# Tof-SIMS spectra of historical inorganic pigments: Copper-, zinc-, arsenic-, and phosphorus-containing pigments in negative polarity

Caroline Bouvier ; Sebastiaan Van Nuffel ; Alain Brunelle

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Surf. Sci. Spectra 31, 025002 (2024)

https://doi.org/10.1116/6.0003723

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# Tof-SIMS spectra of historical inorganic pigments: Copper-, zinc-, arsenic-, and phosphorus-containing pigments in negative polarity F

Cite as: Surf. Sci. Spectra 31, 025002 (2024); doi: 10.1116/6.0003723

Submitted: 27 April 2024 · Accepted: 18 June 2024 ·

Published Online: 10 July 2024

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Caroline Bouvier,<sup>1,2</sup> <sup>ID</sup> Sebastiaan Van Nuffel,<sup>2,3</sup> <sup>ID</sup> and Alain Brunelle<sup>1,a)</sup> <sup>ID</sup>

## AFFILIATIONS

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

<sup>a)</sup>Author to whom correspondence should be addressed: alain.brunelle@cnrs.fr

## ABSTRACT

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is increasingly used to analyze cultural heritage materials because it can simultaneously detect organic and inorganic materials while mapping them on a surface. The precise identification of a pigment in a specific layer of a painting or of remaining color on a statue can inform about the technique used or the time of manufacture as well as expose possible forgeries when anachronistic ingredients are identified. Reference spectra are required to confidently identify a given pigment using ToF-SIMS. This paper focuses on eight pigments containing copper, zinc, arsenic, or phosphate, all manufactured following historical recipes. The negative polarity ToF-SIMS reference spectra using a Bi<sub>3</sub><sup>+</sup> primary ion species are presented here. Presented together, these spectra and corresponding tables of secondary ions provide a valuable help in differentiating these pigments because copper, zinc, arsenic, or phosphate, combined with oxygen, share many mass interferences.

© 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/10.1116/6.0003723

**Accession#:** 01947, 01948, 01949, 01950, 01951, 01952, 01953, and 01954

**Technique:** SIMS

**Specimen:** Peach black, Bone black, Realgar, Bristol yellow medium, Azurite, Malachite, Verdigris, and Zinc white

**Instrument:** IONTOF, TOF SIMS IV

**Major Species in Spectra:** O, H, C, Cu, Zn, P, Ca, As, S, V, Bi, and Cl

**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. This paper provides a comparative ToF-SIMS spectral database for eight historical inorganic pigments, containing copper carbonate, zinc oxide or phosphates, vanadium oxide, calcium phosphates, or arsenic sulfide. Numerous possibilities for mass interferences exist between combinations of these elements. Without being able to refer to comparative datasets that provide an overview of the

fragment ions for each pigment, it would be difficult to accurately identify one of them as an unknown pigment. Although not presented in the paper, titanium oxide, used as a pigment from the 1920s, may exhibit additional interferences to be considered as TiO<sup>-</sup> has an *m/z* of 62.94.

The reference materials were supplied by specialized manufacturers selling pigments reproducing historical recipes as closely as possible, such as Kremer Pigmente GmbH. Pigments were available as finely ground powder of variable particle size (between one and a few tens of µm) conditioned in glass sealed vials. In paintings,

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

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

<footnote n="3"><sup>3</sup>Faculty of Science and Engineering, Maastricht University, Maastricht 6229EN, The Netherlands</footnote>
pigment particles are dispersed in the binder and not dissolved, so all references were analyzed without any preparation treatment. Natural and synthetic pigments may contain impurities, and specimens compositions described below are the major components as found on the material data sheets provided by the suppliers.

A stainless-steel spatula was cleaned with propan-2-ol, and the powder was directly deposited on a 1 × 1 mm² piece of a conductive double-sided tape (3M Electrically Conductive Adhesive Transfer Tape 9703) already fixed to a 1 cm × 1 cm × 0.125 mm stainless steel plate (17-7PH, Goodfellow Cambridge Limited, UK) fitting the dimensions of the sample holder. A hand press covered with a clean aluminum foil was applied onto the powder to fix it to the tape. This allowed to operate in the analysis chamber under ultra-high vacuum (10⁻⁸–10⁻⁹ hPa) while ensuring a flat surface. For highly toxic pigments, such as the arsenic sulfide Realgar (#01949), a pellet with a flat surface was prepared using a press (Mini-Pellet Press P/N GS03940, Specac Ltd, UK) to limit dust formation.

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

Data were calibrated using sets of peaks as similar as possible for all spectra, using peaks that could be confidently identified. Copper and zinc both have distinctive isotopic patterns ensuring confident attribution of the peaks, so #01951, #01952, and #01953 data were calibrated using lists including Cu⁻ and Cu₃O₃⁻ ions, and #01954 data were calibrated using ZnO₂⁻, Zn₂O₃⁻, Zn₃O₄⁻, ⁶⁶Zn₅⁶⁸ZnZn₂O₆⁻, ⁶⁶Zn₅⁶⁸Zn₂Zn₄O₈⁻, and ⁶⁶Zn₅⁶⁸Zn₂Zn₅O₁₀. When possible, data were calibrated using lists including main ions, namely, C⁻, C₂⁻, C₃⁻, C₈⁻, C₁₀, and C₁₃ for #01947, CaO⁻, SiO₂⁻, PO₂⁻, SiO₃⁻, and PO₃ for #01948, and S₂⁻, AsS₂⁻, As₂S₃⁻, and As₃S₄ for #01949. No bismuth- and vanadium-containing ions were used to calibrate the #01950 dataset since bismuth has no isotope and is close in mass to VP₂O₆. Hence, #01950 data were calibrated using hydrocarbon and chlorine ions CH⁻, CH₂, C₂⁻, Cl⁻, C₃⁻, and C₄H⁻. These calibration lists allowed for a good coverage of the mass range of interest for each specimen, and they are fully detailed in the corresponding tables below. Pigments contain diverse metallic oxides, hydroxides, carbonates, and even hydrocarbons. They are found inside painting layers that are mostly organic materials. All these compounds do not follow the same ionization processes and have different ionization kinetics.¹ In this context, the choice for the calibration ions is a crucial step to ensure proper peak attribution. If the analytical question aims at identifying the nature of a pigment particle, then the calibration must include inorganic ions, such as the list above, spanning all the mass range of interest and if possible of the same ion family as those of interest. However, if the analytical question focuses mainly on the identification of organic materials, the calibration must include known low-mass hydrocarbon ions. The safest strategy when interpreting data from a painting

cross section would be to rely on several calibration sets adapted to the ions of interest and that can be confidently defined independently of the sample's unknowns.

Figures and tables presented below contain the major peaks for negative polarity. Each pigment is uniquely identified thanks to an accession number, and they are grouped according to their composition and described in the following section. Their historical relevance is briefly described based on current literature.²⁻⁶ The spectrum ID# refers to that number.

## SPECIMEN DESCRIPTION (ACCESSION # 01947)

**Specimen:** Peach black (Kremer Pigmente Ref. 12010)

**CAS Registry #:** Unknown

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

**Chemical Name:** Amorphous carbon

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** Amorphous carbon (charred peach kernel)

**Form:** Ground pigment powder

**History and Significance:** Black pigments derived from charcoals are rarely detectable by the analytical techniques used to investigate pigments such as XRF, while carbon-based black pigments have been used in every society since the domestication of fire. Peach black, for instance, only requires the calcination of kernels. Identifying this pigment is of interest, as they are omnipresent in historical artistic practice. ToF-SIMS is able to map and identify micrometric particles of carbon-base pigments.

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

**Analyzed Region:** Areas of 250 × 250 µm²

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

**In Situ Preparation:** None

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

**Temp. During Analysis:** 300 K

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

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

## SPECIMEN DESCRIPTION (ACCESSION # 01948)

**Specimen:** Bone black (Kremer Pigmente Ref. 47100)

**CAS Registry #:** 8021-99-6

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

**Chemical Name:** Bone charcoal

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** Amorphous carbon and calcium phosphates

**Form:** Ground pigment powder
**History and Significance:** Bone black is made by carbonization of animal bones at temperatures over 400 °C but not above 800 °C. It mainly consists of calcium phosphate and carbonized organics. It is very frequently used in paintings, especially in preparation layers.

**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 a conductive double-sided tape attached to stainless steel $1 \times 1 cm^2$ plates. The resulting deposit of powder had a flat surface and was fixed in a suitable way for the vacuum chamber. The plate was directly mounted on a “backmount” sample holder (IONTOF).

**In Situ Preparation:** None

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

**Temp. During Analysis:** 300 K

**Pressure During Analysis:** Between $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

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

## SPECIMEN DESCRIPTION (ACCESSION # 01949)

**Specimen:** Realgar/red orpiment (Kremer Pigmente Ref. 10800)

**CAS Registry #:** 1303-33-9

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

**Chemical Name:** Arsenic (III) sulfide (natural mineral)

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** Natural arsenic sulfide $\alpha$-As$_4$S$_4$

**Form:** Ground pigment powder

**History and Significance:** A mineral prized for its bright red color that was used until the beginning of the 19th century. Found in volcanic and geothermal regions, its geographic origin varies. It was found on luxurious articles in antiquity to show opulence and was used as ritual offerings and in cosmetics, despite its high toxicity. It exists in rare natural and synthetic forms. Its occurrence is difficult to investigate due to light instability, converting it to yellow pararealgar ($As_4S_4$), thereby often mistaken for other yellow As pigments unless crystalline phases can be differentiated by the analytical techniques used. Red realgar can be found in environments where the absence of light preserves it.

**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:** Because of the toxicity of arsenic sulfide, a pellet was prepared using a Specac Mini Pellet Press. A flat surface was obtained, and dust formation was limited when handling the sample. The pellet was directly mounted on a “backmount” sample holder (IONTOF).

**In Situ Preparation:** None

**Charge Control Conditions and Procedures:** A low-energy electron flood gun was used. Bias voltage between 20 and -30 V.

Flood gun filament current of 2.35 A. Surface potential was corrected (sample dependent).

**Temp. During Analysis:** 300 K

**Pressure During Analysis:** Between $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

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

## SPECIMEN DESCRIPTION (ACCESSION # 01950)

**Specimen:** Bristol yellow medium (Kremer Pigmente Ref. 43111)

**CAS Registry #:** 7779-90-0 and 14059-33-7

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

**Chemical Name:** Trizinc bis(ortho)phosphate + bismuth vanadium tetraoxide

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Zn_3(PO_4)_2 + BiVO_4$

**Form:** Ground pigment powder

**History and Significance:** Due to their toxicity, lead pigments have been gradually prohibited over the past two centuries. Alternative yellow pigments such as modified bismuth yellows (Bristol yellows) were produced to replace them. Bristol yellows have been used since the 20th century to imitate Naples yellow as they have similar optical properties. Copper and zinc compounds can have mass interference with Bristol yellow ions, so their distinction is of interest.

**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 a conductive double-sided tape attached to stainless steel $1 \times 1 cm^2$ plates. The resulting deposit of powder had a flat surface and was fixed in a suitable way for the vacuum chamber. The plate was directly mounted on a “backmount” sample holder (IONTOF).

**In Situ Preparation:** None

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

**Temp. During Analysis:** 300 K

**Pressure During Analysis:** Between $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

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

## SPECIMEN DESCRIPTION (ACCESSION # 01951)

**Specimen:** Azurite (Kremer Pigmente Ref. 10207)

**CAS Registry #:** 12069-69-1

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

**Chemical Name:** Basic copper (II) carbonate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Cu_3(CO_3)_2(OH)_2$

**Form:** Ground pigment powder

**History and Significance:** A natural blue to turquoise-blue-green copper carbonate that results from the erosion of copper deposits. It was used in many contexts over the centuries and was considered a fairly precious material.
**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 a conductive double-sided tape attached to stainless steel $1 \times 1 \ cm^2$ plates. The resulting deposit of powder had a flat surface and was fixed in a suitable way for the vacuum chamber. The plate was directly mounted on a “backmount” sample holder (IONTOF).

**In Situ Preparation:** None

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

**Temp. During Analysis:** 300 K

**Pressure During Analysis:** Between $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

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

## SPECIMEN DESCRIPTION (ACCESSION # 01952)

**Specimen:** Malachite, natural (Kremer Pigmente Ref. 10300)

**CAS Registry #:** 1319-53-5

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

**Chemical Name:** Basic cupric carbonate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $CuCO_3 \cdot Cu(OH)_2$

**Form:** Ground pigment powder

**History and Significance:** A natural green to turquoise-green copper carbonate, which results from the erosion of copper deposits. It is one of the earliest known bright green pigments, and a dominant one until the mid-18th century. It was considered a fairly precious material. It consists of rather large spherical particles.

**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 a conductive double-sided tape attached to stainless steel $1 \times 1 \ cm^2$ plates. The resulting deposit of powder had a flat surface and was fixed in a suitable way for the vacuum chamber. The plate was directly mounted on a “backmount” sample holder (IONTOF).

**In Situ Preparation:** None

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

**Temp. During Analysis:** 300 K

**Pressure During Analysis:** Between $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

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

## SPECIMEN DESCRIPTION (ACCESSION # 01953)

**Specimen:** Verdigris, synthetic (Kremer Pigmente Ref. 44450)

**CAS Registry #:** 6046-93-1

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

**Chemical Name:** Copper-(II)-acetate-1-hydrate

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** $Cu(CH_3COO)_2 \cdot [Cu(OH)_2]_3 \cdot 2H_2O$

**Form:** Ground pigment powder

**History and Significance:** A family of synthetic pigments, containing variations in copper acetate, with green to blue-green hues. Synthesized since antiquity, it is an acetate copper salt produced by the reaction of acetic acid with copper and has been particularly common in wine-growing regions. It has a characteristic vinegar odor. A better knowledge of the ion signal of Verdigris pigments is of interest. Indeed, considered unstable, it reacts with binders and other pigments forming soaps and other copper salts, respectively, making its identification in a painting often ambiguous. Degradation products result in a brown tint.

**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 a conductive double-sided tape attached to stainless steel $1 \times 1 \ cm^2$ plates. The resulting deposit of powder had a flat surface and was fixed in a suitable way for the vacuum chamber. The plate was directly mounted on a “backmount” sample holder (IONTOF).

**In Situ Preparation:** None

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

**Temp. During Analysis:** 300 K

**Pressure During Analysis:** Between $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

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

## SPECIMEN DESCRIPTION (ACCESSION # 01954)

**Specimen:** Zinc white (Kremer Pigmente Ref. 46300)

**CAS Registry #:** 1314-13-2

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

**Chemical Name:** Zinc oxide

**Source:** Kremer Pigmente GmbH

**Specimen Composition:** ZnO

**Form:** Ground pigment powder

**History and Significance:** A widely used substitute for lead-containing whites that was first produced in the 19th century by Winsor & Newton (1834) with Michael Faraday.

**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 a conductive double-sided tape attached to stainless steel $1 \times 1 \ cm^2$ plates. The resulting deposit of powder had a flat surface and was fixed in a suitable way for the vacuum
chamber. The plate was directly mounted on a “backmount”
sample holder (IONTOF).

**In Situ Preparation:** None

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

**Temp. During Analysis:** 300 K

**Pressure During Analysis:** Between $1 \times 10^{-5}$ and $1 \times 10^{-6}$ Pa

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

## INSTRUMENT CONFIGURATION

**Manufacturer and Model:** IONTOF, TOF SIMS IV

**Analyzer Type:** Time-of-flight

**Sample Rotation:** No

**Rotation Rate:** 0 rpm

**Oxygen Flood Source:** None

**Oxygen Flood Pressure:** N/A

**Other Flood Source:** None

**Other Flood Pressure:** N/A

**Unique Instrument Features Used:** None

**Energy Acceptance Window:** 20 eV

**Post-acceleration Voltage:** 10 000 eV

**Sample Bias:** 10-20 eV

**Specimen Normal-to-analyzer (Θe):** 0°

### Ion sources

#### Ion source 1 of 2

**Purpose of this Ion Source:** Analysis beam

**Ion Source Manufacturer:** IONTOF GmbH

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

**Beam Mass Filter:** Yes

**Beam Species and Charge State:** $Bi_3^+$

**Beam Gating Used:** Double pulsed + Bunched

**Additional Beam Comments:** None

**Beam Voltage:** 25 000 eV

**Net Beam Voltage (impact voltage):** 25 000 eV

**Ion Pulse Width:** 0.8-1.2 ns

**Ion Pulse Rate:** 5-10 kHz

**DC Beam Current:** ~10 nA

**Pulsed Beam Current:** ~0.0004 nA

**Current Measurement Method:** Faraday cup

**Beam Diameter:** ~2 µm

**Beam Raster Size:** 250 × 250 µm$^2$

**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 gas cluster ion beam (GCIB)

**Beam Mass Filter:** Yes

**Beam Species and Charge State:** $Ar_n^+$ with n = 1500-2000

**Beam Gating Used:** Wien filter

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

**Beam Voltage:** 20 000 eV

**Net Beam Voltage (impact voltage):** 20 000 eV

**Ion Pulse Width:** N/A

**Ion Pulse Rate:** N/A

**DC Beam Current:** ~10 nA

**Pulsed Beam Current:** N/A

**Current Measurement Method:** Faraday cup

**Beam Diameter:** ~50 µm

**Beam Raster Size:** 500 × 500 µm$^2$

**Rotor Pixel Dimensions:** N/A

**Beam Incident Angle:** 45°

**Source-to-Analyzer Angle:** 45°

## ACKNOWLEDGMENTS

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

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

³E. Robert and L. Feller, *Artists' Pigments: A Handbook of Their History and Characteristics*, Vol. 1 (Archetype Publications, London, 1986).

⁴A. Roy, *Artists' Pigments: A Handbook of Their History and Characteristics*, Vol. 2 (Archetype Publications, London, 1993).

⁵E. W. FitzHugh, *Artists' Pigments: A Handbook of Their History and Characteristics*, Vol. 3 (Archetype Publications, London, 1997).

⁶J. R. Barnett, S. Miller, and E. Pearce, *Opt. Laser Technol.* **38**, 445 (2006).
<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">01947-01</td><td>12.000 (−3.10)</td><td>C<sup>−</sup></td><td>Charcoal</td></tr><tr><td>24.000 (−18.7)</td><td>C<sub>2</sub><sup>−</sup></td><td>Charcoal</td></tr><tr><td>25.008 (−2.87)</td><td>C<sub>2</sub>H<sup>−</sup></td><td>Charcoal</td></tr><tr><td>34.969 (−10.7)</td><td>Cl<sup>−</sup></td><td>—</td></tr><tr><td>36.000 (−17.2)</td><td>C<sub>3</sub></td><td>Charcoal</td></tr><tr><td>47.999 (−26.4)</td><td>C<sub>4</sub></td><td>Charcoal</td></tr><tr><td>60.001 (8.18)</td><td>C<sub>5</sub></td><td>Charcoal</td></tr><tr><td>62.966 (27.8)</td><td>PO<sub>2</sub><sup>−</sup></td><td>—</td></tr><tr><td>63.972 (0.44)</td><td>HPO<sub>2</sub><sup>−</sup></td><td>—</td></tr><tr><td>72.002 (17.1)</td><td>C<sub>6</sub><sup>−</sup></td><td>Charcoal</td></tr><tr><td>78.962 (40.2)</td><td>PO<sub>3</sub><sup>−</sup></td><td>—</td></tr><tr><td>79.967 (2.85)</td><td>HPO<sub>3</sub><sup>−</sup></td><td>—</td></tr><tr><td>84.001 (3.17)</td><td>C<sub>7</sub></td><td>Charcoal</td></tr><tr><td>96.000 (−15.0)</td><td>C<sub>8</sub><sup>−</sup></td><td>Charcoal</td></tr><tr><td>107.999 (−15.4)</td><td>C<sub>9</sub><sup>−</sup></td><td>Charcoal</td></tr><tr><td>119.998 (−19.0)</td><td>C<sub>10</sub></td><td>Charcoal</td></tr><tr><td>121.009 (5.26)</td><td>HC<sub>10</sub></td><td>Charcoal</td></tr><tr><td>131.998 (−19.3)</td><td>C<sub>11</sub></td><td>Charcoal</td></tr><tr><td>143.998 (−16.1)</td><td>C<sub>12</sub><sup>−</sup></td><td>Charcoal</td></tr><tr><td>145.009 (5.84)</td><td>HC<sub>12</sub></td><td>Charcoal</td></tr><tr><td>155.999 (−12.8)</td><td>C<sub>13</sub><sup>−</sup></td><td>Charcoal</td></tr><tr><td>167.997 (−20.2)</td><td>C<sub>14</sub></td><td>Charcoal</td></tr><tr><td>169.010 (10.2)</td><td>HC<sub>14</sub></td><td>Charcoal</td></tr><tr><td>179.998 (−12.5)</td><td>C<sub>15</sub></td><td>Charcoal</td></tr><tr><td>191.996 (−23.4)</td><td>C<sub>16</sub><sup>−</sup></td><td>Charcoal</td></tr><tr><td>193.007 (−9.01)</td><td>C<sub>16</sub>H<sup>−</sup></td><td>Charcoal</td></tr><tr><td>203.994 (−34.1)</td><td>C<sub>17</sub><sup>−</sup></td><td>Charcoal</td></tr><tr><td>217.009 (−34.3)</td><td>C<sub>18</sub>H<sup>−</sup></td><td>Charcoal</td></tr><tr><td>227.995 (−26.6)</td><td>C<sub>19</sub></td><td>Charcoal</td></tr></tbody></table>
<figure><img src="image_11.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01947-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Peach Black—Kremer Pigmente Ref. 12010</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time of flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>1700 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>C<sup>-</sup>, C<sub>2</sub><sup>-</sup>, C<sub>3</sub><sup>-</sup>, C<sub>8</sub><sup>-</sup>, C<sub>10</sub><sup>-</sup>, and C<sub>13</sub><sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>-</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 13 nA</td></tr><tr><td>DC Beam Current:</td><td>10.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>335 s</td></tr><tr><td>Comment:</td><td>ToF-SIMS can be used to characterize carbon-based pigments. Both C<sup>-</sup> and HC<sup>-</sup> are detected until n = 20, even if only the higher ones are labelled on the figure.</td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="10">01948-01</td><td>12.001 (27.4)</td><td>C<sup>-</sup></td><td>Charred material</td></tr><tr><td>15.996 (31.0)</td><td>O<sup>-</sup></td><td>—</td></tr><tr><td>24.001 (21.4)</td><td>C<sub>2</sub><sup>-</sup></td><td>Charred material</td></tr><tr><td>26.004 (20.2)</td><td>CN<sup>-</sup></td><td>Possible protein residue</td></tr><tr><td>34.970 (2.50)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>41.999 (16.9)</td><td>CNO<sup>-</sup></td><td>Possible protein residue</td></tr><tr><td>46.969 (−3.76)</td><td>PO<sup>-</sup></td><td>Calcium phosphate</td></tr><tr><td>55.957 (−14.8)</td><td>CaO<sup>-</sup></td><td>Calcium phosphate</td></tr><tr><td>59.966 (−25.1)</td><td>SiO<sub>2</sub><sup>-</sup></td><td>Aluminosilicate</td></tr><tr><td>62.964 (3.05)</td><td>PO<sub>2</sub><sup>-</sup></td><td>Calcium phosphate</td></tr><tr><td>75.964 (20.2)</td><td>SiO<sub>3</sub><sup>-</sup></td><td>Aluminosilicate</td></tr><tr><td>78.961 (17.9)</td><td>PO<sub>3</sub><sup>-</sup></td><td>Calcium phosphate</td></tr></tbody></table>
<figure><img src="image_12.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01948-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Bone Black—Kremer Pigmente Ref. 47100</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time of flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>3000 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>O<sup>-</sup>, CaO<sup>-</sup>, SiO<sub>2</sub><sup>-</sup>, PO<sub>2</sub><sup>-</sup>, SiO<sub>3</sub><sup>-</sup>, and PO<sub>3</sub><sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sup>3+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>292 s</td></tr><tr><td>Comment:</td><td>Notable low signal intensity for carbon clusters C<sub>n</sub><sup>-</sup> compared to Peach black (#01947 up to n = 6, and no C<sub>n</sub><sup>-</sup> detection for n > 7).</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">01949-01</td><td>31.973 (9.88)</td><td>S<sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>34.970 (21.7)</td><td>Cl<sup>-</sup></td><td>Natural impurity</td></tr><tr><td>47.967 (−19.4)</td><td>SO<sup>-</sup></td><td>—</td></tr><tr><td>63.946 (14.7)</td><td>S<sub>2</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>74.923 (14.6)</td><td>As<sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>79.960 (28.4)</td><td>SO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>90.915 (−21.5)</td><td>AsO<sup>-</sup></td><td>Arsenic oxide</td></tr><tr><td>95.917 (3.55)</td><td>S<sub>3</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>95.953 (9.50)</td><td>SO<sub>4</sub><sup>-</sup></td><td>—</td></tr><tr><td>106.891 (−25.6)</td><td>AsS<sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>106.914 (18.7)</td><td>AsO<sub>2</sub><sup>-</sup></td><td>Arsenic oxide</td></tr><tr><td>122.890 (5.76)</td><td>AsSO<sup>-</sup></td><td>Arsenic oxide</td></tr><tr><td>127.889 (0.58)</td><td>S<sub>4</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>138.868 (14.5)</td><td>AsS<sub>2</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>154.860 (−7.08)</td><td>AsS<sub>2</sub>O<sup>-</sup></td><td>Arsenic oxide</td></tr><tr><td>170.838 (−3.81)</td><td>AsS<sub>3</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>202.810 (−4.31)</td><td>AsS<sub>4</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>213.784 (−16.6)</td><td>As<sub>2</sub>S<sub>2</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>234.781 (−6.40)</td><td>AsS<sub>5</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>245.756 (−14.1)</td><td>As<sub>2</sub>S<sub>3</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>277.730 (−5.85)</td><td>As<sub>2</sub>S<sub>4</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>288.710 (0.64)</td><td>As<sub>3</sub>S<sub>2</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>309.704 (−1.19)</td><td>As<sub>2</sub>S<sub>5</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>320.680 (−4.32)</td><td>As<sub>3</sub>S<sub>3</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>336.681 (12.1)</td><td>As<sub>3</sub>S<sub>3</sub>O<sup>-</sup></td><td>Arsenic oxide</td></tr><tr><td>341.673 (−9.75)</td><td>As<sub>2</sub>S<sub>6</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>352.657 (10.3)</td><td>As<sub>3</sub>S<sub>4</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>368.651 (6.43)</td><td>As<sub>3</sub>S<sub>4</sub>O<sup>-</sup></td><td>Arsenic oxide</td></tr><tr><td>384.627 (2.52)</td><td>As<sub>3</sub>S<sub>5</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>400.660 (11.8)</td><td>As<sub>3</sub>S<sub>5</sub>O<sup>-</sup></td><td>Arsenic oxide</td></tr><tr><td>416.594 (−8.57)</td><td>As<sub>3</sub>S<sub>6</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>427.561 (−33.1)</td><td>As<sub>4</sub>S<sub>4</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>448.552 (−39.9)</td><td>As<sub>3</sub>S<sub>7</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>470.510 (−30.9)</td><td>As<sub>5</sub>S<sub>3</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>480.523 (−38.9)</td><td>As<sub>3</sub>S<sub>6</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>502.496 (−1.95)</td><td>As<sub>5</sub>S<sub>4</sub><sup>-</sup></td><td>α-As<sub>4</sub>S<sub>4</sub></td></tr><tr><td>534.481 (−10.4)</td><td>As<sub>5</sub>S<sub>4</sub>O<sub>2</sub><sup>-</sup></td><td>Arsenic oxide</td></tr><tr><td>560.615 (−26.9)</td><td>PbAs<sub>3</sub>S<sub>4</sub><sup>-</sup></td><td>Natural impurity</td></tr><tr><td>592.624 (5.89)</td><td>PbAs<sub>3</sub>S<sub>4</sub>O<sub>2</sub><sup>-</sup></td><td>Natural impurity</td></tr><tr><td>624.595 (5.15)</td><td>PbAs<sub>3</sub>S<sub>5</sub>O<sub>2</sub><sup>-</sup></td><td>Natural impurity</td></tr><tr><td>656.560 (−6.62)</td><td>PbAs<sub>3</sub>S<sub>6</sub>O<sub>2</sub><sup>-</sup></td><td>Natural impurity</td></tr></tbody></table>
<figure><img src="image_13.png" /></figure>

<table><tr><td>Accession #:</td><td>01949-01</td></tr><tr><td>Specimen:</td><td>Realgar/red orpiment—Kremer Pigmente Ref. 10800</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>3300 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>OH<sup>-</sup>, S<sub>2</sub><sup>-</sup>, AsS<sub>2</sub><sup>-</sup>, As<sub>2</sub>S<sub>3</sub><sup>-</sup>, and As<sub>3</sub>S<sub>4</sub><sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sup>3+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.34 × 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>Unstable, sensitive to light and oxygen. All oxygen-containing ions were localized in round-shaped areas of about 10 µm diameter dispersed within the analyzed surface of 250 × 250 µm<sup>2</sup>, allowing us to confidently determine whether a species contained oxygen or only sulfur.</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">01950-01</td><td>26.004 (10.1)</td><td>CN<sup>-</sup></td><td>—</td></tr><tr><td>42.000 (12.5)</td><td>CNO<sup>-</sup></td><td>—</td></tr><tr><td>46.967 (−52.6)</td><td>PO<sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>62.965 (19.3)</td><td>PO<sub>2</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>78.961 (26.0)</td><td>PO<sub>3</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub></td></tr><tr><td>98.929 (−3.86)</td><td>VO<sub>3</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>114.923 (6.57)</td><td>VO<sub>4</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>181.863 (−0.50)</td><td>V<sub>2</sub>O<sub>5</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>264.796 (−1.62)</td><td>V<sub>3</sub>O<sub>7</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>280.793 (6.97)</td><td>V<sub>3</sub>O<sub>8</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>307.777 (−43.3)</td><td>V<sub>2</sub>P<sub>2</sub>O<sub>9</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>323.772 (−40.7)</td><td>V<sub>2</sub>P<sub>2</sub>O<sub>10</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>323.897 (−22.7)</td><td>BiVO<sub>4</sub></td><td>BiVO<sub>4</sub></td></tr><tr><td>347.732 (5.10)</td><td>V<sub>4</sub>O<sub>9</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>363.730 (11.2)</td><td>V<sub>4</sub>O<sub>10</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>390.704 (−50.8)</td><td>V<sub>3</sub>P<sub>2</sub>O<sub>11</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>406.701 (−44.6)</td><td>V<sub>3</sub>P<sub>2</sub>O<sub>12</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>422.690 (−56.6)</td><td>V<sub>3</sub>P<sub>2</sub>O<sub>13</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>422.824 (−21.5)</td><td>BiV<sub>2</sub>O<sub>7</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>430.660 (−9.62)</td><td>V<sub>5</sub>O<sub>11</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>446.661 (3.97)</td><td>V<sub>5</sub>O<sub>12</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>462.655 (1.43)</td><td>V<sub>5</sub>O<sub>13</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>489.631 (−43.5)</td><td>V<sub>4</sub>P<sub>2</sub>O<sub>14</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>505.641 (−13.7)</td><td>V<sub>4</sub>P<sub>2</sub>O<sub>15</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>513.606 (15.6)</td><td>V<sub>6</sub>O<sub>13</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>529.606 (23.9)</td><td>V<sub>6</sub>O<sub>14</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>545.598 (17.9)</td><td>V<sub>6</sub>O<sub>15</sub><sup>-</sup></td><td>BiVO<sub>4</sub></td></tr><tr><td>572.571 (−26.5)</td><td>V<sub>5</sub>P<sub>2</sub>O<sub>16</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>588.592 (17.9)</td><td>V<sub>5</sub>P<sub>2</sub>O<sub>17</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr><tr><td>604.593 (27.8)</td><td>V<sub>5</sub>P<sub>2</sub>O<sub>18</sub><sup>-</sup></td><td>Zn<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> + BiVO<sub>4</sub></td></tr></tbody></table>
<figure><img src="image_14.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01950-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Bristol Yellow—Kremer Pigmente Ref. 43111</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>CH<sup>-</sup>, CH<sub>2</sub><sup>-</sup>, C<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, C<sub>3</sub><sup>-</sup>, and C<sub>4</sub>H<sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 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 17 nA</td></tr><tr><td>DC Beam Current:</td><td>15.1 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>256 s</td></tr></tbody></table>
<table><caption>SPECTRAL FEATURES TABLE</caption><thead><tr><th>Spectrum ID #</th><th>Mass (Δm), Da</th><th>Species</th><th>Peak Assignment</th></tr></thead><tbody><tr><td rowspan="20">01951-01</td><td>62.931 (10.7)</td><td>Cu<sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>76.985 (-37.5)</td><td>CO<sub>3</sub>OH<sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>78.925 (-0.79)</td><td>CuO<sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>94.919 (-11.5)</td><td>CuO<sub>2</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>95.930 (19.6)</td><td>CuO<sub>2</sub>H<sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>104.947 (59.4)</td><td>CuC<sub>2</sub>H<sub>2</sub>O<sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>118.943 (33.2)</td><td>AlSiO<sub>4</sub><sup>-</sup></td><td>Aluminosilicate interference</td></tr><tr><td>122.915 (-3.49)</td><td>CuCO<sub>3</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>138.909 (-7.33)</td><td>CuCO<sub>4</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>154.902 (-18.3)</td><td>CuO<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>157.856 (39.9)</td><td>Cu<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>173.843 (-6.04)</td><td>Cu<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>178.913 (41.4)</td><td>Si<sub>2</sub>AlO<sub>6</sub><sup>-</sup></td><td>Aluminosilicate interference</td></tr><tr><td>198.887 (-38.4)</td><td>CuO(CO<sub>3</sub>)<sub>2</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>217.835 (4.06)</td><td>Cu<sub>2</sub>O<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>236.772 (-7.29)</td><td>Cu<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>258.842 (20.5)</td><td>Cu<sub>2</sub>C<sub>3</sub>O<sub>6</sub>H<sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>277.823 (14.6)</td><td>Cu<sub>2</sub>O<sub>2</sub>(CO<sub>3</sub>)<sub>2</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>296.759 (-0.68)</td><td>Cu<sub>3</sub>O<sub>3</sub>CO<sub>3</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>315.700 (5.09)</td><td>Cu<sub>4</sub>O<sub>4</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>358.764 (12.3)</td><td>Cu<sub>3</sub>O(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub><sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_15.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01951-01</th></tr></thead><tbody><tr><td>Specimen:</td><td>Azurite—Kremer Pigmente Ref. 10207</td></tr><tr><td>Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time of flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>2000 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Cl<sup>-</sup>, Cu<sup>-</sup>, CuO<sub>2</sub><sup>-</sup>, Cu<sub>3</sub>O<sub>3</sub><sup>-</sup>, and Cu<sub>4</sub>O<sub>4</sub><sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 13 nA</td></tr><tr><td>DC Beam Current:</td><td>10.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 μm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 μm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>335 s</td></tr><tr><td>Comment:</td><td>Aluminosilicates are also found in this sample, a possible impurity.<br>Isotopic ratios for copper cluster ions are impacted by overlapping aluminosilicate ions.<br>The peaks at m/z 59.97 and 75.97 are likely to be, respectively, CO<sub>3</sub><sup>-</sup> and CO<sub>4</sub><sup>-</sup> but also contain near isobaric interferences from, respectively, SiO<sub>2</sub><sup>-</sup> and SiO<sub>3</sub><sup>-</sup>. They are, therefore, not listed in the table. Additional series of peaks are commonly detected in this compound, with lower intensity. They can be attributed to other Cu<sub>x</sub>O<sub>y</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">01952-01</td><td>34.970 (10.4)</td><td>Cl<sup>-</sup></td><td>—</td></tr><tr><td>59.968 (7.61)</td><td>SiO<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>62.930 (−7.31)</td><td>Cu<sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>62.965 (6.21)</td><td>PO<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>78.925 (−0.68)</td><td>CuO<sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>78.963 (54.2)</td><td>PO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>94.921 (6.24)</td><td>CuO<sub>2</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>95.929 (15.5)</td><td>CuO<sub>2</sub>H<sup>-</sup></td><td>Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub></td></tr><tr><td>104.945 (38.3)</td><td>CuC<sub>2</sub>H<sub>2</sub>O<sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>113.896 (17.8)</td><td>CuOCl<sup>-</sup></td><td>—</td></tr><tr><td>120.940 (35.9)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub>Cu<sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>122.918 (27.7)</td><td>CuCO<sub>3</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>132.873 (39.9)</td><td>CuCl<sub>2</sub><sup>-</sup></td><td>—</td></tr><tr><td>138.903 (−51.3)</td><td>CuCO<sub>4</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>142.894 (−21.5)</td><td>CuHCO<sub>2</sub>Cl<sup>-</sup></td><td>—</td></tr><tr><td>154.901 (−27.4)</td><td>CuO<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>157.854 (25.1)</td><td>Cu<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>160.867 (25.0)</td><td>CuCl<sub>2</sub>CO<sup>-</sup></td><td>—</td></tr><tr><td>173.847 (13.3)</td><td>Cu<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>192.847 (−29.7)</td><td>CuCl<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>198.882 (−64.8)</td><td>Cu<sub>2</sub>C<sub>2</sub>O<sub>2</sub>OH<sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>211.799 (34.1)</td><td>Cu<sub>2</sub>Cl<sub>2</sub>O<sup>-</sup></td><td>—</td></tr><tr><td>217.827 (−32.7)</td><td>Cu<sub>2</sub>O<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>220.821 (34.2)</td><td>Cu<sub>2</sub>ClCO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>236.774 (1.20)</td><td>Cu<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>255.784 (5.09)</td><td>Cu<sub>2</sub>Cl<sub>2</sub>CO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>296.752 (−22.3)</td><td>Cu<sub>3</sub>O<sub>3</sub>CO<sub>3</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>299.734 (−11.7)</td><td>Cu<sub>3</sub>ClCO<sub>4</sub><sup>-</sup></td><td>—</td></tr><tr><td>315.700 (5.68)</td><td>Cu<sub>4</sub>O<sub>4</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr><tr><td>378.635 (16.8)</td><td>Cu<sub>5</sub>O<sub>4</sub><sup>-</sup></td><td>CuCO<sub>3</sub>·Cu(OH)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_16.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01952-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Malachite, natural—Kremer Pigmente Ref. 10300</td></tr><tr><td>■ Technique:</td><td>SIMS</td></tr><tr><td>Instrument:</td><td>IONTOF, TOF SIMS IV</td></tr><tr><td>Analyzer Type:</td><td>Time of flight</td></tr><tr><td>Analyzer Mass Resolving Power:</td><td>2000 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Cl<sup>-</sup>, Cu<sup>-</sup>, CuO<sub>2</sub><sup>-</sup>, Cu<sub>3</sub>O<sub>3</sub><sup>-</sup>, and Cu<sub>4</sub>O<sub>4</sub><sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sub>3</sub><sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.35 × 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>0.00013 nA</td></tr><tr><td>DC Beam Current:</td><td>10.4 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>355 s</td></tr><tr><td>Comment:</td><td>Chlorine is detected, as well as copper/chlorine cluster ions. Additional series of peaks are commonly detected in this compound, with lower intensity. They can be attributed to other Cu<sub>x</sub>O<sub>y</sub><sup>-</sup>.</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">01953-01</td><td>41.004 (14.9)</td><td>C<sub>2</sub>OH<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>58.005 (-13.9)</td><td>CO<sub>2</sub>CH<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>59.017 (44.0)</td><td>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>59.983 (-37.0)</td><td>CO<sub>3</sub></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>60.019 (-40.7)</td><td>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub>H<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>62.930 (-3.74)</td><td>Cu<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub>·[Cu(OH)<sub>2</sub>]<sub>3</sub>·2H<sub>2</sub>O</td></tr><tr><td>73.033 (48.7)</td><td>C<sub>3</sub>H<sub>5</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>75.013 (60.0)</td><td>C<sub>2</sub>H<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>77.954 (0.64)</td><td>CuCH<sub>3</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>78.922 (-37.1)</td><td>CuO<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub>·[Cu(OH)<sub>2</sub>]<sub>3</sub>·2H<sub>2</sub>O</td></tr><tr><td>78.961 (20.1)</td><td>PO<sub>3</sub><sup>-</sup></td><td>—</td></tr><tr><td>92.981 (40.5)</td><td>CuC<sub>2</sub>H<sub>6</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>102.921 (-43.5)</td><td>CuC<sub>2</sub>O<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>104.944 (32.2)</td><td>CuC<sub>2</sub>H<sub>2</sub>O<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>118.954 (-20.0)</td><td>CuC<sub>3</sub>H<sub>4</sub>O<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>120.939 (28.9)</td><td>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub>Cu<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>122.951 (-2.71)</td><td>CuC<sub>2</sub>H<sub>3</sub>O<sub>2</sub>H<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>136.972 (38.8)</td><td>CuC<sub>3</sub>H<sub>5</sub>O<sub>2</sub>H<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>146.951 (-2.73)</td><td>CuC<sub>4</sub>H<sub>4</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>148.962 (-35.5)</td><td>CuC<sub>4</sub>H<sub>6</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>150.980 (-20.6)</td><td>CuC<sub>4</sub>H<sub>8</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>157.851 (8.73)</td><td>Cu<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub>·[Cu(OH)<sub>2</sub>]<sub>3</sub>·2H<sub>2</sub>O</td></tr><tr><td>162.947 (7.60)</td><td>CuC<sub>4</sub>H<sub>3</sub>O<sub>2</sub>OH<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>180.962 (27.1)</td><td>CuC<sub>4</sub>H<sub>6</sub>O<sub>4</sub></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>194.942 (30.2)</td><td>CuOC<sub>4</sub>H<sub>4</sub>O<sub>4</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>200.871 (17.2)</td><td>Cu<sub>2</sub>OC<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>215.863 (36.0)</td><td>Cu<sub>2</sub>O<sub>2</sub>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>216.871 (35.2)</td><td>Cu<sub>2</sub>O<sub>2</sub>C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>217.866 (-20.5)</td><td>CuC<sub>2</sub>H<sub>2</sub>O<sub>2</sub>CuO<sub>2</sub>H<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>224.860 (-36.3)</td><td>Cu<sub>2</sub>C<sub>2</sub>OCH<sub>3</sub>COO<sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>236.778 (17.7)</td><td>Cu<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub>·[Cu(OH)<sub>2</sub>]<sub>3</sub>·2H<sub>2</sub>O</td></tr><tr><td>239.958 (-49.4)</td><td>CuC<sub>6</sub>H<sub>9</sub>O<sub>6</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>244.855 (-9.60)</td><td>Cu<sub>2</sub>O<sub>3</sub>C<sub>3</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>259.869 (-47.0)</td><td>Cu<sub>2</sub>OC<sub>4</sub>H<sub>6</sub>O<sub>4</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>278.788 (12.1)</td><td>Cu<sub>3</sub>O<sub>2</sub>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>284.760 (1.94)</td><td>Cu<sub>3</sub>O<sub>6</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>302.885 (-49.6)</td><td>Cu<sub>2</sub>C<sub>6</sub>H<sub>9</sub>O<sub>6</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub>·[Cu(OH)<sub>2</sub>]<sub>3</sub>·2H<sub>2</sub>O</td></tr><tr><td>322.776 (3.07)</td><td>Cu<sub>3</sub>O<sub>4</sub>C<sub>3</sub>H<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>356.718 (46.2)</td><td>Cu<sub>4</sub>O<sub>3</sub>C<sub>2</sub>HO<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>381.810 (-37.8)</td><td>Cu<sub>3</sub>OC<sub>6</sub>H<sub>9</sub>O<sub>6</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>402.710 (8.67)</td><td>Cu<sub>4</sub>O<sub>4</sub>C<sub>3</sub>H<sub>3</sub>O<sub>3</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>420.633 (-14.9)</td><td>Cu<sub>5</sub>O<sub>3</sub>C<sub>2</sub>H<sub>2</sub>O<sub>2</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>440.820 (-39.1)</td><td>Cu<sub>3</sub>OC<sub>8</sub>H<sub>12</sub>O<sub>8</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>444.727 (21.2)</td><td>Cu<sub>4</sub>O<sub>4</sub>C<sub>5</sub>H<sub>5</sub>O<sub>4</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr><tr><td>464.650 (-31.7)</td><td>Cu<sub>5</sub>O<sub>2</sub>C<sub>4</sub>H<sub>6</sub>O<sub>4</sub><sup>-</sup></td><td>Cu(CH<sub>3</sub>COO)<sub>2</sub></td></tr></tbody></table>
<figure><img src="image_17.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01953-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Verdigris, synthetic—Kremer Pigmente Ref. 44450</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>, Cu<sup>-</sup>, CuO<sup>-</sup>, Cu<sub>2</sub>O<sub>2</sub><sup>-</sup>, and Cu<sub>3</sub>O<sub>3</sub><sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>1.0 × 10<sup>13</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>6.7 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 31 nA</td></tr><tr><td>DC Beam Current:</td><td>13.2 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>100 × 100 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>1995 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>617 s</td></tr><tr><td>Comment:</td><td>Surface was not flat, which impacted the mass resolution. Peak at m/z 59.02 attributed to acetate ion C<sub>2</sub>H<sub>3</sub>O<sub>2</sub><sup>-</sup> was saturated.</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">01954-01</td><td>79.925 (0.58)</td><td>ZnO<sup>-</sup></td><td>ZnO</td></tr><tr><td>80.932 (-6.02)</td><td>ZnOH<sup>-</sup></td><td>—</td></tr><tr><td>95.920 (0.39)</td><td>ZnO<sub>2</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>96.927 (-5.50)</td><td>ZnO<sub>2</sub>H<sup>-</sup></td><td>—</td></tr><tr><td>111.914 (-0.95)</td><td>ZnO<sub>3</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>159.849 (-1.06)</td><td>(ZnO)<sub>2</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>175.842 (-8.44)</td><td>Zn<sub>2</sub>O<sub>3</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>176.851 (-3.88)</td><td>Zn<sub>2</sub>O<sub>3</sub>H<sup>-</sup></td><td>—</td></tr><tr><td>191.839 (3.26)</td><td>Zn<sub>2</sub>O<sub>4</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>239.775 (8.80)</td><td>(ZnO)<sub>3</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>255.766 (-6.07)</td><td>Zn<sub>3</sub>O<sub>4</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>256.775 (-1.65)</td><td>Zn<sub>3</sub>O<sub>4</sub>H<sup>-</sup></td><td>—</td></tr><tr><td>319.701 (13.1)</td><td>(ZnO)<sub>4</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>335.693 (4.34)</td><td>Zn<sub>4</sub>O<sub>5</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>336.704 (12.6)</td><td>Zn<sub>4</sub>O<sub>5</sub>H<sup>-</sup></td><td>—</td></tr><tr><td>399.625 (10.2)</td><td>(ZnO)<sub>5</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>415.611 (-11.0)</td><td>Zn<sub>5</sub>O<sub>6</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>416.620 (-9.50)</td><td>Zn<sub>5</sub>O<sub>6</sub>H<sup>-</sup></td><td>—</td></tr><tr><td>495.532 (-16.3)</td><td>Zn<sub>6</sub>O<sub>7</sub><sup>-</sup></td><td>ZnO</td></tr><tr><td>496.543 (-10.2)</td><td>Zn<sub>6</sub>O<sub>7</sub>H<sup>-</sup></td><td>—</td></tr></tbody></table>
<figure><img src="image_18.png" /></figure>

<table><thead><tr><th>Accession #:</th><th>01954-01</th></tr></thead><tbody><tr><td>■ Specimen:</td><td>Zinc White—Kremer Pigmente Ref. 46300</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>4500 m/Δm</td></tr><tr><td>Mass Resolving Power Determined at:</td><td>25 Da</td></tr><tr><td>Species Used for Mass Calibration:</td><td>Cl<sup>-</sup>, ZnO<sub>2</sub><sup>-</sup>, Zn<sub>2</sub>O<sub>3</sub><sup>-</sup>, Zn<sub>3</sub>O<sub>4</sub><sup>-</sup>, <sup>66</sup>Zn<sub>2</sub><sup>68</sup>ZnZn<sub>2</sub>O<sub>8</sub><sup>-</sup>, <sup>66</sup>Zn<sup>68</sup>Zn<sub>2</sub>Zn<sub>4</sub>O<sub>8</sub><sup>-</sup>, and <sup>66</sup>Zn<sub>2</sub><sup>68</sup>Zn<sub>2</sub>Zn<sub>5</sub>O<sub>10</sub><sup>-</sup></td></tr><tr><td>Specimen Normal-to-Analyzer:</td><td>0°</td></tr><tr><td>Source-to-Analyzer Angle:</td><td>45°</td></tr><tr><td>Primary Beam Ion Gun:</td><td>LMIG</td></tr><tr><td>Primary Ion Species:</td><td>Bi<sup>+</sup></td></tr><tr><td>Primary Ion Dose:</td><td>4.37 × 10<sup>11</sup> ion/cm<sup>2</sup></td></tr><tr><td>Primary Ion Pulse Width:</td><td>0.8–1.2 ns</td></tr><tr><td>Primary Ion Pulse Rate:</td><td>5 kHz</td></tr><tr><td>Net Beam Voltage:</td><td>25 000 eV</td></tr><tr><td>Pulsed Beam Current:</td><td>0.000 15 nA</td></tr><tr><td>DC Beam Current:</td><td>14.7 nA</td></tr><tr><td>Beam Diameter:</td><td>~2 µm</td></tr><tr><td>Beam Raster Size:</td><td>250 × 250 µm<sup>2</sup></td></tr><tr><td>Beam Incident Angle:</td><td>45°</td></tr><tr><td>Secondary Source Polarity:</td><td>Negative</td></tr><tr><td>Mass Range Minimum:</td><td>0 Da</td></tr><tr><td>Mass Range Maximum:</td><td>3545 Da</td></tr><tr><td>Spectrum Dead Time Corrected:</td><td>Yes</td></tr><tr><td>Total Spectral Acquisition Time:</td><td>309 s</td></tr><tr><td>Comment:</td><td>Distinctive isotopic pattern for Zn. Peaks attributed to O(ZnO)<sub>x</sub> are commonly present up to x = 10, with lower intensity.</td></tr></tbody></table>