J. Carrillo, S.

Fazilova

Would you like a receipt?

YES

W. Khushaim, Y. Lee

Determination of Bisphenol-A and Bisphenol-S in

Thermal Receipt Paper using Liquid Chromatography

NO

M. Milici, J. Tindal, G. Pillar

Department of Environmental Science & Chemistry, Queens University of Charlotte, Charlotte NC 28274
INTRODUCTION

RESULTS

Bisphenol A (4,4-(propane-2,2-diyl)diphenol; BPA) and

Bisphenol S (4,4-sulfonyldiphenol; BPS) are used as color
developers in thermal paper (Figure 1).

DISCUSSION
In this study, 52 receipts were analyzed where 38 receipts
contained BPS and 10 receipts contained BPA (Figure 6).
Receipts containing BPS ranged from 10.0 to 19.4 mg/g
of receipt paper. Receipts containing BPA ranged from
10.3 to 21.2 mg/g of receipt paper (Table 1).

Table 1. Percent mass content of BPA & BPS with standard deviation and mass range in
thermal receipt paper from different sources in Charlotte, NC, area, and the number of
receipts that did not contain any BPA or BPS.

(b)

(a)

A BPA standard and a BPS standard were analyzed to

identify the retention times (Figure 3). It was determined
that BPA eluted at 3.339 minutes and BPS eluted at 7.896
minutes. The standard curves for both BPA and BPS
were created through serial dilution. The r2 value for
BPA and BPS was .9985 and .9999, respectively. Seven
of the 52 receipts tested had quantifiable concentrations
of an unknown analyte with a retention time of 11.297
minutes (Figure 4). Four of the 52 receipts tested
contained neither BPA or BPS.

Figure 1. The chemical structure of (a) bisphenol A (BPA) and (b)

bisphenol S (BPS).

BPA or BPS are present in the Thermal Reactive Layer of

thermal receipt papers (Figure 2). The purpose of the developer
(BPA and BPS) is to transfer protons to the dye, triggering color
formation (5).
(a)

(b)

Top Coat
Thermal Reactive Layer
Pre-Coat
Dye

Sensitizer

Developer (BPA/BPS)

Binder

Figure 5. Thermal paper receipts were collected from 52 local retail

businesses in Mecklenburg (NC), Union (NC), and Lancaster (SC) counties.

Base Paper
Back Coat
Figure 2. (a) An illustration of the cross-section of thermal paper and (b)

an illustration of the Thermal Reactive Layer of thermal receipt paper

BPA and BPS are applied on thermal receipt papers as a

powdery film and can be readily absorbed into the human skin
where it acts as an endocrine disrupter causing genetic damage
and other human health problems (2).
Global restrictions on the use of BPA has led to the development
and use of alternative bisphenol compounds such as BPS.

METHODS
Sample Collection
Fifty-two receipts were collected from local retail businesses in
and around Charlotte NC between October 15th and November
30th 2015.
Extractions
A representative portion (0.170 g-0.8207 g) of each receipt was
weighed and placed in 50 mL of polypropylene test tube. BPA
and BPS were extracted using 20 mL of methanol. The
solution was sonicated with an ultrasonic probe at 40% power
for 3 minutes and set aside for an hour. The samples were then
decanted and filtered using a 0.45 m nylon disk filters into
vials then diluted (10X) and directly injected to HPLC.
BPA and BPS Analysis
Ten L of each sample was analyzed using high-performance
liquid chromatography (HPLC). The Shimadzu UFLC system
was equipped with a LC-20AT liquid HPLC pump, SIL-20A
HT autosampler and a SPD-M20A diode array detector. The
samples were separated on a Restek Ultra C-18 column (250
mmx x 4.6 nm, with 5 um particle size in a Shimadzu CTO-10A
column oven. A mixture of HPLC grade water (55%) and
acetonitrile (45%) at a flow rate of 1.0 mL / min was used as a
mobile phase in an isocratic elution mode.
Quality Assurance and Quality Control
BPA and BPS standards were obtained from Accustandard
(New Haven, CT). A standard curve was prepared through a
serial dilution and analysis. Sample blanks were analyzed
every 5 samples to identify potential carry over and
contamination.

In a separate study conducted in 2014, 44% of receipts

contained BPA and 52% contained BPS. Of the receipts
analyzed in the Queens Study in 2015, 19% contained
BPA and 73% contained BPS (Table 3). The ratio of the
percentage of receipts containing BPA to BPS in the 2014
study was 44:52. In the Queens study, the ratio was
19:73, with the percentage of receipts containing BPS
being considerably higher than that of BPA. In five other
studies conducted from 2010 to 2015 the concentration of
BPA and BPS in thermal receipt papers were similar to
those found in our study (Table 3).

CONCLUSION
Figure 3. A sample chromatogram (20 ppm standard in method) showing BPS
and BPA retention in a C18 column.

Figure 6. Occurrence of BPA and BPS in thermal receipt paper (n = 52).

Table 3. A comparison of the Queens BPA/BPS study with four other studies. The
amount of receipts retrieved from each source, and the average concentration of BPS or
BPA in mg/g of receipt paper is presented.

Analysis of thermal paper receipts from 52 local stores in

three NC counties (Figure 5) showed presence of bisphenol
analogues. Of those studied, 19.2% of receipts contained
BPA and 73.1% of receipts contained BPS. The Queens
Study conducted in 2015 compared to similar studies
showed a gradual shift toward the use of BPS as a substitute
of BPA (Table 3). Four (7.7%) of the 52 receipts contained
neither BPA or BPS and 7 (13.5%) of the 52 receipts
contained an unidentified compound.
Since BPA and BPS were present on 92.3% of the thermal
receipt papers tested handling the receipts may lead human
exposure. To reduce the possibility of toxic bisphenol
analogue exposure further study of bisphenol alternatives is
necessary.

Figure 4. A sample chromatogram showing the retention of BPS and an

unknown analyte in a receipt from a local pharmacy.

ACKNOWLEDGEMENTS
LITERATURE CITED
1. Van Noort, R. (2011, February 1). Bisphenol A in dental materials. Fact
File.
2. Shelby, M. (2008). NTP-CERHR MONOGRAPH ON THE POTENTIAL
HUMAN REPRODUCTIVE AND DEVELOPMENTAL EFFECTS OF
BISPHENOL A. In CENTER FOR THE EVALUATION OF RISKS TO
HUMAN REPRODUCTION (08-5994 ed., pp. 1-8). Research Triangle Park,
North Carolina: National Toxicology Program.

3. Liao, C., & Kannan, K. (2012). Bisphenol S, a New Bisphenol Analogue, in

Paper Products and Currency Bills and Its Association with Bisphenol A
Residues. ENVIRONMENTAL SCIENCE & TECHNOLOGY.
doi:10.1021/ES300876n
4. Dang, A., Sieng, M., Pesek, J., & Matyska, M. (2014). Determination of
Bisphenol A in Receipts and Carbon Paper by HPLC-UV. Journal of Liquid
Chromatography & Related Technologies, 38(4), 438-442.

doi:10.1080/10826076.2014.913520
5. BISPHENOL A ALTERNATIVES IN THERMAL PAPER. (2014). Design
for the Environment U.S. EPA, (FINAL REPORT).

The authors would like to acknowledge Dr. Greg Pillar, Corey

Brown, Malyk Hannah, Micaela Hayes, Taylor Hill, Lacy LaFever,
Jenna Moore, Charles Rich, and Alan Tran for the collection,
extraction and analysis of thermal receipt samples. This course
research project was supported by a U.S. Department of Education
Title III Strengthening Institutions Grant.