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Because of nickel's high corrosion resistance and heat resistance, it is widely used in alloy products. It has
Received 18th December 2012
Accepted 4th March 2013
been shown that skin contact with these materials on a daily basis may cause nickel allergy. The objective of
this work is to investigate the effects of nickel release in alloy products. The results show that the amount of
DOI: 10.1039/c3ay26575g
nickel release was significantly affected by metal composition and interestingly, can be effectively
www.rsc.org/methods restrained by the addition of noble metals.
Introduction jewellery materials, but required that nickel release rate must be
below 0.2 mg cm2 per week.11 Other countries,12–17 such as
Nickel is a metallic element naturally present in the Earth's America and China, have also established corresponding regu-
crust. Due to its unique physical and chemical properties, lations on nickel release for jewellery.
nickel and nickel-based alloys are used in a wide variety of In this work, we investigated the variation of nickel release
products. However, it has been known for decades that adverse with different metal compositions and the inuence of different
skin reactions can be caused by skin contact with nickel. To immersing conditions to test nickel release. Herein, we report
date, items made from nickel and nickel-based alloys e.g. coins, that the nickel release rate is signicantly affected by metal
jewellery, stainless steels, bra fasteners and eyeglass frames, compositions, and noble metals (e.g. Au and Ag) play an
have become the most frequent causes of skin contact allergy in important role in restraining the nickel release in alloys. We
Europe. Liden and Norberg1 reported that about 10–15% of believe that this nding will have great importance in reducing
women and 2–4% of men in Europe were found to be allergic to the prevalence of nickel allergy from the very rst step.
nickel. Double-blind placebo-controlled studies have shown
that nickel-allergic individuals, but not healthy individuals, may Experimental
develop hand dermatitis if they are repeatedly exposed to nickel
in low concentrations (10 ppm),2–4 or if they are orally exposed to Chemicals
nickel.5 Lactic acid, urea, nitric acid, sodium dodecylbenzene sulfate,
The wide spread of nickel allergy has become a driving force sodium chloride (analytical pure, commercial available), Nickel
to the development of a number of analysis methods and Standard Solution (1000 mg L1, analytical pure, NSI Company
regulations designed to reduce its prevalence. For instance, in of USA).
1994, Northern European countries introduced nickel regula- Degreasing solution: dissolved 5 g sodium dodecylbenzene
tions aimed at the reduction of nickel exposure and prevention sulfate in 1000 mL deionised water.
of nickel allergy.6,7 The “94/27/EC”8 regulation prescribed a Testing solution: mixed 900 mL deionised water, 100 g urea,
nickel release rate of 0.5 mg cm2 per week as an upper limit for 500 g sodium chloride and 100 g lactic acid together in a 1000
items to be in prolonged contact with the skin, and a maximum mL beaker with stirring until dissolved. The testing solution
content of 0.05 wt% nickel for piercing jewellery during should be prepared daily.
epithelialization. In addition, two corresponding test standards,
EN1811 (ref. 9) and EN12472 (ref. 10), were published in 1998. Apparatus
In 2004, the European Union modied the requirement of the
s20 pH meter, Mettler Toledo.
nickel release of piercing jewellery and formulated a new
Inductively Coupled Plasma-Atomic Emission Spectrometry
directive, “2004/96/EC”, which did not limit the use of nickel in
(ICP-AES), Optima7300DV, PerkinElmer Company, USA.
Wb/ob Thermostat Water Bath, Memmert Company,
a
Yiwu Entry-Exit Inspection and Quarantine Bureau, 299 Chengbei Road, Yiwu Germany.
322000, P. R. China. E-mail: xufeizj@126.com; Fax: +86-0579-81579009; Tel: +86-
0579-81579085
Sample preparation
b
Yiwu Academy of Science & Technology for Inspection & Quarantine, Yiwu, P. R. China
c
Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou Cu, Zn and Ni powders were added, in weight proportion to the
310027, P. R. China intermediate frequency induction equipment. The mixture was
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2238 | Anal. Methods, 2013, 5, 2237–2240 This journal is ª The Royal Society of Chemistry 2013
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Fig. 1 Comparing the nickel release from nickel alloys with Au and those
without Au.
0.02 mg cm2 per week was found for a necklace (as shown
in Table 4).
Effect of immersing temperature
No. 8 samples (listed in Table 2) were treated according to the
Summary
standard release procedure at different immersing tempera-
tures, 20 C, 30 C, 38 C, with an immersing time of 168 2 h, EN1811 was applied to analyze the nickel release of different
at pH 6.5. The testing results are listed in Table 3. With compositions of alloys. The inuence of different immersing
increasing immersing time, the resulting released nickel is conditions to test nickel release were studied as well. It was
observably increased. shown that the nickel release rate is mainly inuenced by the
compositions of metals in the alloy. The addition of noble
metals which strengthen the inter-atomic forces can effectively
Effect of immersing time
restrain nickel release. The results showed that the nickel
The results of nickel release from No. 8 samples (listed in Table release increases drastically with increasing immersing
2) immersed in the testing solution for 96 h, 120 h, 168 h, 360 h, temperature. Considering that the inuence of the temperature
480 h, and 600 h are shown in Table 3. From Table 3 we could of the human body affects nickel release, detecting nickel
easily see that the amount of nickel release increased signi-
cantly with increasing duration of extraction with the testing
solution. The largest amount of nickel ions was released aer
Table 4 Results obtained for the nickel release from commercial samples
600 h of immersion in testing solution at 30 C.
Results (mg
Samples cm2 per week)
Nickel release from commercial samples
Earring-1 1.74
Real commercial samples were analyzed using the developed
Earring-2 0.50
procedure and the concentrations were found to be 1.74 and Bracelet-1 0.06
0.50 mg cm2 per week for two types of earrings, and 0.06 and Bracelet-2 0.01
0.01 mg cm2 per week for two different types of bracelets, while Necklace 0.02
This journal is ª The Royal Society of Chemistry 2013 Anal. Methods, 2013, 5, 2237–2240 | 2239
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release at 37 C is more reasonable than the requirement of 6 C. Lidén, Contact Dermatitis, 1992, 26, 73–75.
EN1811, at 30 2 C. 7 T. Menné and K. Rasmussen, Contact Dermatitis, 1990, 23,
57–58.
Acknowledgements 8 European Communities, Off. J. Eur. Communities: Legis.,
1994, 37, 1–2.
This work was supported by grants from the Certication and 9 European Standard, EN 1811, 2011.
Accreditation Administration of the People's Republic of China 10 European Standard, EN 12472, 2005.
(no. CNCA-2012-B07) and the Science Technology Department 11 European Commission, Off. J. Eur. Communities: Legis., 2004,
of Zhejiang Province (2012C37009). We are grateful to Mr 301/51–301/52.
Haiping Lin for technical advice. 12 R. L. Rietschel, J. F. Fowler and E. M. Warshaw, Dermatitis,
2008, 19, 16–19.
Published on 05 March 2013. Downloaded by Temple University on 23/10/2014 14:45:31.
2240 | Anal. Methods, 2013, 5, 2237–2240 This journal is ª The Royal Society of Chemistry 2013