CN109212053B - Gas chromatography for determining trace glufosinate, glyphosate and aminomethylphosphonic acid in drinking water - Google Patents
Gas chromatography for determining trace glufosinate, glyphosate and aminomethylphosphonic acid in drinking water Download PDFInfo
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Abstract
The invention relates to a method for analyzing and detecting trace harmful substances, in particular to a gas chromatography for determining trace glufosinate ammonium, glyphosate and metabolite aminomethyl phosphonic acid thereof in drinking water. The method comprises the steps of enriching a trace amount of target compounds in drinking water by using a novel methane sulfinate-magnesium aluminum type hydrotalcite roasted product adsorbent stone, eluting the target compounds by using a saturated sodium chloride solution, adjusting the pH value by using sodium hydroxide, stepwise deriving the target compounds by using isopropyl chloride and trimethylsilylated diazomethane as derivatizers, and applying gas chromatography for rapid analysis and determination. The novel adsorbent adopted by the method realizes the rapid and efficient adsorption of the target object by adopting a dispersed solid-phase extraction mode, and can save a large amount of adsorption and elution time compared with a solid-phase extraction mode; only a small amount of organic solvent is suitable for extraction, and compared with a liquid-liquid extraction method which needs a large amount of organic solvent, the method has the advantages of safety, environmental protection and economic advantage.
Description
Technical Field
The invention relates to a method for analyzing and detecting harmful trace substances, in particular to a gas chromatography for determining trace glufosinate-ammonium, glyphosate and aminomethyl phosphonic acid in drinking water.
Background
Glyphosate (Glyphosate) and Glufosinate (Glufosinate ammonium) belong to the class of organophosphorus herbicides. Among them, glyphosate is the highest herbicide in global sales market and is the first pesticide variety in worldwide sales, and the sales in 2012 reaches $ 45.75 billion; because the crop plants have problems with glyphosate resistance after continuous glyphosate application in the cultivated area, people usually combine the application of glufosinate to ensure the yield and quality of the crop plants, and the sale of glufosinate in 2012 reaches $ 4.20 million. In recent years, the production amount and the use amount of the two herbicides tend to increase year by year, and the toxicity and the potential food safety hazard of the two herbicides are emphasized.
Because glufosinate-ammonium, glyphosate and metabolites thereof, such as aminomethyl phosphonic acid, are polar small molecular compounds containing amino and carboxyl, after application, the compounds are easily soluble in water and exist in an anionic state, and have the characteristics of strong polarity and difficult solubility in various organic solvents, so that the water body is easily polluted, and the safety of drinking water is harmed. The sanitary Standard for Drinking Water (GB 5749-.
The main methods for detecting glufosinate-ammonium, glyphosate and metabolites thereof, such as aminomethyl phosphonic acid, in drinking water at present are a chromatography and chromatography-mass spectrometry combined method, and a pretreatment method mainly focuses on two methods, namely liquid-liquid extraction and solid-phase extraction. However, the liquid-liquid extraction method has the defect that a large amount of organic solvent is required; the solid phase extraction method has the following defects: firstly, the solid phase extraction filler kind that can adopt is limited, and the current report only has a few available products such as HLB solid phase extraction post and SAX solid phase extraction post, and the product kind is few, secondly adopts solid phase extraction post mode absorption to need to pass through solid phase extraction post with a large amount of water with certain speed, makes adsorbent can adsorb aquatic target in the solid phase extraction post, and this process need consume a large amount of time usually.
Layered Double Hydroxide (LDHs) is a typical Layered material with a supramolecular intercalation structure, and is mainly composed of positively charged laminates formed by combining Hydroxides of divalent and trivalent metals and negatively charged anions intercalated between the laminates. Two notable features of this material are: space adjustability between the laminate layers and replaceability of the intercalated anions. Based on the method, people can modify the LDHs material according to the difficulty of replaceability of intercalation anions of the LDHs material and the adjustability of the distance between the layers, and then select different types of intercalation anions according to the requirements of practical application to modify the material to obtain a functional material with novel application.
Because different intercalation anions are used for modifying the LDHs material, the interlayer spacing of the material and the species of the intercalation ions are adjusted, so that when the LDHs material is used in the field of adsorbents, different modified LDHs are influenced by various factors such as the molecular size, the structure, the polarity and the functional groups of adsorbed targets to show different selective adsorption performances.
Meanwhile, the LDHs modified material is roasted at the temperature of 450-500 ℃, anions inserted between the laminates can be effectively removed, and only a cavity-shaped laminate structure with the interval adjusted is left, so that a roasted product (LDO) is obtained. Generally, in the field of using LDHs and their corresponding LDOs as adsorbents, the adsorption performance of LDOs for certain specific targets is often higher than that of corresponding LDHs, since LDOs have more hollow void structures.
The inventor conducts adsorption selectivity tests on three targets by using the modified LDH and the LDO for the modified LDH in earlier researches, and finds that the methane sulfinate-magnesium aluminum type hydrotalcite calcined product adsorbent conducts adsorption experiments on glufosinate, glyphosate and metabolite aminomethylphosphonic acid in water, and the result shows that the adsorbent has good adsorption effects on the three targets. On the basis, the inventor further optimizes the performance and application method of the three targets in the water, and establishes a gas chromatography for detecting trace glufosinate-ammonium, glyphosate and metabolites thereof, namely aminomethylphosphonic acid, in the drinking water by taking a methane sulfinate-magnesium aluminum type hydrotalcite roasted product as an adsorbent.
Disclosure of Invention
In order to overcome the defect that a large amount of organic solvent is needed in a liquid-liquid extraction method in the detection pretreatment of trace glufosinate ammonium, glyphosate and metabolites thereof, namely aminomethyl phosphonic acid, in the existing drinking water; the invention also provides a method for rapidly adsorbing trace glufosinate ammonium, glyphosate and metabolites thereof in drinking water by a dispersion solid phase extraction method, and aims to solve the technical problems that the variety of usable solid phase extraction products of the solid phase extraction method is few, and a large amount of time is consumed in the adsorption and elution processes.
The invention achieves the above object by the following technical means.
A gas chromatography method for measuring trace glufosinate ammonium, glyphosate and metabolite aminomethyl phosphonic acid in drinking water comprises the following steps:
step 1, adsorption of trace target: storing the collected drinking water sample at 4 ℃ for later use, adding the drinking water sample into a separating funnel when in use, adding 0.20g of methane sulfinate-magnesium aluminum type hydrotalcite roasted product adsorbent into the drinking water sample, and oscillating for a certain time to ensure that the roasted product adsorbent adsorbs residual glufosinate ammonium, glyphosate and aminomethylphosphonic acid target substances in water;
and 4, cleaning an extracting solution and performing derivatization in the second step: adding 1mL of saturated sodium chloride solution into the combined extracting solution, whirling, standing, absorbing the lower layer of sodium chloride aqueous solution, adding 0.4mL of methanol and 0.2mL of trimethylsilylated diazomethane n-hexane solution into a centrifuge tube, sealing, and placing in a water bath for derivatization;
and 5, concentrating, fixing volume and analyzing by gas chromatography: adding 0.05mL of hydrochloric acid solution into the derivative solution, vortexing, adding 0.1g of sodium bicarbonate solid powder, vortexing, placing the derivative solution in a heart-shaped bottle, performing rotary evaporation at 50 ℃ to near dryness, metering volume by using 2.00mL of ethyl acetate solution, filtering, and performing gas chromatography analysis and test according to the following conditions:
a) a chromatographic column: DB-1701 capillary column, 30m × 0.25mm, 0.25 μm film thickness; column flow rate: 2.50 mL/min.
b) Sample inlet temperature: 220 ℃; and (3) sample introduction mode: no shunt sampling; sample introduction amount: 2 μ L.
c) Temperature rising procedure: 70 deg.C (1 min hold), 10 deg.C/min to 160 deg.C (1 min hold), 5 deg.C/min to 250 deg.C (1 min hold).
Wherein the content of the first and second substances,
the drinking water amount in the step 1 is 200mL, and the oscillation adsorption time is 10 min.
The centrifugation speed in the step 2 is 4500rpm, the centrifugation time is 3min, the amount of the added saturated sodium chloride solution is 3mL, the sodium hydroxide is 0.10mL, the concentration is 5.0mol/L, the adjusted pH value is more than 10, and the ultrasonic elution time is 5 min.
The n-hexane solution of the isopropyl chloride in the step 3 is a mixed solution of the isopropyl chloride and n-hexane in a volume ratio of 1:9, and the addition volume is 0.2 mL; the vortex time is 10s, and the ultrasonic reaction time is 2 min; the hydrochloric acid solution is a mixed solution of concentrated hydrochloric acid and water in a volume ratio of 1:2, and the addition volume is 1.00 mL; the addition amount of the anhydrous sodium sulfate is 4.00g to 6.00g, and the volume of the saturated copper sulfate is 0.5 mL; the extraction time is 5min under shaking.
The vortex time in the step 4 is 30s to 60 s; 2mol/L of trimethyl silanization diazomethane normal hexane solution; the water bath temperature is 30-50 ℃, and the derivatization time is 30-60 min.
The hydrochloric acid solution in the step 5 is hydrochloric acid diluent diluted by concentrated hydrochloric acid and water according to the equal volume, the vortex time is 10s to 30s, and an organic phase filter membrane for filtration has the aperture of 0.22 mu m.
The invention needs to be explained as follows: the three targets contain both amino (or imino) and carboxyl, so that the solubility of the three targets in water is high, and the three targets are difficult to salt out under strong electrolyte and extract by using an organic solvent. Therefore, the method adopts stepwise derivatization and extraction for the target substance. Firstly, derivatizing amino (or imino) in a target object by using a normal hexane solution of isopropyl chloride under an alkaline condition, and dissolving the obtained derivative product in water, but extracting by salting out under a strong electrolyte and extracting by using an organic solvent; and then carrying out secondary esterification derivatization aiming at carboxyl on the derivatization product in the first step.
In the process of research and development of the method, the inventor conducts various researches on the aspects of selection of the adsorbent, optimization of the derivation conditions, selection and optimization of the extracting agent, optimization of the chromatographic detection conditions and the like. Meanwhile, considering that the pH range of the drinking water is between 6.0 and 8.0, which is in the pH range where the adsorbent can better adsorb the target substance in the drinking water sample, the present invention does not propose an operation step of adjusting the pH range of the adjusted water.
In addition, in consideration of quantitative accuracy of the target object, the method quantifies the target object by adopting the matrix correction curve on the premise that the isotope of the target object cannot be obtained so as to quantify the target object by an isotope internal standard method, so that systematic errors are eliminated as much as possible, and the quantitative accuracy is improved.
The invention has the advantages that:
(1) the novel roasted product adsorbent methane sulfinate-magnesium-aluminum type hydrotalcite roasted product adsorbent adopted by the invention can quickly adsorb trace glufosinate-ammonium, glyphosate and metabolite aminomethyl phosphonic acid thereof in water by adopting a dispersed solid-phase extraction mode, and can save a large amount of adsorption and elution time compared with a solid-phase extraction mode;
(2) the method is only suitable for using a small amount of organic solvent as the extraction solvent of the target object, and has the advantages of safety, environmental protection and economic advantages compared with the liquid-liquid extraction method which needs to use a large amount of organic solvent.
Drawings
FIG. 1 is a chromatogram of aminomethylphosphonic acid, which is glufosinate, glyphosate and its metabolites in embodiments, wherein 1 is aminomethylphosphonic acid, 2 is glyphosate, and 3 is glufosinate.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
(1) The reagent medicines involved in the embodiments of the present invention are as follows:
solid standard products of glufosinate ammonium, glyphosate and metabolites thereof, such as aminomethyl phosphonic acid, with the purity of more than or equal to 98.0 percent, Germany Dr. Ehrensorfer Co., Ltd;
tert-butyl alcohol, ethyl ether, ethyl acetate, sodium chloride, sodium hydroxide, isopropyl chloride, n-hexane, anhydrous sodium sulfate, sodium bicarbonate and copper sulfate, and is analytically pure;
hydrochloric acid, super pure, group of national medicine; the water is first-grade water meeting the GB/T6682 specification.
Trimethylsilyldiazomethane solution, 2.0M in hexane, Alfa Aesar.
(2) The instruments involved in the examples of the present invention are as follows:
KH-75A type electric heating constant temperature air-blast drying oven, Kangheng instruments ltd, Guangzhou;
model 7890B gas chromatograph equipped with a Flame Photometric Detector (FPD), Agilent technologies, Inc. of America.
(3) Analysis and test conditions of a gas chromatograph:
a) a chromatographic column: DB-1701 capillary column, 30m × 0.25mm, 0.25 μm film thickness; column flow rate: 2.50 mL/min.
b) Sample inlet temperature: 220 ℃; and (3) sample introduction mode: no shunt sampling; sample introduction amount: 2 μ L.
c) Temperature rising procedure: 70 deg.C (1 min hold), 10 deg.C/min to 160 deg.C (1 min hold), 5 deg.C/min to 250 deg.C (1 min hold).
d) A detector: a flame photometric detector with a phosphor filter; detector temperature: 250 ℃; the hydrogen flow rate is 75mL/min, the air flow rate is 100mL/min, and the tail gas flow rate is 60 mL/min.
(4) Preparation of matrix calibration curve and determination of detection limit and quantitative limit
The glufosinate-ammonium, glyphosate and metabolite aminomethyl phosphonic acid standard substance are accurately weighed and dissolved by methanol to a constant volume to prepare a standard stock solution with the concentration of 1000mg/L, and the standard stock solution is stored at the temperature of-4 ℃. When in use, the standard stock solution is gradually diluted by deionized water to prepare standard use solution with the concentration gradient of 10.0 mug/L, 20.0 mug/L, 40.0 mug/L, 100.0 mug/L and 200.0 mug/L.
Step 1, adsorption of trace target: taking five 500mL separating funnels, adding 200mL deionized water into the separating funnels, respectively taking 2.00mL of the standard use solution, preparing a substrate calibration standard curve sample with a series of concentrations, then adding 0.20g of methane sulfinate-magnesium-aluminum type hydrotalcite roasted product adsorbent into each funnel, and oscillating for 10min to enable the roasted product adsorbent to adsorb trace amounts of glufosinate ammonium, glyphosate and metabolite aminomethyl phosphonic acid in water;
and 4, cleaning an extracting solution and performing derivatization in the second step: adding 1mL saturated sodium chloride solution into the combined extracting solution, whirling for 30-60 s, standing, absorbing the lower layer sodium chloride aqueous solution, adding 0.4mL methanol and 0.2mL trimethylsilyl diazomethane n-hexane solution (with the concentration of 2mol/L) into a centrifuge tube, sealing, and placing in a water bath at 30 ℃ for derivatization for 30 min;
and 5, concentrating, fixing volume and analyzing by gas chromatography: adding 0.05mL of hydrochloric acid solution into the derivative solution, swirling for 10s to 30s, adding 0.1g of sodium bicarbonate solid powder, placing the derivative solution into a heart-shaped flask after swirling, performing rotary evaporation at 50 ℃ to nearly dry, fixing the volume by using 2.00mL of ethyl acetate solution, sucking the upper layer of organic solution, passing the upper layer of organic solution through an organic phase filter membrane with the pore diameter of 0.22 mu m, and performing gas chromatography analysis and test.
And taking the concentration of glufosinate-ammonium, glyphosate and metabolite aminomethyl phosphonic acid thereof in the sample solution as an X axis, and taking the chromatographic peak area of the glufosinate-ammonium, glyphosate and metabolite aminomethyl phosphonic acid derivative thereof on a gas chromatograph as a Y axis to draw a matrix standard curve and use the matrix standard curve for quantification by an external standard method.
The triple value of the signal-to-noise ratio S/N is taken as the detection limit of the method (LOD, LOD is 3S/N), the ten times of the signal-to-noise ratio S/N is taken as the quantification limit of the method (LOQ, LOQ is 10S/N), and the detection limit and the quantification limit of each compound in water are calculated by combining the volume of the added matrix.
The relevant parameters of the matrix standard curve, LOD and LOQ are shown in Table 1.
TABLE 1. Standard curves, limits of detection and limits of quantitation for glufosinate-ammonium, glyphosate and its metabolites, aminomethylphosphonic acid substrates
(5) Synthesis of methane sulfinate-magnesium-aluminum type hydrotalcite roasted product adsorbent
In order to enable those skilled in the art to repeatedly carry out the relevant experiments of the present invention, a method for synthesizing the key substance methane sulfinate-magnesium aluminum type hydrotalcite calcined product adsorbent used in the present invention is now provided, as follows:
the reagent medicines involved in the synthesis of the calcined product adsorbent are as follows:
sodium methanesulfinate, analytically pure, pharmaceutical group;
Mg6Al2(OH)16CO3·4H2o, analytical grade, Aldrich, usa.
The apparatus involved in the synthesis of the calcined product adsorbent is as follows:
an EXCEL type microwave digestion instrument, Shanghai Yao Instrument science and technology development Co., Ltd., digestion tank volume of 100 mL; microwave muffle furnace (sintering furnace), CEM corporation, usa; model VD53 vacuum drying cabinet, German Bindd technologies; HJ-5 multifunctional constant temperature stirrer, Kantai Ronghua Instrument manufacturing Co., Ltd; FS-12 type separatory funnel oscillator, New optical technology, Japan; 3K-15 type centrifuge, sigma technologies, germany; BF518945C-1 model box resistance furnace (muffle furnace), Saimer Feishell science, USA.
The concrete steps of synthesizing the roasted product adsorbent are as follows:
(a) first roasting: mg of purchased Mg-Al type hydrotalcite6Al2(OH)16CO3·4H2Placing O in a muffle furnace, heating at a heating rate of 5 ℃/min to 500 ℃, and roasting for 6h to obtain a roasted product Mg6Al2O8(OH)2；
(b) Weighing: 6.125g of intercalation agent sodium methanesulfinate and 7.236g of roasting product Mg are weighed in a microwave digestion tank6Al2O8(OH)2。
(c) Microwave crystallization hydrothermal synthesis: boiling deionized water and keeping for 30min, then adding 60mL into the microwave digestion tank filled with the intercalation agent and the roasting product, sealing, placing the microwave digestion tank into a microwave digestion instrument, and carrying out microwave heating for 30min at 140 ℃ to complete synthesis;
(d) washing and drying: pouring out all solids and liquid in the microwave tank, heating and stirring with deionized water boiled for more than 30min to remove carbon dioxide, shaking, washing, centrifuging, vacuum drying at 90 deg.C for 12h, grinding, and storing.
(e) And (3) second roasting: and (3) placing the synthesized methane sulfinate-magnesium-aluminum type hydrotalcite in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and roasting for 4h to obtain a roasted product adsorbent.
Example 1
In this example 1, tap water was used as a sample matrix to perform a standard recovery experiment to verify the feasibility of the method of the present invention, wherein the tap water sample was taken from technical center of the inspection and quarantine bureau for entry and exit of Fuqing, and the water sample was placed in a refrigerator at 4 ℃ for 1 hour after sampling.
The treatment is carried out according to the following steps:
1. adsorption of trace target:
taking 500mL of separating funnel, adding 200mL of tap water into the separating funnel, respectively taking 2.00mL of the standard use solutions of 10.0 mu g/L, 20.0 mu g/L and 200.0 mu g/L to prepare three-level hexa-parallel labeled positive samples, then adding 0.20g of methane sulfinate-magnesium-aluminum type hydrotalcite roasted product adsorbent into each funnel, and oscillating for 10min to enable the roasted product adsorbent to adsorb trace glufosinate-ammonium, glyphosate and metabolite aminomethyl phosphonic acid in water;
2. desorption of trace targets:
adding water in a separating funnel into a 50mL centrifuge tube with a plug, centrifuging at the rotating speed of 4500rpm for 3min to separate the solid roasted product adsorbent from the aqueous solution and discard the supernatant, combining all the solid roasted product adsorbents at the lower layer into one centrifuge tube, adding 3mL saturated sodium chloride solution into the centrifuge tube, adding 0.10mL sodium hydroxide solution with the concentration of 5.0mol/L to adjust the pH value to be more than 10, and performing ultrasonic elution for 5min after vortex;
3. first step derivatization and extraction of derivatives:
adding 0.2mL of isopropyl chloride n-hexane solution (mixed solution of isopropyl chloride and n-hexane in a volume ratio of 1: 9) into the centrifuge tube, vortexing for 10s, and performing ultrasonic derivatization for 2 min; adding 1.00mL of hydrochloric acid solution (mixed solution of concentrated hydrochloric acid and water in a volume ratio of 1: 2) into a centrifuge tube to dissolve the solid roasted product adsorbent, adding 4.00g of solid anhydrous sodium sulfate and 0.5mL of saturated copper sulfate solution, taking 5mL of 20% tert-butyl alcohol-ether solution as an extracting solution, oscillating for 5min for extraction, standing, absorbing supernate, re-extracting once, and combining the extracting solutions;
4. washing an extracting solution and performing derivatization in a second step:
adding 1mL saturated sodium chloride solution into the combined extracting solution, whirling for 30s, standing, absorbing the lower layer sodium chloride aqueous solution, adding 0.4mL methanol and 0.2mL trimethylsilylated diazomethane n-hexane solution (concentration is 2mol/L) into a centrifuge tube, sealing, and placing in a water bath at 30 ℃ for derivatization for 30 min;
5. concentration constant volume and gas chromatographic analysis:
adding 0.05mL of hydrochloric acid solution into the derivative solution, vortexing for 10s, adding 0.1g of sodium bicarbonate solid powder, vortexing, placing the derivative solution in a heart-shaped bottle, performing rotary evaporation at 50 ℃ to obtain a solution, performing constant volume by using 2.00mL of ethyl acetate solution, sucking the upper layer of organic solution, and performing gas chromatography analysis and test after the upper layer of organic solution passes through an organic phase filter membrane with the pore diameter of 0.22 mu m.
The parameters relevant to the spiking recovery experiment of example 1 are shown in Table 2.
Table 2 experimental data on the addition concentration and recovery rate of the tap water sample (n ═ 6)
Example 2
In this example 2, well water is used as a sample matrix to perform a labeling recovery experiment to verify the feasibility of the method, wherein the well water sample is taken from well water for production of Fuqing Longxiang food Co., Ltd, and the water sample is taken out and returned to a laboratory in a refrigerator at 4 ℃ for analysis and detection.
The treatment is carried out according to the following steps:
1. adsorption of trace target:
taking 500mL of separating funnel, adding 200mL of well water into the separating funnel, respectively taking 2.00mL of the standard use liquid of 10.0 mu g/L, 20.0 mu g/L and 200.0 mu g/L to prepare and obtain three-level hexa-parallel labeled positive samples, then adding 0.20g of methane sulfinate-magnesium-aluminum type hydrotalcite roasted product adsorbent into each funnel, and oscillating for 10min to enable the roasted product adsorbent to adsorb trace glufosinate-ammonium, glyphosate and metabolite aminomethyl phosphonic acid in water;
2. desorption of trace targets:
adding water in a separating funnel into a 50mL centrifuge tube with a plug, centrifuging at the rotating speed of 4500rpm for 3min to separate the solid roasted product adsorbent from the aqueous solution and discard the supernatant, combining all the solid roasted product adsorbents at the lower layer into one centrifuge tube, adding 3mL saturated sodium chloride solution into the centrifuge tube, adding 0.10mL sodium hydroxide solution with the concentration of 5.0mol/L to adjust the pH value to be more than 10, and performing ultrasonic elution for 5min after vortex;
3. first step derivatization and extraction of derivatives:
adding 0.2mL of isopropyl chloride n-hexane solution (mixed solution of isopropyl chloride and n-hexane in a volume ratio of 1: 2) into the centrifuge tube, vortexing for 10s, and performing ultrasonic derivatization for 2 min; adding 1.00mL of hydrochloric acid solution (mixed solution of concentrated hydrochloric acid and water in a volume ratio of 1: 2) into a centrifuge tube to dissolve the solid roasted product adsorbent, adding 4.00g of solid anhydrous sodium sulfate and 0.5mL of saturated copper sulfate solution, taking 5mL of 20% tert-butyl alcohol-ether solution as an extracting solution, oscillating for 5min for extraction, standing, absorbing supernate, re-extracting once, and combining the extracting solutions;
4. washing an extracting solution and performing derivatization in a second step:
adding 1mL saturated sodium chloride solution into the combined extracting solution, whirling for 60s, standing, absorbing lower layer sodium chloride aqueous solution, adding 0.4mL methanol and 0.2mL trimethylsilylated diazomethane n-hexane solution (concentration is 2mol/L) into a centrifuge tube, sealing, and placing in a water bath at 50 ℃ for derivatization for 60 min;
5. concentration constant volume and gas chromatographic analysis:
adding 0.05mL of hydrochloric acid solution into the derivative solution, vortexing for 30s, adding 0.1g of sodium bicarbonate solid powder, vortexing, placing the derivative solution in a heart-shaped bottle, performing rotary evaporation at 50 ℃ to obtain a solution, performing constant volume by using 2.00mL of ethyl acetate solution, sucking the upper layer of organic solution, and performing gas chromatography analysis and test after the upper layer of organic solution passes through an organic phase filter membrane with the pore diameter of 0.22 mu m.
The parameters relevant to the spiking recovery experiment of example 2 are shown in Table 3.
Table 3 experimental data on the addition concentration and recovery rate of the tap water sample (n ═ 6)
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the spirit of the invention, which falls within the scope of the invention, and therefore the scope of the patent of the invention shall be governed by the appended claims.
Claims (6)
1. A gas chromatography method for measuring trace glufosinate, glyphosate and aminomethylphosphonic acid in drinking water is characterized by comprising the following steps:
(1) adsorption of trace target: storing the collected drinking water sample at 4 ℃ for later use, adding 0.20g of methane sulfinate-magnesium aluminum type hydrotalcite roasted product adsorbent into a proper amount of drinking water sample in a separating funnel, and oscillating for a certain time to enable the adsorbent to adsorb residual glufosinate-ammonium, glyphosate and aminomethylphosphonic acid in water;
(2) desorption of trace targets: transferring water in the separating funnel to a centrifuge tube with a plug for centrifugation, removing supernatant, combining all lower-layer solid adsorbents into one centrifuge tube, adding a certain amount of saturated sodium chloride solution, adding sodium hydroxide solution for adjusting the pH value, and performing ultrasonic elution after vortex;
(3) first step derivatization and extraction of derivatives: adding isopropyl chloride-n-hexane solution into the centrifuge tube, and performing ultrasonic derivatization after vortex; adding a hydrochloric acid solution into a centrifugal tube to dissolve a solid adsorbent, adding a solid anhydrous sodium sulfate solution and a saturated copper sulfate solution, performing oscillation extraction by taking 5mL of a 20% tert-butyl alcohol-ether solution as an extracting solution, standing, absorbing a supernatant, performing extraction once again, and combining the extracted solutions;
(4) washing an extracting solution and performing derivatization in a second step: adding 1mL of saturated sodium chloride solution into the combined extracting solution, whirling, standing, absorbing the lower layer of sodium chloride aqueous solution, adding 0.4mL of methanol and 0.2mL of trimethylsilylated diazomethane n-hexane solution into a centrifuge tube, sealing, and placing in a water bath for derivatization;
(5) concentration constant volume and gas chromatographic analysis: adding 0.05mL of hydrochloric acid solution into the derivative solution, vortexing, adding 0.1g of sodium bicarbonate solid powder, vortexing, placing the derivative solution in a heart-shaped bottle, performing rotary evaporation at 50 ℃ to near dryness, metering volume by using 2.00mL of ethyl acetate solution, filtering, and performing gas chromatography analysis and test according to the following conditions:
a) a chromatographic column: DB-1701 capillary column, 30m × 0.25mm, 0.25 μm film thickness; column flow rate: 2.50 mL/min;
b) sample inlet temperature: 220 ℃; and (3) sample introduction mode: no shunt sampling; sample introduction amount: 2 mu L of the solution;
c) temperature rising procedure: maintaining at 70 deg.C for 1min, heating to 160 deg.C at a rate of 10 deg.C/min, maintaining for 1min, heating to 250 deg.C at a rate of 5 deg.C/min, and maintaining for 1 min;
d) a detector: a flame photometric detector with a phosphor filter; detector temperature: 250 ℃; the hydrogen flow rate is 75mL/min, the air flow rate is 100mL/min, and the tail gas flow rate is 60 mL/min.
2. The gas chromatography method for measuring the trace amount of glufosinate, glyphosate and aminomethyl phosphonic acid in drinking water as claimed in claim 1, wherein the drinking water sample in step (1) is 200mL, and the time of oscillation adsorption is 10 min.
3. The gas chromatography method for measuring the trace amount of glufosinate, glyphosate and aminomethyl phosphonic acid in drinking water as claimed in claim 1, wherein the centrifugation speed in step (2) is 4500rpm, the centrifugation time is 3min, the amount of the added saturated sodium chloride solution is 3mL, the amount of sodium hydroxide is 0.10mL, the concentration is 5.0mol/L, the adjusted pH value is more than 10, and the time of ultrasonic elution is 5 min.
4. The gas chromatography for measuring the trace amount of glufosinate-ammonium, glyphosate and aminomethylphosphonic acid in the drinking water as claimed in claim 1, wherein the n-hexane solution of isopropyl chloride in the step (3) is a mixed solution of isopropyl chloride and n-hexane in a volume ratio of 1:9, and the addition volume is 0.2 mL; the vortex time is 10s, and the ultrasonic reaction time is 2 min; the hydrochloric acid solution is a mixed solution of concentrated hydrochloric acid and water in a volume ratio of 1:2, and the addition volume is 1.00 mL; the addition amount of the anhydrous sodium sulfate is 4.00g to 6.00g, and the volume of the saturated copper sulfate is 0.5 mL; the extraction time is 5min under shaking.
5. The gas chromatography method for measuring the trace amount of glufosinate, glyphosate and aminomethylphosphonic acid in drinking water according to claim 1, wherein the vortex time in step (4) is 30s to 60 s; 2mol/L of trimethyl silanization diazomethane normal hexane solution; the water bath temperature is 30-50 ℃, and the derivatization time is 30-60 min.
6. The gas chromatography method for determining the trace amount of glufosinate, glyphosate and aminomethylphosphonic acid in drinking water as claimed in claim 1, wherein the hydrochloric acid solution in step (5) is a diluted hydrochloric acid solution of concentrated hydrochloric acid and water diluted according to equal volume, the vortex time is 10s to 30s, the filter membrane for filtration is an organic phase filter membrane, and the pore size is 0.22 μm.
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