CN103983727A - Method for identifying key toxic substances in pesticide wastewater by taking daphnia magna toxicity as guide - Google Patents
Method for identifying key toxic substances in pesticide wastewater by taking daphnia magna toxicity as guide Download PDFInfo
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- CN103983727A CN103983727A CN201410236171.4A CN201410236171A CN103983727A CN 103983727 A CN103983727 A CN 103983727A CN 201410236171 A CN201410236171 A CN 201410236171A CN 103983727 A CN103983727 A CN 103983727A
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- daphnia magna
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- 241001494246 Daphnia magna Species 0.000 title claims abstract description 33
- 231100000419 toxicity Toxicity 0.000 title claims abstract description 31
- 230000001988 toxicity Effects 0.000 title claims abstract description 31
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000575 pesticide Substances 0.000 title claims abstract description 16
- 231100000614 poison Toxicity 0.000 title abstract description 12
- 239000003440 toxic substance Substances 0.000 title abstract 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000012216 screening Methods 0.000 claims abstract description 16
- 231100000820 toxicity test Toxicity 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 40
- 231100000567 intoxicating Toxicity 0.000 claims description 36
- 230000002673 intoxicating effect Effects 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000003905 agrochemical Substances 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 12
- 238000012850 discrimination method Methods 0.000 claims description 11
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 10
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 10
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- 238000004237 preparative chromatography Methods 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000005556 structure-activity relationship Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 231100000331 toxic Toxicity 0.000 claims description 6
- 230000002588 toxic effect Effects 0.000 claims description 6
- 238000001819 mass spectrum Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 3
- 238000012790 confirmation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 238000004885 tandem mass spectrometry Methods 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims 2
- 239000012530 fluid Substances 0.000 claims 2
- 230000004913 activation Effects 0.000 claims 1
- 238000000622 liquid--liquid extraction Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- 239000000284 extract Substances 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 231100001234 toxic pollutant Toxicity 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 27
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 9
- 239000003480 eluent Substances 0.000 description 8
- CTSLUCNDVMMDHG-UHFFFAOYSA-N 5-bromo-3-(butan-2-yl)-6-methylpyrimidine-2,4(1H,3H)-dione Chemical compound CCC(C)N1C(=O)NC(C)=C(Br)C1=O CTSLUCNDVMMDHG-UHFFFAOYSA-N 0.000 description 7
- CAWXEEYDBZRFPE-UHFFFAOYSA-N Hexazinone Chemical compound O=C1N(C)C(N(C)C)=NC(=O)N1C1CCCCC1 CAWXEEYDBZRFPE-UHFFFAOYSA-N 0.000 description 7
- RMFGNMMNUZWCRZ-UHFFFAOYSA-N Humulone Natural products CC(C)CC(=O)C1=C(O)C(O)(CC=C(C)C)C(O)=C(CC=C(C)C)C1=O RMFGNMMNUZWCRZ-UHFFFAOYSA-N 0.000 description 7
- MMOXZBCLCQITDF-UHFFFAOYSA-N N,N-diethyl-m-toluamide Chemical compound CCN(CC)C(=O)C1=CC=CC(C)=C1 MMOXZBCLCQITDF-UHFFFAOYSA-N 0.000 description 7
- VMSLCPKYRPDHLN-NRFANRHFSA-N humulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)[C@@](O)(CC=C(C)C)C1=O VMSLCPKYRPDHLN-NRFANRHFSA-N 0.000 description 7
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 description 7
- JWUCHKBSVLQQCO-UHFFFAOYSA-N 1-(2-fluorophenyl)-1-(4-fluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanol Chemical compound C=1C=C(F)C=CC=1C(C=1C(=CC=CC=1)F)(O)CN1C=NC=N1 JWUCHKBSVLQQCO-UHFFFAOYSA-N 0.000 description 6
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 description 6
- 239000005787 Flutriafol Substances 0.000 description 6
- 239000005822 Propiconazole Substances 0.000 description 6
- 239000005839 Tebuconazole Substances 0.000 description 6
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 6
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000003851 azoles Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000007096 poisonous effect Effects 0.000 description 4
- 238000003908 quality control method Methods 0.000 description 4
- 238000004617 QSAR study Methods 0.000 description 3
- 230000007059 acute toxicity Effects 0.000 description 3
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- 238000002386 leaching Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 238000012113 quantitative test Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- STMIIPIFODONDC-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(O)(CCCC)CN1C=NC=N1 STMIIPIFODONDC-UHFFFAOYSA-N 0.000 description 1
- 241000244203 Caenorhabditis elegans Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for identifying key toxic substances in pesticide wastewater by taking daphnia magna toxicity as a precursor and belongs to the field of identification of non-target pollutants. The method comprises the following steps: performing enrichment on organic water sample extract; performing a daphnia magna toxicity experiment on an organic water sample extract; performing fractional separation on the organic water sample extract, and separating compounds of different polarities; performing the daphnia magna toxicity experiment on the separated components; and performing qualitative identification and quantitative determination on the compounds in toxic substances. The compounds of different polarities are separated by utilizing a fractional separation technology, the toxic substances are screened to reduce the complexity of a sample, the potential toxic substances are qualitatively identified through a high performance liquid chromatography-time-of-flight mass spectrometry, suspicious toxic substances are quantitatively determined by utilizing a liquid chromatography mass spectrometry, and the defect that key toxic pollutants in a mixing system cannot be obtained by the traditional non-target chemical analysis is overcome. Meanwhile, due to fractional separation and feature object screening, the method is high in resolution ratio, high in accuracy and high in information amount, so that the identification of non-target key toxic substances is relatively convenient and reliable.
Description
Technical field
The present invention relates to a kind of toxicity identification and intoxicating organism mirror method for distinguishing of different pollution level agricultural chemicals waste waters, a crucial intoxicating material discrimination method in the agricultural chemicals waste water that the Daphnia magna toxicity of specifically take is guide, based on the Daphnia magna acute toxicity intoxicating screening substances separated with composite pollution sample classification, qualitative identification and the method for quantitatively confirming.
Background technology
Agricultural chemicals can be used for the biology of kill insects, fungi and the growth of other damages to crops.Due to its high efficiency, China is used in a large number, becomes pesticide producing and uses big country.< < Chinese pesticide market yield monitoring in 2012 is analyzed in > > and is shown that China in 2012 produces 354.9 ten thousand tons, agricultural chemicals, ranks first in the world.And also caused thus a large amount of agricultural chemicals waste waters to discharge.According to incompletely statistics, the annual waste discharge total amount of China's pesticide producing is approximately 300,000,000 tons.These waste water have that complicated component, toxicity are large conventionally, difficult for biological degradation, colourity are high, COD high.Agricultural chemicals waste water be discharged into rivers and lakes havoc ecologic environment, the residual toxicity problem of agricultural chemicals more and more receives people's concern.Therefore find crucial intoxicating thing in agricultural chemicals waste water to be significant.
The eighties in 20th century, in order to assess the industrial waste water of discharge, whether receiving water body is had to ecological risk, the toxicity that U.S. EPA has proposed that toxicity evaluation and chemical analysis means are combined is differentiated assessment (Toxicity Identification Evaluation, TIE) method.< < agro-environment science journal > > the 28th the 7th phase of volume in 2009, upper 1392 pages of article < < agricultural chemicals waste waters that disclose one piece of relevant agricultural chemicals waste water poisonous component tracking were to Caenorhabditis elegans poisonous effect and main poisonous component > > thereof, tentatively having disclosed waste water from pesticide factory water inlet toxicity main source is to be subject to the acid organic poison that regulates impact, and water outlet toxicity main source is to be subject to the organic poison that alkalescence regulates impact.But because organism kinds is various, while identifying intoxicating thing by TIE method, cannot determine organic specific category.
By retrieval, find that current domestic and foreign literature does not also have to report based on agricultural chemicals waste water the acute toxicity to Daphnia magna, by the separated intoxicating component of preparative chromatography, and utilize level Four bar-flight time mass spectrum (Quadrupole Time Of Flight, the toxicity value of ecologic structure activity relationship ECOSAR (Ecological Structure Activity Relationships) the software estimation compound Q-TOF) and in quantitative structure activity relationship (Quantitative Structure Activity Relationships, QSAR) is followed the trail of the crucial intoxicating thing in agricultural chemicals waste water.
Summary of the invention
1, the technical matters that invention will solve:
The problem of crucial intoxicating material extraction, separation, screening and discriminating in poisonous agricultural chemicals waste water for people's growing interest, the object of the present invention is to provide a kind of crucial intoxicating material discrimination method in the agricultural chemicals waste water that Daphnia magna toxicity is guide of take, toxic pollutant classification separation in the agricultural chemicals waste water that the Daphnia magna acute toxicity of take is guide, qualitative identification, screening and the method for confirming, be used for following the trail of crucial intoxicating thing in agricultural chemicals waste water, for the formulation of agricultural chemicals waste water emission standard and environmental criteria provides scientific basis.
2, technical scheme
The present invention is achieved through the following technical solutions to achieve these goals:
In the agricultural chemicals waste water that the Daphnia magna toxicity of take is guide, a crucial intoxicating material discrimination method, the steps include:
(1) Solid-Phase Extraction: water sample filters by the nylon leaching film of glass filter 0.45um, water sample after filtration carries out enrichment by water generation solid-phase extraction column (Waters Oasis HLB), this post activates with normal hexane, methylene chloride, methyl alcohol and deionized water before using successively, flow control is at 1～2 drop/sec, and after extraction finishes, under the rotating speed of 5000r/min, centrifugal 5min removes the moisture in extraction column.
(2) enrichment: with 5mL normal hexane, 10mL methylene chloride and 10mL methyl alcohol, organism is eluted and collect eluent from solid-phase extraction column successively, eluent is revolved to steaming, nitrogen and blow concentratedly, solvent is replaced constant volume again, is transferred in sample introduction bottle and preserves.
(3) Daphnia magna toxicity test: water sample organic extract is replaced to dimethyl sulfoxide (DMSO) DMSO, be mixed with a series of extension rates and be 2 experimental liquid, then in experimental liquid, add 5 24h with the young Magna of interior firm product, arrange 4 parallel, finally put it into incubator and cultivate 24h, the quantity of movable Daphnia magna in each beaker of observed and recorded.
(4) classification is separated: preparative chromatography isolation technics is set up in elution curve and the good Quality Control of based on organic nitrogen pesticide, palycyclic aromatic, nonylphenol, octyl phenol, setting up compound, and water sample organic extract is carried out to separation, and its parameter is as follows:
Preparative chromatograph: water generation is prepared purifying chromatograph (Waters AutoPurification HPLC);
Chromatographic column: water generation preparative column (Waters XBridge C18, is of a size of 19mm * 150mm, and particle diameter is 5um); Flow velocity: 5mL/min; Mobile phase: methyl alcohol, water (being 1 ‰ trifluoroacetic acids containing percent by volume); Collection mode: collect on a time period cut with the glass tube of 15mL specification;
Eluent gradient:
| Time/min | Methyl alcohol percentage composition/% | Water percentage composition/% |
| 0 | 50 | 50 |
| 50 | 100 | 0 |
| 80 | 100 | 0 |
(5) method for concentration of separation component:
(6) the Daphnia magna toxicity test of separation component and toxicity result are calculated: component concentrate replaces to dimethyl sulfoxide (DMSO) DMSO, be mixed with a series of extension rates and be 2 experimental liquid, then in experimental liquid, add 5 24h with the young Magna of interior firm product, arrange 4 parallel, finally put it into incubator and cultivate 24h, the quantity of movable Daphnia magna in each beaker of observed and recorded; The logarithm LogC of the observed reading of Daphnia magna and concentration value is added up with the recurrence Probit in SPSS software, in statistics, find the LogC that 50% inhibiting rate is corresponding, calculate half-inhibition concentration EC50, finally obtain toxic unit (Toxic Unit is called for short TU).
(7) the qualitative identification of compound in component: have the component of effect to obtain accurate relative molecular mass and second order ms figure by high performance liquid chromatography-flight time mass spectrum, database and the network chemline ChemSpider of itself and instrument are compared, finally obtain compound inventory.The parameter of described step (7) Instrumental is as follows:
High performance liquid chromatograph HPLC: Agilent high performance liquid chromatograph (Agilent1260);
Chromatographic column: Agilent chromatographic column (Agilent C18 post, is of a size of 2.1mm * 150mm, and particle diameter is 2.5um); Column temperature: 30 ℃; Flow velocity: 0.3mL/min mobile phase: acetonitrile, water (being 5% acetonitrile containing percent by volume); Eluent gradient:
| Time/min | Water percentage composition/% | Acetonitrile percentage composition/% |
| 0.00 | 100 | 0 |
| 1.00 | 100 | 0 |
| 15.0 | 50 | 50 |
| 25.0 | 0 | 100 |
| 30.0 | 0 | 100 |
| 30.5 | 100 | 0 |
| 40.0 | 100 | 0 |
Mass spectrometer: Triple TOF5600-AB SCIEX; Ion gun: ESI; Ionization pattern: positive ion mode; MS sweep limit: 100-2000m/z; MS-MS sweep limit: 100-1250m/z;
Drive a bunch voltage: 80V; Collision voltage: 35 ± 15eV.
(8) the octanol LogKow of suspicious intoxicating thing screening: the elution curve that obtains compound based on classification separation, thereby determine the distribution of LogKow to the time, utilize LogKow scope to carry out screening compounds, by excavating and resolve the extraction ion of mass spectrogram data software PeakView (the mass spectrum software of AB SCIEX company exploitation), use window (Extrac Ions Using Dialog, XIC) extract accurate mass-to-charge ratio, the molecular formula of utilizing afterwards the mass spectrographic isotopic abundance ratio of one-level and second order ms figure to search for compound, further compare with network chemline ChemSpider the match condition that obtains the inventory of compound and obtain secondary spectrogram.Then by document, find the quantitative ion pair of liquid matter for this compound, will in its ion pair and secondary spectrogram, compare, deserving illustrates in this component and contains this compound.
(9) the quantitative confirmation of suspicious intoxicating thing: the compound screening obtains its toxicity value EC50 by ecologic structure activity relationship ECOSAR (Ecological Structure Activity Relationships) software, and it carries out quantitatively to utilize liquid to verify, obtain the toxic unit TU of compound, calculate the contribution rate of compound in the total toxicity of sample and finally find main intoxicating thing.
3, beneficial effect
This method provides a kind of method that sample complicacy is followed the trail of the crucial intoxicating thing in agricultural chemicals waste water faster and more accurately that reduces, and the present invention is based on preparative chromatography tentatively by the compound of opposed polarity in sample separately, and screening intoxicating component, reduces sample complexity.Utilize level Four bar-flight time mass spectrum (Quadrupole Time OfFlight, Q-TOF) high to the qualitative recognition resolution of compound in intoxicating component, accuracy is high, contains much information, and the compound that screening is obtained is more comprehensive.
Accompanying drawing explanation:
Fig. 1 is organic nitrogen pesticide (bromacil in embodiment 1, piperazine humulone, hexazinone, triazolone, Metadelphene), the elution curve of palycyclic aromatic, nonylphenol, octyl phenol, wherein: what horizontal ordinate represented is the delivery time of compound in preparative chromatography, what ordinate represented is the concentration value of compound under this delivery time, this figure has reacted different octanol LogKow for the distribution of time, and along with the increase of delivery time, the LogKow value of compound increases.
Fig. 2 is organic nitrogen pesticide (bromacil in embodiment 1, piperazine humulone, hexazinone, triazolone, Metadelphene), the Quality Control of palycyclic aromatic, nonylphenol, octyl phenol classification separation, wherein: what horizontal ordinate represented is the acquisition time of compound in preparative chromatography, what ordinate represented is the recovery of compound, and it is reliable that this figure has reacted fractionation method.
Fig. 3 extracts one-level and the secondary spectrogram that ion is used the Tebuconazole (Tebuconazole) that window (Extrac Ions Using Dialog, XIC) screens in embodiment 2, reacted and in sample, had Tebuconazole.
Fig. 4 extracts one-level and the secondary spectrogram that ion is used the own azoles alcohol (Hexaconazole) that window (Extrac Ions Using Dialog, XIC) screens in embodiment 2, reacted and in sample, had own azoles alcohol.
Fig. 5 extracts one-level and the secondary spectrogram that ion is used the propiconazole (Propiconazole) that window (Extrac Ions Using Dialog, XIC) screens in embodiment 2, reacted and in sample, had propiconazole.
Fig. 6 extracts one-level and the secondary spectrogram that ion is used the Flutriafol (Flutriafol) that window (Extrac Ions Using Dialog, XIC) screens in embodiment 2, reacted and in sample, had Flutriafol.
Fig. 7 extracts one-level and the secondary spectrogram that ion is used the tricyclazole (Tricyclazole) that window (Extrac Ions Using Dialog, XIC) screens in embodiment 2, reacted and in sample, had tricyclazole.
Fig. 3-Fig. 7: first little figure is total ion current figure, what horizontal ordinate represented is the time, that ordinate represents is the response intensity Intensity of total ion; Second extraction ion flow graph that little figure is accurate mass number, what horizontal ordinate represented is the time, that ordinate represents is the response intensity Intensity that extracts ion; The 3rd little figure is the isotope distribution plan that extracts ion, and what horizontal ordinate represented is mass number, and that ordinate represents is the response intensity Intensity of this mass number; The 4th structural formula that little figure is compound; The 5th little figure is the fragments matching situation of second order ms figure and compound; The 6th little figure is second order ms figure, and what horizontal ordinate represented is the mass number of secondary fragment, and what ordinate represented is the response intensity of secondary fragment.
Embodiment:
Below in conjunction with embodiment, the present invention is further described
Embodiment 1
The foundation of preparative chromatography isolation technics:
(1) organic nitrogen pesticide (bromacil, piperazine humulone, hexazinone, triazolone, Metadelphene), the foundation of palycyclic aromatic, nonylphenol, octyl phenol elution curve: by organic nitrogen pesticide (bromacil, piperazine humulone, hexazinone, triazolone, Metadelphene), palycyclic aromatic, nonylphenol, octyl phenol standard specimen are separated and concentrated to separated component by preparative chromatography.Utilize high performance liquid chromatography to do quantitative test to palycyclic aromatic, nonylphenol, octyl phenol in separation component.Utilize HPLC-MS to do quantitative test to organic nitrogen pesticide in separation component.Finally obtain the concentration of compound and the distribution of delivery time, set up the elution curve of organic nitrogen pesticide (bromacil, piperazine humulone, hexazinone, triazolone, Metadelphene), palycyclic aromatic, nonylphenol, octyl phenol, as shown in Figure 1.
(2) organic nitrogen pesticide (bromacil, piperazine humulone, hexazinone, triazolone, Metadelphene), the Quality Control of palycyclic aromatic, nonylphenol, octyl phenol classification separation: the foundation based on elution curve obtains the recovery of compound, thereby the reliability of fractionation method is described.The Quality Control result following (as shown in Figure 2) of organic nitrogen pesticide (bromacil, piperazine humulone, hexazinone, triazolone, Metadelphene), palycyclic aromatic, nonylphenol, octyl phenol:
Embodiment 2
A kind ofly take crucial intoxicating material discrimination method in the agricultural chemicals waste water that Daphnia magna toxicity is guide, the steps include: (1) Solid-Phase Extraction: the water inlet of agricultural chemicals waste water treatment plant is filtered by the nylon leaching film of glass filter 0.45um, the 4L water sample measuring after filtration carries out enrichment by water generation solid-phase extraction column (Waters Oasis HLB), this post activates with normal hexane, methylene chloride, methyl alcohol, deionized water before using successively, flow control is at 1～2 drop/sec, the water sample of every pillar enrichment 500mL; After extraction finishes, under the rotating speed of 5000r/min, centrifugal 5min removes the moisture in extraction column.
(2) enrichment: with 5mL normal hexane, 10mL methylene chloride, 10mL methyl alcohol, entering organic matter of water is eluted and collect eluent from solid-phase extraction column successively, by eluent revolve steaming, nitrogen blows concentrated, solvent is replaced and is settled to 1mL again, transfers in sample introduction bottle and preserves.
(3) Daphnia magna toxicity test: water inlet organic extract is replaced to dimethyl sulfoxide (DMSO) DMSO, in 25mL beaker, add 9.95mL water, add inside 50uL to replace to the organic extract of DMSO, be mixed with a series of extension rates and be 2 experimental liquid, then in experimental liquid, add 5 24h with the young Magna of interior firm product, arrange 4 parallel, finally put it into incubator and cultivate 24h, the quantity of movable Daphnia magna in each beaker of observed and recorded.
(4) classification is separated: utilize preparative chromatography that agricultural chemicals waste water organic extract is divided into 11 components, its parameter is as follows:
Preparative chromatograph: water generation is prepared purifying chromatograph Waters AutoPurification HPLC;
Chromatographic column: water generation preparative column (Waters XBridge C18, is of a size of 19mm * 150mm, and particle diameter is 5um); Flow velocity: 5mL/min; Sample size: 500uL, sample introduction 2 times; Mobile phase: methyl alcohol, water (being the mixed liquor of 1 ‰ trifluoroacetic acids and water containing percent by volume); Collection mode: collect on a time period cut with the glass tube of 15mL specification;
Eluent gradient:
| Time/min | Methyl alcohol percentage composition/% | Water percentage composition/% |
| 0 | 50 | 50 |
| 50 | 100 | 0 |
| 80 | 100 | 0 |
Collection method is as follows:
(5) method for concentration of separation component:
(6) the Daphnia magna toxicity test of separation component 1-11 and toxicity result are calculated: component 1-11 concentrate is replaced to dimethyl sulfoxide (DMSO) DMSO, in 25mL beaker, add 9.95mL water, add inside 50uL to replace to the component concentrate of DMSO, be mixed with a series of extension rates and be 2 experimental liquid, then in experimental liquid, add 5 24h with the young Magna of interior firm product, arrange 4 parallel, finally put it into incubator and cultivate 24h, the quantity of movable Daphnia magna in each beaker of observed and recorded; The logarithm LogC of the observed reading of the Daphnia magna of component 1-11 and concentration value is added up with Probit in the recurrence in SPSS software, in statistics, find the LogC that 50% inhibiting rate is corresponding, calculate LC50 EC50, finally obtain the toxic unit TU of component 1-11.The toxicity result of agricultural chemicals waste water organic extract and component 1-11 is as follows:
(7) the qualitative identification of compound in component 3,4,5,7: intoxicating component 3,4,5,7 is obtained to I and II mass spectrogram (as Fig. 3-7) by colleges and universities' sewage sludge.Utilize level Four bar-flight time mass spectrum high to the qualitative recognition resolution of compound in intoxicating component, accuracy is high, contains much information, and the compound that screening is obtained is more comprehensive.Its instrument parameter is as follows:
High performance liquid chromatograph HPLC: Agilent high performance liquid chromatograph (Agilent1260);
Chromatographic column: Agilent chromatographic column (Agilent C18 post, is of a size of 2.1mm * 150mm, and particle diameter is 2.5um); Column temperature: 30 ℃; Flow velocity: 0.3mL/min; Mobile phase: acetonitrile, water (being the mixed liquor of 5% acetonitrile and water containing percent by volume);
Eluent gradient:
| Time/min | Water percentage composition/% | Acetonitrile percentage composition/% |
| 0.00 | 100 | 0 |
| 1.00 | 100 | 0 |
| 15.0 | 50 | 50 |
| 25.0 | 0 | 100 |
| 30.0 | 0 | 100 |
| 30.5 | 100 | 0 |
| 40.0 | 100 | 0 |
Mass spectrometer: Triple TOF5600-AB SCIE; Ion gun: ESI; Ionization pattern: positive ion mode; MS sweep limit: 100-2000m/z; MS-MS sweep limit: 100-1250m/z;
Drive a bunch voltage: 80V; Collision voltage: 35 ± 15eV.
(8) LogKow of suspicious intoxicating thing screening in component 3,4,5,7: utilize the extraction ion that excavates and resolve mass spectrogram data software PeakView (the mass spectrum software of AB SCIEX company exploitation) to use window (Extrac Ions Using Dialog, XIC) extract accurate mass-to-charge ratio, the molecular formula that chemical element condition based on setting utilizes the second order ms figure of the mass spectrographic isotopic abundance ratio of one-level and this mass-to-charge ratio to search for compound afterwards, further compares by network chemline ChemSpider the inventory that obtains compound.Then based on the separated elution curve of classification, obtain the distribution of LogKow to the time, by n-octyl alcohol and water partition coefficient LogKow etc., carry out screening compounds, lock some compounds.Finally find to extract the ion pair information matches that ion is used the one-level of tricyclazole out of Windows filter, propiconazole, Tebuconazole, own azoles alcohol, Flutriafol and secondary spectrogram and document to find, reacted and in sample, had tricyclazole, propiconazole, Tebuconazole, own azoles alcohol, Flutriafol.
(9) the quantitative confirmation of suspicious intoxicating thing: the compound screening is obtained to its toxicity value EC50 by ecologic structure activity relationship ECOSAR (Ecological Structure Activity Relationships) software, and it carries out quantitatively, finally obtaining the toxic unit TU of compound to utilize liquid to verify.The TU of the TU of compound and sample is returned, and related coefficient is greater than 0.8, illustrates that compound is the main intoxicating thing in sample.Finally obtaining main intoxicating thing in agricultural chemicals waste water is: tricyclazole, propiconazole, Tebuconazole, own azoles alcohol, Flutriafol.
Claims (6)
1. in the agricultural chemicals waste water that the Daphnia magna toxicity of take is guide, a crucial intoxicating material discrimination method, the steps include:
(1) Solid-Phase Extraction: water sample filters by the nylon membrane of 0.45um, after filtering, water sample carries out enrichment by solid-phase extraction column;
(2) enrichment: utilize opposed polarity solvent that organism is eluted from solid-phase extraction column, concentrated constant volume;
(3) Daphnia magna toxicity test: after sample is replaced to dimethyl sulfoxide (DMSO) DMSO, the water-soluble variable concentrations that is made into carries out Daphnia magna exposure experiment;
(4) classification is separated: based on organic nitrogen pesticide, palycyclic aromatic, nonylphenol, octyl phenol, set up preparative chromatography isolation technics, and sample is carried out to the complicacy that separation reduces sample;
(5) the Daphnia magna toxicity test of separation component: the component of preparing after separating utilizes liquid-liquid extraction and Solid-Phase Extraction to concentrate, separation component replaces to the water-soluble variable concentrations that is made into of dimethyl sulfoxide (DMSO) DMSO and carries out type Magna exposure experiment;
(6) Daphnia magna toxicity result is calculated: the logarithm LogC of the observed reading of Daphnia magna and concentration value is added up with the recurrence Probit in SPSS software, find the LogC that 50% inhibiting rate is corresponding in statistics, calculate half-inhibition concentration EC50;
(7) the qualitative identification of compound in intoxicating component: utilize high performance liquid chromatography-flight time mass spectrum to scan intoxicating component, obtain one-level and secondary spectrogram;
(8) screening of suspicious intoxicating thing: the elution curve that obtains compound based on fractionation method, thereby determine the distribution of octanol LogKow to the time, utilize LogKow scope to carry out screening compounds, by excavating and resolve mass spectrogram data software PeakView, open one-level secondary spectrogram, its spectrogram is obtained to compound inventory by network chemline ChemSpider search, and the compound quota ion of Literature Consult band pair is mated with secondary spectrogram;
(9) the quantitative confirmation of suspicious intoxicating thing: the compound screening obtains its toxicity value EC50 by ecologic structure activity relationship ECOSAR software, and it carries out quantitatively to utilize liquid to verify, obtain the toxic unit TU of compound, calculate the contribution rate of compound in the total toxicity of sample and finally find main intoxicating thing.
2. according to right 1, require the described crucial intoxicating material discrimination method in the agricultural chemicals waste water that Daphnia magna toxicity is guide of take, it is characterized in that: in described step (1), solid-phase extraction column used is Waters Oasis HLB solid phase extraction column, before using, with normal hexane, methylene chloride, methyl alcohol and deionized water activation, whole process guarantees that pillar is moistening.
3. according to right 1, require the described crucial intoxicating material discrimination method in the agricultural chemicals waste water that Daphnia magna toxicity is guide of take, it is characterized in that: in described step (2), opposed polarity solvent used is 5mL normal hexane, 10mL methylene chloride and 10mL methyl alcohol.
4. according to right 1, require the described crucial intoxicating material discrimination method in the agricultural chemicals waste water that Daphnia magna toxicity is guide of take, it is characterized in that: in described step (4), the parameter of classification separation is as follows:
Preparative chromatograph: Waters AutoPurification HPLC; Chromatographic column: Waters XBridge C18 preparative column, described preparative column is of a size of 19mm * 150mm, and particle diameter is 5um; Flow velocity: 5mL/min; Mobile phase: methyl alcohol is the miscible fluid of 1 ‰ trifluoroacetic acids and water containing percent by volume.
5. according to right 1, require the described crucial intoxicating material discrimination method in the agricultural chemicals waste water that Daphnia magna toxicity is guide of take, it is characterized in that: the instrument parameter in described step (7) is as follows: high performance liquid chromatograph HPLC:Agilent1260; Chromatographic column: Agilent C18 post, described column size is 2.1mm * 150mm, particle diameter is 2.5um; Column temperature: 30 ℃; Flow velocity: 0.3mL/min; Mobile phase: acetonitrile is the miscible fluid of 5% acetonitrile and water containing percent by volume; Mass spectrometer: Triple TOF5600-AB SCIEX; Ion gun: ESI; Ionization pattern: positive ion mode; MS sweep limit: 100-2000m/z; MS-MS sweep limit: 100-1250m/z; Drive a bunch voltage: 80V; Collision voltage: 35 ± 15eV.
6. according to the crucial intoxicating material discrimination method in the agricultural chemicals waste water that Daphnia magna toxicity is guide of take described in any one in right 1-5, it is characterized in that: in described step (8), utilize the extraction ion that excavates and resolve in mass spectrogram data software PeakView to use window to extract accurate mass-to-charge ratio and obtain one-level mass spectrogram, recycling information dependence obtaining mode finds the second order ms figure of this mass-to-charge ratio, utilize one-level and second order ms figure to obtain compound inventory by network chemline ChemSpider search, again the quota ion of bibliographical information compound pair is mated with second order ms figure.
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Application publication date: 20140813 Assignee: JIANGYIN QIUHAO TESTING Co.,Ltd. Assignor: NANJING University Contract record no.: X2024980002272 Denomination of invention: A method for identifying key toxic substances in pesticide wastewater based on the toxicity of Daphnia magna Granted publication date: 20160413 License type: Common License Record date: 20240227 |
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