CN103913529A - Analyzing method for simultaneously determining residues of organophosphorus pesticides and pyrethriods pesticides in soil - Google Patents
Analyzing method for simultaneously determining residues of organophosphorus pesticides and pyrethriods pesticides in soil Download PDFInfo
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Abstract
The invention provides an analyzing method for simultaneously determining residues of organophosphorus pesticides and pyrethriods pesticides in soil. The analyzing method is characterized by comprising the following steps: carrying out ultrasonic extraction on a soil test sample by using an acetonitrile solution containing 1% of acetic acid by volume percent; purifying by using a suitable amount of PSA and C18 mixed fillers; blowing liquid supernatant by nitrogen and concentrating until the liquid supernatant is nearly dried; respectively dissolving by acetone and n-hexane and enabling the volume to be constant; raising the temperature by using DB-1701 and HP-5 quartz capillary columns and separating; carrying out GC/FPD (Gas Chromatograph/Flame Photometric Detector) detection and GC/micro ECD (Electron Capture Detector) detection; and finally, quantifying by using a base material external standard method. A test confirms that the method has a wide linear range; the technical indexes including detection sensitivity, accuracy and precision meet the requirements of a residue analysis; the pre-treatment operation is simple, convenient and rapid and a reliable manner is provided for analytical researches for simultaneously determining the residues of ths pesticides and the pyrethriods pesticides in the soil.e organophosphoru.
Description
Technical field
The present invention relates to the detection method field of persticide residue, be specifically related to one and measure organic phosphates and pyrethroid pesticide remained quantitative analysis method in soil simultaneously, this analytical approach is to adopt improved QuEChERS method that soil is extracted, purified, by vapor-phase chromatography, organophosphorus and pyrethroid pesticide are detected again, to reach quick, easy, reliable object.
Background technology
Organophosphorus pesticide (English name: Organophosphorus pesticides) and pyrethroid pesticide (English name: Pyrethroid pesticides) are two class agricultural chemicals of current China each department widespread use, there is the features such as wide spectrum, efficient, economic, wide in variety, consumption are few, to control disease pest and weed, guarantee that crop yield brought into play vital role.But studies confirm that this two classes agricultural chemicals can produce toxic action to the nervous system of human body, that part kind has is carcinogenic, teratogenesis, mutagenesis and certain property accumulated, and excessive use is likely accumulated in human body, causes chronic accumulate poisoning.In crop pest control process, the agricultural chemicals ratio on target organisms of being directly scattered in is little, major part enters in soil by all means, and organophosphorus and pyrethroid pesticide fat-soluble stronger can be adsorbed in soil for a long time, cause Soil Contamination by Chemical Pesticides, geobiont is worked the mischief, affect soil fertility, and can pass through the approach polluted-waters such as runoff, leaching and affect hydrobiont, and by biological concentration and the enlarge-effect of food chain, be finally detrimental to health.Therefore the residual of this two classes agricultural chemicals in soil detected, monitored, contribute to evaluate its residual situation in soil, to adopting an effective measure, remove and to alleviate pollution by pesticides significant.
Soil is due to self component complexity, and interfering material is more, easily causes agricultural chemicals extraction and cleaning difficulty, and therefore selecting suitable sample-pretreating method is the primary committed step that Pesticide-Polluted Soil detects.In Pesticide-Polluted Soil leaching process, existing report mainly uses the methods such as traditional Soxhlet extraction, liquid-liquid extraction, microwave abstracting, accelerated solvent extraction.Although extracting, Soxhlet there is good extraction effect, but length consuming time (being generally 10～24h), organic solvent consumption large (consumption is 50～400mL conventionally), be unsuitable for the pre-treatment of batch sample, and for a long time Soxhlet leaching process easily causes the decomposition of some agricultural chemicals, causes the recovery on the low side; Although liquid-liquid extraction equipment is simple, technology maturation, solvent-oil ratio is large, loaded down with trivial details time-consuming, and easily produces a large amount of emulsion fluid in extraction process, affects extraction efficiency, causes the recovery to decline; Microwave abstracting and accelerated solvent extraction solvent load are few, and extraction efficiency is high, but need expensive extraction instrument, operating cost is high, some extraction processes also need at high temperature to carry out, easily thermo-responsive agricultural chemicals impacted, and the more loaded down with trivial details purifying step of follow-up common needs.In the purification process of Pesticide-Polluted Soil, current purification method adopts solid phase extraction column method, column chromatography and concentrated acid sulfonation method more.Solid phase extraction column solvent load is few, simple to operate, and the recovery is high, is easy to automation mechanized operation, but cost is higher; Column chromatography purifies more complete, be applicable to the retention analysis of most of sample Pesticides, but solvent-oil ratio is large, and formality is loaded down with trivial details, requires high to column packing technique; The clean-up effect of concentrated acid sulfonation is better, but applicable pesticide species is very limited, has the problems such as sour unstable agricultural chemicals decomposition, and the heat that concentrated sulfuric acid dissolution discharges can accelerate organic solvent volatilization, generation quantitative error.
Summary of the invention
The invention provides one and measure organic phosphates and pyrethroid pesticide remained quantitative analysis method in soil simultaneously, the detection method length consuming time, complex operation, consumption organic solvent that its object is to solve organic phosphates and pyrethrin pesticide in existing mensuration soil mainly with and the problem such as testing result is reliable and stable not.
For achieving the above object, the technical solution used in the present invention is: one is measured organic phosphates and pyrethroid pesticide remained quantitative analysis method in soil simultaneously, and described analytical approach is made up of two parts:
Part I, sets up respectively the tested organophosphorus pesticide of known gradient concentration and the typical curve of pyrethroid pesticide by vapor-phase chromatography; The foundation of described typical curve is made up of following steps:
The first step, prepares blank matrix extract, and preparation method is made up of following steps:
(1) take 5.0g after measured not containing the blank pedotheque of tested organophosphorus pesticide and pyrethroid pesticide in 50mL centrifuge tube, in centrifuge tube, add 2mL ultrapure water again, vortex mixes, infiltrate 10～20min, add again 10mL to contain the acetonitrile solution that volume fraction is 1% acetic acid, mix, ultrasonic extraction 10～15min, add 2g anhydrous sodium acetate and 2g anhydrous magnesium sulfate, vortex 2min, with the centrifugal 4min of 9000r/min rotating speed, get supernatant and be blank matrix extract to be clean;
(2) separately get a 10mL centrifuge tube, add 0.15g C18,0.15g N-propyl group ethylenediamine and 0.3g anhydrous magnesium sulfate, add blank matrix extract to be clean described in 4mL, vortex 1.5min～2.5min, with the centrifugal 4.5min～5.5min of rotating speed of 9000r/min; After centrifugal, pipette in 2 portions of supernatants to 2 scale test tube, every portion of supernatant is 1.5mL, then under 50～60 ℃ of water-baths, every portion of supernatant is slowly blown to 50～70 μ L with nitrogen; In a supernatant, add acetone to be settled to 0.75mL therein again, cross after organic system filter membrane, obtain the blank matrix extract for preparing organophosphorus pesticide, in another portion of supernatant, add normal hexane to be settled to 0.75mL, cross after organic system filter membrane, obtain the blank matrix extract of pyrethroid pesticide;
Second step, prepare respectively the matrix hybrid standard working solution of organophosphorus pesticide and the matrix hybrid standard working solution of pyrethroid pesticide take the blank matrix extract that obtains in the described first step as solvent, wherein, described organophosphorus pesticide refers to DDVP, Rogor, chlopyrifos, parathion-methyl, malathion, fenifrothion, Hostathion, and described pyrethroid pesticide refers to Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis; In the matrix hybrid standard working solution of described organophosphorus pesticide, in the concentration range of each organophosphorus pesticide and the matrix hybrid standard working solution of described pyrethroid pesticide, the concentration range of each pyrethroid pesticide is:
| Agricultural chemicals | Concentration range/(mg/L) |
| DDVP | 0.01～1.0 |
| Rogor | 0.04～4.0 |
| Chlopyrifos | 0.02～2.0 |
| Parathion-methyl | 0.02～2.0 |
| Malathion | 0.02～2.0 |
| Fenifrothion | 0.02～2.0 |
| Hostathion | 0.04～4.0 |
| Fenpropathrin | 0.01～1.0 |
| Gamma cyhalothrin | 0.004～0.4 |
| Permethrin | 0.02～2.0 |
| Cyfloxylate | 0.01～1.0 |
| Cypermethrin | 0.02～2.0 |
| Fenvalerate | 0.02～2.0 |
| Decis | 0.02～2.0 |
The 3rd step, with chromatographic peak retention time and the chromatographic peak area of each pesticide composition in the matrix hybrid standard working solution of organophosphorus pesticide described in gas chromatography determination and the matrix hybrid standard working solution of pyrethroid pesticide, qualitative with chromatographic peak retention time, then take mass concentration as horizontal ordinate, draw out the typical curve of organophosphorus pesticide and pyrethroid pesticide take chromatographic peak area as ordinate;
Wherein, the chromatographic condition of mensuration organophosphorus pesticide is:
Chromatographic column: the capillary chromatographic column that model is DB-1701, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 ℃, dottle pin purges 3mL/min; Column temperature: 90 ℃ of initial temperatures, keep 1min, 20 ℃/min rises to 200 ℃, keeps 9min, and 30 ℃/min rises to 245 ℃, keeps 8min; Carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 3mL/min; Detecting device: flame photometric detector (FPD); Detector temperature: 245 ℃; Hydrogen: flow is 75mL/min; Air: flow is 100mL/min; Make-up gas: high pure nitrogen, flow is 60mL/min;
The chromatographic condition of measuring pyrethroid pesticide is:
Chromatographic column: the capillary chromatographic column that model is HP-5, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 ℃, dottle pin purges 3mL/min; Column temperature: 80 ℃ of initial temperatures, keep 0.3min, 30 ℃/min rises to 180 ℃, keeps 5min, and 20 ℃/min rises to 260 ℃, keeps 23min: carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 1mL/min; Detecting device: micro-pond electron capture detector; Detector temperature: 300 ℃; Make-up gas: high pure nitrogen, 60mL/min;
Part II, measures 7 kinds of organophosphorus pesticides and 7 kinds of pyrethroid pesticide residual quantities in Part I described in pedotheque, and analytical approach comprises the following steps:
The first step, extracts pedotheque;
Take the pedotheque of having pulverized, be placed in 50mL centrifuge tube, in centrifuge tube, add 2mL ultrapure water again, vortex mixes, and infiltrate 10～20min, then to add containing volume fraction is the acetonitrile solution of 1% acetic acid, wherein, the input ratio of described pedotheque and described acetonitrile solution, for to dropping into acetonitrile solution described in 1mL in every 0.5g pedotheque, mixes ultrasonic extraction 10～15min; Add again anhydrous sodium acetate and anhydrous magnesium sulfate, wherein, described pedotheque, anhydrous sodium acetate and anhydrous magnesium sulfate three's mass ratio is 5:2:2, vortex 1.5min～2.5min, with the centrifugal 3.5min～4.5min of rotating speed of 9000r/min, get supernatant and be pedotheque extract to be clean;
Second step, purifies described pedotheque extract to be clean;
Separately get a 10mL centrifuge tube, add C18, N-propyl group ethylenediamine and anhydrous magnesium sulfate, add described pedotheque extract to be clean, wherein, the content of C18, N-propyl group ethylenediamine and the anhydrous magnesium sulfate dropping in pedotheque extract to be clean is respectively 37.5mg/mL, 37.5mg/mL and 75mg/mL, vortex 1.5min～2.5min, with the centrifugal 4.5min～5.5min of rotating speed of 9000r/min; After centrifugal, pipette in 2 portions of supernatants to 2 scale test tube, every portion of supernatant is 1.5mL, under 50～60 ℃ of water-baths, every portion of supernatant is slowly blown to 50～70 μ L with nitrogen; In a supernatant, add acetone to be settled to 0.75mL therein again, cross after organic system filter membrane, obtain the pedotheque extraction and cleaning liquid for measuring organophosphorus pesticide, in another portion of supernatant, add normal hexane to be settled to 0.75mL, cross after organic system filter membrane, obtain for measuring the residual pedotheque extraction and cleaning liquid of pyrethroid pesticide;
The 3rd step, residual with organophosphorus pesticide and pyrethroid pesticide in pedotheque extraction and cleaning liquid described in gas chromatography determination, record chromatographic peak retention time and chromatographic peak area, after qualitative by chromatographic peak retention time, the organophosphorus pesticide that the chromatographic peak area that described pedotheque extraction and cleaning liquid is detected and described Part I obtain and the typical curve of pyrethroid pesticide compare, the every kind of organophosphorus pesticide that obtains containing in described pedotheque extraction and cleaning liquid and the measured value of pyrethroid pesticide; Again described measured value is brought in quantitative computing formula, finally obtains organophosphorus pesticide residual quantity to be measured and pyrethroid pesticide residual quantity in pedotheque;
Quantitatively computing formula: ω=(ρ × v × f)/m, in formula: ω is organophosphorus pesticide residual quantity to be measured or pyrethroid pesticide residual quantity to be measured in pedotheque, and unit is mg/kg; ρ is measured value, and unit is mg/L; M is the sample size taking, and unit is g; V is constant volume, and unit is mL; F is extension rate;
Wherein, measure the chromatographic condition of organophosphorus pesticide in organophosphorus pesticide and the chromatographic condition of pyrethroid pesticide and the 3rd step of described Part I in described pedotheque extraction and cleaning liquid and pyrethroid pesticide identical.
Related content in technique scheme is explained as follows:
1, in such scheme, preferably scheme be the condition of ultrasonic extraction in the first step of described Part I and the first step of described Part II be ultrasonic power between 80W～100W, ultrasonic temperature is at 20～30 ℃.
2, in such scheme, the standard reserving solution mass concentration of described DDVP, Rogor, chlopyrifos, parathion-methyl, malathion, fenifrothion, Hostathion, Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, these 14 kinds of agricultural chemicals of decis is 1000mg/L, is purchased from Inst. of Environment Protection & Scientific Research Monitor, Ministry of Agric;
Normal hexane is HPLC level, and manufacturer is Oceanpak company of Sweden; Acetone is HPLC level, and manufacturer is Shanghai Chemical Reagent Co., Ltd., Sinopharm Group; N-propyl group ethylenediamine (English referred to as PSA), particle diameter is 40～60 μ m, manufacturer is Agela Technologies company of the U.S.; C18, aperture 6nm, granularity 40～60 μ m, manufacturer is Sepax Technologies company of the U.S.; Acetonitrile, acetic acid, anhydrous sodium acetate, anhydrous magnesium sulfate, all need be at 620 ℃ of calcination 4h, are analysis pure, and manufacturer is Shanghai Chemical Reagent Co., Ltd., Sinopharm Group; Experimental water is ultrapure water (18.4M Ω).
3, in such scheme, before the preparation matrix hybrid standard working solution of organophosphorus pesticide and the matrix hybrid standard working solution of pyrethroid pesticide, first prepare organophosphorus pesticide hybrid standard storing solution and pyrethroid pesticide hybrid standard storing solution, agricultural chemicals hybrid standard storing solution prepares to be placed in 4 ℃ of refrigerators and preserves, and is mixed with the agricultural chemicals matrix hybrid standard working solution of debita spissitudo when use take blank matrix extract as solvent;
Wherein, the compound method of organophosphorus pesticide hybrid standard storing solution is: 7 kinds of organophosphorus pesticide standard reserving solution concentration are 1000mg/L, get respectively 1mL and are placed in 5mL volumetric flask, use acetone diluted constant volume, being mixed with concentration is single mark solution of 200mg/L, preserves in-20 ℃ of lucifuge sealings.Response according to each agricultural chemicals on FPD detecting device, single mark solution DDVP is got 0.5mL, and Rogor, Hostathion are respectively got 2mL, and all the other organophosphorus list mark solution are respectively got 1mL, are placed in 10mL volumetric flask, use acetone constant volume.In 7 kinds of organophosphorus pesticide hybrid standard storing solutions: DDVP concentration is 10mg/L, chlopyrifos, parathion-methyl, fenifrothion, malathion concentration are respectively 20mg/L, and Rogor, Hostathion concentration are respectively 40mg/L;
The compound method of pyrethroid pesticide hybrid standard storing solution is: 7 kinds of pyrethroid pesticide standard reserving solution concentration are 1000mg/L, get respectively 1mL and be placed in 5mL volumetric flask, dilute constant volume with normal hexane, being mixed with concentration is single mark solution of 200mg/L, preserves in-20 ℃ of lucifuge sealings.Response according to each agricultural chemicals on μ ECD detecting device, single mark solution gamma cyhalothrin is got 0.1mL, and Fenpropathrin, cyfloxylate are respectively got 0.25mL, and all the other pyrethroid pesticide list mark solution are respectively got 0.5mL, be placed in 10mL volumetric flask, use normal hexane constant volume.In 7 kinds of pyrethroid pesticide hybrid standard storing solutions: gamma cyhalothrin concentration is 2mg/L, Fenpropathrin, cyfloxylate concentration are respectively 5mg/L, and Permethrin, cypermethrin, fenvalerate, decis concentration are respectively 10mg/L.
4, in such scheme, use 7 kinds of organophosphorus pesticides of gas chromatography determination and 7 kinds of pyrethroid pesticides, qualitative with retention time, peak area external standard method is quantitative; For the pyrethroid pesticide that contains more than 2 and 2 isomeride, calculate the measured value of this kind of pyrethroid pesticide with the peak area sum of each isomeride.
Principle of work of the present invention and beneficial effect are: 2003, the people such as the Anastassiades M of agricultural research service centre of United States Department of Agriculture have proposed one and have been called as " QuEChERS " (Quick, Easy, Cheap, Effective, Rugged and Safe) many residual sample of novel agrochemical preparation method.The method dirigibility is strong, and applied range can be per sample and the feature of target analytes, select applicable extraction solvent and purify filler, there is the advantages such as quick, easy, efficient, safe, be widely applied in food security field, and application report in soil is less.
During for organic phosphates and pyrethroid pesticide detection, need to distinguish sample preparation, the deficiency of pre-treatment complex operation, and soil matrix complexity, factor and less these present situations of examination criteria such as chaff interference is more, method that the present invention adopts improved " QuEChERS ", the extraction and purification methods of this two classes agricultural chemicals is carried out to combination, use capillary gas chromatography, on different detecting device FPD (being gas chromatographic flame photometric detector) and μ ECD (being micro-pond electron capture detector), measure respectively content, set up the carbamate insecticides of this two classes agricultural chemicals in soil, method is fast and convenient, save time reliable, improve accuracy of analysis, reduce experimentation cost, for soil quality control provides monitoring method and the foundation of science, there is certain popularizing value.
Soil pattern is the ultrasonic extraction of acetonitrile solution of 1% acetic acid with containing volume fraction, purify with appropriate PSA and C18 mixed fillers again, supernatant liquid nitrogen blows concentrated near dry, use respectively acetone and n-hexane dissolution constant volume, DB-1701 separates with HP-5 quartz capillary column and programmed temperature, GC/FPD and GC/ μ ECD detect, and finally use matrix external standard method quantitative.Adopt the calibration of matrix matching standard solution quantitatively, reduced the matrix effect of agricultural chemicals to be measured, measurement result is more accurate.Confirm by test, the method range of linearity is wide, the technical indicators such as detection sensitivity, accuracy and precision all meet the requirement of retention analysis, for organophosphorus in soil especially tea garden soil and pyrethroid pesticide remained analysis and research provide reliable means.
Compare with national standard method with existing Pesticide-Polluted Soil detection method, pre-treatment of the present invention is simple to operate, and extraction and cleanup only needs several steps to complete, and adopting ultrasonic method while extracting, result is stable, reproducible, facilitate the processing of follow-up batch sample, practicality is stronger; Purification process avoids using decontaminating column and a large amount of solvent elution, and agricultural chemicals loss is few, and the recovery is high, and the time and the organic solvent that expend greatly reduce simultaneously, save testing cost, and environmental pollution is little, also safer to operator.Detect and analyze the conventional gas chromatograph (being furnished with FPD and μ ECD) in employing laboratory, moderate cost, Operation and Maintenance is simple, and technical requirement is strict not as application of gas chromatorgraphy/mass, is more suitable for applying in testing agency of vast basic unit.Quantivative approach adopts the calibration of matrix matching standard solution quantitatively, has reduced the matrix effect of agricultural chemicals to be measured, and measurement result is more accurate.Analytical approach of the present invention can be measured organophosphorus and pyrethroid pesticide remained amount in soil simultaneously, fast and easy, and on the indices such as accuracy, precision, sensitivity, all meet the requirement that pesticide multi-residues is analyzed, for soil quality control provides monitoring method and the foundation of science, there is certain popularizing value.
Accompanying drawing explanation
Accompanying drawing 1 is the matrix hybrid standard working solution chromatogram of 7 kinds of organophosphorus pesticides in the embodiment of the present invention;
Accompanying drawing 2 is the matrix hybrid standard working solution chromatogram of 7 kinds of pyrethroid pesticides in the embodiment of the present invention;
Accompanying drawing 3 is 14 kinds of agricultural chemicals matrix effect figure in soil in the embodiment of the present invention;
Accompanying drawing 4 is for adding 7 kinds of organophosphorus pesticide standard colors spectrograms for the soil of the recovery and precision mensuration in the embodiment of the present invention;
Accompanying drawing 5 is for adding 7 kinds of pyrethroid pesticide standard colors spectrograms for the soil of the recovery and precision mensuration in the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment: one is measured organic phosphates and pyrethroid pesticide remained quantitative analysis method in soil simultaneously
Be yellow soil for examination soil, gather from the tea place in area, Dongshan, Suzhou, sampling depth is 0～15cm.Soil sample is removed to the foreign material such as grass roots, stone, manually smash to pieces, in basin or other appropriate vessel, fully mix, get a certain amount of for subsequent use by inquartation, the pedotheque preparing should be analyzed as early as possible, preserves otherwise put into-20 ℃ of refrigerators, and physiochemical properties of soil is: pH4.1～4.7, clay content 14%～17%, the content of organic matter 23.41～59.83g/kg.Described analytical approach is made up of two parts:
Part I, sets up respectively the tested organophosphorus pesticide of known gradient concentration and the typical curve of pyrethroid pesticide by vapor-phase chromatography; The foundation of described typical curve is made up of following steps:
The first step, prepares blank matrix extract, and preparation method is made up of following steps:
(1) take 5.0g after measured not containing the blank pedotheque of tested organophosphorus pesticide and pyrethroid pesticide in 50mL centrifuge tube, in centrifuge tube, add 2mL ultrapure water again, vortex mixes, infiltrate 15min, add again 10mL to contain the acetonitrile solution that volume fraction is 1% acetic acid, mix, (ultrasonic power is between 80W～100W for ultrasonic extraction 10～15min, ultrasonic temperature is at 20～30 ℃), add 2g anhydrous sodium acetate and 2g anhydrous magnesium sulfate, vortex 2min, with the centrifugal 4min of 9000r/min rotating speed, get supernatant and be blank matrix extract to be clean,
(2) separately get a 10mL centrifuge tube, add 0.15g C18,0.15g N-propyl group ethylenediamine and 0.3g anhydrous magnesium sulfate, add blank matrix extract to be clean described in 4mL, vortex 1.5min～2.5min, with the centrifugal 4.5min～5.5min of rotating speed of 9000r/min; After centrifugal, pipette in 2 portions of supernatants to 2 scale test tube, every portion of supernatant is 1.5mL, then under 50～60 ℃ of water-baths, every portion of supernatant is slowly blown to 50～70 μ L with nitrogen; In a supernatant, add acetone to be settled to 0.75mL therein again, cross after organic system filter membrane, obtain the blank matrix extract for preparing organophosphorus pesticide, in another portion of supernatant, add normal hexane to be settled to 0.75mL, cross after 0.22 μ m organic system filter membrane, obtain the blank matrix extract of pyrethroid pesticide;
Second step, prepare respectively the matrix hybrid standard working solution of organophosphorus pesticide and the matrix hybrid standard working solution of pyrethroid pesticide take the blank matrix extract that obtains in the described first step as solvent, wherein, described organophosphorus pesticide refers to DDVP, Rogor, chlopyrifos, parathion-methyl, malathion, fenifrothion, Hostathion, and described pyrethroid pesticide refers to Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis; In the matrix hybrid standard working solution of described organophosphorus pesticide, in the concentration range of each organophosphorus pesticide and the matrix hybrid standard working solution of described pyrethroid pesticide, the concentration range of each pyrethroid pesticide is:
| Agricultural chemicals | Concentration range/ |
| ? | (mg/L) |
| DDVP | 0.01～1.0 |
| Rogor | 0.04～4.0 |
| Chlopyrifos | 0.02～2.0 |
| Parathion-methyl | 0.02～2.0 |
| Malathion | 0.02～2.0 |
| Fenifrothion | 0.02～2.0 |
| Hostathion | 0.04～4.0 |
| Fenpropathrin | 0.01～1.0 |
| Gamma cyhalothrin | 0.004～0.4 |
| Permethrin | 0.02～2.0 |
| Cyfloxylate | 0.01～1.0 |
| Cypermethrin | 0.02～2.0 |
| Fenvalerate | 0.02～2.0 |
| Decis | 0.02～2.0 |
The 3rd step, with chromatographic peak retention time and the chromatographic peak area of each pesticide composition in the matrix hybrid standard working solution of organophosphorus pesticide described in gas chromatography determination and the matrix hybrid standard working solution of pyrethroid pesticide, qualitative with chromatographic peak retention time, then take mass concentration as horizontal ordinate, draw out the typical curve of organophosphorus pesticide and pyrethroid pesticide take chromatographic peak area as ordinate;
Wherein, the chromatographic condition of mensuration organophosphorus pesticide is:
Chromatographic column: the capillary chromatographic column that model is DB-1701, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 ℃, dottle pin purges 3mL/min; Column temperature: 90 ℃ of initial temperatures, keep 1min, 20 ℃/min rises to 200 ℃, keeps 9min, and 30 ℃/min rises to 245 ℃, keeps 8min; Carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 3mL/min; Detecting device: flame photometric detector (FPD); Detector temperature: 245 ℃; Hydrogen: flow is 75mL/min; Air: flow is 100mL/min; Make-up gas: high pure nitrogen, flow is 60mL/min;
The chromatographic condition of measuring pyrethroid pesticide is:
Chromatographic column: the capillary chromatographic column that model is HP-5, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 ℃, dottle pin purges 3mL/min; Column temperature: 80 ℃ of initial temperatures, keep 0.3min, 30 ℃/min rises to 180 ℃, keeps 5min, and 20 ℃/min rises to 260 ℃, keeps 23min: carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 1mL/min; Detecting device: micro-pond electron capture detector; Detector temperature: 300 ℃; Make-up gas: high pure nitrogen, 60mL/min;
Part II, measures 7 kinds of organophosphorus pesticides and 7 kinds of pyrethroid pesticide residual quantities in Part I described in pedotheque, and analytical approach comprises the following steps:
The first step, extracts pedotheque;
Take the pedotheque that 5.0g has pulverized, be placed in 50mL centrifuge tube, in centrifuge tube, add 2mL ultrapure water again, vortex mixes, infiltrate 15min, then add 10mL to contain the acetonitrile solution that volume fraction is 1% acetic acid, mix, ultrasonic extraction 12min (ultrasonic power is between 80W～100W, and ultrasonic temperature is at 20～30 ℃); Add 2g anhydrous sodium acetate and 2g anhydrous magnesium sulfate, vortex 2min, with the centrifugal 4min of rotating speed of 9000r/min, gets supernatant and is pedotheque extract to be clean again;
Second step, purifies described pedotheque extract to be clean;
Separately get a 10mL centrifuge tube, add 0.15g C18,0.15g N-propyl group ethylenediamine and 0.3g anhydrous magnesium sulfate, add described pedotheque extract to be clean, vortex 2min, with the centrifugal 5min of rotating speed of 9000r/min; After centrifugal, pipette in 2 portions of supernatants to 2 scale test tube, every portion of supernatant is 1.5mL, under 50～60 ℃ of water-baths, every portion of supernatant is slowly blown to 50～70 μ L with nitrogen; In a supernatant, add acetone to be settled to 0.75mL therein again, cross after organic system filter membrane, obtain the pedotheque extraction and cleaning liquid for measuring organophosphorus pesticide, in another portion of supernatant, add normal hexane to be settled to 0.75mL, cross after 0.22 μ m organic system filter membrane, obtain for measuring the residual pedotheque extraction and cleaning liquid of pyrethroid pesticide;
The 3rd step, residual with organophosphorus pesticide and pyrethroid pesticide in pedotheque extraction and cleaning liquid described in gas chromatography determination, record chromatographic peak retention time and chromatographic peak area, after qualitative by chromatographic peak retention time, the organophosphorus pesticide that the chromatographic peak area that described pedotheque extraction and cleaning liquid is detected and described Part I obtain and the typical curve of pyrethroid pesticide compare, the every kind of organophosphorus pesticide that obtains containing in described pedotheque extraction and cleaning liquid and the measured value of pyrethroid pesticide; Again described measured value is brought in quantitative computing formula, finally obtains organophosphorus pesticide residual quantity to be measured and pyrethroid pesticide residual quantity in pedotheque;
Quantitatively computing formula: ω=(ρ × v × f)/m, in formula: ω is organophosphorus pesticide residual quantity to be measured or pyrethroid pesticide residual quantity to be measured in pedotheque, and unit is mg/kg; ρ is measured value, and unit is mg/L; M is the sample size taking, and unit is g; V is constant volume, and unit is mL; F is extension rate;
Wherein, measure the chromatographic condition of organophosphorus pesticide in organophosphorus pesticide and the chromatographic condition of pyrethroid pesticide and the 3rd step of described Part I in described pedotheque extraction and cleaning liquid and pyrethroid pesticide identical.
In above embodiment, instrument and equipment used has: 7890A gas chromatograph, be furnished with flame photometric detector (FPD) (FPD), the micro-pond of 63Ni electron capture detector (μ ECD), 7693 automatic samplers and Chemstation chromatographic work station (Agilent company of the U.S.); KQ-500DE numerical control supersonic instrument (Kunshan Ultrasonic Instruments Co., Ltd.); TG16-WS table model high speed centrifuge (Hunan Xiang Yi Laboratory Instruments development corporation, Ltd.); HSC-24B Nitrogen evaporator (Tianjin Hengao Technology Development Co., Ltd.); K600 type comminutor (German Bo Lang company); VM-10 vortex oscillator (Daihan Scientific company of Korea S); SX2-4-10 muffle furnace (Shanghai leap Medical Devices Co., Ltd.); EXCEED-AD-24 type ultrapure water machine (Chengdu Tangshi Kangning Science and Technology Development Co., Ltd).
Medicine used and reagent: DDVP, Rogor, chlopyrifos, parathion-methyl, malathion, fenifrothion, Hostathion, Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis, mass concentration is 1000mg/L, is purchased from Inst. of Environment Protection & Scientific Research Monitor, Ministry of Agric; Normal hexane, HPLC level (Oceanpak company of Sweden); Acetone, HPLC level (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group); N-propyl group ethylenediamine (PSA), 40～60 μ m (Agela Technologies company of the U.S.); Ketjenblack EC (GCB), 120～400mesh (Agela Technologies company of the U.S.); C18, aperture 6nm, granularity 40～60 μ m (SepaxTechnologies company of the U.S.); Acetonitrile, acetic acid, anhydrous sodium acetate, anhydrous magnesium sulfate (620 ℃ of calcination 4h) are analyzes pure (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group); Experimental water is ultrapure water (18.4M Ω).
The preparation of hybrid standard storing solution:
The compound method of organophosphorus pesticide hybrid standard storing solution is: 7 kinds of organophosphorus pesticide standard reserving solution concentration are 1000mg/L, get respectively 1mL and be placed in 5mL volumetric flask, use acetone diluted constant volume, being mixed with concentration is single mark solution of 200mg/L, preserves in-20 ℃ of lucifuge sealings.Response according to each agricultural chemicals on FPD detecting device, single mark solution DDVP is got 0.5mL, and Rogor, Hostathion are respectively got 2mL, and all the other organophosphorus list mark solution are respectively got 1mL, are placed in 10mL volumetric flask, use acetone constant volume.In 7 kinds of organophosphorus pesticide hybrid standard storing solutions: DDVP concentration is 10mg/L, chlopyrifos, parathion-methyl, fenifrothion, malathion concentration are respectively 20mg/L, and Rogor, Hostathion concentration are respectively 40mg/L;
The compound method of pyrethroid pesticide hybrid standard storing solution is: 7 kinds of pyrethroid pesticide standard reserving solution concentration are 1000mg/L, get respectively 1mL and be placed in 5mL volumetric flask, dilute constant volume with normal hexane, being mixed with concentration is single mark solution of 200mg/L, preserves in-20 ℃ of lucifuge sealings.Response according to each agricultural chemicals on μ ECD detecting device, single mark solution gamma cyhalothrin is got 0.1mL, and Fenpropathrin, cyfloxylate are respectively got 0.25mL, and all the other pyrethroid pesticide list mark solution are respectively got 0.5mL, be placed in 10mL volumetric flask, use normal hexane constant volume.In 7 kinds of pyrethroid pesticide hybrid standard storing solutions: gamma cyhalothrin concentration is 2mg/L, Fenpropathrin, cyfloxylate concentration are respectively 5mg/L, and Permethrin, cypermethrin, fenvalerate, decis concentration are respectively 10mg/L.
Above-mentioned agricultural chemicals hybrid standard storing solution is all placed in 4 ℃ of refrigerators and preserves, and when use, is the matrix hybrid standard working fluid that solvent is mixed with respectively debita spissitudo with blank matrix extract.
The test findings of the present embodiment:
1, the gas chromatography of test agricultural chemicals separates
Adopt above-mentioned GC conditions to measure the matrix hybrid standard working solution of 7 kinds of organophosphorus pesticides and the matrix hybrid standard working solution of 7 kinds of pyrethroid pesticides, standard specimen separating effect is better, peak shape symmetry, and baseline stability, illustrates that instrument condition is applicable to.Under this chromatographic condition, the retention time of the each agricultural chemicals of organophosphorus is about respectively DDVP 5.941min, Rogor 13.099min, chlopyrifos 15.787min, parathion-methyl 15.915min, malathion 16.479min, fenifrothion 16.607min, Hostathion 22.684min is (shown in accompanying drawing 1, in accompanying drawing 1, label 1 is DDVP, concentration is 0.25mg/L, label 2 is Rogor, concentration is 1mg/L, label 3 is chlopyrifos, concentration is 0.5mg/L, label 4 is parathion-methyl, concentration is 0.5mg/L, label 5 is malathion, concentration is 0.5mg/L, label 6 is fenifrothion, concentration is 0.5mg/L, label 7 is Hostathion, concentration is 1mg/L), the each agricultural chemicals retention time of pyrethroid is about respectively Fenpropathrin 16.497min, gamma cyhalothrin 17.865min, Permethrin 19.400min, 19.693min, cyfloxylate 21.499min, cypermethrin 21.834min, 22.130min, 22.501min, fenvalerate 25.183min, 26.086min, (shown in accompanying drawing 2, in accompanying drawing 2, label 1 is Fenpropathrin to decis 28.760min, and concentration is 0.1mg/L, label 2 is gamma cyhalothrin, and concentration is 0.04mg/L, and label 3 is Permethrin, concentration is 0.2mg/L, and label 4 is cyfloxylate, and concentration is 0.1mg/L, label 5 is cypermethrin, concentration is 0.2mg/L, and label 6 is fenvalerate, and concentration is 0.2mg/L, label 7 is decis, and concentration is 0.2mg/L).
2, matrix effect
Matrix effect refers to the impact of the matrix components of other except determinand on determinand measured value in sample.Matrix effect is for the situation of different samples and determinand and difference.In gas chromatographic analysis, most of agricultural chemicals show matrix enhancement effect in various degree, be the agricultural chemicals of the same concentrations response in matrix than it height in neat solvent, the existence of being commonly considered as sample mesostroma composition has reduced the chance of chromatographic system avtive spot and determinand molecular action, and determinand detection signal is strengthened.The method of eliminating matrix effect impact has matrix matching standard solution method, standard addition method, multiple purifying method, analysis protectant application and statistical method correction etc.In the present invention, adopt the ratio of the response of determinand in matrix hybrid standard working solution and neat solvent mixed standard solution to represent matrix effect, ratio more approaches 1, shows that matrix effect is less.
Test findings shows, all there is matrix enhancement effect in various degree in 14 kinds of agricultural chemical compounds analyzing, wherein the matrix enhancement effect of Fenpropathrin, gamma cyhalothrin is not obvious, and the matrix effect of other 11 kinds of agricultural chemicals such as DDVP, Rogor is stronger, as shown in Figure 3.So the present invention, when quantitative by external standard method, is that solvent is prepared standard specimen with blank matrix extract, to eliminate matrix interference, reduces error.(in accompanying drawing 3, label 1 represents the matrix hybrid standard working solution and the neat solvent mixed standard solution that contain DDVP, and concentration is 0.05mg/L; Matrix hybrid standard working solution and the neat solvent mixed standard solution of label 2 for containing Rogor, concentration is 0.2mg/L; In like manner, label 3 represents to contain chlopyrifos, and concentration is 0.1mg/L; Label 4 represents to contain parathion-methyl, and concentration is 0.1mg/L; Label 5 represents to contain malathion, and concentration is 0.1mg/L; Label 6 is fenifrothion, and concentration is 0.1mg/L; Label 7 is Hostathion, and concentration is 0.2mg/L; Label 8 is Fenpropathrin, and concentration is 0.1mg/kg; Label 9 is gamma cyhalothrin, and concentration is 0.04mg/kg, and label 10 is Permethrin, and concentration is 0.2mg/kg; Label 11 is cyfloxylate, and concentration is 0.1mg/kg; Label 12 is cypermethrin, and concentration is 0.2mg/kg; Label 13 is fenvalerate, and concentration is 0.2mg/kg; Label 14 is decis, and concentration is 0.2mg/kg; Am represents the response of each agricultural chemicals in matrix matching mixed standard solution; As represents the response of each agricultural chemicals in neat solvent mixed standard solution).
3, the range of linearity of method, regression equation and detection limit
7 kinds of pyrethroid pesticide matrix mixed standard solutions of preparation mass concentration be 0.01～4.0mg/L 7 kinds of organophosphorus pesticide matrix mixed standard solutions and 0.004～2.0mg/L, measure by the organophosphorus pesticide in the 3rd step of described Part I and the chromatographic condition of pyrethroid pesticide respectively, (represent with ρ with mass concentration, unit is mg/L) be horizontal ordinate, take peak area (y) as ordinate drawing standard curve, 14 kinds of agricultural chemicals are good in its concentration range internal linear, related coefficient (r2) is all greater than 0.996, is shown in Table 1.Respectively with 3 times of noise signal in minimum interpolation horizontal chromatography figure and 10 times detection limit (LOD) and the quantitative limit (LOQ) of calculating each agricultural chemicals.As calculated, the LOD of 7 kinds of organophosphorus pesticides is between 0.0038～0.022mg/kg, and LOQ is between 0.013～0.072mg/kg; The LOD of 7 kinds of pyrethroid pesticides is between 0.0018～0.0088mg/kg, and LOQ is between 0.0058～0.029mg/kg, referring to below shown in table 1.
Table 1 is for the range of linearity, regression equation, related coefficient, detection limit and the quantitative limit of examination agricultural chemicals
4, the recovery of method and precision
Adopt blank sample mark-on method to carry out the method recovery and precision mensuration.Take 5.0g after measured not containing some parts of the blank pedotheque for examination agricultural chemicals, add respectively the agricultural chemicals hybrid standard working fluid of 3 kinds of variable concentrations levels, the interpolation level of organophosphorus pesticide is 0.025～1.0mg/kg, the interpolation level of pyrethroid pesticide is 0.01～0.5mg/kg, parallel 3 duplicate samples of each concentration level, after vortex mixes, standing 1h makes standard solution fully be absorbed by sample, carries out sample pre-treatments and chromatographic condition mensuration according to described Part II.Adopt matrix external standard method quantitative, calculate average recovery rate and the relative standard deviation (being RSD) thereof of each agricultural chemicals, ginseng is shown in Table 2, and sample mark-on chromatogram is referring to accompanying drawing 4 and accompanying drawing 5.
As shown in Table 2, in soil, the average recovery rate of organophosphorus pesticide is that 73.9%～96.6%, RSD (n=3) is 1.3%～9.4%; The average recovery rate of pyrethroid pesticide is that 91.6%～100.3%, RSD (n=3) is 1.3%～9.8%, and illustration method has good accuracy and repeatability.
Table 214 kind reclaims result (n=3) for trying the interpolation of agricultural chemicals in soil
Wherein, in accompanying drawing 4, label 1 is DDVP, and concentration is 0.25mg/L, label 2 is Rogor, and concentration is 1mg/L, and label 3 is chlopyrifos, concentration is 0.5mg/L, and label 4 is parathion-methyl, and concentration is 0.5mg/L, label 5 is malathion, concentration is 0.5mg/L, and label 6 is fenifrothion, and concentration is 0.5mg/L, label 7 is Hostathion, and concentration is 1mg/L; In accompanying drawing 5, label 1 is Fenpropathrin, and concentration is 0.1mg/L, and label 2 is gamma cyhalothrin, concentration is 0.04mg/L, and label 3 is Permethrin, and concentration is 0.2mg/L, label 4 is cyfloxylate, concentration is 0.1mg/L, and label 5 is cypermethrin, and concentration is 0.2mg/L, label 6 is fenvalerate, concentration is 0.2mg/L, and label 7 is decis, and concentration is 0.2mg/L.
5, actual sample analysis
Adopt this method to the pedotheque of taking from local certain tea plantation in Suzhou totally 16 parts carried out 14 kinds of Detecting Pesticide, wherein 4 parts all detect effective cypermethrin, and content is respectively 0.0107mg/kg, 0.0075mg/kg, 0.0134mg/kg, 0.0086mg/kg; 1 part detects cyfloxylate, and content is 0.038mg/kg.Result of study shows, this method can be used for the detection of 14 kinds of residues of pesticides in soil.
Above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that Spirit Essence is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (2)
1. measure organic phosphates and a pyrethroid pesticide remained quantitative analysis method in soil simultaneously, it is characterized in that: described analytical approach is made up of two parts:
Part I, sets up respectively the tested organophosphorus pesticide of known gradient concentration and the typical curve of pyrethroid pesticide by vapor-phase chromatography; The foundation of described typical curve is made up of following steps:
The first step, prepares blank matrix extract, and preparation method is made up of following steps:
(1) take 5.0 g after measured not containing the blank pedotheque of tested organophosphorus pesticide and pyrethroid pesticide in 50 mL centrifuge tubes, in centrifuge tube, add 2 mL ultrapure waters again, vortex mixes, infiltrate 10～20min, adding 10 mL is the acetonitrile solution of 1% acetic acid containing volume fraction again, mix, ultrasonic extraction 10～15 min, add 2 g anhydrous sodium acetates and 2 g anhydrous magnesium sulfates, vortex 2 min, with the centrifugal 4min of 9000 r/min rotating speed, get supernatant and be blank matrix extract to be clean;
(2) separately get 10 mL centrifuge tubes, add 0.15g C18,0.15g N-propyl group ethylenediamine and 0.3g anhydrous magnesium sulfate, add blank matrix extract to be clean described in 4mL, vortex 1.5min ~ 2.5min, with the centrifugal 4.5min ~ 5.5min of rotating speed of 9000 r/min; After centrifugal, pipette in 2 portions of supernatants to 2 scale test tube, every portion of supernatant is 1.5 mL, then under 50～60 ℃ of water-baths, every portion of supernatant is slowly blown to 50 ~ 70 μ L with nitrogen; In a supernatant, add acetone to be settled to 0. 75 mL therein again, cross after organic system filter membrane, obtain the blank matrix extract for preparing organophosphorus pesticide, in another portion of supernatant, add normal hexane to be settled to 0. 75 mL, cross after organic system filter membrane, obtain the blank matrix extract of pyrethroid pesticide;
Second step, prepare respectively the matrix hybrid standard working solution of organophosphorus pesticide and the matrix hybrid standard working solution of pyrethroid pesticide take the blank matrix extract that obtains in the described first step as solvent, wherein, described organophosphorus pesticide refers to DDVP, Rogor, chlopyrifos, parathion-methyl, malathion, fenifrothion, Hostathion, and described pyrethroid pesticide refers to Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis; In the matrix hybrid standard working solution of described organophosphorus pesticide, in the concentration range of each organophosphorus pesticide and the matrix hybrid standard working solution of described pyrethroid pesticide, the concentration range of each pyrethroid pesticide is:
The 3rd step, with chromatographic peak retention time and the chromatographic peak area of each pesticide composition in the matrix hybrid standard working solution of organophosphorus pesticide described in gas chromatography determination and the matrix hybrid standard working solution of pyrethroid pesticide, qualitative with chromatographic peak retention time, then take mass concentration as horizontal ordinate, draw out the typical curve of organophosphorus pesticide and pyrethroid pesticide take chromatographic peak area as ordinate;
Wherein, the chromatographic condition of mensuration organophosphorus pesticide is:
Chromatographic column: the capillary chromatographic column that model is DB-1701, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 ℃, dottle pin purges 3mL/min; Column temperature: 90 ℃ of initial temperatures, keep 1min, 20 ℃/min rises to 200 ℃, keeps 9min, and 30 ℃/min rises to 245 ℃, keeps 8min; Carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 3mL/min; Detecting device: flame photometric detector (FPD); Detector temperature: 245 ℃; Hydrogen: flow is 75 mL/min; Air: flow is 100 mL/min; Make-up gas: high pure nitrogen, flow is 60mL/min;
The chromatographic condition of measuring pyrethroid pesticide is:
Chromatographic column: the capillary chromatographic column that model is HP-5, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 ℃, dottle pin purges 3mL/min; Column temperature: 80 ℃ of initial temperatures, keep 0.3min, 30 ℃/min rises to 180 ℃, keeps 5min, and 20 ℃/min rises to 260 ℃, keeps 23min: carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 1mL/min; Detecting device: micro-pond electron capture detector; Detector temperature: 300 ℃; Make-up gas: high pure nitrogen, 60mL/min;
Part II, measures 7 kinds of organophosphorus pesticides and 7 kinds of pyrethroid pesticide residual quantities in Part I described in pedotheque, and analytical approach comprises the following steps:
The first step, extracts pedotheque;
Take the pedotheque of having pulverized, be placed in 50 mL centrifuge tubes, in centrifuge tube, add 2 mL ultrapure waters again, vortex mixes, and infiltrate 10～20min, then to add containing volume fraction is the acetonitrile solution of 1% acetic acid, wherein, the input ratio of described pedotheque and described acetonitrile solution, for to dropping into acetonitrile solution described in 1mL in every 0.5g pedotheque, mixes ultrasonic extraction 10～15 min; Add again anhydrous sodium acetate and anhydrous magnesium sulfate, wherein, described pedotheque, anhydrous sodium acetate and anhydrous magnesium sulfate three's mass ratio is 5:2:2, vortex 1.5min ~ 2.5min, with the centrifugal 3.5min ~ 4.5min of rotating speed of 9000 r/min, get supernatant and be pedotheque extract to be clean;
Second step, purifies described pedotheque extract to be clean;
Separately get 10 mL centrifuge tubes, add C18, N-propyl group ethylenediamine and anhydrous magnesium sulfate, add described pedotheque extract to be clean, wherein, the content of C18, N-propyl group ethylenediamine and the anhydrous magnesium sulfate dropping in pedotheque extract to be clean is respectively 37.5mg/mL, 37.5mg/mL and 75mg/mL, vortex 1.5min ~ 2.5min, with the centrifugal 4.5min ~ 5.5min of rotating speed of 9000 r/min; After centrifugal, pipette in 2 portions of supernatants to 2 scale test tube, every portion of supernatant is 1.5 mL, under 50～60 ℃ of water-baths, every portion of supernatant is slowly blown to 50 ~ 70 μ L with nitrogen; In a supernatant, add acetone to be settled to 0. 75 mL therein again, cross after organic system filter membrane, obtain the pedotheque extraction and cleaning liquid for measuring organophosphorus pesticide, in another portion of supernatant, add normal hexane to be settled to 0. 75 mL, cross after organic system filter membrane, obtain for measuring the residual pedotheque extraction and cleaning liquid of pyrethroid pesticide;
The 3rd step, residual with organophosphorus pesticide and pyrethroid pesticide in pedotheque extraction and cleaning liquid described in gas chromatography determination, record chromatographic peak retention time and chromatographic peak area, after qualitative by chromatographic peak retention time, the organophosphorus pesticide that the chromatographic peak area that described pedotheque extraction and cleaning liquid is detected and described Part I obtain and the typical curve of pyrethroid pesticide compare, the every kind of organophosphorus pesticide that obtains containing in described pedotheque extraction and cleaning liquid and the measured value of pyrethroid pesticide; Again described measured value is brought in quantitative computing formula, finally obtains organophosphorus pesticide residual quantity to be measured and pyrethroid pesticide residual quantity in pedotheque;
Quantitatively computing formula: ω=(ρ × v × f)/m, in formula: ω is organophosphorus pesticide residual quantity to be measured or pyrethroid pesticide residual quantity to be measured in pedotheque, and unit is mg/kg; ρ is measured value, and unit is mg/L; M is the sample size taking, and unit is g; V is constant volume, and unit is mL; F is extension rate;
Wherein, measure the chromatographic condition of organophosphorus pesticide in organophosphorus pesticide and the chromatographic condition of pyrethroid pesticide and the 3rd step of described Part I in described pedotheque extraction and cleaning liquid and pyrethroid pesticide identical.
2. according to claim 1ly measure organic phosphates and pyrethroid pesticide remained quantitative analysis method in soil simultaneously, it is characterized in that: in the first step of described Part I and the first step of described Part II the condition of ultrasonic extraction be ultrasonic power between 80W ~ 100W, ultrasonic temperature is at 20～30 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104407090A (en) * | 2014-12-30 | 2015-03-11 | 郭庆龙 | Method for determining residue of spirotetramat in fruits and vegetables by GC-NCI-MS (gas chromatography-negative chemical ionization-mass spectrometry) |
| CN105891354A (en) * | 2016-03-31 | 2016-08-24 | 山东五洲检测有限公司 | Detection method for content of fenthion in sorghum planting soil |
| CN106198519A (en) * | 2016-07-05 | 2016-12-07 | 广州市食品检验所 | The ninhydrin colorimetry of cypermethrin content in a kind of quick detection vegetable or fruit |
| CN106442781A (en) * | 2016-09-20 | 2017-02-22 | 浙江省海洋水产研究所 | Ultra-high performance liquid chromatography-mass spectrometry detection method of triazophos in bottom mud sediment |
| CN106483232A (en) * | 2016-10-18 | 2017-03-08 | 山东拜尔检测有限公司 | The method for quick of Multiple Pesticides residual in a kind of soil |
| CN108845053A (en) * | 2018-07-11 | 2018-11-20 | 内蒙古恒胜测试科技有限公司 | The method of six six six and DDT in ultrasonic extraction-Soil by Gas Chromatography |
| CN112129873A (en) * | 2020-09-22 | 2020-12-25 | 广州中科检测技术服务有限公司 | Method for detecting cyanophos pesticide residue in soil |
| CN112730672A (en) * | 2020-12-23 | 2021-04-30 | 武汉市农业科学院 | Method for rapidly determining organophosphorus pesticide residue in soil |
| CN112946141A (en) * | 2021-03-15 | 2021-06-11 | 上海国齐检测技术有限公司 | Method for detecting phosmet in soil |
| CN112946147A (en) * | 2021-02-03 | 2021-06-11 | 东华理工大学 | Pretreatment method for extracting pesticide residues in biological food |
| CN113203804A (en) * | 2021-04-07 | 2021-08-03 | 清华大学深圳国际研究生院 | Method for detecting organic phosphate in soil/sediment |
| CN113219093A (en) * | 2021-05-06 | 2021-08-06 | 河北百润环境检测技术有限公司 | Method for detecting pyridaphenthion, pyridaben, cypermethrin and lambda-cyhalothrin in soil or sediment |
| CN113607858A (en) * | 2021-09-02 | 2021-11-05 | 吉安市农产品质量安全检测中心(吉安市农产品质量安全监管局) | Vegetable pretreatment method and method for detecting contents of various pesticides in vegetables |
| CN113960197A (en) * | 2021-10-15 | 2022-01-21 | 中农新科(苏州)有机循环研究院有限公司 | Method for measuring 39 pesticide residues in soil or sediment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103472150A (en) * | 2013-09-22 | 2013-12-25 | 邬金飞 | Gas chromatography method for detecting pesticide residue amounts of seven pyrethroids in soil |
| CN103472175A (en) * | 2013-09-18 | 2013-12-25 | 邬金飞 | Gas chromatographic method for detecting residues of high-toxic organophosphorus pesticides in soil |
-
2014
- 2014-04-24 CN CN201410169609.1A patent/CN103913529B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103472175A (en) * | 2013-09-18 | 2013-12-25 | 邬金飞 | Gas chromatographic method for detecting residues of high-toxic organophosphorus pesticides in soil |
| CN103472150A (en) * | 2013-09-22 | 2013-12-25 | 邬金飞 | Gas chromatography method for detecting pesticide residue amounts of seven pyrethroids in soil |
Non-Patent Citations (4)
| Title |
|---|
| MIKI AKAMATSU ET AL.: "Pesticide Residue Analyses of Soils Collected from Suburban Agricultural Fields around Bangkok", 《TROP. AGR. DEVELOP》, vol. 57, no. 1, 31 December 2013 (2013-12-31) * |
| 周勇 等: "QuEChERS-气相色谱法检测苎麻及其土壤中8种有机磷农药残留", 《农药学学报》, vol. 15, no. 2, 31 December 2013 (2013-12-31) * |
| 徐倩 等: "茶叶有机磷及菊酯类农药残留检测中净化处理的研究", 《食品科学》, vol. 26, no. 8, 31 December 2005 (2005-12-31) * |
| 陈玲珑 等: "气相色谱法测定茶叶及土壤中的高效氯氟氰菊酯残留量", 《色谱》, vol. 28, no. 8, 31 August 2010 (2010-08-31) * |
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