GB/T 14552-2003 Determination of organophosphorus pesticides in water and soil by gas chromatography
Some standard content:
ICS 13. 060. 01
National Standard of the People's Republic of China
GB/T14552-2003
Replaces GB/F14552—1993
Method of gas chroniatographic for detcrmination oforganophosphorus pesticides in water and soil
Promulgated on 2003-11-10
National Quality Supervision, Inspection and Quarantine Commission of the People's Republic of China
Implemented on 2004-04-01
GB/T14552—2003
This standard is a revision of GB/T14552.-1993 "Method of gas chroniatographic for detcrmination oforganophosphorus pesticides in water and soil" with the following contents!
In the original standard, 2.3 Reagents and materials used in the preparation of chromatographic columns, 3.6 Chromatographic columns, and 5.2.3 Calibration data are all replaced;
In Chapter 5, the chromatographic determination operation procedures, determination conditions B, determination conditions and spectra using nitrogen-phosphorus detector and capillary column, determination conditions (, determination conditions and graphs using flame photometric detector and capillary column) are added. The data tables of 6.2.2 Precision, 6.2.3 Accuracy, and 6.2.4 Detection Limit are all put into Appendix A. The original precision expressed in standard deviation is changed to relative standard deviation. This standard adds A This standard is an informative appendix. It is proposed and managed by the Ministry of Agriculture of the People's Republic of China. The originator of this standard is the Environmental Protection Research and Monitoring Institute of the Ministry of Agriculture. The main drafters of this standard are Huang Tuzhong, Liu Manwei, Huang Yongchun, Gan Jijun, Mai Guangxi, Xu Yingming, Li Zhiyang, and Zhang Keqiang. HTiKNiKAca
1 Scope
Determination of organophosphorus pesticides in water and soil
Gas chromatography
GB/T 14552--2003
This standard specifies the determination method for multi-component residues of mevinphos, phorate, diazinon, iprohenfos, parathion-methyl, fenitrothion, bromophos, isocarbophos, phenthoate and methidathion in surface water, groundwater and soil. This standard is applicable to the analysis of organophosphorus pesticide residues in surface water, groundwater and soil. 2 Normative references
The clauses in the following documents become clauses of this standard through reference in this standard. For any dated referenced document, all subsequent amendments (excluding errata) or revisions are not applicable to this standard; however, the parties to an agreement based on this standard are encouraged to report. Study whether the latest versions of these documents can be used. For any un-dated referenced documents, the latest versions shall apply to this standard. GB/T5009.20—1996 Method for determination of organophosphorus pesticide residues in food NY/F'395 Technical specification for monitoring environmental quality of agricultural soil NY/T396 Technical specification for monitoring environmental quality of farmland water sources 3 Principle
The organophosphorus pesticide residues in water and soil samples are extracted with organic solvents, and then the interferences are removed by liquid-liquid partitioning and condensation purification steps, and then the gas chromatography is used to determine the residual organophosphorus pesticide residues in water and soil samples. Detection by spectral phosphorus detector (NPL) or flame photometric detector (FPD), qualitative analysis based on the retention time of the chromatographic peak, quantitative analysis by external standard method 4 Reagents and materials
4.1 Carrier gas and auxiliary gas
4.1.1 Carrier gas: nitrogen, purity 299.99% 4.1.2 Fuel gas: hydrogen.
4.1.3 Fuel-supporting gas: air.
4.2 Reagents and materials for preparing standard samples and/or sample analysis: The reagents used are analytically pure unless otherwise specified, and the water is distilled water. 4.2.1 Pesticide standards Organic phosphine pesticides such as chlorpyrifos: purity is 95.0%~99.0%. 4.2.1.1 Preparation of pesticide standard solution: Accurately weigh a certain amount of pesticide standard sample (accurate to 0.0001g), use acetone as solvent, prepare 0.5mg/ml concentration of fenthion, phorate, diazinon, bromophos, methyl parathion, fenthion, and 0.7mg/ml stock solution of fenthion, isothioate, bromophos, and fenthion, and store them in refrigerator. 4.2.1.2 Preparation of pesticide standard intermediate solution: Use a pipette to accurately measure a certain amount of the above 10 stock solutions in a 50ml volumetric flask and dilute to the mark with acetone, then prepare 50mg/ml concentration of fenthion, phorate, diazinon, bromophos, methyl parathion, fenthion, and 100g/ml standard intermediate solution of fenthion, isothioate, bromophos, and fenthion, and store them in refrigerator. 4.2.1.3 Preparation of standard working solution for bag medicine: Use a pipette to take 10mL or 100mL of each intermediate solution into a volumetric flask, and use acetone to make up to the mark to obtain a mixed standard working solution. The standard working solution should be stored in a refrigerator. 4.2.2 Acetone (CH,COCH;), fumigated.
4.2.3 Right oil ether, boil at 60℃~90℃, redistilled, 4. 2. 4 Fluoromethane (CH,Cl2), redistilled. GB/T14552-—2003
4.2.5 Ethyl acetate (CH,COO2H,).
4.2.6 CaCl2
4.2.7 Anhydrous sodium sulfate (Na,SO.), dry at 300°C for 4h and put into a desiccator for use. 4.2.8 Filter aid Ceilite545.
4.2.9 Phosphoric acid (H2PO4): 85%.
4.2.10 Ammonium fluoride (NII, C).
Condensate: 20g ammonium oxide and 40tnl of 85% acid are dissolved in 400ml of distilled water, and the volume is made up to 2000mL with distilled water, 4.2.11
for later use.
5 Instruments
5.1 Vibrator.
5.2 Rotary oscillator,
5.3 Vacuum pump.
5.4 Water boiler.
5.5 Micro-mixer
5.6 Gas chromatograph: with nitrogen-phosphorus detector or flame photometric detector, and equipped with packed column or capillary column. 6 Samples
6.1 Sample properties
6.1.1 Sample type: water, upper,
6.1.2 Sample state: liquid, straight,
6.1.3 Sample stability; in water, organic phosphorus pesticides in soil are unstable and easy to decompose. 6.2 Sample collection and storage method
Collect in accordance with NY/T395 and NY/T396. 6.2.1 Water sample: Take representative surface water or groundwater, and use a ground glass bottle to take [000ml]. Before filling with water, rinse the sample bottle with water sample 2~3 times
62.2 Soil sample: Collect soil sample in the field according to relevant regulations, mix thoroughly, take 500g for standby, put it in the sample bottle, and take another 20 to measure the water content. 6.2.3 Sample storage: Water sample is stored in a refrigerator at 4℃; soil is stored in a cold storage box at -18℃ for standby. 7 Analysis steps
7. Extraction and purification
7.1.1 Extraction of water sample and purification by method A
Put 100.0 mL of water sample in a separatory funnel, add 50 mL of acetone and shake 30 times, take out 100 mL, equivalent to half of the sample volume, transfer it to another 500 mL separatory funnel, add 10 mL~15 mL of coagulation solution and use c(K)H)-0.5 mol/I, potassium hydroxide (KOFI) solution (adjusted to pFI value of 4.5~5.0) and 1 filter aid, shake 20 times, let stand for 3min, filter into another 500mL separatory funnel. Add 3g sodium fluoride, extract three times with 50tml, 50ml..30ml. dichloromethane, combine the organic phases, filter through a simple funnel filled with 1g anhydrous sodium sulfate and 1g filter aid, collect in a 250mL flat-bottom flask. Add 0.5ml. ethyl acetate, first concentrate to 3mL with a rotary radiator, concentrate to nearly dryness with nitrogen or air at room temperature, make up to 5mL with acetone, and provide gas chromatography determination. 7.1.2 Method B purification
Follow the purification steps in 6.2 of GB/T5009,20-1996. 7.1.3 Soil sampling and method A purification
Weigh the soil sample with the highest water content of 20.0g and place it in a 300ml stoppered conical flask. Add water so that the sum of the added water and the water content of the 20.0g sample is 20mL. Let it stand for 10 minutes after scooping.Add 100 mL of a mixture of acetone and water (acetone (V)/water (V)-TIKAoNIKAca
GB/T 14552---2003
1/5), soak for 6 h to 8 h, then shake for 1 h. Pour the extract into a Büchner funnel covered with two layers of filter paper and one layer of filter aid and filter under reduced pressure. Take 80 mL of the filter (covering two-thirds of the sample). Except for coagulating 2 to 3 times in the following steps, the rest is the same as 7.1.1. 7.1, 4B method purification
Follow the purification steps in 6.2 of GB/T 5009.20. 7.2 Gas chromatography determination
7.2.1 Determination conditionsA
7.2. 1. 1 Column;
a) Glass column: 1.0m×2mm(id), filled with ChromQ coated with 5% 0V-17, 80-100 mesh support b) Glass column: 1.0m×2m(i.tl), filled with ChrnmsorhW-HP coated with 5% 0V-101, 100-120 mesh support. 7.2.1.2 Temperature: Column box 200℃, vaporization chamber 230℃, detector 250℃. 7.2.1.3 Gas flow rate: Nitrogen (N2) 36mL/min-~40mL/min Chlorine (Hz) 4.5mL/min~~6nl./tin; Air 60 mL/min~80 mL/min.
7. 2. 1. 4
Detector: Nitrogen phosphorus detector (NPD).
7. 2. 2 Determination conditions B
Column: Junying elastic capillary column HP-5, 30 m×0.32 (id). 7.2.2.1
7. 2. 2. 2 Source: Column humidity is programmed. Temperature 3 mins5℃/m-140℃ Pre-shoot 6 m-140℃, injection port 220℃, calibrator (NPD) 300℃. 130℃-
7.2.2.3 Gas flow rate: oxygen 3.5mL/min, hydrogen 3mL/min, air 60ml./min, tail blowing (nitrogen) 10mL/min. 7.2.3 Conditions C
7.2.3.1 Column: quartz elastic capillary column DB-17, 30 m×0.53 (id). 7.2.3.2 Concentration: 150 mg/250℃, 10250℃, injection port 22℃, detector (FPD) 300℃. 7.2.3.3 Gas flow rate: Fluorine 9.8mL/min: Hydrogen 75mL/min Air 100lL/min: Tail blowing (nitrogen) 10mL/min7.2.4 In gas phase immunoassay, the sample injection volume is the same as the sample injection volume, and the response value of the standard sample is close to the response value of the sample. When a standard sample is injected twice in succession, the relative deviation of its peak height or peak area is not greater than 7%, which means that the instrument is in a stable state. In actual measurement, the standard sample and the sample should be cross-injected for analysis.
7.2.5 Injection
7.2.5.1 Injection method: syringe injection. 7.2. 5.2 Injection volume: 1 μl ~4 μl. 7.2.6 Chromatograms
7.2.6.1 Chromatograms
Figure 1 Using packed column a and NPD detector1Figure 2 Using capillary column and NPD detector: Figure 3 Using capillary column and FPD detector. 7.2.6.2 Qualitative analysis
7.2.6.2.1 Chromatograms of analysis
Mefenthion, phorate, diazinon, isothion, methyl parathion, spirulophate, isothion, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos. 7.2.6.2.2 Check for possible interference: After determination with 5% V-17 (hr0mQ, 80-100 mesh) chromatographic column, use 5% (0.1u1) ChromsarbW-HP, 100-120 mesh chromatographic column to perform verification chromatographic analysis under the same conditions to determine the separation and impurity interference of each organophosphorus pesticide. 7.2.6.3 Quantitative analysis
7.2.6.3.1 Gas chromatography determination
Take 1 μL of mixed standard solution and inject it into the gas chromatograph, record the retention time and peak height (or peak area) of the chromatographic peak. Then take 1 μL of IG/T14552-2003
sample and inject it into the gas chromatograph, record the retention time and peak height (or peak area) of the chromatographic peak, and use the external standard method for qualitative and quantitative analysis based on the retention time and peak height (or peak area) of the chromatographic peak. 7.2.6.3. 2 Calculation
Where:
X$xxH(s)xy
V, XH,(S.) Xm
The pesticide residue in the sample, in milligrams per dry gram or milligrams per liter (ing/k.mg/l.); The concentration of the main component pesticide in the standard solution, in micrograms per milliliter (g/mL); The injection volume of the standard solution, in microliters (μI); The final volume of the sample solution, in milliliters (mL): V The injection volume of the sample solution, in microliters (μL); H.(S.)
The peak value of the i component pesticide in the standard solution =Height (mm or peak area in mm) Height (mm or peak area in mm) of the i-component pesticide in the sample solution; - Sample weight in grams (g) (here only 2/3 of the extract is used, so multiply by 2/3): . Ammonium chloride,
Sodium chloride:
Monophosphorus:
Isopropylamine
Methyl parathion;
Snail thiocarb:
. Carbothion,
. Bromothion
Monophosphorus Powder;
10 strips of phosphorus.
Figure 110 kinds of organic phosphorus gas chromatogram
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Suyan phosphorus,
2-methyl-p-butylphosphorus;
One explosion,
Iridoblastic acid net:
Pingbi parathion:
6·Tianhu phosphorus;
Amodimethoate,
Bromophos;
-Daofengsan:
O·kill Phosphorus.
Methoate:
Phorate:
.Sengar:
Isopropylamine:
Methyl parathion;
Thiothion:
Isopropylamine+
Fluothion:
Daofengao;
Methoate:
GB/T14552—2003
Figure 210 Gas chromatogram of organic phosphorus
Figure 310 Organic phosphorus gas chromatography
GB/T145522003
8. Expression of results
8.1 Qualitative results
Determine the component names of each organic phosphorus coating drug in the tested sample according to the retention time of each component in the chromatogram of the standard sample. 8.2 Quantitative results
8.2.1 Content expression method
According to the calculated content of each component, the result is expressed in img/kg or tng/l. 8.2.2 Sugar density
Coefficient of variation (%): 2.71%~11.29%. See Table A.1.A.2. 8.2.3 Accuracy
Recovery rate of spiked solution (%): 86.5%~~98.4%. See Table A, 3.8.2.4 Detection limit
Minimum detection concentration, 0.86×10-*mg/kg-~0.29×10=2 tng/kg. See Table A, 4. KNiKabzxz.net
(Informative Appendix)
Method precision, accuracy and detection limit See Table A.1 and Table A.2 for method precision.
Table A.1 Precision of water samples
Name of pesticide
Methodinophos
Methodinophos
Ethioprolin
Methyl parathion
Bromophos
Amidophos
Thioprolin
Addition rate/(mg/L)
0, 009 2
0, 126 0
, 186
Coefficient of variation CV/(%)
Note: The collaborative laboratories consist of 5 laboratories, each of which conducts 5 tests for each addition rate. GB/T14552—2003
Additional difference/(%)
13, 14
GB/T 14552---2003
Pesticide Name
Methiophos
Lanzipro
Isopropylamine
Methyl parathion
Bromophos
Isopropylamine
Daofengsan
Chapoben
Concentration/(mg/kg)
Heart,0280
0, 005 6
0,460 0
G,6250
Table A.2 Precision of soil samples
Coefficient of variation CV/(%)
Note: Collaboration: There are 5 laboratories; each laboratory conducts a replicate test FTKANTKAa for each added concentration
Tolerance/(%)
2Method accuracy Table A, 3,
Agricultural economic name
Sufenphos
Dihydrochloride
Isopropylamine
Tribasic phosphorus
Condensate
Amine phosphorus
Taofengsan
Thiazolidine
Added concentration tg/1.）
c, co9 2
0.142. 49
0. 286 0)
0,0058
Table A, 3 Method accuracy
Accuracy (specified recovery)
Additional concentration/(mg/kg)
, 143c
Also, there are 5 collaborating laboratories; each experimental case and each addition concentration are repeated 5 times, GB/T 14552—2003
Accuracy (specified recovery>/(%)
Soil sample
GB/T14552—2003
The minimum detection amount and minimum detection concentration of the method are shown in Table A, 4, and the minimum detection accuracy is shown in formula (A.1) A4 Method detection limit
Pesticide name
Methiothion||t t||Methiothion
Isopropylamine
Methyl parathion
Methoate
Bromophos
Amine
Mubansan
Methiothion
Minimum detection amount (g)
3.1461XJ0-1
3.8736×10-m
5, 661 5×10-2
1,0080×10-
7. 573 3×10-#
9.1857×10-1
1.1428×10-11
2.2880X10-11
1.7600×10~1
1. 694 8×10 11
Water (mg/L)
0,8600×10-1
0.9600×10-4
0.1415×10-
0,2520×10-3
0.1893×10!
5. 237 2 × 10 2
0. 286 0×10-3
0.572 0×I03
0.1400×10~3
0. 424 0 × 10 -s
Minimum detection concentration
Tuzhen (rng/kg)
0,1308×10-3
0,484 3×.10-
0. 7078×10: 4
0.1260×10-2
0. No. 94 8×10-*
1. 185 8 × 10~5
0.142 8×10-2
0.2860×10*2
0.220C×102
0. 211 8×10 2
Minimum detection amount (g) × sample solution volume (mI) minimum detection degree of the method
sample solution injection volume () sample mass (g) KNTKAa
...+-t A. 1)
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