CN101122588A - Method for determining polycyclic aromatic hydrocarbons in sludge - Google Patents
Method for determining polycyclic aromatic hydrocarbons in sludge Download PDFInfo
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Abstract
The invention is a method for determining polycyclic aromatic hydrocarbons in sludge. Basing on an analyzing method of polycyclic aromatic hydrocarbons in conventional soil which includes steps of soxhlet extraction, column chromatography and gas mass spectrometry detection, a process that concentrated sulfate is used to wash eluent is added after the column chromatography. The method of the invention can eliminate a great amount of organic compounds in sludge and reduce interferences of other organic compounds on the polycyclic aromatic hydrocarbons content detection. The sensitivity and the accuracy of the gas mass spectrometry detection on the polycyclic aromatic hydrocarbons are improved.
Description
Technical field
The present invention relates to the assay method of palycyclic aromatic in the mud, detect, just can finish the mensuration of 16 kinds of palycyclic aromatics in the mud, obtain result accurately through Soxhlet extraction, column chromatography for separation, solvent wash and gas phase-mass spectrometer.
Background technology
Palycyclic aromatic (PAH) is that a class has three persistence organic pollutants that cause effect (carcinogenic, teratogenesis and cause gene mutation), mainly is present in atmosphere, the water and soil earth.Palycyclic aromatic is that organism and fossil fuel rough burning produce, and causes the polycyclic aromatic hydrocarbons contaminated reason in whole world today to mainly contain four kinds: the flue dust that (1) family and life cooking stove, Industrial Boiler etc. produce; (2) various generations and use the industrial process of tar, as coking, petroleum cracking, coal tar refine, pitch is paved the way etc.; (3) various artificial open burnings and fire; (4) various motor vehicles and I. C. engine exhaust.
Because the content of these compounds in environment is very low, how from environmental sample, their are separated and enrichment is come out and done further analysis, be a most important step in the whole analytical technology, because it directly has influence on ultimate analysis result's accuracy.
The analytical approach of palycyclic aromatic mainly contains: column chromatography and thin-layered chromatography, ultraviolet absorption method, vapor-phase chromatography (GC), high performance liquid chromatography, mass spectroscopy etc.Column chromatography and thin-layered chromatography have certain separating effect, but can't carry out qualitative and quantitative analysis accurately; Vapor-phase chromatography (GC), high performance liquid chromatography and mass spectroscopy can be carried out qualitative and quantitative analysis simultaneously, but very high to sample requirement, need anticipate, and remove a large amount of impurity.At present, the analytical approach of palycyclic aromatic normally adopted cable-styled extraction-column chromatography for separation-gaseous mass spectrum determination method in the soil, and concrete grammar is that soil or sediment sample place apparatus,Soxhlet's, with benzene/methyl alcohol or methylene chloride/acetone backflow 18-24 hour, add copper powder, concentrate; By anhydrous sodium sulfate/silica gel/alumina column chromatography, with normal hexane, eluent methylene chloride, concentrator concentrates, constant volume; Adopt gas chromatography/mass spectrometry logotype instrument (GC/MS), utilize standard items to carry out qualitative and quantitative measurement.
But for mud, can there be a large amount of organic substances in the analytical approach iff adopting palycyclic aromatic in the soil, thereby have disturbed the measurement result of GC/MS to palycyclic aromatic.
Summary of the invention
The purpose of this invention is to provide palycyclic aromatic method for measuring in the mud that a kind of accuracy is good, detection efficiency is high.
The present invention measures that the method for polycyclic aromatic hydrocarbon content comprises the steps: in the mud
1. sample is air-dry: the sludgd deposition sample that collection comes need be removed moisture wherein earlier, so that repeatability and accuracy that accurate quantification and assurance are measured.Because it is volatile that organism is heated, lucifuge is carried out natural air drying when sample drying is handled.When drying processing if any special requirement, temperature is difficult for above 40 ℃.
2. sample grinding, sub-sieve: dried sample grinds, sub-sieve makes its uniform component distribution, guarantees that the sample of measuring is representative.General sample grinding back is crossed the 60-100 order and is got final product, and collects the screening (screen underflow) of sieving and treats the use of the 3rd step.
3. organic extraction: the screening of sieving that takes by weighing previous step, sample is placed the filter paper sleeve of cable type extractor according, in the flask of extraction apparatus, add benzene/methyl alcohol (2: 1～1: 2) (v/v) or methylene chloride/acetone (2: 1～1: 2) mixed liquor (v/v) with solid-liquid ratio 1g: 3～10mL, refluxed 18～24 hours, temperature is controlled at 50～70 ℃, and adds a small amount of copper powder desulfurization.After extraction is finished, take out extract, solution decompression is concentrated, obtain sample extraction liquid.
4. sample purifying: through said extracted, also contain the organic impurities of a large amount of coexistences in the sample extraction liquid, need carry out purification process, generally can adopt various chromatography methods to it.Accurately taking by weighing chromatography with each 5～20 gram of aluminium oxide, chromatographic silica gel and anhydrous sodium sulfate, is that solvent is by the order wet method dress post of chromatography with aluminium oxide, chromatographic silica gel and anhydrous sodium sulfate with the normal hexane; With sample on the sample extraction liquid that obtains in the step 3; Eluent is respectively normal hexane, normal hexane: 60～200 milliliters of methylene chloride (4: 1～1: 1) mixed liquors (v/v), collect all cuts.
5. concentrated sulphuric acid washing:, there be serious the interference in follow-up GC/MS detection though, still contain large amount of organic impurities in the cut of collecting through column chromatography.The present invention has increased the washing process of a step concentrated sulphuric acid, because the chemical property of palycyclic aromatic is more stable, be not easy oxidized decomposition, and other organism is easier to by concentrated sulphuric acid oxidation, particularly compounds such as ester class, alcohols.The cut of collecting behind the column chromatography is poured in the separating funnel, added 4～10 milliliters of the concentrated sulphuric acids, vibration bleeds off concentrated sulphuric acid layer after leaving standstill, and repeated washing is removed substantially to other impurity and got final product (becoming light color with concentrated sulphuric acid phase color is as the criterion).Add the aqueous solution that contain 1%～4% sodium sulphate (mass percent) isopyknic with it in organic phase, the cyclic washing several is until the concentrated sulphuric acid is cleaned.Sample transfer after the washing adds excessive anhydrous sodium sulfate to Erlenmeyer flask, to remove the moisture in the sample, obtain the sample behind the purifying.
6. sample concentration, constant volume: the sample volume behind the purifying is usually at tens milliliters, must take concentration when the detection that is lower than analytical approach when testing concentration is limited the quantity of.Adopt rotation reduction vaporization or nitrogen stream to dry up, use methylene chloride constant volume 1～10mL again, obtain mud concentrating sample to be determined.Note during the rotation reduction vaporization temperature controlling not surpassing 60 ℃, to prevent the loss of object.
7. blank assay: blank assay is divided into two batches, a collection of sludgd deposition sample that do not add, and the extraction of sample, purification, washing and concentrated constant volume are identical with the sludgd deposition sample, and be as blank analysis liquid 1, to be determined; Another batch do not add the sludgd deposition sample, and the extraction of sample, purification and concentrated constant volume are identical with the sludgd deposition sample, just do not carry out the washing of the concentrated sulphuric acid, and be as blank analysis liquid 2, to be determined.
8. reclaim experiment: in order relatively to add with behind the concentrated sulphuric acid washing step, reliability to experimental result is analyzed, the accuracy of verification method, we will reclaim experiment and be divided into two batches, all do not add the sludgd deposition sample, a collection of adding 3 μ L～20 μ L palycyclic aromatic titers (seeing Table 3), the extraction of sample, purification, washing and concentrated constant volume are identical with the sludgd deposition sample, as reclaiming analytic liquid 1, to be determined; Another batch adds the palycyclic aromatic titer of same volume, and the extraction of sample, purification and concentrated constant volume are identical with the sludgd deposition sample, just do not carry out the washing of the concentrated sulphuric acid, and be as reclaiming analytic liquid 2, to be determined.
9. sample determination:, generally need to use chromatogram analysis method, as gas chromatography (GC), high performance liquid chromatography (HPLC), gas chromatograph-mass spectrometer (GCMS) (GC/MS) because the content of palycyclic aromatic in environment is very low.In order to carry out qualitative and quantitative analysis fast, the GC/MS method is comparatively commonly used.
The A.GC/MS condition:
Injector temperature: 280 ℃;
Monitor temperature: 300 ℃;
Temperature programme: 60 ℃ keep 3min, are warming up to 180 ℃ with 10 ℃/min, keep 2min, again with 5 ℃/min
Rise to 280 ℃, keep 10min;
Carrier gas (high-purity N
2) flow velocity: 1.2mL/min;
Electron bombardment ionization source: ion gun (EI);
The voltage of electron-multiplier: 1800eV;
Quality of scanning scope: 50～550amu.
B. measure: under identical chromatographic condition, inject mud concentrating sample, blank analysis liquid, recovery analytic liquid and the palycyclic aromatic titer of equal volume (1 μ L～3 μ L) respectively, measure the retention time and the chromatographic peak area of each component, carry out the qualitative and quantitative analysis.
C. qualitative: as to utilize the retention time of palycyclic aromatic standard items and mass spectrometric data storehouse picture and specimen to compare and confirm.
D. quantitative Analysis:, utilize external standard and internal standard method content by various palycyclic aromatics in the regression equation calculation sample of each standard solution according to chromatographic peak area.
The reagent of the pure above purity of the equal operational analysis of all reagent among the present invention, water is deionized water; All glasswares all swing with deionized water to be washed more than 3 times; The parallel triplicate of all samples, gained as a result relative standard deviation in 4%, with guarantee experimental result accurately.
The present invention has increased the step of the washing of the concentrated sulphuric acid, by relatively reclaiming the experimental result of analytic liquid 1 and recovery analytic liquid 2, see Table 2, can find that the washing of the concentrated sulphuric acid is very little to the influence of palycyclic aromatic, and can remove simultaneously a large amount of other organism, particularly compounds such as ester class, alcohols.This step not only can reach the purpose that purifies sample, protection chromatographic column; can improve simultaneously sensitivity and precision that GC/MS detects greatly; and the recovery of palycyclic aromatic remains unchanged substantially, and is between 50%～101.50%, consistent with the assay method result of other palycyclic aromatics.The present invention has the accuracy height, the advantage of favorable reproducibility.
The present invention can remove other organism to the interference that palycyclic aromatic detects, and is applicable to the mensuration of palycyclic aromatic in mud, soil and other environment, and it is wide to have analyst coverage, characteristics such as analysis efficiency height.
Embodiment
Further specify the present invention below in conjunction with embodiment.
1, sample collecting and storage
Mud sample picks up from 2 sewage treatment plants of Shanghai City Tao Pu and Quyang, sees Table 1, uses gravity column bottom sampler to gather, and sample ground 80 mesh sieves at laboratory lucifuge natural air drying, and the screening of sieving places the sealing bag cryopreservation, treats sample pretreatment.
2, sample extraction
Accurately weighing 20 restrains dry mud sample, sample is placed the filter paper sleeve of cable type extractor according, add methylene chloride in the flask of extraction apparatus: acetone (1: 1) mixed liquor 150mL (v/v), temperature is controlled at 65 ℃, and adds a small amount of copper powder backflow 20 hours.Be cooled to room temperature, filter, the rotation reduction vaporization is concentrated into 1mL.
3, sample purifying
Add the 40mL normal hexane in having the glass chromatography column of core, add 10g chromatographic aluminium oxide, 5g chromatographic silica gel and 5g anhydrous sodium sulfate successively, the limit edged strikes in the filling process, uses normal hexane drip washing, stablizes chromatographic column;
All transfer to sample concentration liquid on the chromatographic column, use 30mL normal hexane, 30mL normal hexane respectively: methylene chloride (4: 1) mixed liquor and 30mL normal hexane (v/v): methylene chloride (2: 1) mixed liquor (v/v), with the speed drip washing sample chromatographic column of 1mL/min, collect leacheate;
Leacheate is poured in the separating funnel, added concentrated sulphuric acid 4mL, vibration bleeds off concentrated sulphuric acid layer after leaving standstill, and this acid cleaning process repeats 2～4 times.Add the aqueous solution that contain 2% sodium sulphate isopyknic with it in organic phase, the cyclic washing several is until the concentrated sulphuric acid is cleaned.Sample transfer after the washing adds excessive anhydrous sodium sulfate to Erlenmeyer flask, to remove the moisture in the sample.
4, sample concentration, constant volume
Sample filtering behind the purifying concentrates with the rotation reduction vaporization, is settled to 5mL with methylene chloride.
5, blank sample analysis
Except that not adding the sludgd deposition sample, the extraction of sample, purification, washing and concentrated constant volume are identical with the sludgd deposition sample, are settled to 5mL as blank.
6, reclaim experiment
Do not add the sludgd deposition sample, add 10 μ L palycyclic aromatic standard solution, the extraction of sample, purification, washing and concentrated constant volume are identical with the sludgd deposition sample, are settled to 5mL, as reclaiming experiment contrast.
7, GC/MS analyzes
Chromatographic column: HP-5 chromatographic column (30m * 250 μ m * 0.25 μ m);
Injector temperature is 280 ℃, 300 ℃ of monitor temperature, and the temperature programme condition: 60 ℃ keep 3min, are warming up to 180 ℃ with 10 ℃/min, keep 2min, rise to 280 ℃ with 5 ℃/min again, keep 10min;
Carrier gas (high-purity N
2) flow velocity: 1.2mL/min;
Electron bombardment ionization source is ion gun (EI);
The voltage of electron-multiplier: 1800eV;
Quality of scanning scope: 50～550amu.
Get each 2 μ L injection GC/MS instrument of mud sample, blank analysis liquid and recovery analytic liquid respectively and carry out assay determination, measure the retention time and the chromatographic peak area of each component; Utilize retention time and the mass spectrometric data storehouse picture and the specimen comparison of palycyclic aromatic standard items, carry out the qualitative analysis of sample; Utilize external standard method and internal standard method regression equation, carry out quantitative test, calculate the content of each palycyclic aromatic in the sample by each standard solution.
External standard method adopts 16 kinds of palycyclic aromatic standard models, and internal standard method adopts pyrene-d10 standard items.
The content of 16 kinds of palycyclic aromatics (μ g/kg) in table 1. peach Pu and Quyang sewage plant sludge
| Palycyclic aromatic | Quyang | The peach Pu |
| Luxuriant and rich with fragrance anthracene fluoranthene pyrene benzo (a) anthracene of naphthalene acenaphthylene acenaphthene fluorenes is bent benzo (b) fluoranthene benzo (k) fluoranthene benzo (a) pyrene indeno (1,2,3-cd) pyrene dibenzo (a, h) anthracene benzo (ghi) perylene | 93.6 4.7 1.1 42.5 156.7 186.5 126.9 1.3 110.4 109.9 108.0 82.9 69.3 19.6 43.3 0 | 100.9 4.5 101.0 161.1 700.0 757.2 597.4 588.2 585.1 583.7 290.7 266.4 347.4 155.1 96.8 0 |
The comparison of 15 kinds of palycyclic aromatic recovery in two kinds of distinct methods of table 2.
| Blank value | Use H 2SO 4Washing unit (μ g/mL) | Without H 2SO 4Washing unit (μ g/mL) | Regression equation | Related coefficient | |||||
| True average | Detect mean value | The recovery | True average | Detect mean value | The recovery | ||||
| Luxuriant and rich with fragrance anthracene fluoranthene pyrene benzo (a) anthracene of acenaphthylene acenaphthene fluorenes is bent benzo (b) fluoranthene benzo (k) fluoranthene benzo (a) pyrene indeno (1,2,3-cd) (a, h) (15 kinds of palycyclic aromatics of ghi) perylene return the anthracene benzo pyrene dibenzo | 0.055 0 0.182 0.338 0.011 0.045 0.012 0.042 0.030 0.049 0.562 0.753 0.208 0 0.006 | 19.0 9.50 1.90 0.95 0.95 1.90 0.95 0.95 0.95 1.90 0.95 0.95 0.95 1.90 1.90 | 18.39 9.69 1.77 1.11 0.75 1.56 0.63 0.64 0.85 1.36 1.43 1.43 0.76 1.25 1.14 | 0.965 1.020 0.834 0.811 0.778 0.798 0.651 0.626 0.863 0.688 0.918 0.717 0.584 0.656 0.597 | 23.00 11.50 2.30 1.15 1.15 2.30 1.15 1.15 1.15 2.30 1.15 1.15 1.15 2.30 2.30 | 31.55 12.65 1.95 1.23 0.72 1.81 0.96 0.71 0.79 1.27 1.63 1.63 0.94 1.24 1.54 | 1.369 1.100 0.769 0.773 0.618 0.767 0.823 0.582 0.657 0.532 0.930 0.764 0.635 0.539 0.660 | Y＝0.0000861x+0.00397 Y＝0.0000691x+0.00299 Y＝0.0001082x-0.00119 Y＝0.0001680x-0.00134 Y＝0.0001870x-0.00840 Y＝0.0001860x-0.000173 Y＝0.0001920x+0.00268 Y＝0.0001074x-0.011322 Y＝0.0000983x-0.008520 Y＝0.0000273x-0.002133 Y＝0.0000453x-0.004880 Y＝0.0000453x-0.004881 Y＝0.0000074x-0.000588 Y＝0.0000054x-0.000861 Y＝0.0000062x-0.000777 | 0.9976 0.9977 0.9966 0.9968 0.9959 0.9937 0.9958 0.9904 0.9930 0.9890 0.9844 0.9844 0.9903 0.9721 0.9734 |
| The mean value of yield | 0.804 | 0.768 | |||||||
Table 3.16 kind of palycyclic aromatic (PAH) standard mixes liquid (1mL)
| Chinese | English name | Specification |
| Luxuriant and rich with fragrance anthracene fluoranthene pyrene benzo (a) anthracene of naphthalene acenaphthylene acenaphthene fluorenes is bent benzo (b) fluoranthene benzo (k) fluoranthene benzo (a) pyrene indeno (1,2,3-cd) pyrene dibenzo (a, h) anthracene benzo (ghi) perylene | Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(1，2，3-cd)pyrene Dibenzo(a，h)anthracene Benzo(ghi)perylene | 1000μg/mL 2000μg/mL 1000μg/mL 200μg/mL 100μg/mL 100μg/mL 200μg/mL 100μg/mL 100μg/mL 100μg/mL 200μg/mL 100μg/mL 100μg/mL 100μg/mL 200μg/mL 200μg/mL |
Claims (5)
1. method of measuring palycyclic aromatic in the mud, it is characterized in that measuring palycyclic aromatic in the soil by cable-styled extraction, column chromatography and gaseous mass spectrum, wash collected cut with the concentrated sulphuric acid after column chromatography, and then carry out gaseous mass spectrum and detect, concrete assay method is:
(1) mud sample is placed the dark place natural air drying, the mud sample after air-dry is ground and cross 60～100 mesh sieves, collect the screening of sieving for next step use;
(2) get the screening of sieving of previous step mud sample, carrying out Soxhlet as extract with solid-liquid ratio 1g: 3～10mL with benzene/methyl alcohol volume ratio 2: 1～1: 2 or methylene chloride/mixed liquor of 2: 1～1: 2 of acetone volume ratio extracts, backflow 18-24 hour,, obtain sample extraction liquid again with solution concentration;
(3) with sample on the sample extraction liquid, the chromatographic column of packing into and filling with aluminium oxide, silica gel and anhydrous sodium sulfate, with normal hexane, normal hexane: the mixed liquor of methylene chloride volume than 4: 1～1: 1 carries out column chromatography as eluant, eluent, collects all cuts;
(4) add the concentrated sulphuric acid in the cut of behind column chromatography, collecting, leave standstill after the vibration and remove concentrated sulphuric acid layer, repeatedly repeat, after being light color to concentrated sulphuric acid phase color, in organic phase, add the aqueous solution that contain mass percent 1%～4% sodium sulphate isopyknic, wash to the concentrated sulphuric acid clean with it, add excessive anhydrous sodium sulfate again, to remove the moisture in the sample, sample is rotated reduction vaporization or nitrogen stream dries up, be the dissolution with solvents sample with methylene chloride again;
(5) use gaseous mass spectrum logotype instrument, temperature programme, measuring samples is utilized the retention time and the mass spectrometric data storehouse picture of palycyclic aromatic standard items, carries out the qualitative analysis of sample;
(6) carry out quantitative test with external standard method and internal standard method, calculate the content of palycyclic aromatic in the mud.
2. method according to claim 1 is characterized in that gas chromatographic column is HP-5 post or DB-5 post.
3. method according to claim 1 is characterized in that gas chromatographic column is the HP-5 post.
4. method according to claim 1 is characterized in that temperature programme is to adopt at 60 ℃ to keep 3min in above-mentioned (5); Be warming up to 180 ℃ with 10 ℃/min, keep 2min; Rise to 280 ℃ with 5 ℃/min, keep the temperature programme of 10min.
5. method according to claim 1, it is characterized in that the palycyclic aromatic of measuring be naphthalene, acenaphthylene, acenaphthene, fluorenes, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, bend, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (1,2,3-cd) pyrene, dibenzo (a, h) anthracene or benzo (ghi) perylene.
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