CN108956826A - The extraction and detection method of pendimethalin in rice-fishing system cultivation aquatic products - Google Patents
The extraction and detection method of pendimethalin in rice-fishing system cultivation aquatic products Download PDFInfo
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- CN108956826A CN108956826A CN201810248486.9A CN201810248486A CN108956826A CN 108956826 A CN108956826 A CN 108956826A CN 201810248486 A CN201810248486 A CN 201810248486A CN 108956826 A CN108956826 A CN 108956826A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/04—Preparation or injection of sample to be analysed
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Abstract
The present invention provides the extractions and detection method of pendimethalin in a kind of rice-fishing system cultivation aquatic products, which includes: to weigh (5.00 ± 0.01) g ~ (10.00 ± 0.01) g aquatic products sample；The aquatic products sample is extracted at least twice using the ethyl acetate solution containing 0.1% acetic acid；The supernatant being obtained by extraction is rotated to dry；Using the residue after methanol/water solution (8:2, v/v contain 0.1% acetic acid) dissolution revolving, extraction concentrate is obtained；The extraction concentrate is purified using scavenging material.The present invention realizes the detection to pendimethalin in aquatic products, while ensure that the accuracy of detection by completely extracting pendimethalin from the aquatic products that rice-fishing system cultivates as far as possible.
Description
Technical field
The present invention relates to the Detection Technologies of Pesticide Residues field, in particular to two in a kind of rice-fishing system cultivation aquatic products
The extraction and detection method of penta spirit of first.
Background technique
Pendimethalin (Pendimethalin) belongs to dinitroaniline herbicide, have become be only second to glyphosate and
The third-largest herbicide after paraquat.Its main control object is annual gramineous weed, part broadleaf weeds, can be extensive
For the various crops farmland weeding such as corn and soybean, garlic, green onion, wild cabbage, tobacco, peanut, cotton, rice.With pendimethalin
A large amount of uses, the eco-toxicity of pendimethalin more and more causes the concern of people.Some researches show that pendimethalin is to water
Lively object has certain toxicity, and is mankind's suspecious carcinogen.Environmental Protection Agency pendimethalin classify in persistence,
Bioaccumulation and toxicant (toxicity category III), possible carcinogenic toxicity (grade C).With pushing away for rice fishing plant breeding model
Extensively, pendimethalin is residual in rice-fishing system cultivation aquatic products (such as Procambius clarkii, freshwater shrimp, the former chela crab of China, loach)
Problem is stayed increasingly to cause the care of people.Therefore, pendimethalin in rice-fishing system cultivation aquatic products is accurately detected
Seem particularly significant.
Summary of the invention
The embodiment of the invention provides the extraction of pendimethalin in a kind of rice-fishing system cultivation aquatic products and detection sides
Method is realized by completely extracting pendimethalin from the aquatic products that rice-fishing system cultivates as far as possible to diformazan penta in aquatic products
The detection of spirit, while ensure that the accuracy of detection.
The extracting method of pendimethalin in a kind of rice-fishing system cultivation aquatic products characterized by comprising
Weigh (5.00 ± 0.01) g ~ (10.00 ± 0.01) g aquatic products sample；
The aquatic products sample is extracted at least twice using the ethyl acetate solution containing 0.1% acetic acid；
The supernatant being obtained by extraction is rotated to dry；
Using the residue after methanol/water solution (8:2, v/v contain 0.1% acetic acid) dissolution revolving, extraction concentrate is obtained；
The extraction concentrate is purified using scavenging material.
Optionally,
It is described to extract the aquatic products sample at least twice using the ethyl acetate solution containing 0.1% acetic acid, comprising:
The ethyl acetate solution and the aquatic products sample blending of 0.1% acetic acid will be contained not less than 15mL, at room temperature sonic oscillation
Extract at least 5min；
It is centrifuged 5min at least 4000r/min, isolates supernatant liquor；
Repeat to extract supernatant liquor primary, that merging extraction and separation twice go out to the seabed sediment after separation.
Optionally,
It is described to purify the extraction concentrate using scavenging material, comprising:
After the concentrate peracidity alumina column, 0.1g ketjenblack EC powder is added, at least 4000r/min centrifugation
5min takes supernatant liquor.
Optionally,
Said extracted method further comprises:
The edible part of water intaking product is processed into no more than 0.5cm × 0.5cm × 0.5cm fritter, mixes, blend at a high speed simultaneously
It sufficiently stirs evenly, obtains aquatic products sample, seal, label is spare in -18 DEG C of freezen protectives.
Optionally,
The aquatic products sample, comprising:
The edible muscle parts of Procambius clarkii, the edible muscle parts of freshwater shrimp, Eriocheir sinensis edible part, the edible muscle portion of swamp eel
Point and the edible muscle parts of loach in any one.
The detection method of pendimethalin in a kind of rice-fishing system cultivation aquatic products, which is characterized in that using any of the above-described
The extracting method of pendimethalin, extracts pendimethalin from aquatic products sample, obtains in the rice-fishing system cultivation aquatic products
Obtain purified extraction concentrate；Further include:
Measure the purified extraction concentrate of 1mL；
It is detected by the extraction concentrate of the high performance liquid chromatography-series connection triple quadrupole mass spectrometer to measurement, wherein
Chromatographic condition: Symmetry C18 liquid-phase chromatographic column (100mm × 2.1mm × 3.5 μm)；Column temperature is 35 DEG C；Flow velocity is 0.3mL/
min；Mobile phase are as follows: A:80% methanol, B:20% water (contain 0.1% acetic acid), and sample volume is 10 μ L；Mass Spectrometry Conditions: heated atmospheric air piezoelectricity
Spraying HESI is as mass ion source；Ionization mode: positive ion mode；Scanning mode: selection ionic reaction monitoring pattern
(SRM)；Spray voltage: 3500V；Boil-off gas temperature: 200 DEG C；Sheath gas and auxiliary gas are high pure nitrogen, and pressure is 5bar；
Collision gas is high-purity argon gas, 1.5m Torr；Ion transfer capillary temperature: 350 DEG C；Q1 PW 0.7, Q3 PW 0.7.Monitoring
Ion pair: pendimethalin m/z:282.1/211.9(quota ion), 282.1/193.9, impact pressure is respectively 17V, 11V.
Optionally,
Further comprise:
Blank aquatic products sample is extracted with any of the above-described extracting method, blank sample solution is prepared；
The pendimethalin standard reserving solution that mass concentration is 100mg/L is prepared with methanol；
Dilute the pendimethalin standard reserving solution using the blank sample solution, prepare mass concentration be 1.0,2.0,5.0,
10.0, the bare substrate matching criteria liquid of 20.0 μ g/L；
Construct the relational expression between the chromatographic peak area and concentration of blank sequence matrix matching titer；
According to the peak area of the relational expression and detected pendimethalin, pendimethalin in aquatic products sample is calculated
Concentration.
Optionally,
The cultivation subject sample, comprising:
The edible muscle parts of Procambius clarkii, the edible muscle parts of freshwater shrimp, Eriocheir sinensis edible part, the edible muscle portion of swamp eel
Point and the edible muscle parts of loach in any one.
The embodiment of the invention provides the extraction of pendimethalin in a kind of rice-fishing system cultivation aquatic products and detection sides
Method, by weighing (5.00 ± 0.01) g ~ (10.00 ± 0.01) g aquatic products sample；It is molten using the ethyl acetate containing 0.1% acetic acid
Liquid extracts the aquatic products sample at least twice；The supernatant being obtained by extraction is rotated to dry；Using methanol/water solution (8:2,
V/v contains 0.1% acetic acid) residue after revolving is dissolved, obtain extraction concentrate；The extraction is purified using scavenging material to be concentrated
Liquid is detected by high performance liquid chromatography-series connection triple quadrupole mass spectrometer, by the experimental results showed that, said extracted mistake
Journey can to extract other miscellaneous than more completely extracting pendimethalin in aquatic products sample, while can avoid as far as possible
Matter, the integrality of extraction and the interference for reducing impurity, ensure that the accuracy of detection.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the extraction of pendimethalin in a kind of rice provided by one embodiment of the present invention-fishing system cultivation aquatic products
The flow chart of method；
Fig. 2 is the chromatogram of pendimethalin standard solution provided by one embodiment of the present invention；
Fig. 3 is the chromatogram of blank Procambius clarkii mark-on sample provided by one embodiment of the present invention.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments, based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Rice-fishing system refer in paddy field aquaculture product such as Procambius clarkii, freshwater shrimp, Eriocheir sinensis, swamp eel with
And loach etc., therefore rice-fishing system cultivation aquatic products are detected, aquatic products such as Procambius clarkii, blueness can be monitored
The safety of shrimp, Eriocheir sinensis, swamp eel and loach etc..In addition, since pendimethalin amount is very low, meanwhile, aquatic products
There are many impurity, therefore, it is necessary to be interfered with despumation by being extracted to pendimethalin existing for it, and be concentrated
Pendimethalin.And diformazan can be helped to improve than more completely extracting pendimethalin and reducing the extraction to impurity to the greatest extent
The accuracy of penta spirit detection.
As shown in Figure 1, the embodiment of the invention provides the extractions of pendimethalin in a kind of rice-fishing system cultivation aquatic products
Method, this method may comprise steps of:
Step 101: weighing (5.00 ± 0.01) g ~ (10.00 ± 0.01) g aquatic products sample；
Step 102: extracting the aquatic products sample at least twice using the ethyl acetate solution containing 0.1% acetic acid；
Step 103: the supernatant being obtained by extraction is rotated to dry；
Step 104: using the residue after methanol/water solution (8:2, v/v contain 0.1% acetic acid) dissolution revolving, obtaining extraction concentration
Liquid；
Step 105: purifying the extraction concentrate using scavenging material.
In the embodiment shown in fig. 1, by weighing (5.00 ± 0.01) g ~ (10.00 ± 0.01) g aquatic products sample；Benefit
The aquatic products sample is extracted at least twice with the ethyl acetate solution containing 0.1% acetic acid；By the supernatant being obtained by extraction rotate to
It is dry；Using the residue after methanol/water solution (8:2, v/v contain 0.1% acetic acid) dissolution revolving, extraction concentrate is obtained；Using net
Change and extract concentrate described in materials purification, is detected by high performance liquid chromatography-series connection triple quadrupole mass spectrometer, pass through reality
Test the result shows that, said extracted process can be than more completely extracting pendimethalin in aquatic products sample, while can to the greatest extent can
Avoiding for energy extracts other impurities, and the integrality of extraction and the interference for reducing impurity ensure that the accuracy of detection.
Throughout the extraction process, guarantee that pendimethalin is in always in the environment of 0.1% acetic acid, enable to diformazan penta
Spirit is constantly in stable state, to keep subsequent detection more accurate.
In an embodiment of the invention, in order to avoid extracting unnecessary impurity as far as possible, above-mentioned steps 102 are sharp
The specific embodiment of the aquatic products sample at least twice is extracted with the ethyl acetate solution containing 0.1% acetic acid: will be not less than
Ethyl acetate solution and the aquatic products sample blending of the 15mL containing 0.1% acetic acid, sonic oscillation extracts at least at room temperature
5min；It is centrifuged 5min at least 4000r/min, isolates supernatant liquor；Seabed sediment after separation is repeated to extract once,
Merge the supernatant liquor that extraction and separation twice go out.
During pendimethalin extracts in aquatic products, in order to as complete as possible from the fat of aquatic products
It is whole extract pendimethalin, and avoid other materials such as pigment and other impurities be extracted out, select ethyl acetate solution
Extraction at least twice, and when ethyl acetate is as extractant, extracts aquatic products sample, extract liquor clear,
The chromatogram miscellaneous peak of acquisition is less, and peak shape is good, and high sensitivity, the rate of recovery is up to 90% or so.Illustrate ethyl acetate solution conduct
Extractant, almost without the impurity in aquatic products is extracted, and the rate of recovery is high.
In addition, select the residue after methanol/water solution (8:2, v/v, contain 0.1% acetic acid) dissolution revolving, be because of methanol/
Aqueous solution (8:2, v/v contain 0.1% acetic acid) dissolved residue is during carrying out subsequent detection, the chromatographic peak of formation, peak width
It is relatively narrow, and peak shape is sharp, high sensitivity.
In addition, the preparation for aquatic products sample, comprising: for aquatic products decaptitating, decladding, edible muscle parts are taken, it can
Food muscle parts are cut into no more than 0.5cm × 0.5cm × 0.5cm fritter, are mixed, are mixed after being blended with high speed pulper, close
Envelope, it is spare in -18 DEG C of freezen protectives.
The specific embodiment of the extraction concentrate is purified using scavenging material: by the concentrate peracidity aluminium oxide
After column, 0.1g ketjenblack EC powder is added, 5min is centrifuged at least 4000r/min, takes supernatant liquor.By the purification process,
The rate of recovery of pendimethalin can be made to reach 95% or more, the rate of recovery is higher, so that the accuracy of subsequent detection is also higher.
Above-mentioned aquatic products sample, comprising: the edible muscle parts of Procambius clarkii, the edible muscle parts of freshwater shrimp, Sinensis
Any one in chela crab edible part, the edible muscle parts of swamp eel and the edible muscle parts of loach.
The detection method of pendimethalin in a kind of rice-fishing system cultivation aquatic products, comprising:
Using the extracting method of pendimethalin in any of the above-described rice-fishing system cultivation aquatic products, from aquatic products sample
Middle extraction pendimethalin obtains purified extraction concentrate；
Measure the purified extraction concentrate of 1mL；
It is detected by the extraction concentrate of the high performance liquid chromatography-series connection triple quadrupole mass spectrometer to measurement, wherein
Chromatographic condition: Symmetry C18 liquid-phase chromatographic column (100mm × 2.1mm × 3.5 μm)；Column temperature is 35 DEG C；Flow velocity is 0.3mL/
min；Mobile phase are as follows: A:80% methanol, B:20% water (contain 0.1% acetic acid), and sample volume is 10 μ L；Mass Spectrometry Conditions: heated atmospheric air piezoelectricity
Spraying HESI is as mass ion source；Ionization mode: positive ion mode；Scanning mode: selection ionic reaction monitoring pattern
(SRM)；Spray voltage: 3500V；Boil-off gas temperature: 200 DEG C；Sheath gas and auxiliary gas are high pure nitrogen, and pressure is 5bar；
Collision gas is high-purity argon gas, 1.5m Torr；Ion transfer capillary temperature: 350 DEG C；Q1 PW 0.7, Q3 PW 0.7.Monitoring
Ion pair: pendimethalin m/z:282.1/211.9(quota ion), 282.1/193.9, impact pressure is respectively 17V, 11V.
In order to verify the feasibility of said extracted method and detection method, according to said extracted method without pendimethalin
Blank Procambius clarkii tissue, and add the pendimethalin standard solution of certain content, the color provided using above-mentioned detection method
Spectral condition and Mass Spectrometry Conditions are detected, and are analyzed testing result, according to the flat of 7 blank sample organization baseline noises
Mean value is pressedS/N=3 HesS/NThe detection limit and quantitative limit of=10 calculation methods, respectively 0.2 μ g/kg and 0.6 μ g/kg, meet residual
Stay the requirement of analysis.
Chromatographic condition and Mass Spectrometry Conditions detection the pendimethalin standard provided according to said extracted method, detection method is molten
Liquid, blank Procambius clarkii mark-on sample, the chromatogram of acquisition is as shown in Figures 2 and 3, from figures 2 and 3, it will be seen that passing through
Above-mentioned chromatographic condition and Mass Spectrometry Conditions can make pendimethalin appearance time in 5min or so, and peak smoother is sharp, does not have
Hangover, peak shape are preferable.
The specific concentration of pendimethalin further comprises in an alternative embodiment of the invention in aquatic products in order to obtain:
Blank aquatic products sample is extracted with any of the above-described extracting method, blank sample solution is prepared；
The pendimethalin standard reserving solution that mass concentration is 100mg/L is prepared with methanol；
Dilute the pendimethalin standard reserving solution using the blank sample solution, prepare mass concentration be 1.0,2.0,5.0,
10.0, the bare substrate matching criteria liquid of 20.0 μ g/L；
Construct the relational expression between the chromatographic peak area and concentration of blank sequence matrix matching titer；
According to the peak area of the relational expression and detected pendimethalin, pendimethalin in aquatic products sample is calculated
Concentration.
Wherein, bare substrate matching criteria liquid is injected into the source ESI with peristaltic pump, to diformazan penta under positive ion detection mode
When spirit carries out first mass spectrometric analysis, using bare substrate matching criteria liquid with methanol/water solution (8:2, v/v contain 0.1% acetic acid)
Mobile phase injection mode, this kind of injection mode make object ion peak it is obvious that response it is higher.
Wherein, the specific side of the relational expression between the chromatographic peak area and concentration of blank sequence matrix matching titer is constructed
Formula:
It is that abscissa (X, mg/L) draws blank using the chromatographic peak area of pendimethalin as ordinate (Y), corresponding mass concentration
Matrix matching standard working curve.The results show that pendimethalin is linearly related within the scope of 1.0-20.0 μ g/L, linear equation is
Y=281453.07X+143052.24, related coefficient (R2) it is 0.9947.
The aquatic products sample that above-mentioned detection method is directed to, comprising: the edible muscle parts of Procambius clarkii, the edible muscle of freshwater shrimp
Partially, any one in the edible muscle parts of Eriocheir sinensis edible part, swamp eel and the edible muscle parts of loach.
In order to clearly demonstrate the extraction and detection method of pendimethalin in rice-fishing system cultivation aquatic products, under
It is unfolded to discuss with several specific embodiments in face.
The relational expression between chromatographic peak and pendimethalin concentration is constructed in advance:
Blank aquatic products sample is extracted, blank sample solution is prepared；
The pendimethalin standard reserving solution that mass concentration is 100mg/L is prepared with methanol；
Dilute the pendimethalin standard reserving solution using the blank sample solution, prepare mass concentration be 1.0,2.0,5.0,
10.0, the bare substrate matching criteria liquid of 20.0 μ g/L；
Construct the relational expression between the chromatographic peak area and concentration of blank sequence matrix matching titer；
It is that abscissa (X, mg/L) draws blank using the chromatographic peak area of pendimethalin as ordinate (Y), corresponding mass concentration
Matrix matching standard working curve.The results show that pendimethalin is linearly related within the scope of 1.0-20.0 μ g/L, linear equation is
Y=281453.07X+143052.24, related coefficient (R2) it is 0.9947；
Embodiment 1:
It extracts and detects in rice-Procambius clarkii mixed breeding system pendimethalin in Procambius clarkii and remain:
Procambius clarkii decaptitating, removes shrimp line at decladding, takes edible muscle parts, is processed into no more than 0.5cm × 0.5cm × 0.5cm
Fritter, mix, blend at a high speed and sufficiently stir evenly, obtain Procambius clarkii sample, seal, label, in -18 DEG C of freezen protectives,
It is spare；
(5.00 ± 0.01) g Procambius clarkii sample is weighed, is placed in 50mL tool plug centrifuge tube, 15mL is contained to the second of 0.1% acetic acid
Acetate solution and the Procambius clarkii sample, whirlpool mix 1min, and sonic oscillation extracts 5min at room temperature；With 5000r/
Min is centrifuged 5min, isolates supernatant liquor into chicken heart bottle；Repeat to extract primary, merging two to the seabed sediment after separation
The supernatant liquor that secondary extraction and separation go out；The supernatant being obtained by extraction is rotated to dry；Using 2mL methanol/water solution (8:2, v/v,
Containing 0.1% acetic acid) residue after revolving is dissolved, obtain extraction concentrate；After the concentrate peracidity alumina column, it is added
0.1g ketjenblack EC powder is centrifuged 5min with 5000r/min, takes supernatant liquor；
Measure 1mL supernatant liquor；It is concentrated by the extraction of the high performance liquid chromatography-series connection triple quadrupole mass spectrometer to measurement
Liquid is detected, wherein chromatographic condition: Symmetry C18 liquid-phase chromatographic column (100mm × 2.1mm × 3.5 μm)；Column temperature is 35
℃；Flow velocity is 0.3mL/min；Mobile phase are as follows: A:80% methanol, B:20% water (contain 0.1% acetic acid), and sample volume is 10 μ L；Mass spectrum item
Part: heated atmospheric air piezoelectric atomizer HESI is as mass ion source；Ionization mode: positive ion mode；Scanning mode: selection ion
Reaction monitoring mode (SRM)；Spray voltage: 3500V；Boil-off gas temperature: 200 DEG C；Sheath gas and auxiliary gas are high pure nitrogen, pressure
Power is 5bar；Collision gas is high-purity argon gas, 1.5m Torr；Ion transfer capillary temperature: 350 DEG C；Q1 PW 0.7, Q3
PW 0.7.Monitor ion pair: pendimethalin m/z:282.1/211.9(quota ion), 282.1/193.9, impact pressure difference
For 17V, 11V.
Embodiment 2:
It extracts and detects in rice-freshwater shrimp mixed breeding system pendimethalin in freshwater shrimp and remain:
Freshwater shrimp decaptitating, removes shrimp line at decladding, takes edible muscle parts, is processed into small no more than 0.5cm × 0.5cm × 0.5cm
Block mixes, blends at a high speed and sufficiently stir evenly, and obtains freshwater shrimp sample, seals, and label is spare in -18 DEG C of freezen protectives；
(8.00 ± 0.01) g freshwater shrimp sample is weighed, is placed in 50mL tool plug centrifuge tube, 25mL is contained to the ethyl acetate of 0.1% acetic acid
Solution and the freshwater shrimp sample, whirlpool mix 1min, and sonic oscillation extracts 10min at room temperature；It is centrifuged with 4000r/min
5min isolates supernatant liquor into chicken heart bottle；Repeat to extract primary, merging extraction point twice to the seabed sediment after separation
The supernatant liquor separated out；The supernatant being obtained by extraction is rotated to dry；Using 2mL methanol/water solution, (8:2, v/v contain 0.1% second
Acid) residue after revolving is dissolved, obtain extraction concentrate；After the concentrate peracidity alumina column, 0.1g graphite is added
Change carbon black powder, 5min is centrifuged with 6000r/min, takes supernatant liquor；
Measure 1mL supernatant liquor；It is concentrated by the extraction of the high performance liquid chromatography-series connection triple quadrupole mass spectrometer to measurement
Liquid is detected, wherein chromatographic condition: Symmetry C18 liquid-phase chromatographic column (100mm × 2.1mm × 3.5 μm)；Column temperature is 35
℃；Flow velocity is 0.3mL/min；Mobile phase are as follows: A:80% methanol, B:20% water (contain 0.1% acetic acid), and sample volume is 10 μ L；Mass spectrum item
Part: heated atmospheric air piezoelectric atomizer HESI is as mass ion source；Ionization mode: positive ion mode；Scanning mode: selection ion
Reaction monitoring mode (SRM)；Spray voltage: 3500V；Boil-off gas temperature: 200 DEG C；Sheath gas and auxiliary gas are high pure nitrogen, pressure
Power is 5bar；Collision gas is high-purity argon gas, 1.5m Torr；Ion transfer capillary temperature: 350 DEG C；Q1 PW 0.7, Q3
PW 0.7.Monitor ion pair: pendimethalin m/z:282.1/211.9(quota ion), 282.1/193.9, impact pressure difference
For 17V, 11V.
Embodiment 3:
It extracts and detects in rice-Eriocheir sinensis mixed breeding system pendimethalin in freshwater shrimp and remain:
Eriocheir sinensis decaptitating, decladding take edible muscle parts, are processed into no more than 0.5cm × 0.5cm × 0.5cm fritter,
It mixes, blends at a high speed and sufficiently stir evenly, obtain Eriocheir sinensis sample, seal, label is spare in -18 DEG C of freezen protectives；
(10.00 ± 0.01) g Eriocheir sinensis sample is weighed, is placed in 50mL tool plug centrifuge tube, by 35mL containing 0.1% acetic acid
Ethyl acetate solution and the Eriocheir sinensis sample, whirlpool mix 1min, and sonic oscillation extracts 10min at room temperature；With
8000r/min is centrifuged 5min, isolates supernatant liquor into chicken heart bottle；Seabed sediment after separation is repeated to extract once,
Merge the supernatant liquor that extraction and separation twice go out；The supernatant being obtained by extraction is rotated to dry；Using 2mL methanol/water solution (8:
2, v/v, contain 0.1% acetic acid) residue after revolving is dissolved, obtain extraction concentrate；By the concentrate peracidity alumina column
Afterwards, 0.1g ketjenblack EC powder is added, 5min is centrifuged with 5000r/min, takes supernatant liquor；
Measure 1mL supernatant liquor；It is concentrated by the extraction of the high performance liquid chromatography-series connection triple quadrupole mass spectrometer to measurement
Liquid is detected, wherein chromatographic condition: Symmetry C18 liquid-phase chromatographic column (100mm × 2.1mm × 3.5 μm)；Column temperature is 35
℃；Flow velocity is 0.3mL/min；Mobile phase are as follows: A:80% methanol, B:20% water (contain 0.1% acetic acid), and sample volume is 10 μ L；Mass spectrum item
Part: heated atmospheric air piezoelectric atomizer HESI is as mass ion source；Ionization mode: positive ion mode；Scanning mode: selection ion
Reaction monitoring mode (SRM)；Spray voltage: 3500V；Boil-off gas temperature: 200 DEG C；Sheath gas and auxiliary gas are high pure nitrogen, pressure
Power is 5bar；Collision gas is high-purity argon gas, 1.5m Torr；Ion transfer capillary temperature: 350 DEG C；Q1 PW 0.7, Q3
PW 0.7.Monitor ion pair: pendimethalin m/z:282.1/211.9(quota ion), 282.1/193.9, impact pressure difference
For 17V, 11V.
Embodiment 4:
It extracts and detects in rice-swamp eel mixed breeding system pendimethalin in freshwater shrimp and remain:
Swamp eel decaptitating takes edible muscle parts, is processed into no more than 0.5cm × 0.5cm × 0.5cm fritter, mixes, high-speed stirring
It is broken and sufficiently stir evenly, swamp eel sample is obtained, is sealed, label is spare in -18 DEG C of freezen protectives；
(5.00 ± 0.01) g swamp eel sample is weighed, is placed in 50mL tool plug centrifuge tube, 15mL is contained to the ethyl acetate of 0.1% acetic acid
Solution and the swamp eel sample, whirlpool mix 1min, and sonic oscillation extracts 10min at room temperature；It is centrifuged with 5000r/min
5min isolates supernatant liquor into chicken heart bottle；Repeat to extract primary, merging extraction point twice to the seabed sediment after separation
The supernatant liquor separated out；The supernatant being obtained by extraction is rotated to dry；Using 2mL methanol/water solution, (8:2, v/v contain 0.1% second
Acid) residue after revolving is dissolved, obtain extraction concentrate；After the concentrate peracidity alumina column, 0.1g graphite is added
Change carbon black powder, 5min is centrifuged with 4000r/min, takes supernatant liquor；
Measure 1mL supernatant liquor；It is concentrated by the extraction of the high performance liquid chromatography-series connection triple quadrupole mass spectrometer to measurement
Liquid is detected, wherein chromatographic condition: Symmetry C18 liquid-phase chromatographic column (100mm × 2.1mm × 3.5 μm)；Column temperature is 35
℃；Flow velocity is 0.3mL/min；Mobile phase are as follows: A:80% methanol, B:20% water (contain 0.1% acetic acid), and sample volume is 10 μ L；Mass spectrum item
Part: heated atmospheric air piezoelectric atomizer HESI is as mass ion source；Ionization mode: positive ion mode；Scanning mode: selection ion
Reaction monitoring mode (SRM)；Spray voltage: 3500V；Boil-off gas temperature: 200 DEG C；Sheath gas and auxiliary gas are high pure nitrogen, pressure
Power is 5bar；Collision gas is high-purity argon gas, 1.5m Torr；Ion transfer capillary temperature: 350 DEG C；Q1 PW 0.7, Q3
PW 0.7.Monitor ion pair: pendimethalin m/z:282.1/211.9(quota ion), 282.1/193.9, impact pressure difference
For 17V, 11V.
Embodiment 5:
It extracts and detects in rice-loach mixed breeding system pendimethalin in loach and remain:
Loach decaptitating takes edible muscle parts, is processed into no more than 0.5cm × 0.5cm × 0.5cm fritter, mixes, high-speed stirring
It is broken and sufficiently stir evenly, loach sample is obtained, is sealed, label is spare in -18 DEG C of freezen protectives；
(10.00 ± 0.01) g swamp eel sample is weighed, is placed in 50mL tool plug centrifuge tube, 40mL is contained to the acetic acid second of 0.1% acetic acid
Ester solution and the loach sample, whirlpool mix 1min, and sonic oscillation extracts 10min at room temperature；It is centrifuged with 4000r/min
10min isolates supernatant liquor into chicken heart bottle, repeats to extract once to the seabed sediment after separation, merging extracts twice
The supernatant liquor isolated；The supernatant being obtained by extraction is rotated to dry；Using 2mL methanol/water solution, (8:2, v/v contain 0.1%
Acetic acid) residue after revolving is dissolved, obtain extraction concentrate；After the concentrate peracidity alumina column, 0.1g stone is added
Inkization carbon black powder is centrifuged 5min with 7000r/min, takes supernatant liquor；
Measure 1mL supernatant liquor；It is concentrated by the extraction of the high performance liquid chromatography-series connection triple quadrupole mass spectrometer to measurement
Liquid is detected, wherein chromatographic condition: Symmetry C18 liquid-phase chromatographic column (100mm × 2.1mm × 3.5 μm)；Column temperature is 35
℃；Flow velocity is 0.3mL/min；Mobile phase are as follows: A:80% methanol, B:20% water (contain 0.1% acetic acid), and sample volume is 10 μ L；Mass spectrum item
Part: heated atmospheric air piezoelectric atomizer HESI is as mass ion source；Ionization mode: positive ion mode；Scanning mode: selection ion
Reaction monitoring mode (SRM)；Spray voltage: 3500V；Boil-off gas temperature: 200 DEG C；Sheath gas and auxiliary gas are high pure nitrogen, pressure
Power is 5bar；Collision gas is high-purity argon gas, 1.5m Torr；Ion transfer capillary temperature: 350 DEG C；Q1 PW 0.7, Q3
PW 0.7.Monitor ion pair: pendimethalin m/z:282.1/211.9(quota ion), 282.1/193.9, impact pressure difference
For 17V, 11V.
Embodiment 6:
It extracts and detects pendimethalin in rice-Procambius clarkii system Procambius clarkii:
It is extracted and testing conditions are consistent with embodiment 3, and details are not described herein.
Embodiment 7:
It extracts and detects pendimethalin in rice-Procambius clarkii system Procambius clarkii:
It is extracted and testing conditions are consistent with embodiment 5, and details are not described herein.
Embodiment 8:
It extracts and detects pendimethalin in rice-Procambius clarkii system Procambius clarkii:
It is extracted and testing conditions are consistent with embodiment 4, and details are not described herein.
Embodiment 9:
It extracts and detects pendimethalin in rice-Eriocheir sinensis system Procambius clarkii:
It is extracted and testing conditions are consistent with embodiment 1, and details are not described herein.
The testing result of above-described embodiment 1 to 9 shows that only 7 two samples of embodiment 1 and embodiment have pendimethalin inspection
Out, concentration is respectively 0.803 μ g/kg and 0.711 μ g/kg.
In order to further verify the feasibility of said extracted method and detection method, embodiment 1, embodiment 6 and reality are chosen
It applies example 8 and carries out recovery testu, recovery testu process: add basic, normal, high (1.2,6.0,12.0 μ g/kg) respectively
3 horizontal pendimethalin standard items, each pitch-based sphere do 7 parallel samples simultaneously.The relative standard deviation of calculated result
For 6.89%-14.52%(n=7), the rate of recovery is in 63.33%-104.65%(n=7).As shown in table 1.
Table 1
Above-described embodiment at least has the following beneficial effects:
1, by weighing (5.00 ± 0.01) g ~ (10.00 ± 0.01) g aquatic products sample；Utilize the ethyl acetate for containing 0.1% acetic acid
Solution extracts the aquatic products sample at least twice；The supernatant being obtained by extraction is rotated to dry；Using methanol/water solution (8:
2, v/v, contain 0.1% acetic acid) residue after revolving is dissolved, obtain extraction concentrate；The extraction is purified using scavenging material to be concentrated
Liquid is detected by high performance liquid chromatography-series connection triple quadrupole mass spectrometer, by the experimental results showed that, said extracted mistake
Journey can to extract other miscellaneous than more completely extracting pendimethalin in aquatic products sample, while can avoid as far as possible
Matter, the integrality of extraction and the interference for reducing impurity, ensure that the accuracy of detection.
2, in the aquatic products of rice provided in an embodiment of the present invention-fishing system cultivation pendimethalin extracting method, it is main logical
Pendimethalin can be extracted as extracted, eluting, purify by crossing some shirtsleeve operations, during the extraction process selected material
It is simple easy, keep the extraction process easy to operate.
3, extracting method provided by the invention is mentioned in pendimethalin extraction process in rice-fishing system cultivation aquatic products
The rate of recovery of the imidacloprid of taking-up is up to 95% or more, and therefore, the extracting method rate of recovery provided by the invention is higher.
4, detection method provided by the invention can detect that Gamma Magnitude to pendimethalin in rice-fishing system cultivation aquatic products
Content, therefore, detection method high sensitivity provided by the invention.
5, the pendimethalin that detection method provided by the invention obtains pendimethalin in rice-fishing system cultivation aquatic products
Peak shape is sharp, symmetrical, free from admixture peak interference, so that testing result is more accurate.
It should be noted that, in this document, such as first and second etc relational terms are used merely to an entity
Or operation is distinguished with another entity or operation, is existed without necessarily requiring or implying between these entities or operation
Any actual relationship or order.Moreover, the terms "include", "comprise" or its any other variant be intended to it is non-
It is exclusive to include, so that the process, method, article or equipment for including a series of elements not only includes those elements,
It but also including other elements that are not explicitly listed, or further include solid by this process, method, article or equipment
Some elements.In the absence of more restrictions, the element limited by sentence " including one ", is not arranged
Except there is also other identical factors in the process, method, article or apparatus that includes the element.
Finally, it should be noted that the foregoing is merely presently preferred embodiments of the present invention, it is merely to illustrate skill of the invention
Art scheme, is not intended to limit the scope of the present invention.Any modification for being made all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., are included within the scope of protection of the present invention.
Claims (8)
1. the extracting method of pendimethalin in a kind of rice-fishing system cultivation aquatic products characterized by comprising
Weigh (5.00 ± 0.01) g ~ (10.00 ± 0.01) g aquatic products sample；
The aquatic products sample is extracted at least twice using the ethyl acetate solution containing 0.1% acetic acid；
The supernatant being obtained by extraction is rotated to dry；
Using the residue after methanol/water solution (8:2, v/v contain 0.1% acetic acid) dissolution revolving, extraction concentrate is obtained；
The extraction concentrate is purified using scavenging material.
2. the method according to claim 1, wherein described extracted using the ethyl acetate solution containing 0.1% acetic acid
The aquatic products sample is at least twice, comprising:
The ethyl acetate solution and the aquatic products sample blending of 0.1% acetic acid will be contained not less than 15mL, at room temperature sonic oscillation
Extract at least 5min；
It is centrifuged 5min at least 4000r/min, isolates supernatant liquor；
Repeat to extract supernatant liquor primary, that merging extraction and separation twice go out to the seabed sediment after separation.
3. the method according to claim 1, wherein described purify the extraction concentrate using scavenging material,
Include:
After the concentrate peracidity alumina column, 0.1g ketjenblack EC powder is added, at least 4000r/min centrifugation
5min takes supernatant liquor.
4. the method according to claim 1, wherein further comprising:
The edible part of water intaking product is processed into no more than 0.5cm × 0.5cm × 0.5cm fritter, mixes, blend at a high speed simultaneously
It sufficiently stirs evenly, obtains aquatic products sample, seal, label is spare in -18 DEG C of freezen protectives.
5. method according to any one of claims 1 to 4, which is characterized in that the aquatic products sample, comprising:
The edible muscle parts of Procambius clarkii, the edible muscle parts of freshwater shrimp, Eriocheir sinensis edible part, the edible muscle portion of swamp eel
Point and the edible muscle parts of loach in any one.
6. the detection method of pendimethalin in a kind of rice-fishing system cultivation aquatic products, which is characterized in that utilize claim 1
Into 5 any rice-fishing system cultivation aquatic products, the extracting method of pendimethalin, extracts diformazan from aquatic products sample
Penta spirit, obtains purified extraction concentrate；Further include:
Measure the purified extraction concentrate of 1mL；
It is detected by the extraction concentrate of the high performance liquid chromatography-series connection triple quadrupole mass spectrometer to measurement, wherein
Chromatographic condition: Symmetry C18 liquid-phase chromatographic column (100mm × 2.1mm × 3.5 μm)；Column temperature is 35 DEG C；Flow velocity is 0.3mL/
min；Mobile phase are as follows: A:80% methanol, B:20% water (contain 0.1% acetic acid), and sample volume is 10 μ L；Mass Spectrometry Conditions: heated atmospheric air piezoelectricity
Spraying HESI is as mass ion source；Ionization mode: positive ion mode；Scanning mode: selection ionic reaction monitoring pattern
(SRM)；Spray voltage: 3500V；Boil-off gas temperature: 200 DEG C；Sheath gas and auxiliary gas are high pure nitrogen, and pressure is 5bar；
Collision gas is high-purity argon gas, 1.5m Torr；Ion transfer capillary temperature: 350 DEG C；Q1 PW 0.7, Q3 PW 0.7.Monitoring
Ion pair: pendimethalin m/z:282.1/211.9(quota ion), 282.1/193.9, impact pressure is respectively 17V, 11V.
7. according to the method described in claim 6, it is characterized in that, further comprising:
Blank aquatic products sample is extracted with any extracting method of claim 1 to 5, blank sample solution is prepared；
The pendimethalin standard reserving solution that mass concentration is 100mg/L is prepared with methanol；
Dilute the pendimethalin standard reserving solution using the blank sample solution, prepare mass concentration be 1.0,2.0,5.0,
10.0, the bare substrate matching criteria liquid of 20.0 μ g/L；
Construct the relational expression between the chromatographic peak area and concentration of blank sequence matrix matching titer；
According to the peak area of the relational expression and detected pendimethalin, pendimethalin in aquatic products sample is calculated
Concentration.
8. method according to claim 6 or 7, which is characterized in that the aquatic products sample, comprising:
The edible muscle parts of Procambius clarkii, the edible muscle parts of freshwater shrimp, Eriocheir sinensis edible part, the edible muscle portion of swamp eel
Point and the edible muscle parts of loach in any one.
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