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HJ 896-2017Water quality. Determination of butyl xanthate. Purge and trap/gas chromatography-mass spectrometry (English PDF)

水质丁基黄原酸的测定吹扫捕集气相色谱-质谱法

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Issued by

Ministry of Ecology and Environment

Level / Type

National · Mandatory

Issue date

December 21, 2017

Implementation date

February 1, 2018

Scope

HJ 896-2017 is the English-translated version of 水质丁基黄原酸的测定吹扫捕集气相色谱-质谱法.

HJ 896-2017 — This standard specifies the determination of butyl xanthate in water by purge trap/gas chromatography - mass spectrometry. This standard applies to the determination of butyl xanthogen in surface water, groundwater, domestic sewage and industrial wastewater.

This standard does not apply to salts containing more than 25 g/L of high salt industrial wastewater and the presence of dexamethasone (manganese) pesticides or diethyl disulfide Substitution of carbamates (eg copper reagents) and other substances in water samples.

If the water samples were detected butyl xanthic acid, if necessary, can be used to further confirm other analytical methods. When the sample volume was 5 ml, the detection limit of butyl xanthogen was 0.04 g/L, and the lower limit of determination was 0.16 g/L.

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Document preview — HJ 896-2017

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 references
3 Method principle
4 Interference and eliminate
5 Reagents and materials
6 Instruments and equipment
7 Samples
7.1 Sample collection
7.2 Sample preservation
8 Analysis steps
8.1 Instrument reference conditions
8.2 Calibration curve drawing reference method
8.3 Determination
8.4 Blank test
9 Results calculated and expressed
9.2 Target quantification
9.3 Results show

Foreword

In order to carry out "Law of the People's Republic of China on Environmental Protection" and "Water Pollution Prevention and Control Law of the People's Republic of China", protect the environment and protect people Body health, regulate the determination of butyl xanthic acid in water, the development of this standard.

This standard specifies the determination of butyl xanthate in water by purge trap/gas chromatography - mass spectrometry.

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. China Environmental Monitoring Station.

This standard verification unit. Beijing Environmental Protection Monitoring Center, Environmental Monitoring Center of Hebei Province, Zhejiang Province Environmental Monitoring Center, heavy Qing City Ecological Environment Monitoring Center, Ningbo City Environmental Monitoring Center and Yangzhou City Environmental Monitoring Center Station.

This standard MEP approved on December 21, 2017.

This standard since February 1, 2018 implementation.

This standard is interpreted by the MEP.

Water quality - Determination of Butyl Xanthic Acid - Purge and Trap/Gas Chromatography - Mass Spectrometry

1 Scope of application

This standard specifies the determination of butyl xanthate in water by purge trap/gas chromatography - mass spectrometry.

This standard applies to the determination of butyl xanthogen in surface water, groundwater, domestic sewage and industrial wastewater.

If the water samples were detected butyl xanthic acid, if necessary, can be used to further confirm other analytical methods.

When the sample volume was 5 ml, the detection limit of butyl xanthogen was 0.04 g/L, and the lower limit of determination was 0.16 g/L.

2 Normative references

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

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

3 Method principle

Butyl xanthogen in water decomposes under acidic conditions to produce carbon disulfide (CS2), which is indirectly determined by the determination of CS2 Acid concentration. CS2 is purged with high-purity helium (or nitrogen) and adsorbed into the trap. The trap is quickly heated and purged with high-purity helium (or nitrogen Gas) backflushing, the CS2 that is thermally desorbed is separated by gas chromatography and detected with a mass spectrometer. Through the standard solution with butyl xanthogen the retention time and mass spectra of liquid reaction generated CS2 were compared qualitatively with internal standard method.

4 Interference and eliminate

The presence of CS2 in the water sample can interfere with the assay and can be subtracted from the difference between the measured values before and after the addition of the acid.

The presence of oxidizing substances in the water sample will make the determination result is low, may be appropriate to add 5 ~ 20 mg sodium thiosulfate removal.

5 Reagents and materials

Unless otherwise specified, the analysis of the use of analytical standards in line with national standards of chemical reagents, experimental water for the target does not contain pure water.

5.1 methanol (CH3OH). Chromatography pure.

5.2 concentrated phosphoric acid (H3PO4). = 1.69 g/ml.

5.3 Sodium hydroxide (NaOH).

5.4 Sodium thiosulfate (Na2S2O3 · 5H2O).

25.5 Potassium butylxanthate (C4H9OCSSK). Purity >=95%.

5.6 phosphoric acid solution. 1 6.

5.7 Sodium hydroxide solution. (NaOH) = 400 g/L.

Weigh 10 g of sodium hydroxide (5.3) and dissolve to 25 ml with water.

5.8 Sodium hydroxide solution. (NaOH) = 40 g/L.

The sodium hydroxide solution is diluted with water (5.7).

5.9 Sodium hydroxide solution. (NaOH) = 0.08 g/L.

Take.200 l sodium hydroxide solution (5.7) was added to 1L of water.

5.10 butyl xanthic acid standard stock solution. (C4H9OCSSH) = 100 g/ml.

Accurately weigh 0.0330 g potassium butylxanthate (5.5), dissolve in a small amount of water and add 100 l sodium hydroxide solution (5.7), and dilute with water to 250 ml, about 4 C refrigerated, stable for two weeks.

5.11 butyl xanthic acid standard solution. (C4H9OCSSH) = 10.0 g/ml.

With sodium hydroxide solution (5.9) accurate dilution of butyl xanthic acid standard stock solution (5.10), with the current service.

5.12 butyl xanthate standard solution. (C4H9OCSSH) = 1.00 g/ml.

With sodium hydroxide solution (5.9) accurate dilution of butyl xanthic acid standard solution (5.11), with the current available.

5.13 Internal standard solution. fluorobenzene, = 100 g/ml, the solvent is methanol, a certified standard solution on the market.

5.14 Internal standard solution. fluorobenzene, = 10.0 g/ml.

Use methanol (5.1) to accurately dilute the internal standard solution (5.13).

5.15 Helium. Purity >=99.999%.

5.16 Nitrogen. Purity >=99.999%.

6 Instruments and equipment

6.1 Gas Chromatography - Mass Spectrometer. The gas chromatograph section has a split/splitless inlet that can be programmed to temperature and the mass spectrometer EI source.

6.2 Purge and Trap. with autosampler and 5 ml purge. Trap tube using 1/3Tenax, 1/3 silica gel, 1/3 activated carbon mixed Adsorbent or other equivalent adsorbent.

6.3 Column. Quartz capillary column with a column length of 60 m, an inner diameter of 0.20 mm, a membrane thickness of 1.12 µm and a stationary phase of 6% cyanopropylidene/94% Dimethylpolysiloxanes, or other equivalent capillary columns.

6.4 Vials. 40 ml brown glass bottle, screw cap with Teflon coated gaskets.

6.5 Volumetric bottles. brown, 50 ml and 250 ml.

6.6 Syringes. 20 l, 100 l and 500 l, with acid-resistant polytetrafluoroethylene piston.

36.7 General laboratory equipment and equipment.

7 Samples

7.1 Sample collection

Collect samples according to HJ/T 91 and HJ/T 164, with a minimum of two bottles per sample.

When collecting the sample, slowly introduce the sample into the sample bottle (6.4). Near the full bottle, add the sodium hydroxide solution (5.8) so that the sample the pH is around 10 and finally filled.

7.2 Sample preservation

After about 4 C sample collection refrigeration, dark storage and transport, 1d analysis is completed. If not timely analysis, should be added 5 ~ 20 mg Sodium thiosulfate (5.4), about 4 C refrigerated, dark conditions can be stored for two weeks. Sample storage area should be free of carbon disulfide interference.

8 Analysis steps

8.1 Instrument reference conditions

8.1.1 Purge and trapping conditions

Sample volume. 5 ml; Purge temperature. 40 ° C; Purge flow rate. 40 ml/min; Purge time. 11 min; Desorption temperature. 180 ° C;

Desorption time. 1 min; baking temperature. 190 C; baking time. 10 min; other parameters refer to the instrument user manual to set.

8.1.2 GC analysis conditions

Program temperature. 40 C for 1.0 min, with 5 C/min rose to 120 C, hold 1.0 min, and then 20 C/min rose to 250 C, Hold for 2.0 min; Inlet temperature. 230 ° C; Carrier gas flow. 1.0 ml/min; Injection mode. Split injection (split ratio 10.1).

8.1.3 Mass Spectrometry Conditions

Electron impact source. EI source; Ionization energy. 70 eV; Ion source temperature. 230 ° C; Transmission line temperature. 280 ° C; Scanning mode Scanning range. 30-300 amu; Quadrupole temperature. 150 ° C; Solvent delay time. 6 min; Other parameters reference instrument User's Manual for setting.

Note. In order to increase the sensitivity, the method of selective ion scan can also be used for analysis. For the characteristic ion selection, refer to 9.2.

8.2 Calibration curve drawing reference method

Pipette a certain amount of butyl xanthate standard solution (5.11,5.12), were added to the sodium hydroxide solution (5.9) of the 50 ml Volumetric flask (6.5), the preparation of low and high concentrations of two standard series, with sodium hydroxide solution (5.9) volume.

Low concentrations of the test target water samples selected low concentration standard series, followed by the concentration of 0.20 g/L, 1.00 g/L, 2.00 g/L, 10.0 g/L, 20.0 g/L, the volume of butyl xanthogen standard solution (5.12) is 0.01 ml, 0.05 ml, 0.10 ml, 0.50 ml, 1.00 ml; high concentration of the test target concentration of water samples selected standard series, the concentration of 10.0 g/L, 50.0 g/L, 100 g/L,.200 g/L, 500 g/L, the amount of butyl xanthogen standard solution (5.11) volume of 0.05 ml, 0.25 ml, 0.50 ml, 41.00 ml, 2.50 ml.

Transfer the standard series to a 40 ml sample vial (6.4), fill up and seal, remove.200 l with needle (6.6), then inject Needle (6.6) plus 20 l internal standard solution (5.14), so that the internal standard concentration of 5 g/L, and finally with the needle (6.6) quickly added to 100 l phosphoric acid solution (5.6). According to the instrument reference conditions (8.1), from low concentration to high concentration followed by determination, record CS2 and fluorobenzene retention Time and quantitative ion response.

Note. It is also possible to automatically add an internal standard to the autosampler according to the autosampler operating instructions.

Under the reference instrument conditions of this standard, the total ion chromatogram of the target compound is shown in Figure 1.

Figure 1 Total ion current plot of target compounds

8.2.1 Average relative response factor method

The relative response factor (RRFi) of butyl xanthogen in point i of the standard series was calculated according to equation (1).

i IS

ISi i

RRF

Where. RRF

- The relative response factor for the CS2 point i in the standard series;

- the standard series of points i CS2 response value;

ISi

- standard series of i-point internal standard response value;

- standard series of internal standard concentration, µg/L;

- Standard Series i point butyl xanthic acid concentration, µg/L.

Butyl xanthic average relative response factor RRF, calculated according to equation (2).

RRF

5 Where. RRF - butyl xanthic acid average relative response factor;

RRFi - the relative response factor for CS2 at point i in the standard series;

n - standard series of points.

The standard deviation of the RRF is calculated according to equation (3).

RRFRRF

Where. SD - standard deviation of RRF;

RRF - average relative response of butyl xanthogen;

RRFi - the relative response factor for CS2 at point i in the standard series;

n - standard series of points.

The relative standard deviation of RRF is calculated according to equation (4).

RRF

RSD (4)

Where. RSD - relative standard deviation ofRFF;

SD - Standard deviation of RFF;

RRF - average relative response of butyl xanthogen.

8.2.2 Calibration curve method

If the Relative Standard Deviation (RSD) 若20% of the relative response factor (RRF) of butyl xanthogenate is used, calibration curves are required Line calibration. To butyl xanthic acid concentration as abscissa, CS2 response value and the ratio of internal standard response value for the vertical axis, the calibration curve line.

8.3 Determination

All samples should be equilibrated to room temperature and then measured. Samples and add internal standards according to standard solution pre-treatment procedure (8.2) to each aliquot One of the bottles of the product is added with 100 l of phosphoric acid solution (5.6) and the other bottle is filled with 100 l of water according to the instrument reference conditions (8.1) 8.2 calibration curve was measured.

Note 1. Determination of higher concentrations of butyl xanthic acid water samples, it is recommended diluted with sodium hydroxide solution (5.9) after the determination.

Note 2. For strong alkaline wastewater (water sample bottom pH > 10), the volume or concentration of phosphoric acid solution (5.6) can be appropriately increased according to the actual situation.

8.4 Blank test

Replace the sample with sodium hydroxide solution (5.9) and perform the blank test according to the same measurement procedure (8.3) as the sample.

9 Results calculated and expressed

9.1 The nature of the target

6 According to the sample of butyl xanthogen acid generated by the reaction of carbon disulfide retention time, mass spectrometry, fragment ion mass ratio and its abundance Degree and other information and standard solution after qualitative comparison. The calibration solution should be analyzed more than once to obtain the mean retention time of the target, on average the standard deviation of ± 3 times the retention time is the retention time window, and the retention time of the target in the sample should be within its range.

All ions with a relative abundance higher than 10% in the target standard spectrum should exist in the sample spectrum, and the sample mass spectrum and standard the relative abundance deviation of the above characteristic ions in the mass spectrum should be within ± 30%.

9.2 Target quantification

After the qualitative identification of the target compound, according to the quantitative ion response value, calculated by internal standard method. Quantitative ions and auxiliary target Ions see Table 1.

Table 1 list of target and internal standard ions and auxiliary ions

Target Name Type Quantitative ion-assisted ion Carbon disulfide target 76 32,44 Fluorobenzene internal standard 96 70

9.2.1 Quantify with the average relative response factor

When the target compound is calculated using the average relative response factor, the mass concentration of butyl xanthogenate in the sample According to formula (5) Calculation.

Where.

- sample mass concentration of butyl xanthic acid, µg/L;

- Response value of quantitative ion of acid sample CS2;

ISx

- Acidic sample internal standard quantitative ion response value;

- The response of the CS2 ion without the acid sample;

ISo

- The response of internal standard ion quantification without acid;

- Internal standard mass concentration, µg/L;

f - dilution factor

RRF - average relative response of butyl xanthogen.

9.2.2 Quantitative calibration curve

When the target compound is quantified using a calibration curve, the mass concentration of butyl xanthogenate in the sample Calculate according to formula (6).

Where.

- sample mass concentration of butyl xanthic acid, µg/L;

- Response value of quantitative ion of acid sample CS2;

ISx

- Acidic sample internal standard quantitative ion response value;

- The response of the CS2 ion without the acid sample;

ISo

- The response of internal standard ion quantification without acid;

b - calibration curve intercept;

f - dilution factor

a - calibration curve slope.

9.3 Results show

When the measurement result

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This preview omits tables, figures, formulas and parts of the technical clauses. The complete document — 7 pages — is available in the English PDF.

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