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HJ 744-2015Water quality. Determination of phenols compounds. Gas chromatography mass spectrometry (English PDF)

水质酚类化合物的测定气相色谱-质谱法

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Issued by

Ministry of Ecology and Environment

Level / Type

National · Mandatory

Issue date

May 4, 2015

Implementation date

July 1, 2015

Scope

HJ 744-2015 is the English-translated version of 水质酚类化合物的测定气相色谱-质谱法.

HJ 744-2015 — This standard specifies the determination of phenolic compounds in water by gas chromatography-mass spectrometry.

This standard applies to surface water, groundwater, domestic sewage and industrial wastewater phenol, 2-chlorophenol, 4-chlorophenol, pentachlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, 2,3,4,6-tetrachlorophenol, 4- Nitrophenol, 2-methyl Phenol, 3-cresol, 4-cresol, 2,4-xylenol and other 14 kinds of phenolic compounds.

Other phenolic compounds are verified by methods Using this method. When the sampling volume was 250 ml, the method of detection of 14 phenolic compounds was 0.1 g/L when the selective ion scanning mode was used ~ 0.2 g/L, the lower limit of determination is 0.4 g/L ~ 0.8 g/L, see Appendix A.

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Document preview — HJ 744-2015

National Standard of the People's Republic of China

ICS: 13.060
Classification: Z 16

Issued by: Ministry of Ecology and Environment

Foreword
1 Scope of application
2 Normative reference documents
3 Principle of the method
4 Reagents and materials
24.10 Anhydrous sodium sulfate (Na2SO4)
51 Strength of 19-60% of 19 pieces of.199.199% of the strength of 198 fragments of 5-9%
68 Strength less than 69 pieces of debris 2% 275 strength of 198 fragments of 10-30%
70 Strength Less than 69 pieces of 2% 365 Strength greater than 198% of debris 1%

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, Human health, regulate the determination of phenolic compounds in water, the development of this standard.

This standard specifies the determination of phenolic compounds in water by gas chromatography-mass spectrometry.

This standard is the first release.

Appendix A of this standard is a normative appendix, Appendix B is an informative appendix.

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

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

The standard verification unit. Taizhou City Environmental Monitoring Center Station, Nanjing Environmental Monitoring Center Station, Chongqing Environmental Monitoring Center Station, Dalian Environmental Monitoring Center, the State Environmental Protection Department of Nanjing Environmental Science Research Institute and Henan Province Environmental Monitoring Center.

The environmental protection department of this standard approved on May 4, 2015.

This standard has been implemented since July 1, 2015.

This standard is explained by the Ministry of Environmental Protection.

Determination of water quality phenolic compounds - Gas chromatography - mass spectrometry WARNING. The solvents and reagents used in the test are subject to toxicity and the sample pretreatment should be carried out in a fume hood, Operation should be required to wear protective equipment, to avoid direct contact with solvents and reagents skin and clothing.

1 Scope of application

This standard specifies the determination of phenolic compounds in water by gas chromatography-mass spectrometry.

When the sampling volume was 250 ml, the method of detection of 14 phenolic compounds was 0.1 g/L when the selective ion scanning mode was used ~ 0.2 g/L, the lower limit of determination is 0.4 g/L ~ 0.8 g/L, see Appendix A.

2 Normative reference documents

The contents of this standard refer to the following documents or their terms. For undated references, the valid version applies to this standard.

Technical guidance for sampling of water quality lakes and reservoirs GB/T 14581 Technical specification for surface water and wastewater monitoring Technical specification for groundwater environmental monitoring Technical specification for preservation and management of water quality samples

3 Principle of the method

Under the acidic condition (pH<=1), the phenolic compounds in the water samples were extracted by liquid-liquid extraction or solid-phase extraction.

After derivatization, the samples were separated by gas chromatography-mass spectrometry (GC-MS). The chromatographic retention time and mass spectrometry were characterized by ion characterization.

Or internal standard method quantitative.

4 Reagents and materials

Unless otherwise stated, analytical reagents and experimental water in accordance with national standards are used for analysis.

4.1 ethyl acetate (CH3COOC2H5). pure chromatography.

4.2 n-hexane (C6H14). pure chromatography.

4.3 Acetone (CH3COCH3). Chromatographic pure.

4.4 Methanol (CH3OH). Chromatographic pure.

4.5 dichloromethane (CH2Cl2). chromatographic purity.

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

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

4.8 Potassium carbonate (K2CO3).

4.9 Sodium hydroxide (NaOH).

24.10 Anhydrous sodium sulfate (Na2SO4)

Baked in a muffle oven at 400 ° C for 4 h, cooled to room temperature, placed in a glass jar, and stored in a desiccator.

4.11 Sodium chloride (NaCl) Baked in a muffle oven at 400 ° C for 4 h, cooled to room temperature, placed in a glass jar, and stored in a desiccator.

4.12 Pentafluorobenzyl bromide (C7H2BrF5).

4.13 Dichloromethane-n-hexane mixed solution. 2 1.

Mixed with dichloromethane (4.5) and n-hexane (4.2) at a volume ratio of 2. 1.

4.14 Dichloromethane-ethyl acetate mixed solution. 4 1.

Mixed with dichloromethane (4.5) and ethyl acetate (4.1) in a 4. 1 by volume ratio.

4.15 dichloromethane - ethyl acetate mixed solution. 1 1.

And mixed with methylene chloride (4.5) and ethyl acetate (4.1) in a 1. 1 by volume ratio.

4.16 sulfuric acid solution. 1 1.

Measure 50 ml of concentrated sulfuric acid (4.6) and slowly add to 50 ml of water.

4.17 hydrochloric acid solution. C (HCl) = 0.05 mol/L.

Measure 0.44 ml of concentrated hydrochloric acid (4.7) and slowly add to 100 ml of water.

4.18 Potassium carbonate solution (K2CO3). rho (K2CO3) = 0.1 g/ml.

Weigh 1.0 g of potassium carbonate (4.8) in water and set to 10.0 ml.

4.19 Sodium hydroxide solution. rho (NaOH) = 0.4 g/ml Weigh 40 g of sodium hydroxide (4.9) in water and set to 100 ml.

4.20 Pentafluorobenzyl bromide derivatization reagent Weigh 0.500 g of pentafluorobenzyl bromide (4.12), dissolved in 9.5 ml of acetone (4.3) and stored at 4 ° C for 2 weeks.

4.21 Phenol compound standard stock solution. rho = 100 mg/L to 2000 mg/L Contains 14 kinds of target phenolic compounds. It can be prepared by diluting pure standard with isopropanol. The standard solution is cold and sealed at 4 ° C Possession, can be saved for six months. Can also be directly purchased certified standard solution, storage time, see the standard solution certificate of the relevant instructions.

4.22 Phenolic compounds Standard use. rho = 10.0 mg/L the standard stock solution (4.21) was diluted with acetone (4.3).

4.23 Standard stock solution. rho = 1000 mg/L the use of 2,5-dibromotoluene as the determination of methyl phenol, dimethyl phenol, monochlorophenol and dichlorophenol and other relatively low boiling point of phenols the internal standard of the compound, 2,2'5,5'-tetrabromobiphenyl is used as a phenolic compound for the determination of higher boiling point such as trichlorophenol, tetrachlorophenol and nitrophenol the internal standard. Can be directly purchased certified standard solution, or diluted with pure isopropyl alcohol standard material preparation. 4 °C under refrigeration, can be stored for six months.

4.24 Standard use of liquid. rho = 100 mg/L.

The standard stock solution (4.23) was diluted with n-hexane (4.2).

4.25 Substitute Standard stock solution. rho =.2000 mg/L 2-fluorophenol, 2,4,6-tribromophenol can be used as a substitute. Can be directly purchased certified standard solution, or diluted with isopropyl alcohol pure standard Quasi-material preparation. 4 °C under the cold storage, can be stored for six months.

4.26 Substitutes Standard use. rho = 10.0 mg/L.

The standard stock solution (4.25) was diluted with acetone (4.3).

34.27 decafluorotriphenylphosphine (DFTPP) solution. rho = 1000 mg/L, the solvent is dichloromethane.

4.28 decafluorotriphenylphosphine using liquid. rho = 50.0 mg/L Remove 500 µl of decafluorotriphenylphosphine (DFTPP) solution (4.27) into a 10 ml volumetric flask with n-hexane (4.2) Marking, mixing.

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

5 instruments and equipment

5.1 Sampling bottle. grind brown glass bottle.

5.2 Gas Chromatography-Mass Spectrometer. EI Source

5.3 Capillary column. 30 m x 0.25 mm, 0.25 µm thick (5% - phenyl-methylpolysiloxane fixative), or other equivalent capillary column.

5.4 solid phase extraction device.

5.5 Solid phase extraction column. polystyrene-divinylbenzene-vinyl pyrrolidone (6 ml, 500 mg) or equivalent solid phase extraction column.

5.6 Concentration device. nitrogen blown gas mixer, rotary evaporator, KD concentrator or equipment with considerable function.

5.7 Glass separatory funnel. 500 ml.

5.8 General laboratory equipment and equipment commonly used.

6 samples

6.1 sample collection and preservation Water samples are collected and preserved according to the relevant regulations of GB/T 14581, HJ/T 91, HJ/T 164 and HJ/T 493. Collect samples when the product is not ready, the bottle can not be pre-washed with water. After the sample was collected, the sample was adjusted to pH <= 2 with sulfuric acid solution (4.16). Water samples should be Fill the vials and seal them, save them at 4 ° C. If the water sample can not be measured in time, should be extracted within 7 d. The extract was incubated at 4 ° C Keep away from light and complete the analysis within 20 days.

6.2 Preparation of the sample Surface water, groundwater and other clean water samples may not be purified Direct extraction analysis, the substrate is more complex water samples should be alkaline aqueous solution stripping Take (6.2.1) purification.

6.2.1 Sample purification Take water sample 250 ml in a glass separatory funnel, adjust the water sample to pH >= 12 with sodium hydroxide solution (4.19), add 25 ml of bis Methyl chloride-n-hexane mixed solution (4.13), and the mixture was extracted for 5 min. The organic solvent was discarded until further sample was extracted.

6.2.2 Extraction

Measure the amount of 250 ml of water or purified water (6.2.1). If you want to use the substitute to indicate the efficiency of the whole sample recovery, Add 10.0 µl of the substitute standard using the solution (4.26) so that the concentration of the substitute is near the midpoint of the standard curve.

Water samples were added sulfuric acid solution (4.16), adjust the water sample pH <= 1. Select Liquid Extraction 6.2.2.1 or Solid Phase Extraction 6.2.2.2 Extract the target.

6.2.2.1 Liquid-liquid extraction Weigh 15 g of sodium chloride (4.11) into the water sample and gently shake it to dissolve it. Measure the amount of 25 ml of dichloromethane-ethyl acetate Solution (4.14) and shaken for 10 min. The organic phase was allowed to stand until the organic phase and the aqueous phase were separated, and the organic phase was collected and washed with anhydrous sodium sulfate (4.10) in addition to water. The above extraction step was repeated three times, and the combined extracts were collected in a concentrated tube. Concentrate and replace to acetone as described in step 6.2.4 Solvent, constant volume to about 8 ml.

46.2.2.2 Solid phase extraction

The solid phase extraction column (5.5) was washed with 9 ml of dichloromethane (4.5) and the column was drained. And then with 9 ml of methanol (4.4) and 9 ml of hydrochloric acid solution (4.17) leaching column, all keep the stigma infiltration. The water sample is fed at a flow rate of about 20 ml/min After the collection, the column was purged with nitrogen and the column was dried. And then mixed with 8 to 10 ml of dichloromethane-ethyl acetate (4.15) at about 3 ml/min the eluate was collected and the eluate was collected in a receiving tube and concentrated and replaced in acetone solvent as described in 6.2.4 to a volume of about 8 ml.

6.2.3 Derivatization reaction to the above 8 ml of the above acetone extraction concentrate (6.2.2.1 or 6.2.2.2), 100 µl of pentafluorobenzyl bromide derivatization reagent (4.20) and 100 µl K2CO3 solution (4.18). Cover the stopper, gently shake, mix well. Placed at 60 ° C for 60 min, and cooled to room temperature. The solvent system was changed to n-hexane by 6.2.4 and concentrated to 1.0 ml.

To quantify the internal standard method, in the above-mentioned solution after the solution to accurately add 5.0 µl standard use of liquid (4.24), so that the internal standard the concentration of the solution in the solution is 500 µg/L.

6.2.4 Concentrate and replace the solvent the extract is concentrated by means of a nitrogen purge concentrator and the solvent is replaced. Other enrichment devices (5.6) may also be used.

Nitrogen blowing and replacement of solvent reference conditions. nitrogen blowing concentrator set the temperature of 30 °C, a small flow of nitrogen concentration of the extract to 1.5 ~ 2.0 Ml, wash the concentrator tube wall with 5 ~ 10 ml solvent to be replaced, and then concentrate to 0.5 ml with small flow of nitrogen, repeat the above leaching twice Tube wall and concentrated operation, and finally with the need to replace the solvent volume.

6.3 Preparation of blank sample the experimental sample was prepared in the same manner as in Sample Preparation (6.2) instead of the actual sample.

7 Analysis steps

7.1 Instrument reference conditions

7.1.1 Gas chromatographic conditions Inlet temperature. 270 ° C, splitless injection; column flow. 1.0 ml/min (constant current); oven temperature. 50 ° C at 8 ° C/min the temperature was raised to 250 ° C and maintained for 10 min. Injection volume. 1.0 µl.

7.1.2 Mass spectrometry reference analysis conditions Quadrupole temperature. 150 ° C; ion source temperature. 230 ° C; transmission line temperature. 280 ° C; scanning mode. selective ion scanning (SIM) the main characteristics of phenolic compounds derivatives (such as phenol pentafluorobenzyl bromide derivatives referred to as phenol-PFB) are shown in Table 1. Solvent extension Time. 5 min.

Table 1 Phenolic compounds Derivatives of the peak sequence and the main characteristics of ions

No. Retention Time Compound Characteristic Ion (M/Z) 1 14.86 2,5-dibromotoluene (internal standard) 250 */169/88 2 17.06 2-fluorophenol-PFB (substitute) 292 */293/181 3 17.40 Phenol-PFB 274 */275/181 4 18.38 3-Cresol-PFB 288 */289/181 5 18.73 2-cresol-PFB 288 */289/181 6 18.87 4-Cresol-PFB 288 */289/181 7 19.70 2-Chlorophenol-PFB 308 */310/181 8 19.72 2,4-Xylphenol-PFB 302 */121/181 59 20.33 4-Chlorophenol-PFB 308 */310/181 10 21.20 2,6-Dichlorophenol-PFB 342 */133/181 11 21.98 2,4-Dichlorophenol-PFB 342 */133/181 12 22.86 2,4,6-trichlorophenol-PFB 376 */378/181 13 23.89 2,4,5-trichlorophenol-PFB 376 */378/181 14 24.30 4-Nitrophenol-PFB 319 */182/181 15 25.19 2,3,4,6-tetrachlorophenol-PFB 412 */203/181 16 26.41 2,4,6-Tribromophenol-PFB (Substitute) 301 */512/181 17 27.27 Pentachlorophenol-PFB 446 */444/181 18 28.58 2,2 ', 5,5'-tetrabromobiphenyl (internal standard) 470 */150/389 Note. Add the number of ions for the phenolic compounds pentafluorobenzyl bromide derivatives quantitative ions.

7.2 Calibration

7.2.1 Instrument performance check Prior to sample analysis, the gas chromatographic-mass spectrometry system was calibrated with 1 µl of decafluorotriphenylphosphine (DFTPP) solution (4.27) can check that the abundance of the obtained mass ions should meet the requirements of Table 2.

Table 2 DFTPP critical ion and ion abundance evaluation table

Mass ion m/z abundance evaluation quality ion m/z abundance evaluation

51 Strength of 19-60% of 19 pieces of.199.199% of the strength of 198 fragments of 5-9%

68 Strength less than 69 pieces of debris 2% 275 strength of 198 fragments of 10-30%

70 Strength Less than 69 pieces of 2% 365 Strength greater than 198% of debris 1%

127 Strength of 196 pieces of 40-60% 441 present but no more than 443 pieces of strength

197 Strength Less than 198% of debris 442 Strength greater than 198% of debris 40% 198 base, relative strength 100% 443 strength of 442 fragments of 17-23%

7.2.2 Preparation of standard series (422) 10 µl, 20 µl, 40 µl, 100 µl, 240 µl, for example, when the sample was analyzed, the substitutes indicate the full recovery efficiency, then in the above series of standard solutions should be synchronized with the standard use of phenolic standard solution of the same volume Replace the standard use of the liquid (4.26), then acetone volume to 8.0 ml. At this time the target phenolic compounds and substitutes were 12.5 µg/L, 25.0 µg/L, 50.0 µg/L, 125 µg/L, 300 µg/L.

7.2.3 Derivation of the standard series After the above standard series of solutions were derivatized in accordance with 6.2.3, the solvent system was replaced according to 6.2.4 and the volume was set to 1.0 ml, to be tested. The concentration of phenolic compounds and substitute derivatives in the 1.0 ml concentrate was 0.100 mg/L, 0.200 mg/L, 0.400 mg/L, 1.00 mg/L, 2.40 mg/L.

For the use of internal standard method, in the above-mentioned solution after the solution are accurately added 5 µl standard internal standard liquid (4.24), so that the concentration of the target substance in the solution is 500 µg/L,

7.2.4 Drawing of standard curves Analyze according to the instrument reference condition (7.1) to obtain the mass spectra of the target compounds at different concentrations, and record the target compounds (Or peak height), according to the external standard method (7.2.4.1) to draw the standard curve or internal standard method (7.2.4.2) to calculate the average relative to the corresponding factor.

7.2.4.1 External standard method the peak area (or peak height) of the quantified ions of the corresponding phenolic compounds pentafluorobenzyl bromide derivatives with the standard series of concentrations as abscissa, 6 for the ordinate, draw the standard curve.

7.2.4.2 Internal standard method the peak area (or peak height) of the quantitative ion of the pentafluorobenzyl bromide derivative at each concentration point in the standard series was compared with that of the internal standard substance of the peak area (or peak height) ratio, the relative concentration of each point of the response factor, and calculate the average relative to the response child.

7.2.5 Reference Standard Gas Chromatography/Mass Spectrometry the total ion current of the phenolic compounds pentafluorobenzyl bromide derivatives is shown in Fig. 1 under the reference chromatographic conditions.

3-phenol-PFB; 4-3-cresol-PFB; 5-2-cresol- PFB; 6-5-2,4-xylphenol-PFB; 9-2-chlorophenol-PFB; 10-2, 6-dichlorophenol-PFB; 4-dichlorophenol-PFB;

12-2,4,6-trichlorophenol-PFB; 13-2,4,5-trichlorophenol-PFB; 14-4- nitrophenol-PFB; 15-2,3,4,6-tetrachloride Phenol-PFB; 16-2,4,6-tris Bromophenol-PFB (substitutes); 17-pentachlorophenol-PFB; 18-2,2,5,5-tetrabromobiphenyl (internal standard) Fig.1 Total ion flow chart of phenolic compounds pentafluorobenzyl bromide derivatives

7.3 Determination

Take 1.0 µl of sample (6.2) into the gas chromatograph-mass spectrometer to record the retention time of the chromatographic peak and quantify the ionospheric peak Peak area (or peak height).

7.4 blank test

In the same batch of samples to do blank test, take 1.0 µl blank sample (6.3) for determination.

8 results calculated and expressed

8.1 Qualitative analysis the retention time (RRT) of the target in the sample and the ratio of the auxiliary qualitative ion to the target ion peak area (Q) were compared with the standard sample Comparison to qualitative. The difference between the retention time of the target in the sample and the retention time of the compound in the standard sample should be within ± 0.03 s the relative ratio of the target qualitative ion and target ion peak area to the desired Q value (ie, the Q value of the standard sample) Poor should be within ± 30%.

8.2 Quantitative analysis

8.2.1 External standard method According to the peak area or peak height of the phenolic compound pentafluorobenzyl bromide derivative in the sample, the phenolic compound was calculated by the formula (1) concentration.

Where. rhos - target compound mass concentration, µg/L;

Ax - the target compound has the peak area (or peak height) of the characteristic ions;

A - the slope of the standard curve;

B - the intercept of the standard curve;

V1 - sampling volume, ml;

V2-sample extract is derived and concentrated volume, ml.

8.2.2 Internal standard method Using the average relative response factor quantitative, according to formula (2) calculation.

RRFv

S xx

Is1

Iss2

ARRF

Ii = RRFRRF (4)

Where. rhos - the target compound mass concentration, µg/L;

As-target compound Quantitative ion peak area;

Ais - the peak area of the quantitative ion of the internal standard compound;

rhois - internal standard compound concentration, µg/L;

V1 - sampling volume, ml;

V2 - sample extract derived after concentration volume, ml;

RRF-standard series of the relative response of the target factor, dimensionless;

RRF - the average relative response factor of the target, dimensionless;

N-standard series points.

8.3 results show

When the result is less than 100 µg/L, the result is one after the decimal point. When the result is greater than or equal to 100 µg/L, the result is Leaving three valid digits.

Precision and accuracy 9.1 precision Six laboratories for phenolic compounds 0.4 µg/L, 4.0 µg/L, 20.0 µg/L three ...

......
This preview omits tables, figures, formulas and parts of the technical clauses. The complete document — 16 pages — is available in the English PDF.

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