CN105301124B - Assay method while organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide in surrounding medium - Google Patents
Assay method while organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide in surrounding medium Download PDFInfo
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Abstract
The invention discloses assay method while organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide in a kind of surrounding medium：(1) the solid waste sample containing organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide is gathered, takes air-drying sample or wet sample to carry out to be analyzed；(2) solid, semisolid matrix solid waste sample, the solid waste sample of fluid matrix, solid waste leachate are extracted using different extracting process；(3) sample purification is carried out to complex matrices environment by gel permeation chromatography automatic purification method and Solid phase extraction pattern；(4) pesticide composition content is separated and determined by gas-chromatography-mass spectrometry after the concentrated constant volume of sample after purifying.The present invention establishes the received text of the gaschromatographic mass spectrometry simultaneous analysis method of a set of solid waste and its leachate Pesticide Residues, the blank of the art standard is filled up, new environmental management requirement is adapted to, its detection limit disclosure satisfy that the requirement of existing control standard and environmental quality standards.
Description
Technical field
It is organic the present invention relates to a kind of assay method of surrounding medium Pesticide Residues, more particularly in a kind of surrounding medium
Assay method while phosphorus agricultural chemicals, pyrethrin pesticide and heterocyclic pesticide, belongs to environmental quality detection field.
Background technology
The residual of organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide directly affects quality of agricultural product in surrounding medium,
China has formulated the residual limit of organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide in more comprehensive food and agricultural product
Value, but in the relevant surrounding medium of existing promulgation such object control standard limited value except several toxicity are relatively strong and forbidden
Be almost blank outside the organophosphorus pesticide of production, the analysis method of such object that standard auxiliary is implemented also it is corresponding very
It is few.
Solid waste management is the most important thing of environmental protection management instantly, and Chinese Ministry of Environmental Protection has put into effect many solid waste administrative provisions,《Country
Hazardous Waste List》、《Hazardous waste judging standard》In standards and guidelines such as (0GB5085), some pesticide producing processes
The solid waste of middle generation, expired product are included into solid waste management area, and in real work, the mirror of the soil of pollution by pesticides
Not, the solid waste discriminating for being related to pesticide chemical happens occasionally.China is large agricultural country, organophosphorus pesticide, heterocyclic pesticide and chrysanthemum ester
Class agricultural chemicals is suffered from widely using in China, and part must be had in use and is flowed into surrounding medium (solid waste),
But corresponding discriminatory analysis program is almost blank, so then generates the contradiction between management and technical support.
The content of the invention
In order to solve the above technical problems, the present invention proposes organophosphorus pesticide in a kind of surrounding medium, pyrethrin pesticide and miscellaneous
Assay method while ring class agricultural chemicals, its energy effective detection goes out the residual of agricultural chemicals.
The GC conditions of this assay method are as follows：Quartz capillary column：A length of 30m, internal diameter is 0.32mm, and thickness is
0.25μm；Stationary phase is the 14% cyanogen propyl group dimethyl polysiloxane of phenyl -86%；Chromatogram column temperature is 40 DEG C of holding 1min, with
30 DEG C/min is warming up to 130 DEG C, then is warming up to 250 DEG C with 5 DEG C/min, then is warming up to 280 DEG C with 10 DEG C/min, keeps 5min；
Carrier gas uses helium, and its purity >=99.999%, flow velocity is 1.4ml/min；Injector temperature is 270 DEG C；GC/MS interface temperatures
For 280 DEG C；Sample size is 1 μ l；Mass spectrograph selects ion measurement method.
In order to achieve the above object, technical scheme is as follows：Organophosphorus pesticide, chrysanthemum esters in a kind of surrounding medium
Assay method while agricultural chemicals and heterocyclic pesticide, this method comprises the following steps：
(1) method object is selected：Gather the solid waste sample containing organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide
Product, take air-drying sample or wet sample to carry out to be analyzed；
(2) extraction of sample：To solid matrix sample, semisolid matrix solid waste sample, the solid waste sample of fluid matrix, solid
Useless leachate is extracted using different extracting process；
(3) purification of sample：By gel permeation chromatography automatic purification method and Solid phase extraction pattern to complicated base
Matter environment carries out sample purification；
(4) agricultural chemicals is separated and determined by gas-chromatography-mass spectrometry after the concentrated constant volume of sample after purifying
Constituent content.
Preferably, in step (2) to solid matrix sample and semisolid matrix solid waste sample using surname extraction or
Person's accelerated solvent extraction method；The solid waste sample and solid waste leachate of fluid matrix are extracted using liquid-liquid extraction method.
Preferably, using gel permeation chromatography or aminopropyl bonded silica gel Solid phase extraction pattern in step (3)
Purified treatment is carried out to matrix complex sample.
Preferably, carrying out sample analysis by gas chromatograph-Low Resolution Mass Spectra instrument in step (4).
Beneficial effects of the present invention：The present invention establishes organophosphorus pesticide in a set of solid waste and its leachate (37 kinds), chrysanthemum
The received text of the gas chromatography-mass spectrum simultaneous analysis method of ester pesticides (10 kinds) and heterocyclic pesticide (2 kinds), has filled up this
The blank of art standard, meanwhile, adapt to new environmental management requirement.The method detection limit of exploitation disclosure satisfy that existing control
The requirement of standard and environmental quality standards processed.
Brief description of the drawings
Fig. 1 is detection method flow chart of the invention；
Fig. 2 is pyrethrin pesticide total ion current figure；
Fig. 3 is organophosphorus pesticide and heterocyclic pesticide total ion current figure；
Embodiment
With reference to embodiment, the present invention is further detailed explanation.
As shown in figure 1, measure side while organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide in a kind of surrounding medium
Method：
The GC conditions of this assay method are as follows：Quartz capillary column：A length of 30m, internal diameter is 0.32mm, and thickness is
0.25μm；Stationary phase is the 14% cyanogen propyl group dimethyl polysiloxane of phenyl -86%；Chromatogram column temperature is 40 DEG C of holding 1min, with
30 DEG C/min is warming up to 130 DEG C, then is warming up to 250 DEG C with 5 DEG C/min, then is warming up to 280 DEG C with 10 DEG C/min, keeps 5min；
Carrier gas uses helium, and its purity >=99.999%, flow velocity is 1.4ml/min；Injector temperature is 270 DEG C；GC/MS interface temperatures
For 280 DEG C；Sample size is 1 μ l；Mass spectrograph selects ion measurement method.
Its specific assay method is as follows：
(1) method object is selected：Gather the solid waste sample containing organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide
Product, take air-drying sample or wet sample to carry out to be analyzed according to sample different qualities；
For current domestic organophosphor, chrysanthemum esters and heterocyclic pesticide production situation and existing surface water environment quality
The requirement of standard and wastewater discharge standard, creatively chooses more than the 90% conventional organophosphor agriculture for accounting for China's total output respectively
2 kinds of heterocyclics that 10 kinds most of pyrethroid active compound of 37 kinds of medicine, log-on count and Chinese Ministry of Environmental Protection's relevant criterion are clearly limited
Agricultural chemicals, such material is brought into same analysis detection architecture simultaneously.In this way, on the one hand ensuring that the method set up can be met
All kinds of environmental management requirements, make its popularity and applicability stronger；On the other hand the country that can change again for such material shows
There is the scattered and existing method of environment measuring standard method mainly for water quality or food, biological species medium, the phase in solid waste
The present situation that analysis method is almost blank is closed, so that the method set up according to body series can be as such in surrounding medium
The important reference of material.
(2) extraction of sample：To solid matrix sample, semisolid matrix solid waste sample using surname extraction, acceleration solvent
Extraction or other solid phase extractions patterns are extracted, and the solid waste sample, solid waste leachate to fluid matrix use liquid-liquid extraction side
Method is extracted.
(3) purification of sample：By gel permeation chromatography automatic purification method and Solid phase extraction pattern to complicated base
Matter environment carries out sample purification；
The matrix of solid waste sample is sufficiently complex, for the complexity problem, in order to improve sensitivity and the accuracy of analysis,
This method meets the requirement of purification analysis using gel permeation chromatography automatic purification method；On the other hand, it is contemplated that automation
The popularization of equipment not enough, is firstly introduced aminopropyl bonded silica gel Solid phase extraction pattern and carries out sample to complex matrices environment
Purification, to reduce pre-treatment expense.
(4) agricultural chemicals is separated and determined by gas-chromatography-mass spectrometry after the concentrated constant volume of sample after purifying
Constituent content, carries out sample analysis using gas chromatograph-Low Resolution Mass Spectra instrument in this step.
In such as Fig. 2, peak sequence：The trans allethrins of 1-；2- Biphenthrins；3,4- tetramethrins+Fenpropathrin；5- deinsectization
Chrysanthemum ester；6- Permethrins；The cis lambda-cyhalothrins of 7-；8- cypermethrins；9- fenvalerates；10- decises.
In such as Fig. 3, peak sequence：11- DDVP；12- Menites；13- demeton；14- thionazins；15- ethoprops；
16- thimets；17- sulfoteps；18- basudin；19- disulfotons；20- Rogor；21- Nankors；22- chlopyrifos；23,24- first
Base parathion+trichloronate；25,26,27- formothions+Entex+malathion；28,29- triadimefons+parathion；30,31,32,
33,34,35- Ruelene+thimet sulfone+Afos+Toyodan+merphos+Le Bensong；36- mephosfolans；37- carbophenothions；
38- Butacides；39,40- Frontlines+fensulfothion；41- Entex sulfones；42- 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfuric esters；43- fenisobromolates；44,45- bromobenzenes
Phosphorus+phenothiazide；46,47,48- fenamiphos sulfoxide+fenamiphos sulfone+pyraclofos；49- Resistox.
The validity for the standard method set up for checking, this six laboratory of laboratory federated environment monitoring system is to method
Verified, the result is as follows：
Embodiment one：
1. solid waste sample verifies conclusion
Detection limit and Determination Limit：When sample size is 10.0g, the method detection of object is limited to 0.2~1.4mg/kg,
Determination Limit is 0.8~5.6mg/kg.
Precision：6 laboratories are respectively to system of the solid waste sample Pesticides content for 1.0mg/kg and 5.0mg/kg
One sample is determined：Relative standard deviation is respectively 2.04%~39.2%, 0.068%~49.02% in laboratory；It is real
Relative standard deviation is respectively 4.36%~64.5%, 3.90%~116% between testing room；Repeatability limit is respectively 0.109mg/kg
~0.596mg/kg, 0.283mg/kg~2.19mg/kg；Repeatability limit is respectively 0.187mg/kg~1.16mg/kg,
0.613mg/kg~6.63mg/kg.
The degree of accuracy：6 laboratories are determined to solid waste matrix mark-on sample, and sample mark-on amount is not to be
1.0mg/kg and 5.0mg/kg, recovery of standard addition scope is respectively 51.8%~121%, 35.7%~89.2%.
2. leachate verifies conclusion
Detection limit and Determination Limit：When leachate is 500ml, the method detection of object is limited to 5.8~23.1 μ g/L,
Determination Limit is 23.2~92.4 μ g/L.
Precision：6 laboratories are carried out to leachate Pesticides content for 20 μ g/L and 100 μ g/L unified sample respectively
Determine：Relative standard deviation is respectively 1.06%~8.11%, 3.10%~42.4% in laboratory；Laboratory monitoring is relative to be marked
Quasi- deviation is respectively 5.95%~49.1%, 4.31%~50.8%；Repeatability limit is respectively the μ g/L of 4.43 μ g/L~12.3,
The μ g/L of 6.89 μ g/L~25.9；Repeatability limit is respectively the μ g/L of 5.02 μ g/L~23.7 μ g/L, 15.9 μ g/L~121.
The degree of accuracy：6 laboratories are determined to leachate matrix mark-on sample, and it is not 20 μ g/L that sample mark-on amount, which is,
With 100 μ g/L, recovery of standard addition scope is respectively 70.2%~105%, 76.0%~104%.
Embodiment two：
The Ningbo Chemical Co., Ltd. of the main production malathion of selection, and production lambda-cyhalothrin and Deltamethrin
The solid waste that Zhejiang Chemical Co., Ltd. produces carries out the measure of solid waste Pesticides content, the results are shown in Table 1 and 2.
The Ningbo Chemical Co., Ltd. solid waste testing result of table 1
The Zhejiang Chemical Co., Ltd. solid waste testing result of table 2
Embodiment three：
Certain pesticide producing base sludge of sewage treatment plant solid waste sample and its leachate sample is taken to carry out matrix mark-on parallel
Analysis.The actual solid waste samples of 6 parts of 10.0g are taken, 50 μ g standard items is separately added into and carries out matrix mark-on experiment, by pre-treatment
Afterwards, 1.0ml is settled to, with Instrumental Analysis, the precision and the rate of recovery (being shown in Table 3) of solid waste method is calculated, then take 6 parts
500ml sludge leachate samples, are separately added into 50 μ g standard specimens and carry out matrix mark-on experiment, after pre-treatment, be settled to
1.0ml, with Instrumental Analysis, calculates the precision and the rate of recovery (being shown in Table 4) of leachate method.
Measurement result during 3 solid waste sample matrices mark-on 5.0mg/kg of table
Measurement result during 4 solid waste leachate matrix 100 μ g/L of mark-on of table
Claims (2)
1. assay method while organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide in a kind of surrounding medium, its gas phase color
Spectral condition is as follows：Quartz capillary column：A length of 30m, internal diameter is 0.32mm, and thickness is 0.25 μm；Stationary phase is 14% cyanogen propyl group
The dimethyl polysiloxane of phenyl -86%；Chromatogram column temperature is 40 DEG C of holding 1min, and 130 DEG C are warming up to 30 DEG C/min, then with 5
DEG C/min is warming up to 250 DEG C, then is warming up to 280 DEG C with 10 DEG C/min, keeps 5min；Carrier gas uses helium, and its purity >=
99.999%, flow velocity is 1.4ml/min；Injector temperature is 270 DEG C；GC/MS interface temperatures are 280 DEG C；Sample size is 1 μ l；
Mass spectrograph selects ion measurement method, it is characterised in that the assay method of the agricultural chemicals comprises the following steps：
(1) method object is selected：The solid waste sample containing organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide is gathered,
Air-drying sample or wet sample is taken to carry out to be analyzed；
(2) extraction of sample：Surname extraction or accelerated solvent extraction are used to solid matrix sample, semisolid matrix solid waste sample
Take method；Solid waste sample, solid waste leachate to fluid matrix are extracted with liquid-liquid extraction method；
(3) purification of sample：Pass through gel permeation chromatography automatic purification method and aminopropyl bonded silica gel Solid phase extraction mould
Formula carries out sample purification to complex matrices environment；
(4) pesticide composition is separated and determined by gas-chromatography-mass spectrometry after the concentrated constant volume of sample after purifying
Content.
2. surveyed in surrounding medium according to claim 1 while organophosphorus pesticide, pyrethrin pesticide and heterocyclic pesticide
Determine method, it is characterised in that sample analysis is carried out by gas chromatograph-Low Resolution Mass Spectra instrument in step (4).
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| CN108732267A (en) * | 2018-04-19 | 2018-11-02 | 佛山市梅雨科技有限公司 | The detection method of TrinexAN_SNacethyl and carbofuran and its metabolin in a kind of soil |
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