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HJ 809-2016Water quality - Determination of nitrosamine compounds - Gas chromatography (English PDF)

水质亚硝胺类化合物的测定气相色谱法（发布稿）

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Issued by

Ministry of Ecology and Environment

Level / Type

National · Mandatory

Issue date

July 26, 2016

Implementation date

October 1, 2016

Scope

HJ 809-2016 is the English-translated version of 水质亚硝胺类化合物的测定气相色谱法（发布稿）.

HJ 809-2016 — This standard specifies the determination of nitrosamines in water by gas chromatography. This standard applies to surface water, groundwater, industrial wastewater and domestic sewage N-nitrosodimethylamine, N-nitroso Determination of diethylamine, N-nitroso-n-propylamine and N-nitrosodiphenylamine.

When the sampling volume of 250 ml, the standard method of detection limit were. N-nitrosodimethylamine 0.6 µg/L, N-nitrosodiamine 0.5 µg/L, N-nitrosodi-n-propylamine 0.5 µg/L, N-nitrosodiphenylamine 0.4 µg/L; The lower limits are.

N-nitrosodimethylamine 2.4 µg/L, N-nitrosodiethylamine 2.0 µg/L, N-nitrosodi-n-propylamine 2.0 Mg/L, N-nitrosodiphenylamine 1.6 µg/L.

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Document preview — HJ 809-2016

National Standard of the People's Republic of China

Classification: Z 16

Issued by: Ministry of Ecology and Environment

Preface .ii
1 Scope of application
2 Normative reference documents
3 Principle of the method
4 Reagents and materials
5 Instruments and equipment
6 Sample
7 Analysis steps
8 Results are calculated and expressed
9 Precision and accuracy
10 Quality assurance and quality control
11 Waste treatment
Appendix A (informative) method of precision and accuracy
Appendix B (informative) Reference conditions for auxiliary qualitative columns

Foreword

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

This standard specifies the determination of surface water, groundwater, industrial wastewater and domestic sewage nitrosamines in gas chromatography law.

This standard is the first release.

Appendix A and Appendix B of this standard are informative.

This standard is organized by the Ministry of Environmental Protection Science and Technology Standards Division.

The main drafting unit of this standard. Gansu Province Environmental Monitoring Center Station.

The standard verification unit. Fujian Province Environmental Monitoring Center Station, Shaanxi Province Environmental Monitoring Center Station, Qinghai Province Environmental Monitoring Heart station, Lanzhou City Environmental Monitoring Station, Zhangye City Environmental Monitoring Station and China Petroleum Lanzhou Petrochemical Branch Environmental Monitoring Station.

The environmental protection department of this standard approved on July 26, 2016.

This standard has been implemented since October 1, 2016.

This standard is explained by the Ministry of Environmental Protection.

Water quality - Determination of nitrosamines - Gas chromatographic method Warning. nitrosamines are carcinogens, their standard substances and standard stock solution in use, to avoid contact Skin, eyes, etc .; should be in a well-ventilated indoor fume hood to operate; use of dichloromethane, ether, pentane and other tests , Should wear protective equipment, avoid inhalation or contact with skin and clothing.

1 Scope of application

This standard specifies the determination of nitrosamines in water by gas chromatography.

This standard applies to surface water, groundwater, industrial wastewater and domestic sewage N-nitrosodimethylamine, N-nitroso Determination of diethylamine, N-nitroso-n-propylamine and N-nitrosodiphenylamine.

The lower limits are. N-nitrosodimethylamine 2.4 µg/L, N-nitrosodiethylamine 2.0 µg/L, N-nitrosodi-n-propylamine 2.0 Mg/L, N-nitrosodiphenylamine 1.6 µg/L.

2 Normative reference documents

The contents of this standard refer to the following documents or their terms. Any annotated file that does not specify the date, its valid version Applicable to this standard.

Technical specification for surface water and wastewater monitoring Technical specification for groundwater environmental monitoring

3 Principle of the method

Extraction of nitrosamines from the sample with dichloromethane, dehydration and concentration, florisil column or alkaline oxidation Aluminum column after purification capacity. Separation by capillary column, hydrogen flame ionization detector (FID) determination. To retain the time qualitative, External standard method.

4 Reagents and materials

Unless otherwise stated, analytical pure chemical reagents are used in accordance with national standards. The experimental water is freshly prepared Deionized water or distilled water.

4.1 dichloromethane (CH2Cl2). pesticide residues.

4.2 Methanol (CH3OH). Pesticide level.

4.3 Acetone (C3H6O). pesticide residues.

4.4 pentane (C5H12). pesticide residues.

4.5 ether [(C2H5) 2O]. pesticide residues.

4.6 sodium thiosulfate (Na2S2O3). excellent grade pure.

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

Before use, should be in the muffle furnace at 450 °C for 4 h, after cooling into the grinding glass bottle sealed, placed in the dry Save the device.

4.8 Sodium chloride (NaCl). excellent grade pure.

Before use, should be in the muffle furnace at 350 °C for 4 h, after cooling into the grinding glass bottle sealed, placed in the dry Save the device.

4.9 sulfuric acid. rho (H2SO4) = 1.84 g/ml, excellent grade pure.

4.10 sulfuric acid solution. 1 4 (v/v).

Prepared with sulfuric acid (4.9).

4.11 sodium hydroxide (NaOH). excellent grade pure.

4.12 Sodium hydroxide solution. c (NaOH) = 2 mol/L.

Weigh 8.0 g of sodium hydroxide (4.11) in the appropriate amount of water, to be cooled to room temperature and then diluted to 100 ml, mixed uniform. Transferred to the plastic reagent bottle to save.

4.13 Florisil. 60 mesh to 100 mesh.

In the muffle furnace at 650 °C for 5 h, after cooling stored in a glass plug or lined with aluminum foil screw cap glass Inside the container. Before use, take the appropriate amount of calcined silica, in a lined aluminum foil screw cap glass container at 130 °C Activate for 16 h, add 2 ml of water, shake for 10 min, and allow to stand for at least 2 h.

4.14 Alumina. 100 mesh to.200 mesh.

Weigh l00.0 g Alumina in 500 ml glass flasks with glass stoppers or aluminum foil screw caps, add 2 ml Water, shake fully mixed for 10 min, standing for at least 2 h after use.

4.15 Mixed standard stock solution. rho =.2000 mg/L.

Respectively, weighed 0.200 g (accurate to 0.0001 g) N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitroso N-propylamine and N-nitrosodiphenylamine were dissolved in an appropriate amount of dichloromethane (4.1) and transferred to a 10 ml volumetric flask.

Methane (4.1) constant volume to the mark, mix, at 4 °C below the cold, dark and sealed can be stored for 6 months. Can also be direct Purchase commercially available standard solution.

4.16 Mixing standard liquid. rho =.200 mg/L.

Accurate removal of 1.00 ml of mixed standard stock solution (4.15) in a 10 ml volumetric flask with dichloromethane (4.1) to the mark line, mix, at 4 °C below the cold, dark and sealed can be stored for 2 months.

4.17 Glass wool. commercially available silanized glass wool.

4.18 nitrogen. purity >=99.999%.

4.19 Hydrogen. purity >=99.99%.

4.20 Combustion gas. oil-free compressed air, purified by 5Å molecular sieve.

5 Instruments and equipment

5.1 Gas Chromatograph. with a hydrogen flame ionization detector (FID), with split/splitless inlet, oven can be programmed to rise temperature.

5.2 Column I. quartz capillary column, length 30 m × diameter 0.25 mm, film thickness 0.25 µm, stationary phase 5% diphenyl-95% dimethylpolysiloxane, or other equivalent column.

5.3 Column II. quartz capillary column, length 30 m × diameter 0.25 mm, film thickness 0.25 µm, stationary phase 35% diphenyl-65% dimethylpolysiloxane, or other equivalent column.

5.4 Concentration device. rotary evaporator (or with the same function of the concentration device) and nitrogen blowing concentrator.

5.5 Columns. Approx. 400 mm length x 22 mm ID, used for Florisil column purification.

5.6 Column II. about 300 mm length × 10 mm diameter for alkaline alumina column purification method.

5.7 separatory funnel. 500 ml, with polytetrafluoroethylene plug.

5.8 General laboratory equipment and equipment commonly used.

6 Samples

6.1 Collection and storage of samples

Samples were collected with reference to the relevant provisions of HJ/T 91 and HJ/T 164. With a hard grinding glass bottle or with polytetrafluoroethylene material the sample should be filled with vials and stamped, sealed at 4 ° C, Save and transport. After sampling, the sample should be extracted within 7 days. If it can not be measured in time after extraction, it should be below 4 °C Cold storage, dark and sealed preservation, 30 d to complete the analysis and determination.

6.2 Preparation of the sample

6.2.1 Extraction and concentration

6.2.1.1 Measure 250 ml of sample in a 500 ml separatory funnel (5.7) with sulfuric acid solution (4.10) or sodium hydroxide Solution (4.12) adjust the sample pH value of 6 to 9, add 50 ml of dichloromethane (4.1), the oscillation extraction 2 min, static 10 min, two phase stratification, collecting organic phase, repeated extraction 2 ~ 3 times. Combine the organic phase in a conical flask and add Anhydrous sodium sulfate (4.7) dehydrated and dried.

Note 1. If emulsification occurs during extraction, add 10 g of sodium chloride (4.8) to the sample, or use centrifugation, sonography, etc.

Mechanical way to break the milk, can also be used to freeze the way to break the milk.

6.2.1.2 Sample without purification, concentrate the extract to 1 ml (V1) using the concentrator (5.4), to be tested. need Purify the sample and concentrate the extract to 5 ml using a concentrator (5.4) to be purified.

Note 2. If concentrated by using a rotary evaporator, it should be carried out at a heating temperature of 40 ° C and a rotation speed of 60 ° C/min.

6.2.2 Purification

For the complex composition of surface water, industrial wastewater and domestic wastewater, after extraction using Florisil (4.13) column or Alkaline alumina (4.14) column for purification.

6.2.2.1 Purple silica column cleaning

A glass wool (4.17) of about 0.5 cm thick was placed on the bottom of column I (5.5) and 22.0 g of activated Lori Silica (4.13), tap the pillars to keep the contents down, add about 0.5 cm thick to the top of the Florian layer of anhydrous sodium sulfate (4.7). The column was washed with 40 ml of ether/pentane (15 85, v/v), the eluent was discarded, Before the sodium sulfate layer was exposed to air, add the concentrated 5 ml extract (6.2.1.2).

The first elution was carried out with 90 ml of ether/pentane (15 85, v/v) followed by 100 ml of acetone/diethyl ether (5 95, V/v) for the second elution, and the combined eluate was collected twice. The collected eluate was concentrated using a concentrator (5.4) to 1.0 ml (V1), to be tested.

6.2.2.2 Alkaline alumina column purification

Place about 0.5 cm thick glass wool (4.17) at the bottom of column II (5.6) and place 12.0 g of the prepared base Alumina (4.14), tapping the column to make its contents down to the top, add about 1 cm thick to the top of the alkaline alumina layer Anhydrous sodium sulfate (4.7). The column was eluted with 10 ml of ether/pentane (3, 7 v/v), the eluent was discarded, Before the sodium layer was exposed to air, add the concentrated 5 ml extract (6.2.1.2).

The first elution was carried out with 10 ml of ether/pentane (3 7, v/v) followed by 60 ml of ether/pentane (1 1, v/v) A second elution was performed and the combined eluate was collected twice. The collected eluate was concentrated to 1.0 using a concentrator (5.4) Ml (V1), to be tested.

Note 3. Both purification methods can meet the experimental needs, according to the actual situation of the laboratory to choose. If the method is verified by the method in addition, other purification methods may be used.

6.3 Preparation of blank samples

A sample of 250 ml of the same batch of test water was used in place of the sample. The same procedure as in the preparation of the sample (6.2) White sample.

7 Analysis steps

7.1 Instrument reference conditions

Different models of gas chromatography the best working conditions are different, should be in accordance with the instructions to operate the instrument. This standard is given the instrument reference conditions are as follows.

Inlet temperature. 250 ° C.

Injection method. split injection, split ratio of 5. 1.

Oven temperature. the initial temperature of 50 °C, keep 2.5 min, at 30 °C/min rate rose to 220 °C, keep 4 min.

Column flow. nitrogen 1.2 ml/min.

Injection volume. 1.0 µl.

Detector temperature. 300 °C; Gas. hydrogen flow 30 ml/min; Assist gas. air flow 400 ml/min.

7.2 Drawing of calibration curves

Take 6 5ml volumetric flask, add appropriate amount of dichloromethane (4.1), were added 25.0 µl, 50.0 µl, 100.0 Ml, 150.0 µl,.200.0 µl, 250.0 µl mixed standard using the liquid (4.16), with methylene chloride (4.1) constant volume, shake, the concentration of four kinds of nitrosamines were 1.00 mg/L, 2.00 mg/L, 4.00 mg/L, 6.00 mg/L, 8.00 mg/L and 10.0 mg/L mixed standard series. According to the instrument reference conditions (7.1), from low to high concentration Times for determination. The concentration of nitrosamines (mg/L) is the abscissa, the peak area or peak height is the ordinate, Draw a calibration curve.

7.3 Determination of samples

Accurately remove 1.00 µl of the prepared sample (6.2), according to the same instrument reference conditions as the drawing calibration curve (7.1) and step (7.2).

7.4 Blank test

Accurately remove 1.00 µl of the prepared blank sample (6.3), according to the same instrument reference as the test sample (7.1) and step (7.3).

Calculation and representation of results

8.1 Qualitative analysis

The target compound was characterized according to the retention time of the component. In this standard reference chromatographic conditions, four kinds of nitrosamines the standard chromatogram of the compound is shown in Fig. When there is interference peak, available column II (5.3) to do the auxiliary qualitative, chromatography the standard chromatograms of the four nitrosamines in column II are given in Appendix B.

8.2 Quantitative analysis

The mass concentration (µg/L) of the target compound in the sample was calculated according to the formula (1) using the external standard method.

31 10 x

Where. i - mass concentration of the target compound i in the sample, µg/L;

- the concentration of the target compound i, mg/L, found on the calibration curve;

1V - the concentration of the extract is fixed volume or the volume of the concentrated volume, ml;

V - sample sampling volume, ml.

Figure 1 Standard sample chromatograms of four nitrosamines (column I)

8.3 Results show

When the result is less than 10.0 µg/L, it will be retained to one decimal place; when the result is greater than or equal to 10.0 µg/L , Retain three valid digits.

9 Precision and accuracy

9.1 Precision

(8 µg/L, 20 µg/L, 40 µg/L) containing four kinds of nitrosamines, the relative standard deviations in the laboratory were 1.8% ~ 13.0%, 1.2% ~ 12.7% and 0.4%, respectively, ~ 12.7%; the relative standard deviations were 8.5% ~ 14.5%, 10.3 ~ 10.9% and 8.6% ~ 13.2%, respectively;

The limits were 0.9 µg/L -1.7 µg/L, 2.3 µg/L to 2.9 µg/L and 4.4 µg/L to 6.6 µg/L, respectively. The reproducibility limits were 2.3 µg/L to 2.7 µg/L, 4.4 µg/L to 5.2 µg/L and 8.3 µg/L to 14.4 µg/L.

9.2 Accuracy

Six laboratories carried out spike analysis of three types of surface water, domestic sewage and industrial wastewater respectively the titer of the titer was 2.0 µg, 5.0 µg and 10.0 µg, respectively. The recoveries were as follows. N-nitrosodimethylamine 48.9% to 85.8%, 54.9% to 82.3% of N-nitrosodiethylamine, 54.9% to 84.3% of N-nitrosodi-n-propylamine, Nitro-diphenylamine 63.3% ~ 98.5%.

For the precision and accuracy of the four nitrosamines, see Appendix A.

10 Quality assurance and quality control

10.1 Each batch of reagents shall be subjected to a blank test. The reagent blank value shall be lower than the method detection limit.

10.2 samples per 20 samples or per batch (less than 20 samples) should be analyzed at least one laboratory blank, blank should be lower than the method detection limit.

10.3 The correlation coefficient of the calibration curve should be greater than or equal to 0.995.

10.4 Continuous calibration. Each calibration sample shall be measured for every 20 samples or for each batch (less than 20 samples).

Point concentration of the standard solution, the measurement results and calibration curve of the point of the relative deviation of the concentration should be less than 20%, or should be re-Draw a calibration curve. Continuous calibration should be performed prior to laboratory blank and sample analysis.

10.5 Each batch of samples should be measured at least 10% of the parallel sample, the number of samples less than 10, should be measured at least a parallel the relative deviation of the results should be less than 20%.

10.6 Every 20 samples or each batch (less than 20 samples) should be measured at least one matrix spiked sample, N-nitroso the recoveries of dimethylamine should be between 45% and 120%, N-nitrosodiethylamine, N-nitrosodipropylamine, N-nitroso the recoveries of diphenylamine should be between 70% and 120%.

11 Waste treatment

Nitrosamines are carcinogenic organic pollutants, the standard substances used in the course of the test and all organic residues Liquid, should be placed in a suitable closed container to collect and collect, commissioned by qualified units.

Appendix A

(Informative)

Method of precision and accuracy

Table A.1 and Table A.2 show the precision and accuracy of the method, respectively.

Table A.1 The precision of the method

Target

Precision statistics results Determination frequency average value (Mg/L) Laboratory phase on standard deviation RSDi (%) Laboratory phase on standard deviation RSD '(%) Repetitive limit r (Mg/L) Reproducibility R (Mg/L) N-nitroso Dimethylamine 6 5.3 1.76 ~ 9.93 14.5 0.9 2.3 6 12.4 1.22 to 11.0 10.9 2.5 4.4 6 25.3 1.08 to 10.4 10.2 4.4 8.3 N-nitroso Diethylamine 6 6.5 2.41 to 11.3 13.3 1.4 2.7 6 14.2 3.35 to 11.9 10.3 2.9 4.9 6 32.6 0.71 to 12.2 8.65 6.2 9.7 N-nitroso Di-n-propylamine 6 6.5 2.53 ~ 9.62 12.6 1.2 2.5 6 13.6 2.07 to 12.7 10.9 2.3 4.6 6 32.6 0.36 to 11.7 10.5 5.8 11.0 N-nitroso Diphenylamine 6 7.4 2.08 to 13.0 8.53 1.7 2.4 6 16.0 2.09 ~ 8.71 10.4 2.6 5.2 6 35.4 0.53 ~ 12.7 13.2 6.6 14.4

Table A.2 The accuracy of the method

Target Substrate Accelerated Spike (%) Range Spike Recovery Final Value (%) N-nitroso Dimethylamine Surface water 53.6 ~ 85.8 66.0 ± 21.8 Wastewater Treatment Plant Wastewater 1 48.3 ~ 62.6 57.0 ± 10.4 Sewage treatment plant sewage 2 59.4 ~ 74.4 66.0 ± 10.2 N-nitroso Diethylamine Surface water 57.6 ~ 82.3 71.4 ± 15.8 Sewage treatment plant sewage 1 54.9 ~ 74.2 64.5 ± 15.4 Sewage treatment plant sewage 2 64.5 ~ 80.9 71.4 ± 13.4 N-nitroso Di-n-propylamine Surface water 59.6 ~ 84.3 71.5 ± 17.4 Sewage treatment plant sewage 1 54.9 ~ 70.1 62.2 ± 10.8 Wastewater Treatment Plant Wastewater 2 70.2 ~ 84.0 77.9 ± 11.0 N-nitroso Diphenylamine Surface water 63.3 ~ 98.5 81.5 ± 24.2 Wastewater Treatment Plant Wastewater 1 63.4 ~ 83.6 69.5 ± 16.0 Sewage treatment plant sewage 2 78.6 ~ 93.6 85.9 ± 10.0 Appendix B (Informative) Auxiliary qualitative column instrument reference conditions 1, auxiliary qualitative instrument reference conditions.

Inlet temperature. 250 °C; injection method. split injection, split ratio of 5. 1; oven temperature. the initial temperature of 50 °C, Hold for 2.5 min at 23 ° C/min at 220 ° C for 4 min; column flow rate. nitrogen 1.2 ml/min;

Sample volume. 1.0 µl; detector temperature. 300 ° C; gas. hydrogen flow rate 30 ml/min; combustion gas. air flow 400 ml/min.

2, the reference standard chromatogram shown in Figure 2.

Figure 2 Standard sample chromatograms of four nitrosamines (column II)

Min 6 7 8 9 10 11 12 13 PA .6 .5

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