CN104034566A - Pretreatment method for rapidly extracting ten nitro aromatic compounds in soil - Google Patents
Pretreatment method for rapidly extracting ten nitro aromatic compounds in soil Download PDFInfo
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Abstract
The invention provides a pretreatment method for rapidly extracting ten nitro aromatic compounds in soil. The method comprises the steps of soil sample preparation, oscillation extraction and centrifugal separation. Specifically, soil and purified anhydrous sodium sulfate and diatomite are mixed to achieve the effects of removing water and dispersing a matrix; an effect of dissolving active ingredients contained in soil media such as a soil solution and soil organic matter by an extraction solvent is guaranteed through extraction with hydrophobic and hydrophilic mixed solvents; a soil breaking effect is achieved by a mechanical shaking mode, and the extraction efficiency is improved; solid-liquid separation between a soil sample and the extraction solvent is finished through low-temperature high-speed centrifuging, so that an extracting solution is rapidly extracted. Compared with traditional methods for extracting nitro aromatic compounds in soil, such as Soxhlet extraction, ultrasonic extraction and accelerated solvent extraction, the pretreatment method has the obvious advantages of high one-step sample treatment capacity, small amount of organic solvents, simple steps, high extraction efficiency, low-price and simple equipment and the like.
Description
Technical field
The present invention relates to a kind of pre-treatment abstraction technique for 10 kinds of Nitro-aromatic Compounds in Differents in contaminated soil, specifically, a pre-treating method for 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil, be a kind of using heterogeneous mixing polar organic solvent as extraction agent, use the pre-treating method of mechanical jolting mode, high-speed low temperature centrifugation 10 kinds of nitro-aromatic compounds of rapid extraction from pedotheque.
Background technology
Nitro-aromatic is the general name of nitro-aromatic compounds of group, is that dyestuff is synthetic, the intermediate of paint, plastics, explosive, medicine and agricultural chemicals manufacture etc.Nitro-aromatic pollutant in environment mainly comprises the materials such as nitrobenzene, chloronitrobenzene, nitrotoluene.
Most of nitro-aromatic compound has the feature of stable chemical nature, high toxicity and biological concentration, belongs to high toxicity pollutant, is put in the screen priority pollutants list of American National Environmental Protection Administration (EPA) and China.This compounds can cause human body poisoning through respiratory tract, alimentary canal and skin, and Main Function, in blood, liver and central nervous system, can make haemoglobin become methemoglobin, loses the ability of transport oxygen, causes anoxic.Nitro-aromatic Compounds in Different belongs to lasting toxicity organic contaminant, there is the sudden change of causing, cause cancer, lead deforming health risk, in industries such as printing and dyeing, agricultural chemicals as intermediate; Chloronitrobenzene is that one can cause sudden change, cause cancer, lead deforming chemical substance, in industries such as printing and dyeing, agricultural chemicals as intermediate; Dinitro benzene when concentration reaches 10mg/L in water body, can cause fish and hydrobiological death, has inflammable, explosively, has severe toxicity, has carcinogenicity.The current every basic work progress of Soil Pollution Control of China comparatively lags behind, environmental supervision and administration system is unsound, for the monitoring capability weakness of the high toxicity organic pollutant in soil, the Study on Monitoring Technology of therefore carrying out nitro-aromatic compound in soil is significant to assessment China soil environment security risk.
Pretreatment technology is the gordian technique of environmental sample quantitative test, main object is from soil media, by Separation of Solid and Liquid, it to be transferred in liquid-phase system from solid system with less loss active principle to be extracted, so that next step instrumental analysis.Such as obtaining difficult volatility or half volatile organic component in the solid sample such as soil, sediment, conventionally need to use organic solvent effectively to extract treated solid, semi-solid sample.
The current Specifications of Monitoring Technology about Nitro-aromatic Compounds in Different, China does not still have correlation technique directive/guide and the standard for the pre-treatment of nitro-aromatic compound in soil, only have the relevant criterion method about nitro-aromatic compound in water environment, as " the mensuration vapor-phase chromatography of water quality nitrobenzene, nitrotoluene, nitro-chlorobenzene, dinitrotoluene (DNT) " in existing method standard (GB13194-91); " the mensuration vapor-phase chromatography of water quality nitrobenzene compounds " (HJ592-2010); Ministry of Water Resources's industry standard " the mensuration resin adsorption/vapor-phase chromatography of Analysis of Organic Substances method Trace Nitrobenzene compounds in water " (SL/T273.1-2001), and up-to-date 2013 issue standard method " mensuration liquid-liquid extraction/organophosphorous pesticides method of water quality nitrobenzene compounds " (HJ648-2013) in regulation method.
External relevant soil monitoring technical method mainly contains the correlation technique that Environmental Protection Agency issues, and pretreatment technology method has adopted based on soxhlet extraction, accelerated solvent extraction and ultrasonic extraction technical method:
As used GC/MS for measuring solid waste in the EPA8270C method of Environmental Protection Agency's issue, soil, gas, the detection of water sample, detect object and comprised dinitro benzene, 2, 4-dinitrotoluene (DNT) and 2, the mensuration of 6-dinitrotoluene (DNT), in the method, recommend the extraction of following several relevant pre-treatment extracting process for organic target compound, as method, 3540C has adopted soxhlet extraction, method 3541 adopts automatic soxhlet extraction, method 3545 adopts pressure fluid extraction (PFE) technology, method 3550B has adopted ultrasonic wave extraction, method 3560 adopts supercritical fluid extraction organism as total petroleum hydrocarbon class.
In these pre-treating methods as Soxhlet extract, automatically soxhlet extraction, ultrasonic extraction, in supercritical fluid extraction or heating pressure fluid extracting process, except Soxhlet extracting method equipment is applicable to simple and easy popularization, other extraction modes need to be purchased expensive large-scale instrument, and equipment cost and maintenance cost are higher, the universal difficulty that exists of method.And Soxhlet extractive technique, the solvent-oil ratio that single extraction needs is larger, more than being about hundreds of milliliters, also can bring the problem of solvent contamination while extracting sample in a large number; In addition for ensuring good effect of extracting, a sample extraction time is about more than tens of hours, and this also causes the treatment effeciency of the method lower.Therefore, at present the development trend of organic extraction technology tend to that the toxicity of used extraction solvent is lower, consumption still less, on guarantee good recovery of extraction basis, operation is simple, has higher extraction efficiency can complete at short notice the pre-treatment extraction work of batch samples.
Study on determination method report about nitro-aromatic compound in soil:
In 17 pages of " Shandong environment " the 2nd phases in 1997, introduce a kind of method that uses nitrobenzene in oscillopolarographic detection soil, the monitoring that uses electrochemical method to be correlated with, the soil liquid need to be diluted to a certain amount of electrolysed saline solution obtained, but not report the method determination limit of the method.In 2003 " Guangzhou chemistry " the 2nd phase 45-46 page, introduced a kind of residual quantity of utilizing pentachloronitrobenzene in Soil by Gas Chromatography, the average recovery rate of this method is 98.6%, and minimal detectable concentration is 0.25 μ g/kg, and relative standard deviation is less than 10%.In 2009 " environmental monitoring management and technology " the 1st phase 22-24 page, introduce benzene, aniline and nitrobenzene in a kind of employing headspace gas chromatography Fast Measurement soil, the method is used sherwood oil-acetone mixed solvent as extractant, sample to be soaked after 12h, extract several times, method is good in 0mg/L～100mg/L scope internal linear, the detection limit of benzene, aniline, nitrobenzene is respectively 0.012mg/kg, 0.22mg/kg, 0.083mg/kg, RSD≤1.4% that actual soil sample is measured, recovery of standard addition is 94.0%～102%.
In sum, in soil, the monitoring method of nitro-aromatic compound is less both at home and abroad at present, the determination techniques of selecting is mainly limited to electrochemical method, chromatography, mass spectroscopy, supporting pretreatment technology mainly comprises headspace sampling technology, soaks extraction with it, in these methods, the headspace sampling equipment of value costliness as special in headspace sampling Technology Need completes, and the method for immersion extraction need to be soaked 12h to pedotheque and just can be obtained the more satisfactory recovery later.
Summary of the invention
1. the technical matters that invention will solve:
For the pre-treatment problem existing in nitro-aromatic compound quantitative test process in current soil environmental sample, the invention provides the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in a kind of rapid extraction soil, adopt the organic solvent system that mixes polarity with difference, utilize mechanical jolting crumbling method, use high speed centrifugation method to realize Separation of Solid and Liquid, thereby rapidly and efficiently extract the pre-treatment analytical technology of nitro-aromatic compound in soil, the more traditional pretreatment technology of this technology is at analysis cost, analysis time, manpower consumption, environmental friendliness aspect has obvious advantage, can greatly save traditional soil, bed mud, pre-treatment analysis time and the expense of sediment sample, save solvent consumption, reduce the environmental risk of toxic solvent.
2. technical scheme:
Principle of the present invention:
Component based on opposed polarity in mixed solvent system and the similar characteristic that mixes moisture in soil, hydrophobic components, use mechanical jolting effect to carry out after Mechanical Crushing pedotheque, increase solid, liquid contact area, fully contact with mixed solvent, realize leaching and separate thereby reduce acting force between target extract and sample matrices.
Technical scheme of the present invention is as follows:
The method of using nitro-aromatic compound in mixed solvent system extraction soil, bed mud, sediment, the steps include:
(A) target compound has been selected 10 kinds of nitro-aromatic compounds.
(B) sample preparation: take pedotheque, add simultaneously with the activation of pedotheque equal in quality after zeyssatite or anhydrous sodium sulfate, after mixing, put into clean vial;
(C) sample extraction: according to pedotheque amount, according to the ratio of the quality g/ volume ml ratio 1:1～1:3 of soil and hydrophilic solvent, add hydrophilic solvent, jolting 3～5min, makes soil breaking reach homogenate shape fast; According to the quality g/ volume ml ratio 1:1～1:3 of soil and hydrophobic solvent, add hydrophobic solvent again, jolting 30～60min fast, speed is 200～500r/min;
(D) centrifuging.By the sample after previous step shaking out, put into the centrifugal 3～5min of hydro-extractor (rotating speed is 3000～5000r/min), from supernatant, extract a certain amount of extract, low temperature is preserved or is entered that gas chromatography, gas chromatography mass spectrometry are carried out quantitatively, qualitative analysis;
Wherein instrumental analysis condition, its instrument condition is: select medium or low pole chromatographic column in chromatographic column, 40 DEG C of temperature programmes, keep 2min,, be warming up to 220 DEG C with 20 DEG C/min, be warming up to 280 DEG C with 15 DEG C/min again, finally be warming up to 300 DEG C with 5 DEG C/min, keep 3min, 250 DEG C of injector temperatures; Splitless injecting samples 1uL, carrier gas is used helium, helium purity > 99.999%, flow velocity 1.2mL/min, constant current mode;
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z, carries out quantitative, qualitative analysis.
Target compound in step (A) is: nitrobenzene, o-dinitrobenzene, meta-dinitro-benzent, paradinitrobenzene, m-chloro-nitrobenzene, 2,4-dinitrotoluene (DNT), 1-chloro-2,4-dinitro benzene, TNT, o-chloronitrobenzene, parachloronitrobenzene.Information is in table 1.
Zeyssatite in step (B) or the activation condition of anhydrous sodium sulfate are: 400 DEG C of baking 6h are residual to remove organic substance.
In step (C), hydrophilic solvent can be selected acetone, ethyl acetate, methyl alcohol or acetonitrile; The optional normal hexane of hydrophobic solvent, methylene chloride or cyclohexane, recommend group of solvents to be combined into: acetone and normal hexane, cyclohexane and ethyl acetate, methyl alcohol and methylene chloride or acetonitrile and methylene chloride.The blending ratio suggestion of different solvents is 1:1 volume ratio.
In above-mentioned steps (D) in centrifugal process recommendation low-temperature centrifugation, 4～6 degrees Celsius of temperature controls, avoid the volatilization of organic system.
In step (D), chromatographic column is Agilent HP-5, DB-5, DB-5MS or DB-XLB capillary column.
In above step, related scope is all can the actual scope of implementing, and according to experiment condition, we can select in above scope.
3. beneficial effect:
The invention provides the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in a kind of rapid extraction soil, use heterogeneous mixed solvent, with jolting fragmentation, centrifugal purification mode come fast, the pre-treating method of 10 kinds of nitro-aromatic compounds in high efficiency extraction soil, be characterized in utilizing the heterogeneous organic extraction system combinations of hydrophilic solvent and hydrophobic solvent, certain blending ratio to improve the solid-liquid contact area to soil and extractant, raising extraction efficiency and extraction effect.Concrete effect performance is as follows:
(1) the present invention utilizes the extraction advantage of opposed polarity solvent to target compound, and the extraction efficiency of the system of the organic solvent to various combination is optimized, and has greatly saved the consumption of solvent;
(2) utilize the polarity difference of solvent and the order adding, increase the dissolution properties of soil in solvent, coordinate effect manual or that the quick jolting mode of motor machine reaches fragmentation, mixes, further increase nitro-aromatic compound extraction efficiency in different solvents system in medium, can realize pedotheque in enormous quantities extractive analysis rapidly and efficiently, use manpower and material resources sparingly;
(3) dicyandiamide solution of selecting comprises extraction agent low toxicity, eco-friendly, can substitute the dicyandiamide solution that toxicity is higher, large to human health damage, has environmental friendliness characteristic;
(4) from external technical literature, chromatogram, mass spectrometric hyphenated technique show the progressively Main Analysis instrument as organic analysis using its more excellent sensitivity and selectivity, dicyandiamide solution of the present invention has applicable saturated vapor pressure, can meet the later stage directly in the quantitative and qualitative demand of gas chromatography, Mass Spectrometer Method.
(5) at present China is about the relevant monitoring technology of nitro-aromatic compound in soil still in technological gap, and the present invention provides the technology of Nitro-aromatic Compounds in Different a set of efficient, low consumption extraction soil media from pretreatment technology aspect.
Experimental results show that: use acetone and normal hexane that volume ratio is 1:1, acetone and methylene chloride, cyclohexane and ethyl acetate, methyl alcohol and methylene chloride, methyl alcohol and ethyl acetate, the mixed solvent such as acetonitrile and methylene chloride, to the mean recovery of extraction of 10 kinds of nitro-aromatic compounds of soil between 69.6%～108.1%, wherein the recovery of extraction of p-nitrophenyl component is between 74.1%～103.7%, to the recovery of extraction of o-dinitrobenzene component 65.8%～111.7%, between pair, the recovery of extraction of dinitro component is between 74.7%～106.3%, the recovery of extraction 71.2%～108.0% of paradinitrobenzene component, the recovery of extraction of m-chloro-nitrobenzene component is 72.5%～104.5%, 2, the recovery of extraction of 4-dinitrotoluene (DNT) component is 71.1%～108.5%, 1-chloro-2, the recovery of extraction of 4-dinitro benzene component is 69.9%～110.6%, 2, 4, the recovery of extraction of 6-trinitro-toluene component is 55.3%～126.4%, the recovery of extraction of o-chloronitrobenzene and parachloronitrobenzene component is 71.4%～107.2%, can meet in quantitative test 50～130% recovery requirement.
Brief description of the drawings
Fig. 1 is the recovery of extraction of different extraction solvent systems to nitrobenzene in soil.
Fig. 2 is the recovery of extraction of different extraction solvent systems to adjacent dinitro aromatic hydrocarbons in soil.
Fig. 3 is the recovery of extraction of different extraction solvent systems to dinitro aromatic hydrocarbons in the middle of soil.
Fig. 4 be different extraction solvent systems in soil to dinitro aromatic hydrocarbons the recovery in different extraction system.
Fig. 5 is the recovery of extraction of different extraction solvent systems to m-chloro-nitrobenzene in soil.
Fig. 6 is different extraction solvent systems in soil 2, the recovery of extraction of 4-dinitrotoluene (DNT).
Fig. 7 is the recovery of extraction of different extraction solvent systems to DNCB in soil.
Fig. 8 is the recovery of extraction of different extraction solvent systems to TNT in soil.
Fig. 9 is the recovery of extraction of different extraction solvent systems to o-chloronitrobenzene & parachloronitrobenzene in soil.
Embodiment
Further illustrate by reference to the accompanying drawings by the following examples the present invention.Protection scope of the present invention is not restricted to the present embodiment, and table 1 is the information of 10 kinds of nitro-aromatic compounds
| Sequence number | Chinese | English name | CAS | Molecular weight |
| 1 | Nitrobenzene | Nitrobenzene | 98-95-3 | 123.11 |
| 2 | O-dinitrobenzene | o-Dinitrobenzene | 528-29-0 | 168.109 |
| 3 | Meta-dinitro-benzent | m-Dinitrobenzene | 99-65-0 | 168.109 |
| 4 | Paradinitrobenzene | p-Dinitrobenzene | 100-25-4 | 168.109 |
| 5 | M-chloro-nitrobenzene | m-Chloronitrobenzene | 121-73-3 | 157.55 |
| 6 | 2,4-dinitrotoluene (DNT) | 2,4-Dinitrotoluene | 121-14-2 | 182.14 |
| 7 | DNCB | 1-Chloro-2,4-dinitrobenzene | 97-00-7 | 157.55 |
| 8 | TNT | 2,4,6-trinitro-Toluene | 118-96-7 | 227.13 |
| 9 | O-chloronitrobenzene | o-Chloronitrobenzene | 88-73-3 | 157.55 |
| 10 | Parachloronitrobenzene | p-Chloronitrobenzene | 100-00-5 | 157.55 |
The pre-treating method of nitrobenzene compound in embodiment 1:(soil)
(1) target compound is selected nitrobenzene compound, the nitrobenzene standard solution that compound concentration is 1000ug/mL.
(2) preparation of samples: take blank soil (blank soil processing is through purifying the blank soil thing as an alternative after extracting with physical environment), and add the nitrobenzene standard solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the acetone solvent (chromatographic grade) that adds 10ml, the about 3min of jolting fast, make soil breaking to homogenate shape, add again 10ml normal hexane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 40min fast, speed is 200r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 3500r/min to put into the centrifugal 5min of refrigerated centrifuge, temperature keeps 4 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect from tandem mass spectrum.
Chromatographic condition: chromatographic column adopting DB-5MS chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain the peak area of nitrobenzene compound by integration, quantitatively convert and be extracted the nitrobenzene material concentration (x1) of liquid again, the ratio of concentration x1 and initial concentration x0 (x0=1000ng/ml in this example) is the method recovery of extraction (y1) under acetone/n-hexane extraction system.See Fig. 1.Recovery of extraction under different extraction system refers to Fig. 1.
The pre-treating method of o-dinitrobenzene compound in embodiment 2:(soil)
(1) target compound is selected o-dinitrobenzene compound, the o-dinitrobenzene standard solution that compound concentration is 1000ug/mL.
(2) preparation of samples: take blank soil, and add the solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the acetone solvent (chromatographic grade) that adds 10ml, the about 3min of jolting fast, make soil breaking to homogenate shape, add again 10ml dichloromethane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 40min fast, speed is 200r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 3500r/min to put into the centrifugal 5min of refrigerated centrifuge, temperature keeps 4 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect from tandem mass spectrum.
Chromatographic condition: chromatographic column adopting DB-5MS chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain the peak area of o-dinitrobenzene compound by integration, conversion is extracted o-dinitrobenzene material concentration (x2) in liquid, and the ratio of concentration x2 and o-dinitrobenzene standard items initial concentration (in this example, initial concentration is 1000ng/ml) is the method recovery of extraction (y2) under acetone/dichloromethane extraction system.Recovery of extraction under different extraction system, refers to Fig. 2.
The pre-treating method of embodiment 3:(soil di-nitrobenzene compound)
(1) target compound is selected meta-dinitro-benzent compound, the meta-dinitro-benzent standard solution that compound concentration is 1000ug/mL.
(2) preparation of samples: take blank soil, and add the standard solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the ethyl acetate solvent (chromatographic grade) that adds 10ml, the about 3min of jolting fast, make soil breaking to homogenate shape, add again 10ml cyclohexane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 40min fast, speed is 200r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 3500r/min to put into the centrifugal 5min of refrigerated centrifuge, temperature keeps 4 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect from tandem mass spectrum.
Chromatographic condition: chromatographic column adopting DB-5MS chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain the peak area of meta-dinitro-benzent compound by integration, conversion is extracted liquid di-nitrobenzene material concentration (x3), and the ratio of concentration x3 and meta-dinitro-benzent standard items initial concentration (in this example, initial concentration is 1000ng/ml) is the method recovery of extraction (y3) under ethyl acetate/cyclohexane extraction system.Recovery of extraction under different extraction system, refers to Fig. 3.
The pre-treating method of paradinitrobenzene compound in embodiment 4:(soil)
(1) target compound is selected paradinitrobenzene compound, the paradinitrobenzene standard solution that compound concentration is 1000ug/mL.
(2) preparation of samples: take blank soil, and add the standard solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the methanol solvate (chromatographic grade) that adds 10ml, the about 3min of jolting fast, make soil breaking to homogenate shape, add again 10ml dichloromethane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 40min fast, speed is 200r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 3500r/min to put into the centrifugal 5min of refrigerated centrifuge, temperature keeps 4 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect from tandem mass spectrum.
Chromatographic condition: chromatographic column adopting DB-5MS chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain the peak area of paradinitrobenzene compound by integration, conversion is extracted paradinitrobenzene material concentration (x4) in liquid, and the ratio of concentration x4 and paradinitrobenzene standard items initial concentration (in this example, initial concentration is 1000ng/ml) is the method recovery of extraction (y4) under ethanol/methylene extraction system.Recovery of extraction under different extraction system, refers to Fig. 4.
The pre-treating method of m-chloro-nitrobenzene compound in embodiment 5:(soil)
(1) target compound is selected m-chloro-nitrobenzene compound, the m-chloro-nitrobenzene standard solution that compound concentration is 1000ug/mL.
(2) preparation of samples: take blank soil, and add the standard solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the acetonitrile solvent (chromatographic grade) that adds 10ml, the about 3min of jolting fast, make soil breaking to homogenate shape, add again 10ml dichloromethane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 40min fast, speed is 200r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 3500r/min to put into the centrifugal 5min of refrigerated centrifuge, temperature keeps 4 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect quantitatively from tandem mass spectrum
Chromatographic condition: chromatographic column adopting DB-5MS chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain the peak area of m-chloro-nitrobenzene compound by integration, conversion is extracted m-chloro-nitrobenzene material concentration (x5) in liquid, and the ratio of concentration x5 and m-chloro-nitrobenzene standard items initial concentration (in this example, initial concentration is 1000ng/ml) is the method recovery of extraction (y5) under acetonitrile/dichloromethane extraction system.Recovery of extraction under different extraction system, refers to Fig. 5.
In embodiment 6:(soil 2, the pre-treating method of 4-dinitrotoluene (DNT) compound)
(1) target compound is selected 2,4-dinitro benzene compound, and compound concentration is 1000ug/mL 2,4-dinitrotoluene (DNT) standard solution.
(2) preparation of samples: take blank soil, and add the standard solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the acetone solvent (chromatographic grade) that adds 10ml, the about 3min of jolting fast, make soil breaking to homogenate shape, add again 10ml dichloromethane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 40min fast, speed is 200r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 3500r/min to put into the centrifugal 5min of refrigerated centrifuge, temperature keeps 4 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect quantitatively from tandem mass spectrum
Chromatographic condition: chromatographic column adopting DB-5 chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain 2 by integration, the peak area of 4-dinitrotoluene (DNT) compound, conversion is extracted in liquid 2,4-dinitrotoluene (DNT) material concentration (x6), the ratio of concentration x6 and 2,4-dinitrotoluene (DNT) standard items initial concentration (in this example, initial concentration is 1000ng/ml) is the method recovery of extraction (y6) under acetone/dichloromethane extraction system.Recovery of extraction under different extraction system, refers to Fig. 6.
The pre-treating method of DNCB compound in embodiment 7:(soil)
(1) target compound is selected DNCB compound, the DNCB standard solution that compound concentration is 1000ug/mL.
(2) preparation of samples: take blank soil, and add the standard solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the methanol solvate (chromatographic grade) that adds 15ml, the about 4min of jolting fast, make soil breaking to homogenate shape, add again 15ml dichloromethane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 30min fast, speed is 300r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 3000r/min to put into the centrifugal 4min of refrigerated centrifuge, temperature keeps 5 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect quantitatively from tandem mass spectrum
Chromatographic condition: chromatographic column adopting Agilent DB-5 chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain 1-chloro-2 by integration, the peak area of 4-dinitro benzene compound, conversion is extracted 1-chloro-2 in liquid, 4-dinitro benzene material concentration (x7), the ratio of concentration x7 and DNCB standard items initial concentration (in this example, initial concentration is 1000ng/ml) is the method recovery of extraction (y7) under ethanol/methylene extraction system.Recovery of extraction under different extraction system, refers to Fig. 7.
The pre-treating method of TNT compound in embodiment 8:(soil)
(1) target compound is selected TNT compound, the TNT standard solution that compound concentration is 1000ug/mL.
(2) preparation of samples: take blank soil, and add the standard solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the acetone solvent (chromatographic grade) that adds 5ml, the about 5min of jolting fast, make soil breaking to homogenate shape, add again 5ml normal hexane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 60min fast, speed is 500r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 5000r/min to put into the centrifugal 3min of refrigerated centrifuge, temperature keeps 6 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect quantitatively from tandem mass spectrum
Chromatographic condition: chromatographic column adopting Agilent HP-5MS chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain the peak area of TNT compound by integration, conversion is extracted in liquid 2,4,6-trinitro-toluene material concentration (x8), concentration x8 and 2, the ratio of 4,6-trinitro-toluene standard items initial concentration (in this example, initial concentration is 1000ng/ml) is the method recovery of extraction (y8) under n-hexane/acetone extraction system.Recovery of extraction under different extraction system, refers to Fig. 8.
The pre-treating method of o-chloronitrobenzene, parachloronitrobenzene compound in embodiment 9:(soil)
(1) target compound is selected o-chloronitrobenzene and parachloronitrobenzene compound, the o-chloronitrobenzene & parachloronitrobenzene standard solution that compound concentration is 1000ug/mL.O-chloronitrobenzene & parachloronitrobenzene is two isomers compounds, and the chemical property of two compounds is very approaching, is difficult to separate on chromatogram, places it in as a compounds herein and adds up.
(2) preparation of samples: take blank soil, and add the standard solution of configuration in 1.0ml step (1), make pedotheque 5g, add the rear zeyssatite of 5g activation (toasting 6h to remove organism through 400 DEG C), mixed sample packs in the clean vial of 40ml.
(3) extraction of sample: the methanol solvate (chromatographic grade) that adds 10ml, the about 3min of jolting fast, make soil breaking to homogenate shape, add again 10ml dichloromethane solvent (chromatographic grade), tighten bottle cap, put into oscillator shaking out 40min fast, speed is 200r/min.
(4) sample is centrifugal and concentrated: by the sample after previous step shaking out, (rotating speed is 3500r/min to put into the centrifugal 5min of refrigerated centrifuge, temperature keeps 4 DEG C), by the supernatant concentration obtaining after centrifugal to 1mL, blow near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 DEG C;
(5) testing sample use chromatogram-detect quantitatively from tandem mass spectrum
Chromatographic condition: chromatographic column adopting Agilent HP-5 chromatographic column, specification is 30m × 0.25mm × 0.25 μ m.40 DEG C of temperature programmes (keeping 2min), are warming up to 220 DEG C with 20 DEG C/min, then are warming up to 280 DEG C with 15 DEG C/min, are finally warming up to 300 DEG C (keeping 3min) with 5 DEG C/min.250 DEG C of injector temperatures; Splitless injecting samples 1uL.Carrier gas is used helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode).
Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, 280 DEG C of transmission line temperature, mass scanning scope is 50～350m/z.
Under above chromatogram, mass spectrum condition, by the 1.0ml concentrate sample introduction obtaining in step (4), obtain the peak area of o-chloronitrobenzene and parachloronitrobenzene compound by integration, conversion is extracted o-chloronitrobenzene and parachloronitrobenzene material concentration (x9) in liquid, and (ratio of parachloronitrobenzene standard items initial concentration (in this example, initial concentration is 1000ng/ml) is the method recovery of extraction (y9) under ethanol/methylene extraction system to concentration (x9) with o-chloronitrobenzene &.Other operations are simultaneously identical, and the recovery of extraction under the extraction system of different hydrophilic solvents and hydrophobic solvent, refers to Fig. 9.
Claims (9)
1. a pre-treating method for 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil, the steps include:
(A) target compound is chosen: comprise 10 kinds of nitro-aromatic compounds;
(B) sample preparation: take pedotheque, add simultaneously with the activation of pedotheque equal in quality after zeyssatite or anhydrous sodium sulfate, after mixing, put into clean vial;
(C) sample extraction: according to pedotheque amount, according to the ratio of the quality g/ volume ml ratio 1:1～1:3 of soil and hydrophilic solvent, add hydrophilic solvent, jolting 3～5min, makes soil breaking reach homogenate shape fast; According to the quality g/ volume ml ratio 1:1～1:3 of soil and hydrophobic solvent, add hydrophobic solvent again, jolting 30～60min fast, speed is 200～500r/min;
(D) centrifuging: step C is completed to the sample of extraction, put into hydro-extractor centrifugal, extract extract from supernatant, low temperature is preserved or directly entered that gas chromatography, gas chromatography mass spectrometry are carried out quantitatively, qualitative analysis.
2. according to the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil claimed in claim 1, it is characterized in that, in described step (A), 10 kinds of nitrobenzene compounds are nitrobenzene, o-dinitrobenzene, meta-dinitro-benzent, paradinitrobenzene, m-chloro-nitrobenzene, 2,4-dinitrotoluene (DNT), 1-chloro-2,4-dinitro benzene, 2,4,6-trinitro-toluene, o-chloronitrobenzene and parachloronitrobenzene.
3. according to the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil claimed in claim 1, it is characterized in that, the zeyssatite in described step (B) after activation is the zeyssatite after 400 DEG C of baking 6h
4. the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil according to claim 1, is characterized in that, adds the order of solvent for first adding hydrophilic solvent in described step (C), after add hydrophobic solvent mix; Hydrophilic solvent is selected acetone, ethyl acetate, methyl alcohol or acetonitrile; Hydrophobic solvent is normal hexane, methylene chloride or cyclohexane.
5. according to the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil claimed in claim 4, it is characterized in that, in described step (B), hydrophilic solvent and hydrophobic solvent are combined as: acetone and normal hexane, cyclohexane and ethyl acetate, methyl alcohol and methylene chloride or acetonitrile and methylene chloride.
6. according to the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in the rapid extraction soil described in claim 4 or 5, it is characterized in that, in described step (B), hydrophilic solvent and hydrophobic solvent volume ratio are 1:1.
7. the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil claimed in claim 1, it is characterized in that, the mode that uses centrifugation to separate with extraction solvent as soil in described step (D), control temperature in centrifugal process is at 4～6 DEG C, centrifugation time 3～5min, rotating speed is 3000～5000r/min.
8. according to the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil claimed in claim 1, it is characterized in that, in described step (D), directly enter that gas chromatography, gas chromatography mass spectrometry are carried out quantitatively, qualitative analysis, its instrument condition is: select medium or low pole chromatographic column in chromatographic column, 40 DEG C of temperature programmes, keep 2min, be warming up to 220 DEG C with 20 DEG C/min, be warming up to 280 DEG C with 15 DEG C/min again, finally be warming up to 300 DEG C with 5 DEG C/min, keep 3min, 250 DEG C of injector temperatures; Splitless injecting samples 1uL, carrier gas is used helium, helium purity > 99.999%, flow velocity 1.2mL/min, constant current mode; Mass spectrum condition: ionization mode is EI ionization, ionization voltage 70eV, 250 DEG C of ion source temperatures, mass scanning scope is 50～350m/z, carries out quantitative, qualitative analysis.
9. according to the pre-treating method of 10 kinds of Nitro-aromatic Compounds in Differents in rapid extraction soil claimed in claim 8, it is characterized in that, the chromatographic column using in described step (D) is Agilent HP-5, HP-5MS, DB-5 or DB-5MS capillary column, and specification is 30m × 0.25mm × 0.25 μ m.
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| CN111965287A (en) * | 2020-08-26 | 2020-11-20 | 浙江宏盛科技信息服务有限公司 | Method for determining 5 nitrophenol compounds in soil based on ultrahigh pressure high performance liquid chromatography tandem mass spectrometry |
| CN113495108A (en) * | 2021-07-09 | 2021-10-12 | 生态环境部华南环境科学研究所 | Method for simultaneously detecting 63 persistent organic pollutants in soil |
| CN113495108B (en) * | 2021-07-09 | 2023-07-28 | 生态环境部华南环境科学研究所 | Method for simultaneously detecting 63 persistent organic pollutants in soil |
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