CN104483398B - The extracting method of organophosphorus pesticide and detection method in textile - Google Patents
The extracting method of organophosphorus pesticide and detection method in textile Download PDFInfo
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Abstract
The invention provides extraction and the detection method of organophosphorus pesticide in a kind of textile, comprise the step such as accelerated solvent extraction and carbon nano-tube purification.Extraction of the present invention and detection method are by using volume ratio to be 1: the acetone of (9 ~ 19) and the mixed liquor of water carry out accelerated solvent extraction as extraction solvent, organophosphorus pesticide in textile farthest can not only be extracted, consuming time less, efficiency is high, and on follow-up carbon nano-tube wash-out without impact, also can effectively solve in prior art because of a large amount of with an organic solvent problems brought.Extraction of the present invention and detection method also have the recovery and feature that is highly sensitive, favorable reproducibility, meet and analyze requirement, for the appraisement system improving ecological textile further provides scientific basis.
Description
Technical field
The present invention relates to a kind of extracting method and detection method of organophosphorus pesticide, particularly a kind of method extracted the Determination of Organophosphorus Pesticide in textile simultaneously, detect simultaneously, belongs to examination and analysb technical field.
Technical background
Organophosphorus pesticide (OPPs) becomes China because having the features such as wide spectrum, efficient, wide in variety and Residual time be short and uses maximum, a most widely used class agricultural chemical insecticide, but the toxicity of part OPPs kind to people, animal is larger, easy generation acute poisoning, even also has carcinogenic, teratogenesis and mutagenesis.Therefore, the OPPs in environment pollutes the extensive concern having caused the public, sets up the research direction that easy, quick, sensitive organophosphorus pesticide detection method is the residual examination and analysb of current agriculture.
In prior art, the media such as water quality, soil, fruits and vegetables, food are mainly concentrated on to the research that OPPs measures, and in textile, the detection method of OPPs rarely has report.Textile is the daily necessities of the mankind, and wherein Nature Fibre Textile product are one of the most potential ecological textiles in the market, and natural fiber usually multiple disease and pest can occur in planting process, needs repeatedly to use agricultural chemicals to prevent and treat.These OPPs agricultural chemicals be applied on the plant such as cotton, fiber crops can inevitably pollute fiber itself, though through processing process after agricultural chemicals is absorbed, but still likely remain on the final product, thus by the contact with skin absorb by human body, light then can cause allergic reaction, breathing problem or other toxic reaction, heavy then can cancer be brought out.
Given this, Abroad in Recent Years has formulated relevant rule and standard for ecological textile, and the standard GB/T/T18885-2009 " ecological textile technical requirement " of China has also made clear and definite restriction to the content of the agricultural chemicals such as the organophosphorus in textile.In this national standard, the assay method defining organophosphorus pesticide in textile is GB/T18412, the pre-treatment step of the method standard is: take 2.0g and be accurate to 0.01g) sample, be placed in 100mL tool plug conical flask, add 50mL ethyl acetate, 20min is extracted in ultrasonic generator, by extracting liquid filtering, residue is again with 30mL ethyl acetate ultrasonic extraction 5min, merging filtrate, after the dehydration of anhydrous sodium sulfate post, being collected in 100mL concentrates in bottle, be concentrated near dry in 40 DEG C of water-bath rotary evaporators, 5.0mL is settled to acetone solution, confirm for gas Chromatographic Determination or gas chromatography-mass spectrum and measure.But above-mentioned pre-treating method has following deficiency: the significantly loss that can cause determinand in the rotary evaporation process in (1) the method, thus the precision that impact measures.(2) a large amount of uses of organic solvent ethyl acetate, not only can make testing cost higher, also can cause environmental pollution, to the healthy generation harm of experimenter.
In order to improve the precision that organophosphorus measures, the people such as Wang Li adopt 7 kinds of organophosphorus pesticides such as the malathion of polymethyl siloxane (PDMS) extracting fiber head adsorption and enrichment in textile, parathion-methyl, DDVP, Hostathion, parathion, quinalphos, diazinon, and qualitative and quantitative detection (" in Residues in Textiles by Gas Chromatography-Mass Spectrometry with Solid-phase Microextraction organophosphorus pesticide " is carried out after the injection port thermal desorption of gas chromatography-mass spectrum, Wang Li etc., analytical test journal, 2007,26th volume the 3rd phase, 413-416 page).This detection method is first dissolved in by the organophosphorus pesticide in textile in simulation human sweat, then again the organophosphorus pesticide be dissolved in simulation human sweat is enriched on PDMS extracting fiber head, above-mentioned simulation human sweat is dissolved in a certain amount of ultrapure water by L-Histidine 0.5g, sodium chloride 5.0g, sodium dihydrogen phosphate 2.2g, and it is formulated to be settled to 1L.
Said method adopts the aqueous solution being added with sweat composition to extract textile, water-soluble good 7 kinds of organophosphoruss in textile can be extracted, again by directly adopting PDMS extracting fiber head to adsorb, no longer carry out roto-vap operation, thus effectively can reduce the loss of determinand, there is higher accuracy of detection.But, in above-mentioned prior art for detect textile organophosphorus method still Problems existing be, of a great variety due to organophosphorus pesticide, and water-soluble, polarity of often kind of agricultural chemicals etc. all there are differences, therefore which kind of pre-treating method of the prior art no matter is adopted, all certain limited several organophosphorus effectively can only be extracted and/or extracted, and this just causes the part organophosphorus pesticide in textile cannot to be obtained by pre-treatment, also just cannot detect it.Thus have impact on technician correct assessment is made to the organic phosphorous content in textile.In this case, how setting up a kind of method can carrying out complete detection to OPPs in textile, is the still unsolved technical barriers of those skilled in the art.
Summary of the invention
What the present invention solved is the problem that OPPs detection method of the prior art can only detect certain limited several organophosphorus, so provide that a kind of accuracy is high, favorable reproducibility, can simultaneously to the method that 14 kinds of organophosphorus pesticides extract and detect.
The technical scheme that the present invention solves the problems of the technologies described above employing is:
In textile, an extracting method for organophosphorus pesticide, comprises the steps:
(1) in accelerated solvent extraction, with volume ratio for 1: the acetone of (9 ~ 19) and the mixed liquor of water are extraction solvent, carry out accelerated solvent extraction to textile, extract is collected;
(2) carbon nano-tube be immersed in described extract, collect the carbon nano-tube after soaking, the carbon nano-tube after described immersion is placed in organic solvent and carries out ultrasonic wash-out, collect eluent, described eluent obtains filtrate through membrane filtration.
In step (1), the extraction conditions of described accelerated solvent extraction is: temperature 50 C, pressure 10.3MPa, heat time 5min, static extracting time 5min, quiet cycle number of times are 2 times.
In step (2), the mass ratio of described carbon nano-tube and described textile is (0.005 ~ 0.035): 1, and the soak time of described carbon nano-tube in described extract is 5 ~ 40min.
In step (2), described organic solvent is (3 ~ 5) with the volume/mass ratio of described carbon nano-tube: (0.01 ~ 0.07), the pass of wherein said volume/mass ratio is mL/g.
In step (2), described organic solvent is methylene chloride or ethyl acetate.
In step (2), the temperature of described ultrasonic wash-out is 50 DEG C, the time is 20 ~ 30min.
In step (2), the aperture of described filter membrane is 0.45 μm.
Described organophosphorus pesticide be in acephatemet, DDVP, Menite, flolimat, demeton-methyl, ethoprop, Carbicron, Azodrin, thiometon, Rogor, propetamphos, diazinon, disulfoton, parathion-methyl, fenifrothion, malathion, Entex, parathion, chlorfenviphos, quinalphos, Rilariol, Ravap, Profenofos, De-Green, Hostathion, edifenphos, EPN, azinphos-methyl, azinphos ethyl or Resistox any one or multiple.
Based on the method that said extracted method detects organophosphorus pesticide in textile, comprising:
Under the gas chromatography-mass spectrum condition of setting, described filtrate is detected, namely obtain the quantitative and qualitative analysis data of organophosphorus pesticide in described textile.
The gas chromatography-mass spectrum condition of described setting comprises:
Chromatographic column: 30m × 0.25mm × 0.25 μm, HP-5MS; Input mode: Splitless injecting samples; Sample size: 1 μ L; Temperature programme: initial temperature is 80 DEG C, keeps 1min, is warming up to 180 DEG C with the speed of 20 DEG C/min, keeps 2min, then is warming up to 220 DEG C with the speed of 5 DEG C/min, keeps 3min, then is warming up to 280 DEG C with the speed of 10 DEG C/min, keeps 10min; Carrier gas: helium, purity >=99.999%; Flow rate of carrier gas: 1.0mL/min; Ionization mode: EI; Ionizing energy: 70eV; Injector temperature: 230 DEG C; Transmission line temperature: 280 DEG C; Ion source temperature: 280 DEG C.
The extraction of organophosphorus pesticide and detection method in textile of the present invention, step (1) carries out accelerated solvent extraction to textile, and to limit extraction solvent used be volume ratio is 1: the acetone of (9 ~ 19) and the mixed liquor of water, its advantage is, the present invention is by using the water only containing a small amount of acetone as extraction solvent, in accelerated solvent extraction, accelerated solvent extraction is carried out to textile, in textile 30 kind of organophosphorus pesticide farthest can not only be extracted simultaneously, also effectively can solve existing national standard because of a large amount of with an organic solvent problems caused.Carbon nano-tube is first immersed in described extract by step of the present invention (2), its objective is and utilize the high absorption property of carbon nano-tube by the organophosphorus pesticide adsorption and enrichment that is dissolved in step (1) in extract on the carbon nanotubes, then collect the carbon nano-tube after soaking, and the carbon nano-tube after described immersion is placed in organic solvent carries out ultrasonic wash-out, to make the organophosphorus pesticide in the carbon nano-tube after being enriched in described immersion be dissolved in described organic solvent, and then regather eluent.In addition, limit employing 1 in step of the present invention (1): the acetone of (9 ~ 19) and the mixed liquor of water extract textile, the advantage also had is that described mixed liquor is conducive to organophosphorus pesticide enrichment on the carbon nanotubes and wash-out.And the ratio why the present invention limits acetone and water in mixed liquor is 1: (9 ~ 19), reason is, present inventor finds after further investigation for a long time, organic solvent in extraction solvent can affect the elute effect of absorption organophosphorus pesticide on the carbon nanotubes, with regard to acetone, if containing a large amount of acetone in mixed liquor, so when carrying out wash-out, the acetone being attached to carbon nano tube surface can play the effect of isolation organophosphorus and eluent on the contrary, thus organophosphorus is not easy by wash-out.Therefore, in order to improve elution efficiency, the ratio that inventor limits described acetone and water is 1: (9 ~ 19), namely in mixed liquor, the content of acetone is lower, thus make can to textile in while 30 kinds of organophosphorus pesticides carry out efficient extraction, can also ensure that the organophosphorus adsorbed on the carbon nanotubes can obtain efficient wash-out.
Present invention also defines organic solvent described in step (2) is methylene chloride or ethyl acetate simultaneously, this is because use other organic solvent, as acetone, normal hexane etc. to soak after carbon nano-tube carry out wash-out time, can not wash-out be out effectively by the organophosphorus pesticide in absorption carbon nano-tube after steeping, make the content of organophosphorus pesticide in eluent low, thus the accuracy that impact detects.
Compared with OPPs detection method of the prior art, in textile of the present invention, the extraction of organophosphorus pesticide and detection method tool have the following advantages:
In prior art when with an organic solvent extracting organophosphorus, usually can select the organic mixed solvent containing higher proportion acetone, but acetone on the carbon nanotubes residual is unfavorable for by organophosphorus pesticide from wash-out carbon nano-tube out.The present invention is by using the water only containing a small amount of acetone as extraction solvent, in accelerated solvent extraction, accelerated solvent extraction is carried out to textile, in textile 30 kind of an organophosphorus pesticide farthest can not only be extracted, consuming time less, efficiency is high, and on follow-up carbon nano-tube wash-out without impact.Also can effectively solve in prior art because of a large amount of with an organic solvent and the testing cost brought is high, harm experimenter is healthy and contaminated environment, and problems such as the determinand loss caused in the rotary evaporation process of organic solvent.
In addition, in textile of the present invention, the extraction of organophosphorus pesticide and detection method use carbon nano-tube to adsorb the-purified treatment of wash-out to the organophosphorus pesticide be dissolved in extract, the impurity such as the dyestuff in extract can be reduced to the interference of subsequent detection result, thus effectively improve the accuracy detected.And detection method of the present invention also has the recovery and feature that is highly sensitive, favorable reproducibility, meet and analyze requirement, for the appraisement system improving ecological textile further provides scientific basis.
Accompanying drawing explanation
Fig. 1 obtains the gas chromatogram of organophosphorus pesticide according to the detection method of organophosphorus pesticide in textile of the present invention;
Fig. 2 obtains the mass spectrogram of organophosphorus pesticide Menite according to the detection method of organophosphorus pesticide in textile of the present invention;
Fig. 3 is the composite diagram of the gas chromatogram that the detection method selecting different nano material to carry out organophosphorus pesticide in textile of the present invention obtains.
Embodiment
Below in conjunction with specific embodiment, the extraction of organophosphorus pesticide in textile provided by the invention and detection method are described in detail.Wherein 1 weight portion is 1g, and 1 parts by volume is 1mL.
Embodiment 1
In textile described in the present embodiment, the extraction of organophosphorus pesticide and detection method, comprise the steps:
(1) representative sample is got, shred to 5mm × below 5mm, mixing, take the sample of 2 weight portions, be accurate to 0.01 weight portion, being placed in the abstraction pool of accelerated solvent extraction, is that the acetone of 1: 19 and the mixed liquor of water carry out accelerated solvent extraction to sample by volume ratio, collects extract; Wherein, extraction conditions is: temperature 50 C, pressure 10.3MPa, heat time 5min, static extracting time 5min, quiet cycle number of times are 2 times.
(2) carbon nano-tube of 0.05 weight portion is immersed in 20min in described extract, collect the carbon nano-tube after soaking, carbon nano-tube after described immersion is placed in the methylene chloride of 5 parts by volume, ultrasonic wash-out 20min is carried out under the condition of 50 DEG C, collect eluent, the described eluent the getting 1 parts by volume membrane filtration of 0.45 μm obtains liquid to be measured;
(3) detect described liquid to be measured under the gas chromatography-mass spectrum condition of setting, the gas chromatography-mass spectrum condition of described setting comprises:
Chromatographic column: 30m × 0.25mm × 0.25 μm, HP-5MS; Input mode: Splitless injecting samples; Sample size: 1 μ L; Temperature programme: initial temperature is 80 DEG C, keeps 1min, is warming up to 180 DEG C with the speed of 20 DEG C/min, keeps 2min, then is warming up to 220 DEG C with the speed of 5 DEG C/min, keeps 3min, then is warming up to 280 DEG C with the speed of 10 DEG C/min, keeps 10min; Carrier gas: helium, purity >=99.999%; Flow rate of carrier gas: 1.0mL/min; Ionization mode: EI; Ionizing energy: 70eV; Injector temperature: 230 DEG C; Transmission line temperature: 280 DEG C; Ion source temperature: 280 DEG C.
The present embodiment according to the retention time of chromatographic peak in gas chromatography and mass spectrographic quasi-molecular ions to acephatemet, DDVP, Menite, flolimat, demeton-methyl, ethoprop, Carbicron, Azodrin, thiometon, Rogor, propetamphos, diazinon, disulfoton, parathion-methyl, fenifrothion, malathion, Entex, parathion, chlorfenviphos, quinalphos, Rilariol, Ravap, Profenofos, De-Green, Hostathion, edifenphos, EPN, azinphos-methyl, azinphos ethyl, 30 kinds of organophosphorus pesticides such as Resistox are qualitative, and it is quantitative to above-mentioned organophosphorus pesticide according to the peak area of chromatographic peak, adopt said procedure to heat up and be separated these organophosphorus pesticides, result as illustrated in fig. 1 and 2.
As seen from Figure 1, in the textile according to the present embodiment, the chromatographic peak of each organophosphorus pesticide that the extraction of organophosphorus pesticide obtains with detection method is separated well, and qualitative, quota ion and the retention time of above-mentioned 30 kinds of organophosphorus pesticides are as shown in table 1.
Qualitative, the quota ion of each organophosphorus pesticide of table 1 and retention time
Note: * represents quota ion.
It is 0,0.25,0.50,0.75 that the standard mother liquor of above-mentioned 30 kinds of organophosphoruss is mixed with concentration by the present embodiment successively, the standard working solution of 1.00 μ g/mL, under above-mentioned chromatographic condition, measure the peak area of each organophosphorus pesticide respectively, and with described peak area be ordinate, the concentration of standard working solution is for horizontal ordinate, draw external standard method working curve, thus obtain typical curve equation and the related coefficient thereof of above-mentioned 30 kinds of organophosphorus pesticides, result is as shown in table 2.
The typical curve equation of each organophosphorus pesticide of table 2 and related coefficient thereof
| Numbering | Title | Typical curve equation | Related coefficient |
| 1 | Acephatemet | Y＝12129.8+110026*X | 0.9927 |
| 2 | DDVP | Y＝18056.1+355748*X | 0.9775 |
| 3 | Menite | Y＝23033.8+239831*X | 0.9981 |
| 4 | Flolimat | Y＝5398.53+63890.8*X | 0.9991 |
| 5 | Demeton-methyl | Y＝5498.15+146723*X | 0.9995 |
| 6 | Ethoprop | Y＝8972.49+88921.1*X | 0.9988 |
| 7 | Carbicron | Y＝9825.99+111556*X | 0.9988 |
| 8 | Azodrin | Y＝12956.1+109822*X | 0.9985 |
| 9 | Thiometon | Y＝11572.1+275627*X | 0.9996 |
| 10 | Rogor | Y＝1225.17+165131*X | 0.9990 |
| 11 | Propetamphos | Y＝13564.5+143545*X | 0.9990 |
| 12 | Diazinon | Y＝4885.91+94802.9*X | 0.9980 |
| 13 | Disulfoton | Y＝3787.91+211873*X | 0.9986 |
| 14 | Parathion-methyl | Y＝16987.1+79979.6*X | 0.9915 |
| 15 | Fenifrothion | Y＝4818.91+49823.7*X | 0.9991 |
| 16 | Malathion | Y＝4784.69+66669.5*X | 0.9927 |
| 17 | Entex | Y＝911.267+97434.7*X | 0.9991 |
| 18 | Parathion | Y＝827.243+15483.8*X | 0.9965 |
| 19 | Chlorfenviphos | Y＝2642.03+25755.7*X | 0.9914 |
| 20 | Quinalphos | Y＝5076.93+101692*X | 0.9945 |
| 21 | Rilariol | Y＝11126.3+146810*X | 0.9930 |
| 22 | Ravap | Y＝889.224+24251*X | 0.9973 |
| 23 | Profenofos | Y＝209.389+14781.5*X | 0.9992 |
| 24 | De-Green | Y＝4404.42+82124.5*X | 0.9972 |
| 25 | Hostathion | Y＝2336.46+57305.9*X | 0.9946 |
| 26 | Edifenphos | Y＝14094.6+223023*X | 0.9936 |
| 27 | EPN | Y＝8271.84+53721.6*X | 0.9905 |
| 28 | Azinphos-methyl | Y＝4248.16+51740.2*X | 0.9900 |
| 29 | Azinphos ethyl | Y＝3877.33+54924.1*X | 0.9937 |
| 30 | Resistox | Y＝1895.42+33269.3*X | 0.9967 |
Note: * represents quota ion.
As can be seen from Table 2, in textile of the present invention, the extraction of organophosphorus pesticide and detection method are to the related coefficient of the 29 kinds of organophosphorus pesticides of other except DDVP all more than 0.9900, and this shows that extraction of the present invention and detection method have good correlationship.
For above-mentioned 30 kinds of organophosphorus pesticides, in textile described in the present embodiment, the extraction of organophosphorus pesticide and the detection limit (signal to noise ratio (S/N ratio) is 3: 1) of detection method and the detection limit (signal to noise ratio (S/N ratio) is 3: 1) that measures according to the method for GB GB/T18412.3-2006, as shown in table 3 respectively.
The detection limit (mg/Kg) of the extraction described in table 3 the present embodiment and detection method and GB GB/T18412
As can be seen from Table 3, in textile of the present invention the extraction of organophosphorus pesticide and detection method to except to the detection limit of other the 23 kinds of organophosphorus pesticides except acephatemet, DDVP, Menite, parathion, Profenofos, edifenphos, EPN all not higher than the detection limit of standard GB/T/T18412, this illustrates that extraction of the present invention and detection method have very high sensitivity.
Embodiment 2
In textile described in the present embodiment, the extraction of organophosphorus pesticide and detection method, comprise the steps:
(1) get representative sample, shred to 5mm × below 5mm, mixing, take the sample of 2 weight portions, be accurate to 0.01 weight portion, be placed in the abstraction pool of accelerated solvent extraction, be that the acetone of 1: 9 and the mixed liquor of water carry out accelerated solvent extraction to sample by volume ratio, collect extract; Wherein, extraction conditions is: temperature 50 C, pressure 10.3MPa, heat time 5min, static extracting time 5min, quiet cycle number of times are 2 times.
(2) carbon nano-tube of 0.07 weight portion is immersed in 5min in described extract, collect the carbon nano-tube after soaking, carbon nano-tube after described immersion is placed in the ethyl acetate of 3 parts by volume, ultrasonic wash-out 25min is carried out under the condition of 50 DEG C, collect eluent, the described eluent the getting 1 parts by volume membrane filtration of 0.45 μm obtains liquid to be measured;
(3) under the gas chromatography-mass spectrum condition of embodiment 1, described liquid to be measured is detected.
Embodiment 3
In textile described in the present embodiment, the extraction of organophosphorus pesticide and detection method, comprise the steps:
(1) representative sample is got, shred to 5mm × below 5mm, mixing, take the sample of 2 weight portions, be accurate to 0.01 weight portion, being placed in the abstraction pool of accelerated solvent extraction, is that the acetone of 1: 14 and the mixed liquor of water carry out accelerated solvent extraction to sample by volume ratio, collects extract; Wherein, extraction conditions is: temperature 50 C, pressure 10.3MPa, heat time 5min, static extracting time 5min, quiet cycle number of times are 2 times.
(2) carbon nano-tube of 0.04 weight portion is immersed in 40min in described extract, collect the carbon nano-tube after soaking, carbon nano-tube after described immersion is placed in the methylene chloride of 4 parts by volume, ultrasonic wash-out 30min is carried out under the condition of 50 DEG C, collect eluent, the described eluent the getting 1 parts by volume membrane filtration of 0.45 μm obtains liquid to be measured;
(3) under the gas chromatography-mass spectrum condition of embodiment 1, described liquid to be measured is detected.
Comparative example
For investigating accuracy and the precision of detection method of the present invention, the present invention is also provided with following comparative example.
In textile described in this comparative example, the extraction of organophosphorus pesticide and detection method, comprise the steps:
(1) get representative sample, shred to 5mm × below 5mm, mixing, take the sample of 2 weight portions, be accurate to 0.01 weight portion, be placed in the abstraction pool of accelerated solvent extraction, be that the acetone of 2: 1 and the mixed liquor of water carry out accelerated solvent extraction to sample by volume ratio, collect extract; Wherein, extraction conditions is: temperature 50 C, pressure 10.3MPa, heat time 5min, static extracting time 5min, quiet cycle number of times are 2 times.
(2) carbon nano-tube of 0.05 weight portion is immersed in 20min in described extract, collect the carbon nano-tube after soaking, carbon nano-tube after described immersion is placed in the methylene chloride of 5 parts by volume, ultrasonic wash-out 20min is carried out under the condition of 50 DEG C, collect eluent, the described eluent the getting 1 parts by volume membrane filtration of 0.45 μm obtains liquid to be measured;
(3) under the gas chromatography-mass spectrum condition of embodiment 1 setting, described liquid to be measured is detected.
The present invention to extract sample according to embodiment 1 and comparative example respectively and purifies, and under identical gas chromatography-mass spectrum condition, 5 mark-on recovery tests have been carried out to 13 kinds of organophosphorus pesticides such as propetamphos, diazinon, parathion-methyl, Entex, parathion, chlorfenviphos, quinalphos, Ravap, De-Green, Hostathion, azinphos-methyl, azinphos ethyl, Resistox, result is as shown in table 4 and table 5.
The average recovery of standard addition (n=5) of organophosphorus pesticide and relative standard deviation (RSD) in table 4 embodiment 1
| Numbering | Title | Add scalar/μ g | Average measurement/μ g | Average recovery rate/% | Standard deviation | RSD/％ |
| 11 | Propetamphos | 0.50 | 0.3743 | 74.86 | 0.023844 | 6.37 |
| 12 | Diazinon | 0.50 | 0.3788 | 75.76 | 0.021364 | 5.64 |
| 14 | Parathion-methyl | 0.50 | 0.4739 | 94.79 | 0.015997 | 3.38 |
| 17 | Entex | 0.50 | 0.3821 | 76.42 | 0.022698 | 5.94 |
| 18 | Parathion | 0.50 | 0.4392 | 87.83 | 0.033245 | 7.57 |
| 19 | Chlorfenviphos | 0.50 | 0.4447 | 88.94 | 0.024075 | 5.41 |
| 20 | Quinalphos | 0.50 | 0.4212 | 84.25 | 0.009130 | 2.17 |
| 22 | Ravap | 0.50 | 0.4492 | 89.84 | 0.020544 | 4.57 |
| 24 | De-Green | 0.50 | 0.4936 | 98.72 | 0.025180 | 5.10 |
| 25 | Hostathion | 0.50 | 0.4750 | 95.00 | 0.031222 | 6.57 |
| 28 | Azinphos-methyl | 0.50 | 0.4312 | 86.25 | 0.027444 | 6.36 |
| 29 | Azinphos ethyl | 0.50 | 0.4419 | 88.39 | 0.012727 | 2.88 |
| 30 | Resistox | 0.50 | 0.4450 | 90.00 | 0.029789 | 6.62 |
The average recovery of standard addition (n=5) of organophosphorus pesticide in table 5 comparative example
| Numbering | Title | Add scalar/μ g | Average measurement/μ g | Average recovery rate/% |
| 11 | Propetamphos | 0.50 | 0.0041 | 0.82 |
| 12 | Diazinon | 0.50 | 0.0072 | 1.44 |
| 14 | Parathion-methyl | 0.50 | 0.0122 | 2.44 |
| 17 | Entex | 0.50 | 0.0068 | 1.36 |
| 18 | Parathion | 0.50 | 0.0225 | 4.5 |
| 19 | Chlorfenviphos | 0.50 | 0.0239 | 4.78 |
| 20 | Quinalphos | 0.50 | 0.0387 | 7.74 |
| 22 | Ravap | 0.50 | 0.0068 | 1.36 |
| 24 | De-Green | 0.50 | 0.0941 | 18.82 |
| 25 | Hostathion | 0.50 | 0 | 0 |
| 28 | Azinphos-methyl | 0.50 | 0.0635 | 12.7 |
| 29 | Azinphos ethyl | 0.50 | 0.0423 | 8.46 |
| 30 | Resistox | 0.50 | 0.2385 | 47.7 |
As can be seen from Table 4,5 average recovery rates of the above-mentioned 13 kinds of organophosphorus pesticides obtained according to extraction and the detection method of organophosphorus pesticide in textile of the present invention are between 74.86% ~ 98.72%, relative standard deviation (RSD, n=5) within 8%, this shows extraction of the present invention and detection method precision is high, favorable reproducibility.And the average recovery rate of the above-mentioned 13 kinds of organophosphorus pesticides according to comparative example mensuration of the present invention shown in table 5 is all much smaller than embodiment 1, this illustrates that the present invention adopts volume ratio to be 1: the acetone of (9 ~ 19) and the mixed liquor of water farthest by the Extraction of organophosphorus pesticide in sample out, can ensure that the accuracy of extraction of the present invention and detection method as extraction solvent.
Experimental example
Different nano material contrast test
The extract of step (1) in embodiment 1 is equally divided into 6 parts, the one in the carbon nano-tube of identical weight part, nano aluminium oxide, nano-cerium oxide, nano silicon, nano titanium oxide, nano zine oxide is added respectively in every part of extract, according to the detection method described in embodiment 1, carry out gas Chromatographic Determination to eluent, result as shown in Figure 3.
Can as apparent from Fig. 3, except carbon nano-tube, other nano material is all very poor to the accumulation ability of organophosphorus pesticide, can not meet the demand of test, therefore, the carbon nano-tube that the present invention uses has the effect of more excellent absorption organophosphorus compared to other nano material.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. the extracting method of organophosphorus pesticide in textile, comprises the steps:
(1) in accelerated solvent extraction, take volume ratio as 1:(9 ~ 19) acetone and the mixed liquor of water be extraction solvent, accelerated solvent extraction is carried out to textile, collects extract;
(2) carbon nano-tube be immersed in described extract, collect the carbon nano-tube after soaking, the carbon nano-tube after described immersion is placed in organic solvent and carries out ultrasonic wash-out, collect eluent, described eluent obtains filtrate through membrane filtration.
2. extracting method according to claim 1, it is characterized in that, in step (1), the extraction conditions of described accelerated solvent extraction is: temperature 50 C, pressure 10.3MPa, heat time 5min, static extracting time 5min, quiet cycle number of times are 2 times.
3. extracting method according to claim 1, it is characterized in that, in step (2), the mass ratio of described carbon nano-tube and described textile is (0.005 ~ 0.035): 1, and the soak time of described carbon nano-tube in described extract is 5 ~ 40min.
4. the extracting method according to any one of claim 1-3, it is characterized in that, in step (2), described organic solvent is (3 ~ 5) with the volume/mass ratio of described carbon nano-tube: (0.01 ~ 0.07), the pass of wherein said volume/mass ratio is mL/g.
5. the extracting method according to any one of claim 1-3, is characterized in that, in step (2), described organic solvent is methylene chloride or ethyl acetate.
6. the extracting method according to any one of claim 1-3, is characterized in that, in step (2), the temperature of described ultrasonic wash-out is 50 DEG C, the time is 20 ~ 30min.
7. the extracting method according to any one of claim 1-3, is characterized in that, in step (2), the aperture of described filter membrane is 0.45 μm.
8. the extracting method according to any one of claim 1-3, it is characterized in that, described organophosphorus pesticide be in acephatemet, DDVP, Menite, flolimat, demeton-methyl, ethoprop, Carbicron, Azodrin, thiometon, Rogor, propetamphos, diazinon, disulfoton, parathion-methyl, fenifrothion, malathion, Entex, parathion, chlorfenviphos, quinalphos, Rilariol, Ravap, Profenofos, De-Green, Hostathion, edifenphos, EPN, azinphos-methyl, azinphos ethyl or Resistox any one or multiple.
9., based on the method that the extracting method described in any one of claim 1-8 detects organophosphorus pesticide in textile, comprising:
Under the gas chromatography-mass spectrum condition of setting, the described filtrate in claim 1-8 is detected, namely obtain the quantitative and qualitative analysis data of organophosphorus pesticide in described textile.
10. method according to claim 9, is characterized in that, the gas chromatography-mass spectrum condition of described setting comprises:
Chromatographic column: 30m × 0.25mm × 0.25 μm, HP-5MS; Input mode: Splitless injecting samples; Sample size: 1 μ L; Temperature programme: initial temperature is 80 DEG C, keeps 1min, is warming up to 180 DEG C with the speed of 20 DEG C/min, keeps 2min, then is warming up to 220 DEG C with the speed of 5 DEG C/min, keeps 3min, then is warming up to 280 DEG C with the speed of 10 DEG C/min, keeps 10min; Carrier gas: helium, purity >=99.999%; Flow rate of carrier gas: 1.0mL/min; Ionization mode: EI; Ionizing energy: 70eV; Injector temperature: 230 DEG C; Transmission line temperature: 280 DEG C; Ion source temperature: 280 DEG C.
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| CN104049049A (en) * | 2014-07-09 | 2014-09-17 | 南京大学 | Method for synchronously detecting plurality of organophosphorus fire retardants in bottom mud |
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