.0)</td><td>Pb<sub>3</sub>S<sub>3</sub>O<sub>4</sub>H<sup>−</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>911.881 (−1.02)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>912.879 (−11.5)</td><td>Pb<sub>4</sub>O<sub>5</sub>H<sup>−</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_15.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01923-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Flake White—Sennelier PW no.108</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>3100 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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><sub>3</sub></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>8.3 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 38 nA</td></tr><tr><td>DC Beam Current:</td><td>1.9 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 μm</td></tr><tr><td>Beam Raster Size:</td><td>200 × 200 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>1994 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>161 s</td></tr><tr><td>Comment:</td><td>Contamination with a fatty material, probably from manufacturing process</td></tr></tbody></table>
<figure><img src="image_16.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01923-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Flake White—Sennelier PW no.108</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>3100 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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><sub>3</sub></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>8.3 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 38 nA</td></tr><tr><td>DC Beam Current:</td><td>1.9 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>200 × 200 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>1994 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>161 s</td></tr><tr><td>Comment:</td><td>Contamination with a fatty material, probably from manufacturing process</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="11">01924-01</td><td>34.970 (9.2)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>95.955 (32.1)</td><td>SO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>135.939 (−20.2)</td><td>SiAlO<sub>5</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>178.919 (6.84)</td><td>SiAl<sub>2</sub>O<sub>6</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>195.913 (22.3)</td><td>Si<sub>2</sub>AlO<sub>7</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>207.971 (−28.0)</td><td>Pb<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>223.968 (−18.5)</td><td>PbO<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>239.965 (−8.89)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>258.950 (34.1)</td><td>PbOCl<sup>-</sup></td><td>—</td></tr><tr><td>267.955 (−29.8)</td><td>PbCO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>283.961 (15.6)</td><td>PbCO<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>299.954 (8.88)</td><td>PbO<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>303.945 (53.5)</td><td>PbSO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>320.949 (54.4)</td><td>PbSO<sub>5</sub>H<sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>322.850 (10.1)</td><td>Al<sub>6</sub>O<sub>10</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>338.937 (0.28)</td><td>PbCO<sub>3</sub>NaO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>342.923 (36.9)</td><td>PbOAlSiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>343.941 (−1.17)</td><td>PbOC<sub>2</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>359.936 (−0.71)</td><td>PbO<sub>2</sub>C<sub>2</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>403.910 (60.4)</td><td>PbAl<sub>2</sub>SiO<sub>6</sub>H<sub>2</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>415.964 (23.7)</td><td>Pb<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>431.939 (−23.3)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>447.942 (−3.53)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>463.935 (−8.36)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>464.949 (5.76)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>482.917 (7.15)</td><td>Pb<sub>2</sub>ClO<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>506.949 (−16.7)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>524.948 (32.0)</td><td>Pb<sub>2</sub>O<sub>3</sub>CO<sub>3</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>566.890 (14.1)</td><td>Pb<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>583.904 (34.0)</td><td>Pb<sub>2</sub>O<sub>3</sub>HAISiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>623.940 (15.8)</td><td>Pb<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>639.934 (13.0)</td><td>Pb<sub>3</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>655.914 (−10.1)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>671.928 (19.4)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>687.929 (27.1)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>688.944 (37.3)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>731.915 (21.0)</td><td>Pb<sub>3</sub>O<sub>3</sub>CO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>748.922 (25.8)</td><td>Pb<sub>3</sub>O<sub>3</sub>CO<sub>4</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>790.883 (37.9)</td><td>Pb<sub>3</sub>O<sub>3</sub>AlSiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>807.885 (36.2)</td><td>Pb<sub>3</sub>O<sub>4</sub>AlSiO<sub>4</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>831.926 (23.1)</td><td>Pb<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>911.896 (15.5)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>912.922 (36.0)</td><td>Pb<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>952.896 (12.1)</td><td>Pb<sub>4</sub>C<sub>2</sub>O<sub>6</sub>H<sup>-</sup></td><td>PbCO<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="11">01924-01</td><td>34.970 (9.2)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>95.955 (32.1)</td><td>SO<sub>4</sub><sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>135.939 (−20.2)</td><td>SiAlO<sub>5</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>178.919 (6.84)</td><td>SiAl<sub>2</sub>O<sub>6</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>195.913 (22.3)</td><td>Si<sub>2</sub>AlO<sub>7</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>207.971 (−28.0)</td><td>Pb<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>223.968 (−18.5)</td><td>PbO<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>239.965 (−8.89)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>258.950 (34.1)</td><td>PbOCl<sup>-</sup></td><td>—</td></tr><tr><td>267.955 (−29.8)</td><td>PbCO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>283.961 (15.6)</td><td>PbCO<sub>4</sub></td><td>PbCO<sub>3</sub></td></tr><tr><td>299.954 (8.88)</td><td>PbO<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>303.945 (53.5)</td><td>PbSO<sub>4</sub></td><td>Sulfate from manufacturing process</td></tr><tr><td>320.949 (54.4)</td><td>PbSO<sub>5</sub>H<sup>-</sup></td><td>Sulfate from manufacturing process</td></tr><tr><td>322.850 (10.1)</td><td>Al<sub>8</sub>O<sub>10</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>338.937 (0.28)</td><td>PbCO<sub>3</sub>NaO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>342.923 (36.9)</td><td>PbOAlSiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>343.941 (−1.17)</td><td>PbOC<sub>2</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>359.936 (−0.71)</td><td>PbO<sub>2</sub>C<sub>2</sub>O<sub>6</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>403.910 (60.4)</td><td>PbAl<sub>2</sub>SiO<sub>6</sub>H<sub>2</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>415.964 (23.7)</td><td>Pb<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>431.939 (−23.3)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>447.942 (−3.53)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>463.935 (−8.36)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>464.949 (5.76)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>482.917 (7.15)</td><td>Pb<sub>2</sub>ClO<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>506.949 (−16.7)</td><td>Pb<sub>2</sub>O<sub>2</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>2PbCO<sub>3</sub>·Pb(OH)<sub>2</sub></td></tr><tr><td>524.948 (32.0)</td><td>Pb<sub>2</sub>O<sub>3</sub>CO<sub>3</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>566.890 (14.1)</td><td>Pb<sub>2</sub>O<sub>2</sub>AlSiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>583.904 (34.0)</td><td>Pb<sub>2</sub>O<sub>3</sub>HAISiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>623.940 (15.8)</td><td>Pb<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>639.934 (13.0)</td><td>Pb<sub>3</sub>O<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>655.914 (−10.1)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>671.928 (19.4)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>687.929 (27.1)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>688.944 (37.3)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>731.915 (21.0)</td><td>Pb<sub>3</sub>O<sub>3</sub>CO<sub>3</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>748.922 (25.8)</td><td>Pb<sub>3</sub>O<sub>3</sub>CO<sub>4</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>790.883 (37.9)</td><td>Pb<sub>3</sub>O<sub>3</sub>AlSiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>807.885 (36.2)</td><td>Pb<sub>3</sub>O<sub>4</sub>AlSiO<sub>4</sub>H<sup>-</sup></td><td>Aluminosilicate (possible filler)</td></tr><tr><td>831.926 (23.1)</td><td>Pb<sub>4</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>911.896 (15.5)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>912.922 (36.0)</td><td>Pb<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr><tr><td>952.896 (12.1)</td><td>Pb<sub>4</sub>C<sub>2</sub>O<sub>6</sub>H<sup>-</sup></td><td>PbCO<sub>3</sub></td></tr></tbody></table>
<figure><img src="image_16.png" /></figure>

<table><tr><td>Accession #:</td><td>01924-01</td></tr><tr><td>Specimen:</td><td>Cerussite—Masters Pigments ref. 951010</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>2200 m/Δm</td></tr><tr><td>Mass Resolving Power:</td><td>25 Da</td></tr><tr><td>Determined at:</td><td>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</sub>O<sub>4</sub>H<sup>-</sup></td></tr><tr><td>Species Used for Mass Calibration:</td><td></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8 - 1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 23 nA</td></tr><tr><td>DC Beam Current:</td><td>7.2 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>3542 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>194 s</td></tr><tr><td>Comment:</td><td>The peak at m/z 59.98 can 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. The mass range attributed to CO<sub>3</sub><sup>-</sup> exhibits the same spatial distribution as lead-containing ions, while the mass range attributed to SiO<sub>2</sub> exhibits the same spatial distribution as the other aluminosilicate ions</td></tr></table>
<figure><img src="image_17.png" /></figure>

<table><tr><td>Accession #:</td><td>01924-01</td></tr><tr><td>Specimen:</td><td>Cerussite—Masters Pigments ref. 951010</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>2200 m/Δm</td></tr><tr><td>Mass Resolving Power:</td><td>25 Da</td></tr><tr><td>Determined at:</td><td>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</sub>O<sub>4</sub>H<sup>-</sup></td></tr><tr><td>Species Used for Mass Calibration:</td><td></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8 - 1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 23 nA</td></tr><tr><td>DC Beam Current:</td><td>7.2 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>3542 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>194 s</td></tr><tr><td>Comment:</td><td>The peak at m/z 59.98 can 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. The mass range attributed to CO<sub>3</sub><sup>-</sup> exhibits the same spatial distribution as lead-containing ions, while the mass range attributed to SiO<sub>2</sub> exhibits the same spatial distribution as the other aluminosilicate ions</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">01925-01</td><td>15.996 (11.9)</td><td>O<sup>-</sup></td><td>(saturated)</td></tr><tr><td>34.970 (24.1)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>207.971 (−29.5)</td><td>Pb<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>223.971 (−6.51)</td><td>PbO<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>239.966 (−6.29)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>415.954 (0.12)</td><td>Pb<sub>2</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>431.936 (−28.9)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>447.938 (−13.6)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>463.931 (−17.1)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>464.938 (−17.5)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>482.907 (−10.8)</td><td>Pb<sub>2</sub>ClO<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>623.947 (26.1)</td><td>Pb<sub>3</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>639.939 (21.3)</td><td>Pb<sub>3</sub>O<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>655.932 (17.3)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>671.930 (22.0)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>687.929 (27.6)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>688.937 (27.3)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>706.904 (28.7)</td><td>Pb<sub>3</sub>O<sub>3</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>831.916 (10.8)</td><td>Pb<sub>4</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>911.908 (28.9)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>1039.903 (18.2)</td><td>Pb<sub>5</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>1119.886 (24.9)</td><td>Pb<sub>5</sub>O<sub>5</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>1135.888 (30.9)</td><td>Pb<sub>5</sub>O<sub>6</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<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="20">01925-01</td><td>15.996 (11.9)</td><td>O<sup>-</sup></td><td rowspan="20">(saturated)</td></tr><tr><td>34.970 (24.1)</td><td>Cl<sup>-</sup></td></tr><tr><td>207.971 (-29.5)</td><td>Pb<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>223.971 (-6.51)</td><td>PbO<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>239.966 (-6.29)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>415.954 (0.12)</td><td>Pb<sub>2</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>431.936 (-28.9)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>447.938 (-13.6)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>463.931 (-17.1)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>464.938 (-17.5)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>482.907 (-10.8)</td><td>Pb<sub>2</sub>ClO<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>623.947 (26.1)</td><td>Pb<sub>3</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>639.939 (21.3)</td><td>Pb<sub>3</sub>O<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>655.932 (17.3)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>671.930 (22.0)</td><td>Pb<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>687.929 (27.6)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>688.937 (27.3)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>706.904 (28.7)</td><td>Pb<sub>3</sub>O<sub>3</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>831.916 (10.8)</td><td>Pb<sub>4</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>911.908 (28.9)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>1039.903 (18.2)</td><td>Pb<sub>5</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>1119.886 (24.9)</td><td>Pb<sub>5</sub>O<sub>5</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr><tr><td>1135.888 (30.9)</td><td>Pb<sub>5</sub>O<sub>6</sub><sup>-</sup></td><td>Pb<sub>3</sub>O<sub>4</sub></td></tr></tbody></table>
<figure><img src="image_17.png" /></figure>

<table><tr><td>Accession #:</td><td>01925-01</td></tr><tr><td>■ Specimen:</td><td>Minium—Kremer Pigmente ref.42500</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>4000 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 23 nA</td></tr><tr><td>DC Beam Current:</td><td>7.2 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>3542 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>194 s</td></tr><tr><td>Comment:</td><td>Specific ion Pb<sub>4</sub>O<sub>4</sub><sup>-</sup> is barely detected in minium</td></tr></table>
<figure><img src="image_18.png" /></figure>

<table><tr><td>Accession #:</td><td>01925-01</td></tr><tr><td>Specimen:</td><td>Minium—Kremer Pigmente ref.42500</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>4000 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 23 nA</td></tr><tr><td>DC Beam Current:</td><td>7.2 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>3542 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>194 s</td></tr><tr><td>Comment:</td><td>Specific ion Pb<sub>4</sub>O<sub>4</sub><sup>-</sup> is barely detected in minium</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">01926-01</td><td>34.971 (31.9)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>207.970 (−34.3)</td><td>Pb<sup>-</sup></td><td>PbO</td></tr><tr><td>223.966 (−28.2)</td><td>PbO<sup>-</sup></td><td>PbO</td></tr><tr><td>239.960 (−31.2)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>415.955 (3.48)</td><td>Pb<sub>2</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>431.932 (−39.3)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>PbO</td></tr><tr><td>447.940 (−8.66)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>463.932 (−13.3)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>464.942 (−8.61)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>PbO</td></tr><tr><td>482.911 (−4.13)</td><td>Pb<sub>2</sub>O<sub>2</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>623.950 (30.5)</td><td>Pb<sub>3</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>639.931 (9.00)</td><td>Pb<sub>3</sub>O<sup>-</sup></td><td>PbO</td></tr><tr><td>655.932 (17.2)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>671.922 (10.4)</td><td>Pb<sub>3</sub>O<sub>3</sub></td><td>PbO</td></tr><tr><td>687.925 (21.3)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>688.937 (27.4)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>PbO</td></tr><tr><td>831.917 (12.1)</td><td>Pb<sub>4</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>911.903 (23.1)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>912.910 (22.5)</td><td>Pb<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>PbO</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">01926-01</td><td>34.971 (31.9)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>207.970 (−34.3)</td><td>Pb<sup>-</sup></td><td>PbO</td></tr><tr><td>223.966 (−28.2)</td><td>PbO<sup>-</sup></td><td>PbO</td></tr><tr><td>239.960 (−31.2)</td><td>PbO<sub>2</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>415.955 (3.48)</td><td>Pb<sub>2</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>431.932 (−39.3)</td><td>Pb<sub>2</sub>O<sup>-</sup></td><td>PbO</td></tr><tr><td>447.940 (−8.66)</td><td>Pb<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>463.932 (−13.3)</td><td>Pb<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>464.942 (−8.61)</td><td>Pb<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>PbO</td></tr><tr><td>482.911 (−4.13)</td><td>Pb<sub>2</sub>O<sub>2</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>623.950 (30.5)</td><td>Pb<sub>3</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>639.931 (9.00)</td><td>Pb<sub>3</sub>O<sup>-</sup></td><td>PbO</td></tr><tr><td>655.932 (17.2)</td><td>Pb<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>671.922 (10.4)</td><td>Pb<sub>3</sub>O<sub>3</sub></td><td>PbO</td></tr><tr><td>687.925 (21.3)</td><td>Pb<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>688.937 (27.4)</td><td>Pb<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>PbO</td></tr><tr><td>831.917 (12.1)</td><td>Pb<sub>4</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>911.903 (23.1)</td><td>Pb<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>PbO</td></tr><tr><td>912.910 (22.5)</td><td>Pb<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>PbO</td></tr></tbody></table>
<figure><img src="image_18.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01926-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Litharge—Kremer Pigmente ref. 43010</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>2300 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 23 nA</td></tr><tr><td>DC Beam Current:</td><td>7.2 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>3542 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>194 s</td></tr><tr><td>Comment:</td><td>Specific ion Pb<sub>4</sub>O<sub>4</sub><sup>-</sup> is barely detected in litharge</td></tr></tbody></table>
<figure><img src="image_19.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01926-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Litharge—Kremer Pigmente ref. 43010</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>2300 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>O<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, PbO<sub>2</sub>H<sup>-</sup>, <sup>206</sup>PbPbO<sub>3</sub>H<sup>-</sup>, <sup>206</sup>PbPb<sub>2</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>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 23 nA</td></tr><tr><td>DC Beam Current:</td><td>7.2 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>3542 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>194 s</td></tr><tr><td>Comment:</td><td>Specific ion Pb<sub>4</sub>O<sub>4</sub><sup>-</sup> is barely detected in litharge</td></tr></tbody></table>