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HJ 976-2018Solid waste - Determination of benzene and its analogies - Headspace/gas chromatography-mass spectrometry (English PDF)

固体废物苯系物的测定顶空气相色谱-质谱法

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Issued by

Ministry of Ecology and Environment

Level / Type

National · Mandatory

Issue date

January 1, 1970

Implementation date

January 1, 1970

Scope

HJ 976-2018 is the English-translated version of 固体废物苯系物的测定顶空气相色谱-质谱法.

HJ 976-2018 — This standard specifies the headspace/gas chromatography-mass spectrometry for the determination of benzene in solid waste and its leachate.

This standard applies to solid waste and its leachate in benzene, toluene, ethylbenzene, p-xylene, m-xylene, cumene, Determination of nine benzene compounds such as o-xylene, n-propylbenzene and styrene.

If other benzene compounds are verified, this standard can also be used. Method determination. When the solid waste sample volume is 2 g, the detection limit of the 9 targets is 3~5 µg/kg, and the lower limit is 12~20.

Gg/kg. When the sample volume of solid waste leachate is 10 ml, the detection limit of the nine targets is 0.6~ 1 µg/L. The lower limit is 2.4~4 µg/L. See Appendix A for details.

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Document preview — HJ 976-2018

National Standard of the People's Republic of China

Classification: Z 13

Issued by: Ministry of Ecology and Environment

Foreword
1 Scope of application
2 Normative references
3 Principle of the method
4 Reagents and materials
5 Instruments and equipment
36 Samples
46.3 Preparation of blank samples
57.5 Calibration

Foreword

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 Environmental Pollution by Solid Waste this standard is formulated to protect the ecological environment, protect human health, and regulate the determination of benzene in solid waste and its leachate.

This standard specifies the headspace/gas chromatography-mass spectrometry for the determination of benzene in solid waste and its leachate.

Appendix A of this standard is a normative appendix, and Appendix B to Appendix C are informative appendices.

This standard is the first release.

This standard is formulated by the Department of Eco-Environmental Monitoring, the Department of Regulation and Standards of the Ministry of Ecology and Environment.

This standard was drafted. Anshan City Environmental Monitoring Center Station.

This standard is verified by. Liaoning Provincial Environmental Monitoring Experimental Center, Shenyang Environmental Monitoring Center Station, Dalian Environmental Monitoring Center, Fushun Environmental Monitoring Center Station, Liaoyang Environmental Monitoring Station and Jinzhou Environmental Monitoring Center Station.

This standard is approved by the Ministry of Ecology and Environment on November 13, 2018.

This standard has been implemented since March 1, 2019.

This standard is explained by the Ministry of Ecology and Environment.

1 Determination of benzene series in solid wastes by headspace/gas chromatography-mass spectrometry Warning. The organic solvents and standard solutions used in the experiment are volatile and toxic substances. The reagent preparation and pretreatment process should be Perform in a fume hood; wear protective equipment as required to avoid contact with skin and clothing.

1 Scope of application

This standard specifies the headspace/gas chromatography-mass spectrometry for the determination of benzene in solid waste and its leachate.

Method determination.

When the solid waste sample volume is 2 g, the detection limit of the 9 targets is 3~5 µg/kg, and the lower limit is 12~20.

Gg/kg. When the sample volume of solid waste leachate is 10 ml, the detection limit of the nine targets is 0.6~ 1 µg/L.

The lower limit is 2.4~4 µg/L. See Appendix A for details.

2 Normative references

This standard refers to the following documents or their terms. For undated references, the valid version applies to this standard.

HJ/T 20 Technical Specifications for Sampling and Sample Preparation of Industrial Solid Waste HJ/T 298 Hazardous Waste Identification Technical Specification HJ/T 299 solid waste leaching toxicity leaching method sulfuric acid nitric acid method HJ/T 300 solid waste leaching toxicity leaching method acetic acid buffer solution method

3 Principle of the method

At a certain temperature, the benzene series in the sample in the headspace bottle volatilizes into the upper space, generating vapor pressure and achieving thermodynamic motion.

State balance. The benzene series in the gas phase was separated by gas chromatography and detected by a mass spectrometer. Passing with standard material retention time Qualitative comparison with standard mass spectra and internal standard method.

4 Reagents and materials

Unless otherwise stated, analytically pure reagents that meet national standards were used for the analysis.

4.1 Experimental water. double distilled water or water prepared by pure water equipment. Need to pass a blank test before use, the target is thick the degree is below the method detection limit.

4.2 Methanol (CH3OH). pesticide residue level or equivalent. Confirm the retention time interval of the target by blank test There is no interference peak appearing inside.

4.3 Sodium chloride (NaCl).

Bake in a muffle furnace at 400 ° C for 4 h, cool and transfer to a ground glass bottle and store in a desiccator.

24.4 Phosphoric acid (H3PO4). rho=1.69 g/ml, excellent grade.

4.5 Saturated sodium chloride solution.

Measure 500 ml of water (4.1), add phosphoric acid (4.4) to adjust pH <= 2, add 180 g of sodium chloride (4.3), dissolve and Mix and store at 4 ° C or below.

4.6 Standard stock solution. rho = 1000 mg/L, the solvent is methanol. Can directly purchase certified standard solutions, or standard materials Formulated.

4.7 Standard use solution 1. rho = 10 mg/L, the solvent is methanol.

4.8 Standard use solution 2. rho = 100 mg/L, the solvent is methanol.

4.9 Internal standard solution. rho=250 mg/L, the solvent is methanol.

Fluorobenzene was selected as an internal standard. A certified standard solution can be purchased directly.

4.10 Alternative standard solution. rho =.2000 mg/L, the solvent is methanol.

Toluene-d8 or 4-bromofluorobenzene was used as a substitute.

4.11 Alternative use solution 1. rho = 10 mg/L, the solvent is methanol.

4.12 Alternative use solution 2. rho = 100 mg/L, the solvent is methanol.

4.13 4-bromofluorobenzene (BFB) solution. rho = 25 mg/L, the solvent is methanol.

The certified standard solution can be purchased directly or can be prepared with a high concentration standard solution.

4.14 Quartz sand. 0.30~0.85 mm (50~20 mesh).

It was fired in a muffle furnace at 400 ° C for 4 h, cooled and transferred to a ground glass bottle and sealed for storage.

4.15 Carrier gas. high purity helium (purity >= 99.999%).

5 Instruments and equipment

5.1 Gas Chromatograph. Capillary split/splitless inlet for temperature programming.

5.2 Mass Spectrometer. Electron Bombardment (EI) Ionization Source with 70 eV, NIST Mass Spectrometry Library, Manual/Automatic Tuning, Number According to acquisition, quantitative analysis and library search and other functions.

5.3 Column. Quartz capillary column, 30 m × 0.25 mm × 0.25 m (polyethylene glycol 20M), can also be used He is equivalent to a capillary column.

5.4 Headspace sampler. The temperature control range of the furnace is between room temperature and 120 °C; the temperature control accuracy is ±1 °C.

5.5 Reciprocating Oscillator. The oscillation frequency is 50~250 times/min, and the oscillation amplitude is 20 mm.

5.6 Balance. The sensitivity is 0.01 g.

5.7 Sampling bottle. 60 ml or.200 ml threaded brown wide-mouth glass bottle with Teflon/silica gel liner screw cap.

5.8 Sampling equipment. shovel and stainless steel medicine spoon.

5.9 Portable cooler.

5.10 Microinjectors. 5 µl, 10 µl, 25 µl, 100 µl, 250 µl, 500 µl, 1000 µl.

5.11 Brown compact bottle. 2 ml with Teflon liner and solid screw cap.

5.12 Headspace bottle. 22 ml with gasket (PTFE/silicone) and cap (screw cap or pressure for one use) cover).

5.13 Common instruments and equipment used in general laboratories.

36 Samples

6.1 Sample collection and preservation

6.1.1 Collect and store solid waste samples in accordance with the relevant provisions of HJ/T 20 and HJ/T 298. With a shovel and not the rust steel spoon (5.8) quickly collects the sample into the sample bottle (5.7) and fills it as much as possible. Quickly remove the sampling bottle thread the sample adhered to the outer surface immediately seals the sample bottle. Store in a portable freezer (5.9) and store below 4°C.

Brought back to the lab.

6.1.2 Samples should be analyzed as soon as possible after they are sent to the laboratory. If it cannot be analyzed immediately, it should be sealed and stored below 4 °C.

The limit is no more than 14 days. The sample storage area should be free of target interference.

Note. Do not excessively agitate solid waste during sample collection to avoid volatilization of benzene in the sample.

6.2 Preparation of samples

6.2.1 Preparation of solid waste samples

6.2.1.1 Low content sample Weigh 2 g (accurate to 0.01 g) into the headspace bottle (5.12) and quickly add 10.0 ml to the headspace bottle.

Immediately seal with sodium chloride solution (4.5), 2 µl of internal standard solution (4.9) and 20 µl of alternative solution 1 (4.11).

Oscillate at 150 times/min for 10 min on a reciprocating oscillator (5.5) for testing.

6.2.1.2 High content sample A high content sample should be considered if the target content is greater than 1000 µg/kg. The high content sample is prepared as follows.

Sample bottle (5.7), weigh 2 g (accurate to 0.01 g) sample into the headspace bottle (5.12), quickly add 10.0 to the headspace bottle Methanol (4.2), sealed immediately, and oscillated on a reciprocating oscillator (5.5) at a frequency of 150 times/min for 10 min.

After standing to settle, remove approximately 1 ml of the methanol extract into a 2 ml brown compact bottle (5.11). The extract can be placed in a refrigerated Store in the box below 4 °C, the shelf life is 14 days.

After returning the extract to room temperature before analysis, add 2 g (accurate to 0.01 g) to the empty headspace vial (5.12) Quartz sand (4.14), 10.0 ml saturated sodium chloride solution (4.5), 10~100 µl methanol extract, 2 µl internal standard solution (4.9) and 20 µl of the alternative use solution 1 (4.11), immediately sealed, 150 times/min on the reciprocating oscillator (5.5) the frequency is oscillated for 10 min and is to be tested.

Note 1. If the concentration of benzene in the methanol extract is high, it can be diluted with methanol.

Note 2. If the content is too low or not detected by the high content method, the sample should be re-analyzed using the low content method.

6.2.2 Preparation of solid waste leachate samples Preparation of solid waste water leaching sample according to HJ/T 299 method; preparation of solid waste acetic acid according to HJ/T 300 method Leachate sample. Pipette 10.0 ml of the leachate into the headspace vial (5.12) and add 2 µl of the internal standard solution (4.9) and 20 the µl substitute uses liquid 1 (4.11) and is immediately sealed for testing.

46.3 Preparation of blank samples

6.3.1 Full program blank sample 10.0 ml of saturated sodium chloride solution (4.5) and 2 g (accurate to 0.01 g) of quartz sand (4.14) in the laboratory before sampling Put it into the headspace bottle (5.12), add 2 µl of the internal standard solution (4.9), seal it, take it to the sampling site, and then open it.

Sealed, and then shipped back to the laboratory with the sample, oscillated on the reciprocating oscillator (5.5) at a frequency of 150 times/min for 10 min, to be tested.

6.3.2 Laboratory blank sample

6.3.2.1 Solid waste low content blank sample Weigh 2 g (accurate to 0.01 g) quartz sand (4.14) instead of low-level sample, and prepare low content according to 6.2.1.1 A blank sample was taken.

6.3.2.2 Solid waste high content blank sample Weigh 2 g (accurate to 0.01 g) of quartz sand (4.14) instead of high-content samples, and prepare high-content according to 6.2.1.2 A blank sample was taken.

6.3.2.3 Blank sample of solid waste leachate A blank sample of the leachate was prepared in the same manner as the solid waste leachate preparation (6.2.2).

7 Analysis steps

7.1 Headspace Sampler Reference Conditions Heating equilibrium temperature 85 ° C; heating equilibrium time 50 min; sampling needle temperature 100 ° C; transmission line temperature 110 ° C; pressure the equilibrium time was 1 min; the injection time was 0.2 min; the needle setting time was 0.4 min.

7.2 Gas Chromatograph Reference Conditions Temperature programming. 40 ° C for 6 min, ramp up to 110 ° C at 5 ° C/min, for 1 min, then 6 ° C the heating rate of /min is raised to.200 °C for 3 min; the inlet temperature is 250 °C; the interface temperature is 230 °C; carrier gas.

Helium; injection method. split injection, split ratio. 5.1; column flow. 1.0 ml/min.

7.3 Mass Spectrometer Reference Conditions Scanning range. 35 amu~300 amu; scan at least 5 times per chromatographic peak; ionization energy. 70 eV; ion source Temperature. 230 ° C; quadrupole temperature. 150 ° C; scanning method. select ion scanning (SIM).

7.4 Selecting the ion scan (SIM) program Take 5 µl of Alternative Use Solution 2 (4.12), 5 µl of Standard Use Solution 2 (4.8), and 2 µl of Internal Standard Solution (4.9) Place the headspace vial (5.12) with 10.0 ml of saturated sodium chloride solution and seal immediately. According to the instrument reference conditions (7.1, 7.2 and 7.3) Perform a full scan (SCAN) analysis to determine the ion selection procedure based on retention time, see Appendix B.

57.5 Calibration

7.5.1 Instrument performance check the performance of the gas chromatography-mass spectrometer should be checked before analyzing the sample. Take 1 µl of 4-bromofluorobenzene (BFB) solution (4.13) for direct gas phase chromatography analysis, the resulting BFB mass spectrum should meet the requirements specified in Table 1 or refer to the manufacturer's instructions.

Table 1 4-bromofluorobenzene ion abundance standard

Mass ion abundance standard mass ion abundance standard 50% 95% of the 95% 174 is greater than 50% of the mass 95 75 quality 95% to 60% 175 quality 174 5% to 9% 95 base peak, 100% relative abundance 176 quality 174 95% to 101% 96% 95% 5% to 9% 177 Quality 5% 5% to 9% 173 is less than 2% of mass 174

7.5.2 Establishment of the working curve

7.5.2.1 Establishment of working curve for solid waste Add 2 g (accurate to 0.01 g) of quartz sand (4.14), 10.0 ml of saturated sodium chloride to the headspace bottle (5.12).

Solution (4.5), then add 5 µl, 10 µl, 20 µl of standard use solution 1 (4.7) and substitute solution 1 to each bottle.

(4.11), 5 µl, 10 µl, 20 µl Standard Use Solution 2 (4.8) and Alternative Use Solution 2 (4.12) to prepare benzene series and Substitute masses of 0.05, 0.10, 0.20, 0.50, 1.00 µg, and 2.00 µg, respectively, plus 2.0 µl each Internal standard solution (4.9), immediately sealed. Prepare the standard series on the reciprocating oscillator (5.5) at 150 times/min the frequency is oscillated for 10 min, and analyzed according to the instrument reference conditions (7.1, 7.2, and 7.3) in order to contain the target compound.

The quantity is the abscissa, and the product of the corresponding response value and the ratio of the internal standard and the internal standard content is the ordinate, and the work piece is established.

line. Figure 1 shows the total ion chromatogram of nine benzene species selected ion scans under the conditions specified in this standard.

7.5.2.2 Establishment of working curve for solid waste leachate Add 10.0 ml of leaching agent to the headspace bottle (5.12), and then add 5 µl, 10 µl, 20 µl to each bottle.

Standard use solution 1 (4.7) and alternative use solution 1 (4.11), 5 µl, 10 µl, 20 µl of standard use solution 2 (4.8) and the alternative use of liquid 2 (4.12), the concentration of benzene series and substitutes are 5.0, 10.0, 20.0, 50.0, 100 and in the standard series of.200 µg/L, add 2.0 µl of the internal standard solution (4.9) and seal immediately. According to the instrument reference strip the pieces (7.1, 7.2 and 7.3) are analyzed in turn, with the concentration of the target compound as the abscissa, with its corresponding response value and the product of the ratio of the internal standard and the concentration of the internal standard is the ordinate, and a working curve is established. 9 benzene series selected ion scan total deviation the substream diagram is shown in Figure 1.

61-benzene; internal standard - fluorobenzene; substitute 1-toluene-d8; 2-toluene; 3-ethylbenzene; 4-p-xylene; 5-m-xylene; 6-cumene;

7-o-xylene; 8-n-propylbenzene; 9-styrene; substitute 2-4-bromofluorobenzene.

Figure 1 9 benzene series selected ion scanning total ion current map

7.5.3 Calculation of average relative response factor the relative response factor (RRFi) of the target (or surrogate) in point i of the standard series, calculated according to formula (1) Count.

ISi

RRF x= (1)

In the formula.

RRFi--the relative response factor of the i-th target (or substitute) in the standard series;

Ai--the response value of the quantified ion of the i-th target (or substitute) in the standard series;

AISi--the ith point of the standard series corresponds to the target (or substitute) corresponding to the internal standard quantitation ion response value;

mISi--the content of the internal standard in the standard series, g;

Mi--the content of the i-th target (or substitute) in the standard series, g.

The average relative response factor RRF of the target (or substitute) is calculated according to formula (2).

RRF

In the formula.

iRRF - the average relative response factor of the target (or surrogate);

RRFi--the relative response factor of the i-th target (or substitute) in the standard series;

n--Standard series points.

7.6 Specimen determination Place the prepared sample (6.2) on the headspace sampler (5.4) and follow the same instrument as the working curve.

The measurement of the sample was carried out under the conditions of 7.

7.7 Blank test

Place the prepared blank sample (6.3) on the headspace sampler (5.4) and follow the same instrument strip as the sample.

The measurement of the blank sample was carried out.

8 Calculation and representation of results

8.1 Qualitative analysis it is characterized by the relative retention time (RRT) of the target compound in the sample, the auxiliary ion and the quantitative ion abundance ratio (Q).

The relative retention time of the target compound in the sample is offset from the relative retention time of the target compound at the midpoint of the working curve the difference should be within ±0.06. The characteristic ion relative abundance of the target compound in the sample is at the midpoint of the working curve.

The characteristic ions are within ±30% of the relative abundance.

Calculate the relative retention time (RRT) according to equation (3).

RRT = (3)

In the formula.

RRT--relative retention time;

RTx--the retention time of the target, min;

RTIS-- retention time of internal standard, min.

8.2 Calculation of results

8.2.1 Calculate according to the response value of the target and the internal standard quantitation ion. When the quantitative ions of the target in the sample interfere Auxiliary ion quantification can be used, see Appendix B.

8.2.2 Calculation of target (or substitute) content

8.2.2.1 Calculated using the average relative response factor when the target (or substitute) is calibrated using the average relative response factor, the target content is according to formula (4) Calculation.

RRFA

ISx

x= 1 (4)

In the formula.

M1--the content of the target (or substitute), g;

Ax -- the target (or substitute) quantified ion response value;

AIS - the response value of the internal standard quantitative ion corresponding to the target (or substitute);

8mIS - the content of internal standard, g;

RRF - The average relative response factor of the target (or surrogate).

8.2.2.2 Calculation with working curve when the target is calibrated using the working curve, the target content is calculated from the corresponding working curve.

8.2.2.3 Calculation of results of targets in low-content solid waste the content of benzene series (µg/kg) in low-content solid waste is calculated according to formula (5).

1 10x= (5)

In the formula.

W--the content of the target compound, µg/kg;

M1--calculate the content of the target compound based on the average relative response factor or the working curve, µg;

M--sample amount (wet weight), g.

8.2.2.4 Calculation of results of targets in high-content solid waste the content of benzene series (µg/kg) in high-content solid waste is calculated according to formula (6).

fVm

xxx=

1 10 (6)

In the formula.

W--the content of the target compound, g/kg;

M1--calculate the content of the target compound based on the average relative response factor or the working curve, g;

Vc - methanol extract volume, ml;

M--sample amount (wet weight), g;

Vs - volume of methanol extract used for headspace determination, ml;

f -- the dilution factor of the extract.

8.2.2.5 Calculation of results of solid waste leachate when the solid waste leachate is measured, the concentration of the benzene series is directly determined from the working curve and expressed in µg/L.

8.3 result representation the number of decimal places and the method detection limit are consistent, and up to three significant digits are reserved.

9 Precision and accuracy 9.1 precision Six laboratories for waste sludge treatment at 25 µg/kg, 100 µg/kg and 500 µg/kg the samples were subjected to precision measurement. The relative standard deviations in the laboratory ranged from 4.0% to 19% and 2.0% to 15%, respectively.

91.2%~8.9%; the relative standard deviation between laboratories is 3.9%~9.4%, 3.3%~15% and 1.6%~5.2% respectively;

The renaturation limits ranged from 3 to 13 µg/kg, 8 to 21 µg/kg, and 60 to 81 µg/kg, respectively; the reproducibility limits ranged from 3 to 16 µg/kg, respectively.

13~39 µg/kg and 65~102 µg/kg.

Six laboratories for waste sludge treatment plants with concentration levels of 5.0 µg/L, 20.0 µg/L and 100 µg/L the water leaching samples were tested for precision. The relative standard deviations in the laboratory ranged from 2.6% to 12%.

1.6%~8.6% and 1.8%~7.5%; the relative standard deviations between laboratories are. 3.7%~7.1%, 2.1%~5.1% and 1.2%~4.3%; repeatability limits are. 0.8~2 µg/L, 1.6~2.6 µg/L and 10~14.1 µg/L; reproducibility limits the circumference is. 1~3 µg/L, 2~4 µg/L and 10~16 µg/L.

Six laboratories for waste sludge treatment plants with concentration levels of 5.0 µg/L, 20.0 µg/L and 100 µg/L the acetic acid leaching sample was tested for precision. The relative standard deviations in the laboratory ranged from 2.5% to 12%.

1.3%~9.8% and 1.8%~7.8%; the relative standard deviations between laboratories are. 2.6%~5.6%, 1.8%~5.8% and 0.7%~3.5%; repeatability limits are. 0.7~1 µg/L, 3~4 µg/L and 12.9~15.8 µg/L; reproducibility limits They are. 0.9~2 µg/L, 3~5 µg/L and 13~17 µg/L.

See Appendix C for the fine summary data.

9.2 Accuracy

Six laboratories for the waste sludge of sewage treatment plants with spiked contents of 25 µg/kg, 100 µg/kg and 500 µg/kg the samples were spiked and analyzed. the recoveries ranged from 55.1% to 84.6%, 64.5% to 107%, and 91.7%~107%; the final values of the spiked recovery were 60.0%±7.2%~71.9%±5.6%, 76.8%±14%~97.1%±10% and 96.9% ± 11% ~ 103% ± 3.2%.

Six laboratories for waste sludge treatment at concentrations of 5.0 µg/L, 20.0 µg/L and 100 µg/L the samples of the water leaching liquid were subjected to spike analysis. the recoveries of the spiked standards ranged from 64.7% to 93.5% and 70.9% to 107%, respectively.

93.0%~106%; the final recoveries of the spiked recovery are 75.3%±12%~86.9%±8.7%, 83.6%±14%~101%±4.3% and 95.3% ± 2.3% ~ 103% ± 4.3%.

Six laboratories for waste sludge treatment at concentrations of 5.0 µg/L, 20.0 µg/L and 100 µg/L the samples of acetic acid leaching were analyzed by spike analysis. the recoveries ranged from 68.8%~103% and 78.7%~106% respectively.

And 96.6%~107%; the final recoveries of the spiked recovery are 79.0%±15%~93.7%±11%, 84.7%±11%~102%±7.1%, respectively.

And 98.8% ± 3.3% ~ 105% ± 3.6%.

See Appendix C for summary data for accuracy.

10 Quality Assurance and Quality Control

10.1 Blank test

A full program blank sample and a laboratory blank should be analyzed for every 20 samples or batches (less than 20/batch) for the sample, the target compound...

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