HJ 909-2017Water quality--Determination of polybrominated diphenyl ethers--Gas chromatography mass spectrometry (English PDF)

Foreword

In order to implement the "Law of the People's Republic of China on Environmental Protection" and the "Law of the People's Republic of China on Prevention and Control of Water Pollution", protect the environment, Protection of human health, regulate the determination of PBDE in water, the development of this standard.

This standard specifies the determination of surface water, groundwater, industrial waste water and domestic sewage by polybrominated diphenyl ether gas chromatography - quality Spectrum method.

This standard Appendix A normative appendix, Appendix B ~ Appendix C is an informative annex.

This standard is released for the first time.

This standard by the Environmental Protection Department of Environmental Monitoring Division and Science and Technology Standards Division to develop.

This standard was drafted. National Environmental Analysis Test Center, Environmental Protection Department of Environmental Cooperation Center.

This standard verification unit. Hubei Provincial Environmental Monitoring Center Station, Environmental Monitoring Center of Guangdong Province, Zhejiang Province Environmental Monitoring Center, Ningbo Guoke Monitoring Technology Co., Ltd., China State Environmental Sciences Research Institute of Environmental Criteria and Risk Assessment State Key Laboratory and Island Tianjin Enterprise Management (China) Co., Ltd. Beijing Analysis Center.

This standard MEP approved on December 29, 2017.

This standard since April 1, 2018 come into operation.

This standard is interpreted by the MEP.

Water quality - Determination of polybrominated diphenyl ethers - Gas chromatography - mass spectrometry Warning. The internal standards and standard samples used in the experiment are all toxic and hazardous compounds, the solution preparation should be in the fume hood Conduct, operation should be required to wear protective equipment, to avoid contact with skin and clothing.

1 Scope of application

This standard specifies the determination of polybrominated diphenyl ethers in water by gas chromatography - mass spectrometry.

This standard applies to surface water, groundwater, industrial wastewater and domestic sewage eight kinds of PBDE determination of similar substances.

When the sample volume is 1 L, the final volume of 1 ml, the standard determination of three to seven brominated diphenyl ether method was detected the limit of detection ranged from 0.5 ng/L to 1.6 ng/L. The detection limit of decabromodiphenyl ether was 0.02 µg/L. The detection limit of three to seven brominated diphenyl ethers the lower limit of determination is 2.0 ng/L ~ 6.4 ng/L, and the lower limit of determination of decaBDE is 0.08 µg/L. See Appendix A for details.

2 Normative references

This standard references the following documents or the terms. For undated references, the effective version applies to this book standard.

HJ/T 91 Technical Specifications for Surface Water and Sewerage Monitoring HJ/T 164 Groundwater Environmental Monitoring Technical Specifications

3 Method principle

With dichloromethane extraction of water samples of polybrominated diphenyl ether, the extract was dehydrated, concentrated, purified, after volume, with gas color Spectral separation, mass spectrometry. According to the retention time, fragment ion mass ratio and its abundance than qualitative, internal standard method.

4 Reagents and materials

Unless otherwise specified, the analysis of the use of analytical reagents in line with national standards, the experimental water is not pure water.

4.1 Dichloromethane (CH2Cl2). pesticide residues.

4.2 n-hexane (C6H14). pesticide grade.

4.3 methanol (CH3OH). pesticide grade.

4.4 Sulfuric acid (H2SO4). rho (H2SO4) = 1.84 g/ml.

4.5 Hydrochloric acid (HCl). rho (HCl) = 1.19 g/ml.

4.6 Sodium thiosulfate (Na2S2O3). excellent grade pure.

4.7 PBDE mixed standard solution. rho = 20.0 mg/L, including BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154 and BDE-183 (BDE-209 at a concentration of.200 mg/L). With n-hexane as solvent, using standard Material preparation, below 4 °C sealed dark for six months. You can also buy a certified standard solution, see the standard storage time Liquid certificate related instructions.

4.8 Purification of internal standard solution. rho = 2.00 mg/L including 13C-BDE-28, 13C-BDE-47, 13C- BDE- 99, 13C- BDE- 100, 13C-BDE-153, 13C-BDE-154 and 13C-BDE-183 at a 13C-BDE-209 concentration of 20 mg/L. Commercial permit standards Solution, the solvent is nonane.

4.9 injection of internal standard stock solution. rho = 50.0 mg/L, 13C-PCB-209, a commercially available certified standard solution, the solvent is nonane.

4.10 Polybrominated diphenyl ether mixed standard solution I. rho = 2.00 mg/L (rhoBDE-209 = 20 mg/L).

Pipette 1.00 ml polybrominated diphenyl ether mixed standard solution (4.7) into a 10 ml brown volumetric flask with n-hexane (4.2) Set the volume to mark, mix well. Sealed at 4 °C for 3 months.

4.11 Polybrominated diphenyl ether mixed standard solution II. rho =.200 µg/L (rhoBDE-209 =.2000 µg/L).

Pipette 100 µl of PBDE mixed standard solution I (4.10) and 900 µl of n-hexane (4.2) to 1.5 ml Brown sample vial, mix well. Pro use now with.

4.12 injection internal standard solution. rho = 5.00 mg/L.

Pipette 1.00 ml sample internal standard stock solution (4.9) to 10 ml brown volumetric flask, n-hexane (4.2) to volume Line, mix well. Sealed at 4 °C for 3 months.

4.13 anhydrous sodium sulfate (Na2SO4). excellent grade pure.

Burning at 400 °C 4 h, cooled into the ground glass jar, placed in a desiccator to save.

4.14 Quartz cotton. Before use, burning at 350 °C 2 h, sealed and stored.

4.15 Sodium hydroxide solution. rho (NaOH) = 0.05 g/ml.

Take 50 g of sodium hydroxide (excellent grade pure) dissolved in a small amount of water, diluted to 1 L.

4.16 Silica gel. about 75 µm ~ 180 µm (80 mesh ~.200 mesh) chromatography column packed with silica gel.

In a beaker followed by methanol (4.3) and dichloromethane (4.1) wash, volatile completely, spread out in the evaporating dish, Thickness less than 10 mm. 130 °C drying 16 h, then placed in a desiccator cooling 30 min, into the conical flask, stored in a desiccator.

4.17 chromatography magnesium silicate. 75 µm ~ 180 µm (80 mesh ~.200 mesh).

In a beaker followed by methanol (4.3) and dichloromethane (4.1) wash, volatile completely, spread out in the evaporating dish, Thickness less than 10 mm. 130 °C drying 16 h, then placed in a desiccator cooling 30 min, into the conical flask, stored in a desiccator.

4.18 alkaline silica gel.

Weigh 98 g of silica gel (4.16), add 40 ml of sodium hydroxide solution (4.15) and shake well to become a powder. The Made of silica gel containing 2% (w/w) of sodium hydroxide, which is loaded Erlenmeyer flask, stored in a desiccator.

4.19 acidic silica gel.

Weigh 56 g of silica gel (4.16), add 44 g of sulfuric acid (4.4), shake well and turn into a powder. Made of silicone Contains 44% sulfuric acid, put it into a conical flask and store in a desiccator.

4.20 Composite Silica Column. The following methods can be used to fill, you can also buy commercially available products.

Place a small pool of quartz wool (4.14) on the bottom of the column (5.4) and add 40 ml of n-hexane (4.2). Followed by 1 g Anhydrous sodium sulfate (4.13), 1 g of silica gel (4.16), 2 g of layered magnesium silicate (4.17), 1 g of silica gel (4.16), 3 g of basic silicon (4.18), 1 g of silica gel (4.16), 8 g of acidic silica gel (4.19), 1 g of silica gel (4.16), 1 g of anhydrous sodium sulfate (4.13).

Release n-hexane, so that the liquid level just above the silica gel anhydrous sodium flush, stand-by.

4.21 Dichloromethane - n-hexane mixed solvent. 1 4.

Measure 1 volume of methylene chloride (4.1) and 4 volumes of n-hexane (4.2).

4.22 hydrochloric acid solution. 1 1.

4.23 Carrier gas. helium, purity >=99.999%.

5 Instruments and equipment

5.1 Sampling bottle. 1 ~ 4 L, Teflon lined brown bottle with lid.

5.2 Gas Chromatography Mass Spectrometer (GC-MS). Split/Splitless Inlet with Capillary and Pulsed High Pressure, Programmable Temperature, mass spectral EI source.

5.3 Column. 5% phenyl-methylpolysiloxane with a stationary phase of 15 m × 0.25 mm × 0.1 µm or other equivalent Effect of the column.

5.4 Column. Glass column with inner diameter of 8 mm and length of.200 mm.

5.5 Concentration device. rotary evaporator, KD concentrator or nitrogen enrichment concentrator and other devices.

5.6 separatory funnel. 2 L, with Teflon cocks.

5.7 General laboratory equipment and equipment.

6 Samples

7 Analysis steps

51 Base peak 10% ~ 80%.199 198 Peak 5% ~ 9%

68 2% less than 69 peaks 10% ~ 60% of 275 base peaks 70 less than 2% of peak 69 365 more than 1% of peak 198

127 Base peak 10% ~ 80% 441 Present and less than 442 Peak 24% 197 2% 442 base peak less than 198 peak, or greater than 50% 198 base peak or greater than 50% of 442 peak 443 442 peak 15% to 24%

7.2.2 GC system inspection Gas chromatographic mass spectrometry systems should be examined prior to sample analysis and every 12 hours of operation, and 1.0 µl of p, p'-DDT (5.0 µg/ml), using full scan determination, according to the formula (1) to calculate the degradation rate.

If the degradation rate of DDT >= 15%, then the inlet and column should be maintained, the system can be tested before passing the test.

7.3 Calibration curve establishment

7.3.1 Standard Series (CS) preparation Five 1.5 ml brown gas chromatographic vials were taken, respectively, using n-hexane (4.2), polybrominated diphenyl ether Use liquid I (4.10), PBDE mixed standard solution II (4.11), purify internal standard solution (4.8) and sample internal standard with liquid (4.12), according to Table 2 formulated into five different concentrations of standard series.

Table 2 Preparation of PBDE standard series solution

Standard Series CS-1 CS-2 CS-3 CS-4 CS-5 PBDE Standard Series Solution Concentration/ng/ml 2.00 10.0 50.0.200 500 BDE-209 concentration/ng/ml 20.0 100 500.2000 5000 N-hexane volume/µl 960 920 945 870 720 Polybrominated Diphenyl Ethers Mixed Standard Use Solution I Volume/µl - - 25.0 100 250 PBDE Mixed Standard Solution II Volume/µl 10.0 50.0 - - -Purification of internal standard solution volume/µl 10.0 10.0 10.0 10.0 10.0 Into the sample volume of internal standard/µl 20.0 20.0 20.0 20.0 20.0

7.3.2 Standard curve According to the instrument reference analysis conditions (7.1), GC-MS determination was carried out sequentially from low concentration to high concentration. With standard series the concentration of the target solution in the solution and the internal standard concentration ratio as the abscissa, the target peak corresponding to the chromatographic peak area and the internal standard Peak area ratio of the vertical axis, the establishment of calibration curve.

7.4 Determination of the sample the sample (6.2) is to be tested according to the same instrument conditions as in the calibration curve (7.3).

7.5 blank test

The blank sample (6.3) was measured according to the same procedure as the sample measurement (7.4).

8 results calculated and said

8.1 Qualitative analysis According to the retention time of the target and its isotopes, the charge-to-charge ratio of the fragment ion and its abundance ratio are qualitatively determined. The target in the sample the difference between the retention time of the material and the retention time of the standard is within 20 s, and the relative abundance of the qualitative ion relative to the quantitation ion Relative to the relative abundance of recently obtained standard samples, the relative deviation should be 9 precision and accuracy

9.1 Precision

Six laboratories investigated the effects of PBDEs at concentrations of 4.5 ng/L, 90 ng/L, 350 ng/L (BDE-209 concentration of 0.045 µg/L, 0.90 µg/L, 3.5 µg/L). The relative standard deviations . 2.5% -31%, 3.2% -29%, 4.4% -17%. The relative standard deviations of the laboratories were 9.4% -19% the reproducibility was 0.4 ng/L ~ 2.1 ng/L (BDE-209 was 0.03 µg/L) and 11 ng/L ~ 26 ng/L (0.38 µg/L for BDE-209) and 75 ng/L to 140 ng/L for BDE-209 L to 2.6 ng/L (BDE-209 0.04 µg/L), 16 ng/L to 38 ng/L (BDE-209 0.41 µg/L), 78 ng/L to 160 ng/L (1.4 µg/L for BDE-209).

9.2 Accuracy

Six laboratories investigated the effects of PBDEs at concentrations of 4.5 ng/L, 90 ng/L, 350 ng/L (BDE-209 concentration of 0.045 µg/L, 0.90 µg/L, 3.5 µg/L). The standard additions were 4.5 ng, 90 ng, the recoveries were in the range of 69% -115% (BDE-209 of 111% -179%), 79% -125%, 75% -125%; the final value of spike recovery was 88% ± 24% -95% ± 18% (145% ± 46% for BDE-209), 94% ± 12% to 107% ± 18%, 96% ± 20% to 113% ± 18%.

The results of precision and accuracy are given in Appendix C.

10 Quality Assurance and Quality Control

10.1 Each batch of samples (20 samples in batches) should be done at least one laboratory blank experiment, all blank test results the concentration of the target compound in the fruit should be less than the detection limit of the method. Otherwise, it should promptly identify the reason, until the laboratory blank test After the sample analysis.

10.2 The correlation coefficient of the standard curve should be >=0.997. The determination of the midpoint concentration of a calibration curve for each of 20 samples Quasi-solution, the measured value and the initial concentration of the relative error should be <= 30%.

10.3 Each batch of samples (up to 20 samples) should be analyzed in parallel samples, parallel samples measured relative deviation should be <= 40%.

10.4 Each batch of samples should be not less than 10% blank spike recovery determination. When the spiked concentration <= 10 times the detection limit , The spiked recoveries of three to seven brominated diphenyl ethers should be between 60% and 140%, and the decaBDE should be between 60% and.200% the spiked recoveries of polybrominated diphenyl ethers should be between 60% and 140% when the limit of detection is > 10 times higher than the standard. Net in the sample the internal standard spike recovery should be between 50% to 180%.

10.5 Internal standard deviation of the peak area of the characteristic ion in the sample from the calibration curve should be within 50% to.200% the retention time of the standard in the sample is within 20 seconds of the retention time in the calibration curve.

11 Waste treatment

The waste liquid generated during the experiment should be collected in a centralized manner and properly labeled, such as "toxic waste liquid", commissioned by a qualified unit for processing.

12 Precautions

12.1 When the determination of heptabrominated polybrominated diphenyl ethers and below, the optional column length of 15 m ~ 30 m, the film thickness of 0.1 µ m ~ 0.25 µm capillary column; When measuring BDE-209 containing polybrominated diphenyl ether, the column length must be <= 15 m Thickness 0.1 µm capillary column, ion source EI source or NCI source can be selected.

12.2 BDE-209 is decomposable, taking care to keep the inlet clean. When needed, replace the gas system liner and injection septum, and cut off the column inlet end 10 ~ 30 cm.

12.3 Sample full attention to the dark. Purification before the laboratory out of the curve.

12.4 to reduce the volume of the final volume can reduce the detection limit of the method, the need to be careful to reduce the amount of 13C labeled internal standard.