XÁC ĐỊNH BISPHENOL A TRONG CÁC HỘP NHỰA BẰNG PHƯƠNG SẮC KÝ LỎNG KHỐI PHỔ

Voronezh State Technical University and lecturer of the department of Science and Technology of Thai Nguyen University of Agriculture and Forestry have developed e[r]

DETERMINATION OF BISPHENOL A IN PLASTIC PACKAGING BY USING THE METHOD OF LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY

Tran Hai Dang 1 , O.B Rudakov 2 , E.A Khorokhordina 2 , E.S Logvina 2

1

University of Agriculture and Forestry - TNU

2 Voronezh State Technical University

ABSTRACT

Many studies confirming the toxicity and hazard of bisphenol A to human health have been conducted so far It should be noted that in the EU, the established specific migration limit for bisphenol A is 0.6 mg/kg for the materials based on plastics contacting with food The research objects were 6 samples of plastic packaging widely used in Vietnam, whose materials could contain “free” BPA In the research, the technique of liquid chromatographic-mass spectrometric determination of “free” bisphenol A in plastic packaging was developed In order to extract bisphenol A, the method of liquid extraction from a material with the help of the mixture of

acetonitrile - ethyl acetate (85:15) was proposed The results of the detection of bisphenol A free in

packaging widely used in Vietnam were discussed

Keywords: Bisphenol A, toxic, liquid extraction, HPLC-MS/MS, plastic packaging

Received: 11/12/2018; Revised: 22/12/2018; Approved: 28/12/2018

XÁC ĐỊNH BISPHENOL A TRONG CÁC HỘP NHỰA BẰNG PHƯƠNG SẮC KÝ LỎNG KHỐI PHỔ

Trần Hải Đăng 1

, Rudakov O B. 2 , Khorokhordina E A. 2 , Logvina E S. 2

1 Trường Đại học Nông Lâm - ĐH Thái Nguyên

2 Trường ĐH tổng hợp kỹ thuật Voronezh, LB Nga

TÓM TẮT

Cho đến nay có nhiều nghiên cứu đã được tiến hành để xác nhận độc tính và nguy cơ của bisphenol A đối với sức khỏe con người Tại EU giới hạn của bisphenol A là 0,6 mg/kg đối với các vật liệu nhựa tiếp xúc thực phẩm Đối tượng trong nghiên cứu này là 6 mẫu hộp nhựa dùng đựng thực phẩm được sử dụng rộng rãi tại Việt Nam, các vật liệu này có thể chứa bisphenol A tự

do Trong nghiên cứu đã phát triển kỹ thuật xác định bisphenol A tự do trong các hộp nhựa bằng phương pháp sắc ký lỏng khối phổ Để chiết xuất được bisphenol A, nhóm tác giả đã sử dụng hỗn hợp dung môi trơ acetonitril - ethyl acetate (85:15) Kết quả đã phát hiện bisphenol A tự do trong các hộp nhựa dùng đựng thực phẩm được sử dụng rộng rãi ở Việt Nam

Từ khóa: Bisphenol A, chất độc, chiết xuất lỏng, HPLC-MS/MS, hộp nḥa

Ngày nhận bài: 11/12/2018; Hoàn thiện: 22/12/2018; Duyệt dăng: 28/12/2018

Introduction

Nowadays polymer materials are widely used

in almost all industry sectors in Vietnam and

Russia More often than not, these materials

for technical and domestic purposes are made

of inexpensive polymers, in which the content

of harmful substances such as monomers,

plasticisers and antioxidants can exceed

concentrations safe for human health

Therefore, the analytical control of

ecotoxicants in these materials has become a

pressing problem which should be tackled

For instance, epoxy resins derived from BPA

are applied as a coating on the interior surface

of beverage and food cans “Free” BPA can

be present in polycarbonate plastics It should

be noted that a wide variety of products such

as water and drink bottles, sports equipment,

medical instruments, dental fillings and

sealants, eyeglass lenses and household

appliances are made of these plastics BPA is

not only used as a monomer but also as an

antioxidant in some plasticisers and

polymerisation inhibitor of polyvinyl chloride

[1], [5], [9]

Many studies confirming the toxicity and

hazard of BPA to human health have been

conducted so far [2], [3], [6], [7], [11], [12]

As a synthetic analogue of oestrogen, BPA,

which is an endocrine disruptor, easily

disturbs hormonal balance It causes fertility

decline, breast cancer, obesity, precocious

puberty and diabetes, adversely affects the

central nervous system and shows

embryotoxicity It should be noted that in the

EU, the established specific migration limit

for BPA is 0.6 mg/kg for the materials based

on plastics contacting with food [10]

As part of international cooperation, the

scientists of the department of Chemistry and

Chemical Technology of Materials of

Voronezh State Technical University and lecturer of the department of Science and Technology of Thai Nguyen University of Agriculture and Forestry have developed extraction-chromatographic methodology of

“free” bisphenol A (BPA) determination with the help of HPLC-MS/MS in plastic materials

Experimental part

The research objects were 6 samples of plastic packaging widely used in Vietnam, whose materials could contain “free” BPA The sample of the material was being ground until it reached the size 5×5 mm and then the sample mass of ~ 0.5 g was weighed on the analytical balances The sample weight was put into a conical flat-bottom flask, 10 sm3 of acetonitrile - ethyl acetate mixture (85:15) was added to it, and the flask was shaken by using a vibromixer for 15 minutes Then the analysis was conducted with the help of HPLC-MS/MS method (Fig 1) on a liquid chromatograph Shimadzu consisting of two high pressure pumps LC-20AD XR with the automatic sample injection system SIL-20AC

XR, column InertSustain С18 (granulation was 5 μm, length was 150 mm, diameter was 4.6 mm) (Japan) The volume of the injected sample was 10 μl The mass spectrometer was MS/MS ABSciex 5500 QQQ The ionisation source was ESI, the regime of negative ions, spray voltage was 4 kV The nozzle temperature (IS) was 400 oC The mobile phase was acetonitrile – water, gradient (Table 1)

The sample preparation and analysis were conducted by using the equipment given by the Laboratory of Food Chemistry and Toxicology National Institute for Food Control in Hanoi, Vietnam

Fig 1 Chromatogram of bisphenol A solution in the extraction agent, С=10 ng/ml

Table 1 The gradient of the mobile phase HPLC-MS/MS

Time, min Water, vol.% Acetonitrile, vol % Speed, ml/min

Fig 2 Calibration for the determination of BPA in the extraction agent

Results and discussion

The mixture of acetonitrile - ethyl acetate

(85:15) was chosen as an extraction agent

because it is better at solving BPA and

extracting this analyte from plastic materials

(Acetonitrile and ethyl acetate from

Germany) Furthermore, it is both less

stressed that the addition of 15% of ethyl acetate to acetonitrile increases the degree of the extraction of hydrophobic phenols, to which BPA belongs, up to 98.5% The coefficient of the distribution of hydrophobic phenols between the water and acetonitrile - ethyl acetate mixture (85:15) rises

temperature lower than -10 oC, this mixture as

well as pure acetonitrile is capable of

separating from water, which makes it

suitable for use not only at room temperature

but also under the conditions of

low-temperature liquid-liquid extraction

Consequently, it is possible to apply this

mixture to the process of BPA identification

both in plastic packaging items and products

which are wrapped in them In order to plot a

calibration curve, BPA was gradually

dissolved in the acetonitrile - ethyl acetate

solution (85:15) with the concentrations of

20, 50, 100, 200 ng/ml respectively (Fig 2)

Fig 2 shows the calibration curve The degree

of correlation R=0,9988

The analysis of 6 real samples of typical plastic packaging widely used in Vietnam showed the significant content of BPA in the samples №3 and №6 (Table 2) The chromatograms for certain samples are presented in Figures 3 and 4

Thus, the samples in which the specific migration level of BPA from the material was exceeded should be considered as a serious health hazard Its content in other samples was lower than the dangerous level

Fig 3 Chromatogram of the baby bottle “Zoo” HT04T0414, Vietnam

Fig 4 Chromatogram of the box “Pioneer” PN3165L/2C-P3, Thailand

Table 2 The results of the materials analysis

Sample number Model name Bisphenol A concentration (mg/kg)

2 Food packet “Freshness” BC0175, Vietnam Traces

4 Box “Pioneer” PN3165L/2C-P3, Thailand Traces

*Traces: lower C=0.05 mg/kg)

Therefore, the results of the sample

preparation, which was done taking into

account the conditions of the methodology of

BPA determination by HPLC-MS/MS make it

possible to come to the conclusion that the

control of this contaminant content in plastic

packaging for food and drink is an urgent

task The developed

extraction-chromatographic method of BPA

determination in polymer materials is an

effective and promising way of identifying

BPA not only in plastic packaging but also in

food into which it migrates from plastics

REFERENCES

1 Bilan K Ubiquitous bisphenol is persona non

grata [Electronic resource] Available at:

http://www.epochtimes.ru/content/view/41800/7/

(Accessed 12.09.2018)

2 Dupuis A., Migeot V., Cariot A., Albouy-Llaty

M., Rabouan S (2012) Environmental Science

and Pollution Research, vol 19, i.9, pp

4193-4205

3 Jinhua Li, Xingliang Song (2013) Scientific

Journal of Environment Pollution and Protection,

vol 2, i 4, рр 50-58

4 Khorokhordina E.A., Podolina E.A., Rudakov

O.B Liquid extraction by mixed solvents (2012)

Application in the chemical analysis of phenols

Saarbrocken, LAP Lambert Academic Publishing,

240 p

5 Leonov A.E., Khamitova I.A The hazard of

bisphenol A [Electronic resource] Available at:

http://www.scienceforum.ru/2014/711/5736 (Accessed 12.09.2018)

6 Maroto A., Kissingou P., Diascorn A., Benmansour B (2011) Analytical and Bioanalytical Chemistry, vol 401, i 9, рр

3011-3017

7 N Lin, Y Zou, H Zhang (2013) European Food Research and Technology, vol 237, Is.11 рр.1009-1019

8 Rudakov O.B., Khorokhordina E.A., Preobrazhenskii M.A., Rudakova L.V (2016) Russian Journal of Physical Chemistry A., 2016, vol 90., no 8, pp 1665-1668

9 Rudakov O.B., Khorokhordina E.A., Tran Hai Dang, Bedarev A.A (2014) The Scientific Newsletter of Voronezh State University of Architecture and Civil Engineering Series: Physicochemical problems and high technologies

of materials science in construction, no 8,

pp.106-113

10 Schwarzrlmueller E., Brugger H The aspects

of the influence of beverage packaging on health / Information about environmental policy № 185 [Electronic resource] Available at: http://barley-

malt.ru/wp- content/uploads/2014/03/yssledovanye-pyet_avstryja.pdf Vienna, 2011, 73 p (Accessed 21.09.2015)

11 Torres A , Ramirez C , Valenzuela X., Guarda A., Galotto M J (2015) European Food Research and Technology, , vol 240, i 8, рр

335-343

Vela-Soria F., Ballesteros O., Zafra-Gomez A., Ballesteros L., Navalon A (2014) Analytical and Bioanalytical Chemistry, vol.406, i 8, рр 3773-3785.