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Determination of Alkylphenol, Bisphenol A, p-tert-Octylphenol, Nonylphenol Monoethoxylate and Nonylphenol Diethoxylate in Environmental Waters by GC/MS

memory光阴

2020/09/05
菜鸟分析队

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气质联用（GCMS）

Determination of Alkylphenol, Bisphenol A, p-tert-Octylphenol, Nonylphenol Monoethoxylate and Nonylphenol Diethoxylate in Environmental Waters by gc/MS

1. Scope and application 范围与应用

This method is for the analysis of Alkylphenol, bisphenol A (BPA), p-tert-octylphenol (p-tert-OP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), OP1EO, and OP2EO in aqueous samples. The information of target compounds is listed in Table1.

本方法适用于水中烷基酚、双酚A、对-特-辛基苯酚、短链壬基酚聚氧乙烯醚（NP1EO和NP2EO）、短链辛基酚聚氧乙烯醚（OP1EO和OP2EO）的分析。目标化合物信息列于表1.

2. Principle 原理

Alkylphenol, BPA, p-tert-OP, NP1EO, NP2EO, OP1EO and OP2EO presented in the aqueous samples are serially extracted with DCM using a separatory funnel. The extract is dried, concentrated, and analyzed by gc/MS.

水样中的烷基酚、双酚A、对-特-辛基苯酚、NP1EO、NP2EO、OP1EO和OP2EO用二氯甲烷液-液萃取。萃取液经干燥、浓缩、定容后gc/MS分析。

3. Interferences 干扰

Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from sample source to sample source, depending on variations of the sample matrix.

4. Equipment and apparatus 设备与装置

4.1 Gas chromatography-mass spectrometry: Agilent 6890/5975N gc/MS system with Agilent Chemstation software.

气相色谱-质谱联用仪：安捷伦6890/5975N，配置安捷伦化学工作站软件。

4.2 Column: DB-5MS 30 m x 0.25 mm x 0.25 μm, or equivalent.

色谱柱：DB-5MS 30 m x 0.25 mm x 0.25 μm，或其它同类型色谱柱。

4.3 Autosampler: Agilent Autosamler 7693.

自动进样器：安捷伦7693 自动进样器。

4.4 Separatory funnel: 2000 mL, with polytetrafluoroethylene (PTFE) stopcock.

分液漏斗：2000 mL，配聚四氟乙烯活塞。

4.5 Kuderna-Danish (K-D) apparatus.

K-D浓缩装置。

4.6 Heating bath: capable of temperature control.

水浴锅：温度控制。

5. Standards and reagents 标样与试剂

5.1 Reagents 试剂

5.1.1 Milli-Q water.

5.1.2 Methylene chloride: Pesticide grade, or equivalent.

二氯甲烷：农残级。

5.1.3 Sulfuric acid (1:1, v:v): Carefully add a measured volume of concentrated H2SO4 to an equal volume of Milli-Q water.

硫酸溶液（体积比1:1）：浓硫酸和Milli-Q水1:1混合。

5.1.4 Anhydrous sodium sulfate: heated to 400 ℃ for 4 hours in a muffle furnace.

无水硫酸钠：马弗炉400 ℃烘4小时。

5.1.5 Sodium chloride: heated to 400 ℃ for 4 hours in a muffle furnace.

氯化钠：马弗炉400 ℃烘4小时。

5.2 Standard solutions 标准溶液

5.2.1 Standards

(1) Dr.Ehrenstorfer, Inc. purity ≥ 100% standard solutions 1 (Nonylphenol, 壬基酚).

(2) Dr.Ehrenstorfer, Inc. purity ≥ 99.5% standard solutions 2 (4-Octylphenol, 辛基酚).

(3) Purity ≥ 99.5% standard solutions 3 (Bisphenol A, 双酚A).

(4) Dr.Ehrenstorfer, Inc. purity standard solutions 4 (p-tert-Octylphenol, 对-特-辛基苯酚).

(5) Dr.Ehrenstorfer, Inc. purity standard solutions 5 (POE(1 to 2) nonylphenol, 壬基酚一氧乙烯醚&壬基酚二氧乙烯醚).

(6) OPEO(1,2) standard 6 in DCM: 000 mg/L. 辛基酚一氧乙烯醚和壬基酚二氧乙烯醚：1000 mg/L。

5.2.2 Stock standard solutions

(1) Stock standard solution 1 (1000 mg/L): Nonylphenol standard in DCM.

标准溶液储备液1（1000 mg/L）：壬基酚标样，溶剂为二氯甲烷。

(2) Stock standard solution 2 (1000 mg/L): Octylphenol standard in DCM.

标准溶液储备液2（1000 mg/L）：辛基酚标样，溶剂为二氯甲烷。

(3) Stock standard solution3 (1000 mg/L): Bisphenol A standard in DCM.

标准溶液储备液3（1000 mg/L）：双酚A标样，溶剂为二氯甲烷。

(4) Stock standard solution 4 (1000 mg/L): p-tert-Octylphenol standard in DCM.

标准溶液储备液4（1000 mg/L）：对-特-辛基苯酚标样，溶剂为二氯甲烷。

(5) Stock standard solution 5 (1000 mg/L): POE(1 to 2) nonylphenol standard in DCM.

标准溶液储备液5（1000 mg/L）：NP1EO & NP2EO标样，溶剂为二氯甲烷。

5.2.3 Intermediate standard solution for p-tert-Octylphenol (100 mg/L): Dilute stock standard solution with DCM.

对-特-辛基苯酚标样中间浓度（100 mg/L）：用二氯甲烷稀释至100 mg/L。

5.3 Stock internal standard solutions 内标储备液

5.3.1 AccuStandard, Inc. 4000 mg/L internal standard. The internal standards are 1,4-Dichlorobenzene-d4, Naphthalene-d8, Acenaphthene-d10, Phenanthrene-d10, Chrysene-d12, and Perylene-d12.

内标储备液（4000 mg/L）：内标化合物包括1,4-二氯苯 -d4，萘-d8，二氢苊-d10，菲-d10，屈-d12，和苝-d12.

5.3.2 Intermediate internal standard solution (200 μg/mL). Dilute from stock standard solutions with DCM.

内标中间浓度（200 mg/L）：用二氯甲烷稀释至200 mg/L。

5.4 Working standard solutions 工作曲线溶液

5.4.1 Working standard solutions: Mix and dilute stock standard solutions (1~3, 4, 6)/intermediate standard solution (p-tert-Octylphenol) by DCM.

工作曲线溶液：将各个标准溶液储备液/对-特-辛基苯酚标样中间浓度混合，并用二氯甲烷分别稀释至以下浓度。

Calibration Level	Conc. of Compounds (mg/L)	Vol. of 1.0 mg/L standard solution (μL)	Vol. of DCM (μL)	Final Vol. (μL)
1	10 (1)	10+10+10+10+10+10	940	1000
2	20 (2)	20+20+20+20+20+20	880	1000
3	50 (5)	50+50+50+50+50+50	700	1000
4	100 (10)	100+100+100+100+100+100	400	1000
5	200 (20)	200+200+200+200+200+200	800	2000

If necessary, additional standards may be added to extent the calibration curve. 可根据需用扩展标线范围。

6. Procedure步骤

6.1 Extraction procedure 水样的提取

6.1.1 Take 1 L water sample to 2 L funnel which are frinsed with DCM to remove any organic impurities.

取1 L水样放于用二氯甲烷润洗过的分液漏斗中。

6.1.2 Water sample was adjusted to pH < 2 by sulfuric acid (1:1).

水样用1:1硫酸调节pH值<2。

6.1.3 Add 50 g of NaCl, extract with 60 mL DCM three times. Each time the extractor is shaken vigorously at least 2 min with appropriate venting to relieve pressure build-up.

加入50 g左右的氯化钠，分别用60 mL的二氯甲烷溶液萃取3次。每次萃取时间至少2分钟。要注意放气。

6.1.4 The three 60 mL methylene chloride extracts are combined, dried with anhydrous sodium sulfate, and finally concentrated to 1 mL by K-D equipment.

混合三次萃取液，并放入足够量的Na2SO4进行干燥脱水，最后K-D浓缩至1 mL。

6.1.5 Take 5 μL internal standard (200 mg/L) into 2 mL autosampler vial, and then add 200 μL extracted sample.

加入浓度为200 mg/L的内标5 μL，再加入200 μL的样品放于有内插管的进样瓶中。

6.1.8 The sample was analyzed by gc/MS. The analysis procedure can be obtained from ENV-SH-WI-ORG-001 Determination of SVOC with gc/MS (USEPA 8270d, USEPA 525.2).

样品用gc/MS分析。分析程序参考ENV-SH-WI-ORG-001 Determination of SVOC with gc/MS (USEPA 8270d, USEPA 525.2)。

6.2 Calculation 计算

C (μg/L) = Cinstrument reading (mg/L) x Vfinal (mL) x Dilution Factor/sample volume (L)

6.3 Quality Control质量控制

(1) A method blank is analyzed in each batch or every 20 samples. Target compound should below the limit of report.

每批样品或每20个样品做一个方法空白。目标化合物需低于检出限。

(2) Sample duplicates: The acceptance criterion for sample duplicates is less than 30% RPD.

平行样：RPD应小于30%。

(3) LCS: Spiked amount for AP and APEO are 50 μg and 100 μg, respectively. The acceptance criteria of recoveries should be in the range from 50% to 150%.

实验室控制样品：AP和APEO的加标量分别为 50 μg和100 μg。回收率需控制在50~150%之间。

7. Method Performance 方法可行性

7.1 Table 2 lists the method recovery using laboratory fortified samples with target compounds.

表2列出了目标化合物的加标回收率。

7.2 Table 3 lists LOR for target compounds in this method.

表3列出了本方法目标化合物的检出限。

8. References 参考文献

8.1 USEPA 8270D. Semi-volatile Organic Compounds by Gas Chromatography/Mass Spectrometry (gc/MS).

8.2 ASTM D7065-11. Standard test method for determination of nonylphenol, bisphenol A, p-tert-Octylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate in environmental waters by gas chromatography mass spectrometry.

8.3 USEPA 3510C Separatory Funnel Liquid-Liquid Extraction.

Table 1 Target compounds detected by this method

Compounds	CAS NO.
Nonylphenol (NP)	25154-52-3
Octylphenol (OP)	1806-26-4
Bisphenol A (BPA)	80-05-7
p-tert-Octylphenol	140-66-9
nonylphenol monoethoxylate (NP1EO)	-
nonylphenol diethoxylate (NP2EO)	-
octylphenol monoethoxylate (OP1EO)	-
octylphenol diethoxylate (OP2EO)	-

Table 2 Recoveries for Laboratory control sample in water

Compounds	Spike 10/50/100 μg
Compounds	Result 1	Recovery (%)	Result 2	Recovery (%)	RPD (%)
NP	48	96	44	88	9
OP	47	94	40	80	16
BPA	84	84	83	83	2
p-tert-Octylphenol	7.7	77	7.1	71	8
NP1EO	80	77	79	71	1
NP2EO	82	82	78	78	5
OP1EO	101	101	-	-	-
OP2EO	86	86	-	-	-

Table 3 LOR for alkylphenol ethoxylates in environmental water

Compounds	LOR
Compounds	Water (μg/L)
NP	10
OP	10
BPA	10
p-tert-Octylphenol	1
NP1EO	10
NP2EO	10
OP1EO	10
OP2EO	10