Analysis  of  trace  metals  in  ta0oo  inks  using  Agilent  ICP  MP-­‐AES  Saleh  Al-­‐Khalifa,  Hailey  Butman  and  Chris8ne  H.  Jaworek-­‐Lopes    Department  of  Chemistry,  Emmanuel  College,  Boston,  MA  02115  

Data Analysis Method A calibration curve was constructed using 1000 ppm metal standards (Fischer

Scientific©), including aluminum, arsenic, cadmium, chromium, copper, iron,

lead, and zinc. A correlation of 0.999 and above was obtained for each of the

curves. Samples are heated to room temperature then analyzed using ICP

MP-AES in which 3.5 mL of sample is pumped into the nebulizer. The sample

however, must be free of any undigested particulates. From there, plasma

energy is generated to excite the atoms in the sample to a higher energy

state. When the samples return to a low energy position, emission rays are

released and the emitted wavelengths are characteristic of the various metals

present in the sample. ICP MP-AES calculates the concentrations of these

metals as a linear function for each sample.

Results & Conclusions The concentrations of metals in the tattoo inks that were analyzed revealed

contradictory results compared to the manufacturers MSDS sheets.

Concentrations of copper showed staggering results in the black and blue

pigments which are primarily copper based compounds. One sample in

particular was determined to contain more than 9000 ppm. On the other hand,

aluminum concentrations took the lead in green and red pigments ranging up

to 900 ppm.

Future Work

The majority of the tattoo inks contain titanium dioxide which cannot be fully

digested without the use of hydrofluoric acid. Several methods were proposed

in order to avoid the use of such a strong acid, including the use of

diatomaceous earth (Celite) in order to filer the titanium from the samples.

Preliminary results showed that the Celite itself contained impurities. Current

research focuses on the acid washing of Celite in order to remove all

impurities and filter the titanium from all remaining inks in order to complete

the market survey of all selected inks.

Phthalocyanine Green (PG7) Phthalocyanine Blue (PB15)

References 1. Reed, Carrie E. "Tattoo in Early China." Journal of the American Oriental Society120.3 (2000): 360-76. JStor. Web 2. Mayers, L.B.; Judelson, D.A.; Moriart, B.W.; Rundell, K.W. Prevalence of body art (body piercing and tattooing) in university undergraduates and incidence of medical complications. Mayo Clinic Prof. 2002, 77, 29-34. 3. Think Before You Ink: Are Tattoos Safe? http://fda.gov/forconsumers/consumerupdates/ucm08919.htm (accessed 7/29/2014) US Food and Drug Administration. 4. Engel, E.; Santarelli, F.; Vasold, R.; Baumler, W. Modern tattoos cause high concentrations of hazardous pigments in skin. University of Regensburg. 2008, 228-233. 5. Forte, G.; Petrucci, F.; Cristaudo, A.; Bocca, B. Quantification of Sensitizing Metals in Tattooing Pigments By SF-ICP-MS Technique. 2009, 42-47. 6. Ortiz, A.E; Alster, T.S. Rising Concern over Cosmetic Tattoos. University of California. 2011, 1-6. 7. Engel,E.; Santarelli, F.; Vasold, R.; Ulrich, H.; Maish, T.; Konig, B.; Lanthaler, M.; Gopee N.V.; Howard, P.C.; Baumler, W. University of Regensburg. 2006, 6440-6447. 8. Forte, G.; Petrucci, F.; Cristaudo, A.; Bocca, B. Market survey on toxic metals contained in tattoo inks. Instituto Superiore di Sanita, Viale Regine Elena. 2009, 5997-6002.

Acknowledgments •  Emmanuel College for financial support •  Dr. Christine Jaworek-Lopes for support & leadership •  Dr. Graham Peaslee of Hope College for collaboration •  Tuyen Tran and Courtney Walker for their efforts in Spring 2013 •  Matt Salvi (2010), Rebecca Rose (2011), Kelly Tan (2014), and

Melanie Wieler who pioneered in this research project

Common Pigments Found in Tattoo Inks

Abstract The art of skin tattooing has been practiced since medieval times, but has

increased significantly in popularity since the 1970s. This is problematic as

tattoo inks are not currently regulated by the Food and Drug Administration

(FDA), and manufacturers are not required by law to inform users of the

contents of their products. The minimal information provided, which is solely in

the form of material safety data sheets, is often vague and inaccurate. The

production of tattoo inks is not subject to the same stringent quality control

standards of other cosmetic products, making them subject to significant

safety concerns. The purpose of this research was to quantify the

concentration of metals, particularly heavy metals, in tattoo inks. Using CEM

MARS 6 microwave, we were able to digest the tattoo inks using concentrated

nitric acid. Analysis of unknown concentrations was conducted with ICP MP-

AES using a calibration curve. Results of this market analysis of 50+ inks are

reported, and directions for future research are discussed.

Previous Digestion Method Previous methods included table top digestions, in which 0.125 mL of ink was

added to a 25 mL beaker, followed by the addition of 5.0 mL of concentrated

nitric acid (SIGMA-ALDRICH©) and held in a hot mineral oil bath at 90oC for

ten minutes. An additional 5.0 mL aliquot of concentrated nitric acid was

added to the solution and heated for ten more minutes. Upon completion, the

resulting solution portrayed a transparent yellow product, containing

undigested particles. Vacuum filtration of the final product was necessary for

analysis via atomic absorbance (AA), resulting in inaccurate heavy metal

concentration results.

Current Digestion Method The current method of digestion includes the utilization of a CEM MARS 6

microwave, in which 0.125 mL of ink is added to a digestion vessel, followed

by 5.0 mL of concentrated nitric acid (ACROS©). The vessels are then placed

in the microwave and held at 230oC for 15 minutes. Upon completion of

digestion, samples are cooled to room temperature, placed in 50 mL

volumetric flasks and diluted with distilled water. Additionally, all glassware is

acid-washed with a 1% EDTA solution to eliminate remaining metal ions,

followed by a 1% HCl solution to eliminate excess EDTA. These samples are

then stored at 4oC for a maximum of seven days in order to avoid changes.

45.3

80.0

932.0

636.7

68.9

5.31

8.30

30.1

4940

9220

40.2

4.0

38.3

1.0

80.7

32.0

51.8

4.20

12.5

55.6

1

10

100

1000

10000

Con

cent

ratio

n (p

pm)

Black Blue Green Red

Concentrations of Trace Metals in Selected Samples of Tattoo Inks Displayed on the Logarithmic Scale

Al Cr Cu Fe Pb

Phthalocyanine Blue (PB15 & PW 4)

Figure #1: Table-top digestion method applied to four samples in which the sample second from the left is not fully digested due to inadequate (low) temperatures.

Figure #2: MARS 6 Microwave digestion of an ink sample showing the color before and digestion as well as after the digestion.