主题：【求助】求标准LMBG 82.02-Z 4氨基偶氮苯的测试方法

最好是LMBG 82.02-9，德国最新版

传统AZO检测的补充方法

我也要，好呀

我的邮箱：hongchunding@yahoo.com.cn，有的麻烦传给我，不胜感激！

哦

我这里有一份LMBG 82.02的SOP,应该对你有用
1.  Purpose
This operation procedure is provided to detect the use of certain azo dye, which can release 4-aminoazobenzene during reductive cleavage of its azo bond, from textile or leather commodity articles.

2.  Reference
Amtilche Sammlung von Untersuchungsverfahren nach §35 LMBG
Untersuchung von Bedarfsgegenstaenden (nachweis der Verwendung von Azofarbstoffen, die 4- Aminoazobenzol freisetzen koennen)

3.  Chemicals
4-AAB is a known carcinogen to human being, thus its handling should under special caution. Unless specified, all chemicals should be in analytical grade.
3.1    NaOH (AR)
3.2    Sodium dithionite solution, k1) = 200 mg/mL, freshly prepared
3.3    2% NaOH (solution)
3.4    n-Hexane (AR)
3.5    Methanol (AR)
3.6    Chlorobenzene (AR)
3.7    tert-Butylmethylether (AR)
3.8    NaCl (AR)
3.9    4-Aminoazobenzene (highest grade)
3.10    Internal standard for GC
-    IS1: Naphthaline-d8, CAS# 1146-65-2
-    IS2: 2,4,5-Trichloroaniline, CAS# 636-30-6
-    IS4: Anthracene-d10, CAS# 1719-06-08
3.11    Standard solution
-    4-AAB calibrate solution, k1) = 15.0 μg 4-AAB/mL in an              appropriate solvent
-    internal standard solution, k1) = 10.0 μg IS/mL in an appropriate solvent
-    4-AAB control solution, k1) = 500 μg 4-AAB/mL Methanol; 1) k = measured        concentration

4.  Apparatus
4.1    Analytical balance accurate to 0.1 mg
4.2    20 to 50 mL reaction flask (heat-resistant) with teflon-sealer
4.3    100 mL round bottom flask (NS 29/32) with reflux condenser
4.4    Extraction apparatus (refer to §35 LMBG B82.02-4, figure 1)
4.5    Heater with thermostat
4.6    Centrifuge
4.7    Vacuum rotary evaporator
4.8    Pipette 10 mL, 5 mL, 2 mL, and 1 mL.
4.9    Ultrasonic bath with heat regulator
4.10    Dispenser
4.11    Mechanical shaker providing horizontal shaking motion, IKA HS260 or equivalent
4.12    GC/MS, Agilent 6890GC, with agilent 5975 mass spectrometer or equivalent

5.  Procedure
5.1    Sample preparation
5.1.1    Sample preparation (accessible without extraction)
Comminute more than 1 g of the homogenous commodity article into pieces of around 25 mm2 in size and mix. Weight 1.0 g of this sample into a reaction flask for analysis.
Samples compose of different materials should analyse separately.
5.1.2 Preparation of sample for dyed leather
To degrease the leather sample, pieces of around 25 mm2 comminute sample are put into a 50 mL reaction flask with 20 mL hexane. The suspension is sonicated for 20 min at 40±2 °C. The hexane phase is decanted and this procedure is repeated once.
The specimen is dried and is used for subsequent analysis of 4-AAB. (LMBG 82.02-3) 
5.1.3 Sample preparation (accessible by extracting the fibres)
The sampling and extraction method is conducted according to DIN EN14362-2 (edition December 2003 section 7; and section 8.1-8.3). In section 8.3, the process just follows the steps as: the solvent are completely removed by purging with nitrogen at an elevated temperature (not more than 70°C) and the residue is taken up in 2mL methanol.
Remark 1:
For direct determination of 4-AAB from cleavage of a disperse dye, the residue can be transferred in an appropriate solution for analysis (GC-MS).
5.2    Reductive cleavage
1g prepared sample or the residue from 6.1.3 is treated with 7 g of NaCl, 9 mL of 2% NaOH solution and 1 mL of sodium dithionite solution (200 mg/mL, freshly prepared) subsequently. To ensure the samples are fully soaked, vigorous shaking is required before placing the sample in a heater at 40±2 °C for 30
min. The reaction mixture is cooled down to room temperature within 3 min.
5.3    Separation and adsorption of 4-AAB
To the cooled solution was added 5 mL tert-butylmethylether and this solution is allowed to shake for 45 min at a speed of 5/s. From the organic layer, an aliquot is obtained for subsequent analysis.
Remark 2: The amount of arylamine will diminish as a function of time, any delay in analytical procedure will lead to deviation in measurement.
Remark 3: In case the organic layer cannot be separated from the aqueous layer, centrifugation can be conducted.
Remark 4: Solvents should not be removed by high temperature and strong vacuum, as which will lead to lose of arylamine.

6.  Chromatographic analyses
GC/MS should be used for quantitative analysis of 4-AAB together with an appropriate internal standard.
Remark 5: Analyte might not be stable after the extraction process. Extract should therefore be analyzed as soon as possible after the reduction and extraction process.
Remark 6: As the detected result is dependent on the instrumentation, no universal data can be worked out. However the following parameter should be strictly followed. 
6.1    GC-MS Conditions (see Appendix 1)
6.2    TLC for confirmation (refer to the  SOP of AZO-TLC-method)

7  Checking of the analytical system
To check the procedure, 100 μL of the control solution is treated according to section 5.2 to 5.3 and the recovery rate of 4-AAB should be at least 60%.This check procedure should be conducted once per day.

8.  Quality Control Practice   
8.1    Every week establish a 5-point calibration curve with coefficient of regression at least 0.995.
8.2    Every day inject 2.5 ppm of standard solution before sample injection. The response should be positive.
8.3    Inject calibration check standard solution (CK) at 15 ppm before sample injection every day. The acceptance criteria of the calibration check should be within ±15% of the theoretical value.
8.4    Perform a method blank to check for any contamination every day by repeating steps from clauses 5.2 to 5.3 without sample.
.
9.  Calculation
The amount of 4-AAB is calculated according to the peak area of 4-AAB. This amount is calculated as mass portion w in mg/kg of the specimen according to the following equation:
              Ap x ISk*) x kk x V
w = __________________
                Ak x ISp*) x mE
    Ap =  peak area of 4-AAB in the specimen solution in area units
Ak = peak area of 4-AAB in the calibration solution in area units
kk = concentration of the 4-AAB in the calibration solution in μg/mL
ISp*) = peak area in of the internal standard in the specimen solution in area units
ISk*) = peak area of the internal standard in the calibration solution in area units
V = volume the specimen is made up in mL
mE = weight of the textile specimen  in g
*) = for quantification by means of GC/MS
10.  Test report
The following information concerning this official method should be stated in the test report:
•     Kind, origin and identification of the specimen
•     Sampling method and date
•     Date of receipt and testing period
•     Information of the verification procedure
•     Information of the assignment procedure
•     Test results

4-AAB detected level ≤ 30 mg/kg:
According to the scope of the test, 4-AAB, use of which is prohibited under the Commodity Articles Order, was not detected in the commodity article.
4-AAB detected level > 30 mg/kg
On the basis of the analytical findings, it is assumed that in the manufacture or treatment of the tested commodity article, 4-AAB that is a forbidden amine within the meaning of the Commodity Articles Order has been used.

我也正缺这个，真是太感谢了。

非常感谢提供的方法，正需要！如果以附件形式最好了，还有怎样分配积分？