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Hueco Tanks Pictographs: Technical Analysis in Advance of Possible Laser Cleaning

Andrew Lins, Beth Price, Ken Sutherland, Heather Brown - Philadelphia Museum of Art Tom Tague - Bruker Optics Andrzej Dajnowski - CSOS

HUECO TANKS

OUTLINE Hueco Tanks Site Background Prevalence of Graffiti Challenges for In Situ Analysis

without sampling Analytical Results Next Steps

MAJOR U.S. ROCK CLIMBING SITE

Hueco Tanks Site

HUECO TANKS !

A LACCOLITHIC IGNEOUS INTRUSION OF PORPHYRITIC SYENITE COOLED UNDER A LIMESTONE CAP

C. 35 MILLION YEARS AGO

Hueco Tanks HistoryFirst Layers : Archaic

150 – 1400/1450 AD : Jornada Mogollon

Post 1660: Apache and others

First Graffiti: 1849

Hueco Tanks PictographsTotal close to 5,000; largest site for masks in US (more than 200)

Many Pictographs are from Jornada Mogollon Period, ca 100 -140/1450 AD

‘Closed’ Mask types Dancer variants

Rupestrian CyberscanImage from 5/2011

ENHANCEMENT OF PICTOGRAPH IMAGES

1. Laboratory Analyses of graffiti

Graffiti – microsamples - MFTIR, Py-GCMS, SEM-EDS

2. In Situ Analyses of Pigments/media

Pictographs – no sampling – XRF, Raman, DRIFT

Site E01F – “HC” graffiti

Site E01F “HC”

SAMPLING GRAFFITI August 2010

prior determination of underlying and poorly visible material

Site E01F “HC” – Media

PyGCMS:: Oxidized diterpenes (DHA and 7-oxo DHA); probably Pinaceae Dimethyl and dibutyl phthlates, P, S, Az FA’s (drying oil)

Pyrogram for sample E01F !!!!!!!!!

Site E01F “HC” – Media

MFTIR: Blue-back graffiti paint (top) CN reference spectrum (second) Natural resin phase (third) Natural resin reference spectrum (bottom)

Site E01F “HC” – Pigments

Fe FeCa

CaAlSi S Fe

O

CCa

0 1 2 3 4 5 6 7 8 9 10 11keVFull Scale 1439 cts Cursor: -0.075 (1 cts)

Spectrum 1

Site N19C “Castro”

Site N19C “Castro” – Fillers/Pigments

BaCa BaCaAl

BaNa

SiBa

Ca

Ba

CO

Ba

S

0 1 2 3 4 5 6 7 8 9 10keVFull Scale 1563 cts Cursor: -0.059 (10 cts)

PMAS3869

ZnFe ZnFe Ti

Ti

FeZn K

MgNa

P Ca

KTi

Al

Ca

OCa

SSiKC

0 1 2 3 4 5 6 7 8 9 10 11keVFull Scale 2920 cts Cursor: -0.203 (0 cts)

Spectrum 1

Site N19C, CASTRO: FTIR, filler - gypsum

Site N19C “Castro” – Media

MFTIR: Grey graffiti paint from site (top) Alkyd paint reference (bottom)

PyGCMS: Me-benzoate PE (≥ 1960) Ortho phthlate P, S, Az FAMES

In Situ Analysis of Pictographs• No sampling allowed

In Situ Analysis Challenges

Bruker Instrumentation for on site NDT

XRF Tracer 15 KV, 23 µA: 40KV, 11.2 µA

Alpha DRIFT Res 4cm-1 DTGS detector 375 – 4000 cm-1

Sentinel 80mW @ sample 90 - 2175 cm-1

Res 3.0 cm-1

XRF Set-up

RAMAN CAMERA USES LASER for SAMPLE LOCATION AND WHITE LIGHT FOR IMAGING

Raman set-up

Low ambient light requirement

Measurements after dusk

DRIFT Set-up

Spacing/Gap is 1/2” between pictograph and

instrument

PictographSite E10C “Starry Eyed Man”

Native American, Jonada Mogollon Culture 450-1400 AD

Starry Eye Man Site

Pictograph

~9 feet above cave floor

Site E10C, Starry Eye Man: Pigments – XRF - Green

STONE

PIGMENT

Site E10C Pigments – XRF - Red

STONE

PIGMENT

Site E10C Pigments – Raman : Hematite + Gypsum

First successful in situ NDT Raman analysis for rock art In the US

HC pigment/stone

!PICTOGRAPH EOIF : DANCING FIGURE

Enhanced image

WHITE PIGMENT AND ROCK SUBSTRATE E01C

Raman Shift (Wavenumbers)

Red – White pigment Brown - Rock

1399

.83

1374

.16

1286

.27

1257

.52

1221

.70

1007

.39

1000 1100 1200 1300 1400 1500

-400

000

-200

000

020

0000

4000

0060

0000

8000

0010

0000

0Ra

man

Inte

nsit

y

Gypsum

Oxalate

Carbonate bands from white pigment

E01F, Dancing Figure; pigment vs stone

XRF Data

pigment

stone

EO1C RAMAN OF YELLOW PIGMENT FROM DANCING FIGURE

548.

98

385.

57

296.

89

243.

79

100 200 300 400 500 600

1400

015

000

1600

017

000

1800

019

000

2000

0Ra

man

Inte

nsit

y

Raman Shift (Wavenumbers)

Goethite

NEXT STEPSCREATE SURROGATE SAMPLES OF ‘GRAFFITI’ OVER

‘PICTOGRAPHS’ !

EVALUATE DIFFERENT FLUENCES AND ABSORPTION TO OPTIMIZE CONDITIONS FOR LASER CLEANING

! EXAMINE CLEANED SURROGATE SAMPLES BY SEM-EDS FOR BEAM DAMAGE OR OTHER

SURFACE ALTERATION PRIOR TO FIELD TESTS

Acknowledgements!Texas Parks & Wildlife

Tim Roberts, Wanda Olszewski, Michael Strutt

Bruker

Tom Tague and Bruce Kaiser

PMA

Timothy Rub, Terra Huber, Chris Wasson, with Katherine Lins

Show enhanced image E01F

Transportation Challenges

Site E10C Pigments – XRF Stone

E01F Dancing Figure: XRF Results

Provide Support to Outside Insitutions:Hueco Tanks, Texas Parks & Wildlife Dept

Yellow paint from site (top) Cellulose nitrate (middle-top) Subtraction result (middle-bottom) Alkyd paint reference (bottom)

OUTLINE

Hueco Tanks Site Background Prevalence of Graffiti Challenges for In Situ Analysis without sampling Analytical Results Next Steps

Hueco Tanks Pictographs: Technical Analysis of Graffiti, in Advance of Possible Laser Cleaning

Andrew Lins, Beth Price, Ken Sutherland, Heather Brown, Tom Tague, Andrzej Dajnowski

Hueco Tanks Pictographs: Technical Analysis of Graffiti,

in Advance of Possible Laser Cleaning

• Andrew Lins, Beth Price, Ken Sutherland, Heather Brown, Tom Tague, Andrzej Dajnowski