該要求將于2013年7月21日生效，協(xié)調(diào)標(biāo)準(zhǔn)為EN71-3，目前還在過渡期。 

新EN71-3檢測(cè)元素：鋁、銻、砷、鋇、硼、鎘、鉻(III)、鉻(VI)、鈷、銅、鉛、錳、汞、鎳、硒、鍶、錫、有機(jī)錫、鋅 ；XRF應(yīng)用解決方案！

所需分析儀器：德國(guó)斯派克 熒光光譜儀

EN71-3 2013 Safety of toys - Part 3: Migration of certain elements

玩具安全-第3 部分：元素的遷移

EN71-3: 2013 was officially released on June 5, the official version reduces the Ba (barium) limits. Specific limits are as follows(EN71-3:2013 已于6 月5 號(hào)正式發(fā)布，正式版本中降低了Ba（鋇）的限值。具體的限值如

下：)：

3. Chromium (III) and Chromium (VI) 關(guān)于三價(jià)鉻和六價(jià)鉻的檢測(cè)

As a first action method, the migration of combined chromium can be determined. If the migration of

combined Chromium (i.e. Chromium (III) + Chromium (VI)) is below the maximum limit for Chromium (VI), it

can be inferred that the material complies with the requirements for both Chromium (III) and Chromium (VI).

標(biāo)準(zhǔn)中給出可溶性總鉻的測(cè)試方法，如果測(cè)得可溶性鉻(Cr (III) + Cr (VI))＜0.2mg/kg（六價(jià)鉻的高限值）時(shí)，

可以推斷該材料符合三價(jià)鉻和六價(jià)鉻的要求。

For Chromium VI the method in Annex F the limit of quantification is higher than the migration limit for category

I and II toy materials. Compliance with the limits cannot be demonstrated by a migration test, however other

options are available:

—— determination of the content of combined chromium;

　—— safety assessment of the toy material.

附錄F 中六價(jià)鉻的定量限值高于第一類和第二類材料的遷移限值，不能按照附錄F 的方法測(cè)試，但是可以通過

其它方式評(píng)估：

—— 鉻的總含量

—— 玩具材料的安全評(píng)估

4. Organic tin(有機(jī)錫)

The migration of organic tin shall be calculated by adding the migration values for all the single organic tin

compound s that have been detected. The migration of organic tin is expressed as tributyltin. 10 kinds of

organic tin LOD, LOQ as follows:

有機(jī)錫的遷移通過計(jì)算檢測(cè)出來的單個(gè)有機(jī)錫的總和。有機(jī)錫的遷移值通過三丁基錫來表達(dá)。10種有機(jī)錫的

LOD,LOQ如下：

Typical detection limits (LOD) and quantification limits (LOQ) expressed in mg/kg toy material (有機(jī)錫化合物

的的檢測(cè)限（LOD）和定量限(LOQ))

Annex F（附錄F）

Methods of analysis for speciation of Chromium (III) and (VI)

鉻(III) 和鉻(VI)分析方法

F.1 Principle 原理

This method quantifies Chromium (III) and Chromium (VI) in the migration solution. This method is capable to

determine compliance with the migration limit for category III toy materials. The limit of quantification is higher

than the migration limits for category I and II toy materials . In I.2 guidance is given how compliance can be

demonstrated for category I and II toy materials .

這種方法定量鉻(III) 和鉻(VI)的遷移溶液。這種方法針對(duì)玩具材料的第III類材料。定量限值高于玩具材料的第I類

和第II類的遷移限值，不能按照附錄F的方法測(cè)試，但是可以通過其它方式評(píng)估。

To prevent interconversion of Chromium (III) and Chromium (VI), the migration solution is neutralised directly

after the migration step. Experiments have shown that at a pH of 7.1 both species are stable. Mobile phase is

added, containing EDTA. EDTA reacts to form a complex with Chromium (III). Chromium (III) and Chromium

(VI) are then separated by liquid chromatography using an LC-ICP-MS technique.

為了防止三價(jià)鉻和六價(jià)鉻的相互轉(zhuǎn)化，遷移溶液在樣品遷移之后必須是中性的。實(shí)驗(yàn)表明pH值為7.1的時(shí)候兩種

形態(tài)是穩(wěn)定的。流動(dòng)相要加入EDTA（乙二胺四乙酸）。EDTA反應(yīng)生成三價(jià)鉻的化合物。三價(jià)鉻和六價(jià)鉻通過

LC-ICP-MS技術(shù)分離。

When analysing Chromium (III) and (VI) in one run, a high peak of Chromium (III) may influence the peak of

Chromium (VI). This can be solved by skipping the complexation step with EDTA, thereby only showing the

Chromium (VI) peak in the chromatogram. Chromium (III) can then be determined by either analysing the

migration solution as well after the complexation step, or by determining the migration of combined Chromium:

Chromium (III) = total Chromium – Chromium (VI).

當(dāng)分析三價(jià)鉻和六價(jià)鉻的時(shí)候，三價(jià)鉻有一個(gè)高峰可能會(huì)影響六價(jià)鉻的峰?？梢杂肊DTA絡(luò)合解決這個(gè)問題，因

此色譜圖上只顯示六價(jià)鉻的峰。三價(jià)鉻絡(luò)合后可F.2 Reagents 試劑

Use reagents of highest purity. 所用試劑需要優(yōu)級(jí)純

F.2.1 Water, Milli Q 18.2 M?.cm

F.2.1 水，Milli Q超純水系統(tǒng)生產(chǎn)的電阻率18.2 M?.cm的水

F.2.2 Hydrochloric acid, HCl (30% d = 1,15 g/ml or equal)

F.2.2 鹽酸，HCl (30% d = 1,15 g/ml or 等同)

F.2.3 Tetrabutylammonium hydroxide (TBAH), 40 wt % in water, [CH3(CH2)3]4NOH, CAS# 2052-49-5

F.2.3 TBAH，水中的質(zhì)量分?jǐn)?shù)40%，[CH3(CH2) 3]4NOH, CAS# 2052-49-5

F.2.4 Potassium Ethylenediamine tetraacetic acid, C10H14K2N 2O 8 * 2H2O, CAS# 7379-27-3

F.2.4 乙二胺四乙酸鉀，C10H14K2N 2O 8 * 2H2O, CAS# 7379-27-3

F.2.5 Ammonia, NH3 (25 % in water)

F.2.5 氨NH3 (25 %在水中)

F.2.5.1 Ammonia solution c(NH3 (aq)= (0,07 ± 0.005) mol/L

F.2.5.1氨水溶液 c(NH3 (aq)= (0,07 ± 0.005) mol/L

F.2.6 Acetic acid (glacial), 100 %

F.2.6 冰醋酸，100%

F.2.7 Methanol, CH3OH

F.2.7 甲醇, CH3OH

F.2.8 Hydrochloric acid solution, c(HCl) = (0,07 ± 0,005) mol/L

F.2.8 鹽酸溶液，c(HCl) = (0,07 ± 0,005) mol/L

F.2.9 Chromium (III) 1000 mg/l in water

F.2.9 1000 mg/l三價(jià)鉻溶液

F.2.10 Chromium (VI)1000 mg/l in water

F.2.10 1000 mg/l六價(jià)鉻溶液

F.2.11 Stock solution Chromium (M1)

Prepare a stock solution (M1) diluting 0,5 mL of the commercial available stock solutions of the individual

elements (concentration = 1 000 mg/kg) in mobile phase to a volume of 50 mL. Allow the final solution to stand

for 1 hour at 50 °C.

F.2.11 鉻儲(chǔ)備溶液（M1）

制備一個(gè)儲(chǔ)備溶液（M1），在流動(dòng)相中稀釋0.5ml從商家購(gòu)買的單種元素濃度為1000mg/L的標(biāo)液到50ml。

終的溶液在50 °C下保存一小時(shí)。

F.2.12 Diluted stock solution (M2)

Dilute 0,5 mL of stock solution M1 in mobile phase to 50 mL.

F.2.12 稀釋的儲(chǔ)備溶液（M2）

在流動(dòng)相中稀釋0.5ml儲(chǔ)備溶液M1到50ml。

F.2.13 Working solutions (Calibrating Standards)

Sequentially dilute diluted stock solution (M2) with mobile phase, after addition of 2,5 mL ammonia and 2,5 mL

hydrochloric acid, in order to obtain standards to be used for calibration according to the scheme in Table B.1.

Allow the working solutions to stand for 1 h at 50 °C.

F.2.13工作溶液（校準(zhǔn)溶液）

將稀釋后的儲(chǔ)備溶液（M2）加入流動(dòng)相繼續(xù)稀釋，然后添加2.5ml氨水和2.5ml鹽酸根據(jù)表F.1以獲得校準(zhǔn)溶

液。允許工作溶液在50 °C下保存一小時(shí)。

Table F.1 — Preparation scheme working solutions

dissolve in water. Adjust the pH with acetic acid to 7.1.

F.2.14 流動(dòng)相

稱取647mgTBAH 和243 mg EDTA，加水稀釋，定容到1000ml。用醋酸調(diào)pH 到7.1。

F.3 Apparatus 設(shè)備

F.3.1 Volumetric flasks, glass

F.3.1 玻璃容量瓶

F.3.2 Variable pipettes with disposable tips, variable range

F.3.2 可調(diào)節(jié)移液槍：帶一次性吸頭，可變?nèi)莘e范圍

F.3.3 ICP-MS, equipped with HPLC module

F.3.3 ICP-MS，需配備HPLC 組件

F.3.4 pH-meter

F.3.4 pH 計(jì)

F. 4 Procedure

Use 1 ml of migration solution. Add 1 mL ammonia to 1 mL migration solution. Additionally 8 mL mobile phase

solution is added. Allow the final solution to stand for 1 h at 50 °C.

NOTE 1 When the pH was adjusted, the amount of ammonia added must be equivalent to the total amount of

HCl. The pH of 7.1 is established after addition of 8 ml of mobile phase.

NOTE 2 It has been shown that presence of manganese will lead to oxidation of Chromium (III) into Chromium

(VI).

F. 4 程序

加1ml 氨水到1ml 遷移溶液中，繼續(xù)加入8ml 流動(dòng)相溶液?；旌虾蟮娜芤涸?0 °C 下保存1 h。

備注1：當(dāng)調(diào)pH 值的時(shí)候，添加氨水的量和鹽酸的總量相同。在添加8ml 流動(dòng)相后pH 值為7.1。

備注2：錳的存在會(huì)導(dǎo)致三價(jià)鉻氧化為六價(jià)鉻

F.5 Analysis 分析

F.5.1 General 概要

Inject samples and calibration solutions into the LC - ICP - MS system.

注入樣品和校準(zhǔn)溶液到LC-ICP-MS系統(tǒng)中。

F.5.2 Limit of detection and quantification 檢測(cè)限值和定量限值

In Table F.2 typical limits of detection (LOD )and quantification (LOQ) are given.

Table F.2 — Typical detection limits (LOD) and quantification limits (LOQ) expressed in mg/kg toy material