CN102478556A - Enrichment method of polycyclic aromatic hydrocarbons in environmental water sample - Google Patents
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Abstract
The invention relates to an enrichment method of polycyclic aromatic hydrocarbons in an environmental water sample, comprising the following steps of: a) preparing octadecyl modified magnesium oxide microspheres; b) preparing a solid-phase extraction column by using the octadecyl modified magnesium oxide microspheres as a filling material; c) activating the solid-phase extraction column by respectively using dichloromethane, an organic modification agent and an organic modification agent aqueous solution; and loading a sample containing the organic modification agent; d) leaching the solid-phase extraction column by using an acetonitrile aqueous solution, and carrying out elution on the solid-phase extraction column by using an organic solvent to obtain an eluate; e) volatilizing the solvent from the eluate to obtain the enriched polycyclic aromatic hydrocarbons, making a constant volume by using the acetonitrile aqueous solution, and carrying out high performance liquid chromatography. In comparison with magnesium oxide and commercial Sep-PakC18, higher extraction efficiency is obtained by the method provided by the invention under the condition of the same enrichment factor.
Description
Technical field
The present invention relates to the enrichment method of palycyclic aromatic in the environmental water sample, specifically a kind of magnesium oxide microsphere that utilizes the octadecyl modification carries out the new method of enrichment as solid phase extraction adsorbents to the palycyclic aromatic that exists in the environmental water sample.
Background technology
Palycyclic aromatic is as a kind of environmental contaminants that in environment, extensively exist, because its potential carcinogenic, mutagenic effect has received widely and having paid close attention to.Wherein 16 kinds of palycyclic aromatics are classified as priority pollutants by Environmental Protection Agency.According to a large amount of research and investigation, the carcinogenicity that world's health organizes international cancer research mechanism palycyclic aromatic to be produced the mankind is estimated and is classified.Because palycyclic aromatic is one type of hydrophobic compound, and hydrophobicity increases along with the increase of its molecular weight, thereby determined it in water, to have extremely low solubleness.Therefore in measuring environmental water sample, during the content of palycyclic aromatic, need effective enrichment and abstraction technique.
The enrichment of having reported at present and extracting process comprise that liquid-liquid extraction, SPE, SPME, liquid-phase micro-extraction, accelerated solvent extraction, Stir Bar Sorptive Extraction, cloud point extraction, matrix solid phase dispersion extraction, solid phase are received and extract etc.Wherein SPE has received widely as a kind of general abstraction technique and having used, and the diversity of solid phase extraction adsorbents kind is for realizing that effective enrichment provides guarantee.Silica matrix (C8, C18, C30 and styrene diethylene benzene copoly mer etc.) (Kiss, G., Puchony, Z. V., Hlavay, J., J. Chromatogr. A for example; Erustes, J. A., Eiroa, A. A., Cladera, A. et al., Analyst; Bogusz, M. J., El Hajj, S. A., Ehaideb, Z., et al., J. Chromatogr. A; Li, K., Li, H. F., Liu, L. B., et al., J. Chromatogr. A; Brown, J. N., Peake, B. M., Anal. Chim. Acta.), multi-walled carbon nano-tubes (W.D. Wang, Y.M. Huang; W.Q. Shu, et al., J. Chromatogr. A), functionalized magnetic oxide (Liu, Y., the Li of octadecyl; H. F., Lin, J. M., Talanta), polymkeric substance (Lai, J. P.; Niessner, R., Knopp, D., Anal. Chim. Acta; Yu, J. C., Jiang, Z. T., Liu, H. Y., et al., Anal. Chim. Acta; Zhou, Y. Y., Yan, X. P., Kim, K. N., et al., J. Chromatogr.A; Qi, D. J., Kang, X. J., Chen, L. Q., et al., Anal. Bioanal. Chem.; Krupadam, R. J., Bhagat, B., Wate; S. R., et al., Environ. Sci. Technol.), the hemi-micelle magnetic nanoparticle (A. Ballesteros-G ó mez, S. Rubio, Anal. Chem.) and the magnesium oxide microsphere (Jin that apply; J., Zhang, Z.P., Li, Y.; Et al., Anal. Chim. Acta) etc., yet for the magnesium oxide microsphere that octadecyl is modified, it does not also appear in the newspapers in Application in Environmental Analysis.
Summary of the invention
The magnesium oxide microsphere that the objective of the invention is to modify with octadecyl develops a kind of new method that is suitable for the palycyclic aromatic that exists in the environmental water sample is carried out enrichment as solid phase extraction adsorbents.
For solving the problems of the technologies described above, the technical scheme that the present invention adopted is:
At first prepare the magnesium oxide microsphere that octadecyl is modified; Load solid-phase extraction column with it as filler; Through each factor that influences SPE efficient is optimized, comprise the kind and the concentration of organic modifier in the appearance process then, last appearance flow velocity and volume; The kind of eluent and eluting solvent develops a kind of new method that is suitable for the palycyclic aromatic that exists in the environmental water sample is carried out enrichment.
Concrete operations are:
A) octadecyl is modified the magnesium oxide microsphere preparation:
B) magnesium oxide microsphere of modifying with octadecyl is that filler prepares solid-phase extraction column;
C) use methylene chloride, organic modifier and the certain density organic modifier WS that solid-phase extraction column is carried out activation successively; The water sample that will contain the finite concentration organic modifier is then gone up appearance;
D) use acetonitrile solution that solid-phase extraction column is carried out drip washing, and then solid-phase extraction column is carried out wash-out, get eluent with non-polar organic solvent;
E) promptly obtain palycyclic aromatic after the enrichment behind the eluent solvent flashing, use the acetonitrile solution constant volume then, and carry out efficient liquid phase chromatographic analysis.
Adopting magnesium oxide microsphere and octadecylsilane reagent among the step a is raw material, under the situation that surfactant exists, in non-polar organic solvent, octadecyl is modified the magnesium oxide microsphere surface;
Wherein in magnesium oxide 1.5 g, surfactant 0.01-0.10 g, the consumption of octadecylsilane reagent are 0.5-2.0 mL, and temperature of reaction is 105-120 ℃, and the reaction time is 5-24h;
Specific operation process does; Before the reaction, in 1.5 g magnesium oxide and 0.01-0.10 g surfactant mixtures, join 40-100 mL non-polar organic solvent earlier, be heated 105-120 ℃ then; And continue to stir maintenance 5-20 min, obtain magnesian suspending liquid;
Then according to the ratio 1.5 g:0.5-2 mL of magnesium oxide and octadecylsilane reagent; The octadecylsilane agent dissolves is mixed with the silanization reagent solution in 5-30 mL non-polar solvent; Again this silylating reagent solution is dropwise joined in the continuous stirring ground magnesia magma; Reaction time is 5-24 h, after the gained solid washs 2-3 time respectively with methyl alcohol, toluene successively, can obtain the magnesium oxide microsphere that octadecyl is modified through vacuum drying.
Can add surfactant in the said suspending liquid as spreading agent, purpose is the uniform surface property of regulating modified product, and type can be anionic surfactant, cationic surfactant or non-ionics.
This reacts employed non-polar organic solvent is toluene or normal hexane; 18 silylating reagents are the octadecyl trichlorosilane.
The quality of octadecyl modification magnesium oxide microsphere and the volume ratio of solid phase extraction tube are 200mg:6mL among the step b;
When among the step c solid-phase extraction column being carried out activation, the organic modifier kind should with water sample in to add the organic modifier kind to identical, can be methyl alcohol, acetone, isopropyl alcohol; The concentration of the organic modifier WS (volume ratio) should be identical with the concentration of organic modifier in the water sample; In the time of last kind; Contain the organic modifier that volume ratio is 0%-20% (0% just is meant the concentration when not adding organic modifier, and this concentration is the object of investigating) in the water sample, purpose is to increase the solubleness of palycyclic aromatic in the WS; Reduce the loss of palycyclic aromatic on tube wall in the SPE process; And when the column jecket volume of solid-phase extraction column was 6mL, last appearance flow speed control was at 1-5 mL/min, and the sample solution volume is controlled between the 20-250 mL;
In the steps d; In the drip washing stage, when the column jecket volume of solid-phase extraction column is 6mL, use 1-4 mL volume ratio as the acetonitrile of 0%-20% or methanol in water as eluent; Enrichment that not only can the jamming target analyte, and can remove the segment polarity compound; The wash-out stage can adopt the organic solvent of polar intensity≤methylene chloride polar intensity or its mixed solution that solid-phase extraction column is carried out wash-out.
The eluent evaporating solvent is to 50-100 mL among the step e, and purpose is to reduce the loss of the less palycyclic aromatic of molecular weight as far as possible.
The present invention has following advantage:
(1), for magnesium oxide microsphere and commercial Sep-Pak C18 solid-phase extraction column, during the palycyclic aromatic of this inventive method in being applied to the enrichment environment water sample, shows higher extraction efficiency realizing under the identical condition of enrichment factor; (2) for commercial adsorbent, organic modifier used in the present invention is less, is less than the half the of its consumption.
Description of drawings
Fig. 1 is for adopting the inventive method, through regulating the recovery comparison diagram of the palycyclic aromatic that content of acetone obtains; Naphthalene: NAPH; Acenaphthene: ACEN; Fluorenes: FLUO; Luxuriant and rich with fragrance: PHEN; Anthracene: ANTH; Pyrene: PYR; Benzo [a] pyrene: BaP; Benzo [ghi] perylene: BghiP.
Fig. 2 is for adopting the inventive method, through regulating the recovery comparison diagram of the palycyclic aromatic that isopropanol content obtains; Naphthalene: NAPH; Acenaphthene: ACEN; Fluorenes: FLUO; Luxuriant and rich with fragrance: PHEN; Anthracene: ANTH; Pyrene: PYR; Benzo [a] pyrene: BaP; Benzo [ghi] perylene: BghiP.
Fig. 3 is for adopting the inventive method, through regulating the recovery comparison diagram of the palycyclic aromatic that kind flow velocity obtains; Naphthalene: NAPH; Acenaphthene: ACEN; Fluorenes: FLUO; Luxuriant and rich with fragrance: PHEN; Anthracene: ANTH; Pyrene: PYR; Benzo [a] pyrene: BaP; Benzo [ghi] perylene: BghiP.
Fig. 4 is for adopting the inventive method, through regulating the recovery comparison diagram of the palycyclic aromatic that the sample solution volume obtains; Naphthalene: NAPH; Acenaphthene: ACEN; Fluorenes: FLUO; Luxuriant and rich with fragrance: PHEN; Anthracene: ANTH; Pyrene: PYR; Benzo [a] pyrene: BaP; Benzo [ghi] perylene: BghiP.
Fig. 5 is for adopting the inventive method, through regulating the comparison diagram of the palycyclic aromatic elution efficiency that the eluting solvent kind obtains; Naphthalene: NAPH; Acenaphthene: ACEN; Fluorenes: FLUO; Luxuriant and rich with fragrance: PHEN; Anthracene: ANTH; Pyrene: PYR; Benzo [a] pyrene: BaP; Benzo [ghi] perylene: BghiP.
Fig. 6 compares it for adopting the inventive method with magnesium oxide and Sep-Pak C18, the recovery comparison diagram of acquisition under optimum optimizing condition; Naphthalene: NAPH; Acenaphthene: ACEN; Fluorenes: FLUO; Luxuriant and rich with fragrance: PHEN; Anthracene: ANTH; Pyrene: PYR; Benzo [a] pyrene: BaP; Benzo [ghi] perylene: BghiP.
Fig. 7 is for adopting the inventive method, and palycyclic aromatic carries out resulting high-efficient liquid phase chromatogram after the enrichment in the tap water that reagent blank and palycyclic aromatic standard are mixed; 1: naphthalene; 2: acenaphthene; 3: fluorenes; 4: phenanthrene; 5: anthracene; 6: fluoranthene; 7: pyrene; 8: benzo [a] anthracene; 9: bend; 10: benzo [b] fluoranthene; 11: benzo [k] fluoranthene; 12: benzo [a] pyrene; 13: dibenzo [a, h] anthracene; 14: benzo [g, h, i] perylene; 15: indeno [1,2,3-cd] perylene.
Embodiment
Octadecyl is modified the preparation of magnesium oxide microsphere: adopting magnesium oxide microsphere and octadecyl trichlorosilane is raw material; In the potpourri of 1.5g magnesium oxide and 0.01g neopelex, add in the 40 mL toluene solutions; Then this suspending liquid is heated to 115 ℃, and continues to stir maintenance 10 min, then 0.5 mL octadecyl trichlorosilane is distributed in the 20 mL toluene solutions; And it is dropwise joined in the continuous stirring ground suspending liquid, the reaction time is 10 h.Products therefrom is through simple suction filtration, wash 3 times respectively with 200 mL methyl alcohol and 50 mL toluene successively after, the magnesium oxide microsphere of the octadecyl modification that promptly obtains through vacuum drying disperseing.
Embodiment 1:
The magnesium oxide microsphere that 200 mg octadecyls are modified arrives in the SPE blank pipe (6 mL) through dry-packing, and pad is put supporting filtration sieve plate respectively up and down.Before the last appearance, use methylene chloride, acetone and volume ratio solid-phase extraction column to be carried out activation respectively as the aqueous acetone solution (identical) of 0-15% with the volume ratio of acetone in the sample solution; To contain acetone 0%, 5% then, appearance (contains naphthalene: 3.520 ng mL on the 100 mL deionized waters of 9%, 10% and 15% (volume ratio) in the WS
-1Acenaphthene: 10.200 ng mL
-1Fluorenes: 0.920 ng mL
-1Luxuriant and rich with fragrance: 0.576 ng mL
-1Anthracene: 0.272 ng mL
-1Pyrene: 1.152 ng mL
-1Benzo [a] pyrene: 3.040 ng mL
-1Benzo [ghi] perylene: 1.600 ng mL
-1).Last appearance finishes, and uses 4 mL deionized waters to carry out drip washing.Treat that drip washing finishes, use 5 mL methylene chloride to carry out wash-out, after the gained eluent was concentrated into 50 mL, using volume ratio was that 60% acetonitrile solution carries out constant volume, carries out efficient liquid phase chromatographic analysis at last.As organic modifier, the difference of its content is listed among Fig. 1 the influence of the palycyclic aromatic recovery with acetone.Therefrom can find out, when the acetone consumption is 9%, can realize effective enrichment, thereby confirm the kind and the concentration of organic modifier in this enrichment method palycyclic aromatic.
Embodiment 2:
The magnesium oxide microsphere that 200 mg octadecyls are modified arrives in the SPE blank pipe (6 mL) through dry-packing, and pad is put supporting filtration sieve plate respectively up and down.Before the last appearance, use methylene chloride, isopropyl alcohol and volume ratio solid-phase extraction column to be carried out activation respectively as the isopropanol water solution (identical) of 0%-15% with the volume ratio of isopropyl alcohol in the sample solution; To contain isopropyl alcohol 0%, 5% then, appearance (contains naphthalene: 3.520 ng mL on the 100 mL deionized waters of 9%, 10% and 15% (volume ratio) in the WS
-1Acenaphthene: 10.200 ng mL
-1Fluorenes: 0.920 ng mL
-1Luxuriant and rich with fragrance: 0.576 ng mL
-1Anthracene: 0.272 ng mL
-1Pyrene: 1.152 ng mL
-1Benzo [a] pyrene: 3.040 ng mL
-1Benzo [ghi] perylene: 1.600 ng mL
-1).Last appearance finishes, and uses 4 mL deionized waters to carry out drip washing.Treat that drip washing finishes, use 5 mL methylene chloride to carry out wash-out, after the gained eluent was concentrated into 50 mL, using volume ratio was that 60% acetonitrile solution carries out constant volume, carries out efficient liquid phase chromatographic analysis at last.As organic modifier, the difference of its content is listed among Fig. 2 the influence of the palycyclic aromatic recovery with isopropyl alcohol.Therefrom can find out, when the isopropyl alcohol consumption is 10%, can realize effective enrichment palycyclic aromatic.Simultaneously comparison diagram 1 and Fig. 2 have affirmed that further it is 9% acetone that employed organic modifier in this enrichment method should be volume ratio.
Embodiment 3:
The magnesium oxide microsphere that 200 mg octadecyls are modified arrives in the SPE blank pipe (6 mL) through dry-packing, and pad is put supporting filtration sieve plate respectively up and down.Before the last appearance, using methylene chloride, acetone and volume ratio respectively is that 9% aqueous acetone solution carries out activation to solid-phase extraction column; The 100 mL deionized waters that will contain 9% (volume ratio) acetone then (contain naphthalene: 3.520 ng mL in the WS
-1Acenaphthene: 10.200 ng mL
-1Fluorenes: 0.920 ng mL
-1Luxuriant and rich with fragrance: 0.576 ng mL
-1Anthracene: 0.272 ng mL
-1Pyrene: 1.152 ng mL
-1Benzo [a] pyrene: 3.040 ng mL
-1Benzo [ghi] perylene: 1.600 ng mL
-1).Appearance on the flow velocity of 1-10 mL/min.Last appearance finishes, and uses 4 mL deionized waters to carry out drip washing.Treat that drip washing finishes, use 5 mL methylene chloride to carry out wash-out, after the gained eluent was concentrated into 50 mL, using volume ratio was that 60% acetonitrile solution carries out constant volume, carries out efficient liquid phase chromatographic analysis at last.As can be seen from Figure 3, when last appearance flow speed control is in 5 mL/min, can realizes effective enrichment, thereby confirm the flow velocity in this enrichment method palycyclic aromatic.
Embodiment 4:
The magnesium oxide microsphere that 200 mg octadecyls are modified arrives in the SPE blank pipe (6 mL) through dry-packing, and pad is put supporting filtration sieve plate respectively up and down.Before the last appearance, using methylene chloride, acetone and volume ratio respectively is that 9% aqueous acetone solution carries out activation to solid-phase extraction column; The 100-500 mL deionized water that will contain 9% (volume ratio) acetone then (contains naphthalene: 0.704-3.52 ng mL in the WS
-1Acenaphthene: 2.040-10.200 ng mL
-1Fluorenes: 0.184-0.920 ng mL
-1Luxuriant and rich with fragrance: 0.115-0.576 ng mL
-1Anthracene: 0.054-0.272 ng mL
-1Pyrene: 0.230-1.152 ng mL
-1Benzo [a] pyrene: 0.608-3.040 ng mL
-1Benzo [ghi] perylene: 0.320-1.600 ng mL
-1).With appearance on the flow velocity of 5 mL/min.Last appearance finishes, and uses 4 mL deionized waters to carry out drip washing.Treat that drip washing finishes, use 5 mL methylene chloride to carry out wash-out, after the gained eluent was concentrated into 50 mL, using volume ratio was that 60% acetonitrile solution carries out constant volume, carries out efficient liquid phase chromatographic analysis at last.As can be seen from Figure 4, when the sample solution volume is controlled in the 250mL, can realize effective enrichment, thereby confirm the volume of the sample solution in this enrichment method palycyclic aromatic.
Embodiment 5:
The magnesium oxide microsphere that 200 mg octadecyls are modified arrives in the SPE blank pipe (6 mL) through dry-packing, and pad is put supporting filtration sieve plate respectively up and down.Before the last appearance, using methylene chloride, acetone and volume ratio respectively is that 9% aqueous acetone solution carries out activation to solid-phase extraction column; The 250 mL deionized waters that will contain 9% (volume ratio) acetone then (contain naphthalene: 1.408 ng mL in the WS
-1Acenaphthene: 4.080 ng mL
-1Fluorenes: 0.368 ng mL
-1Luxuriant and rich with fragrance: 0.230 ng mL
-1Anthracene: 0.108 ng mL
-1Pyrene: 0.460 ng mL
-1Benzo [a] pyrene: 1.216 ng mL
-1Benzo [ghi] perylene: 0.640 ng mL
-1) with appearance on the flow velocity of 5 mL/min.Last appearance finishes, and uses the acetonitrile solution of 4 mL 20% to carry out drip washing.Treat that drip washing finishes; Use three kinds of different organic solvents (mixed solution of methylene chloride, normal hexane or methylene chloride and normal hexane) to carry out wash-out respectively; After the gained eluent is concentrated into 50 mL; Using volume ratio is that 60% acetonitrile solution carries out constant volume, carries out efficient liquid phase chromatographic analysis at last.As can be seen from Figure 5; The eluting solvent kind has appreciable impact to the elution efficiency of different molecular weight palycyclic aromatic; And the mixed solution of normal hexane and methylene chloride (volume ratio 1:1) shows best elute effect, thereby has confirmed the kind of eluting solvent in this enrichment method.
Embodiment 6:
The magnesium oxide microsphere of 200 mg magnesium oxide microspheres and octadecyl modification is filled into respectively in the SPE blank pipe (6 mL) through dry method, and pad is put supporting filtration sieve plate respectively up and down.Before the last appearance; (a) using methylene chloride, acetone and volume ratio successively is that 5% aqueous acetone solution carries out activation to MgO; (b) using methylene chloride, acetone and volume ratio is that the magnesium oxide that 9% aqueous acetone solution is modified octadecyl carries out activation, and (c) using methylene chloride, isopropyl alcohol and volume ratio is that 25% isopropanol water solution carries out activation to Sep-Pak C18; The 250 mL deionized waters that will contain 5% acetone, 9% acetone and 25% isopropyl alcohol then (contain naphthalene: 1.408 ng mL in the WS
-1Acenaphthene: 4.080 ng mL
-1Fluorenes: 0.368 ng mL
-1Luxuriant and rich with fragrance: 0.230 ng mL
-1Anthracene: 0.108 ng mL
-1Pyrene: 0.460 ng mL
-1Benzo [a] pyrene: 1.216 ng mL
-1Benzo [ghi] perylene: 0.640 ng mL
-1) respectively with the flow velocity of 5 mL/min through a, b, three kinds of solid-phase extraction columns of c.Last appearance finishes, and uses 4 mL deionized waters that solid-phase extraction column a and c are carried out drip washing respectively, and adopts the acetonitrile solution of 4 mL 20% that b is carried out drip washing.Treat that drip washing finishes, use 5 mL methylene chloride that a and c are carried out wash-out respectively, and adopt the mixed solution (volume ratio 1:1) of 5 mL methylene chloride and normal hexane that b is carried out wash-out; After the gained eluent was concentrated into 50 mL respectively, using volume ratio was that 60% acetonitrile solution carries out constant volume, carries out efficient liquid phase chromatographic analysis at last.As can be seen from Figure 6, for magnesium oxide microsphere and commercial Sep-Pak C18, the magnesium oxide microsphere that the octadecyl that is adopted in this enrichment method is modified shows better concentration effect to the palycyclic aromatic in the WS.
Embodiment 7:
The magnesium oxide microsphere that 200 mg octadecyls are modified arrives in the SPE blank pipe (6 mL) through dry-packing, and pad is put supporting filtration sieve plate respectively up and down.Before the last appearance, using methylene chloride, acetone and volume ratio respectively is that 9% aqueous acetone solution carries out activation to solid-phase extraction column; 250 mL that will contain 9% (volume ratio) acetone then tap water that is mixed (contains naphthalene: 600 ng L
-1Acenaphthene: 1200 ng L
-1Fluorenes, fluoranthene, benzo [b] fluoranthene, dibenzo [a, h] anthracene, benzo [ghi] perylene: 120 ng L
-1Phenanthrene, anthracene, pyrene, benzo [a] anthracene, bend, benzo [k] fluoranthene, benzo [a] pyrene, indeno [1,2,3] perylenes: 60 ng L
-1) with appearance on the flow velocity of 5 mL/min.Last appearance finishes, and uses the acetonitrile solution of 4 mL, 20 % to carry out drip washing.Treat that drip washing finishes, use the mixed solution (volume ratio 1:1) of 5 mL methylene chloride and normal hexane to carry out wash-out, after the gained eluent was concentrated into 50 mL, using volume ratio was that 60% acetonitrile solution carries out constant volume, carries out efficient liquid phase chromatographic analysis at last.As can be seen from Figure 7, after this method enrichment, can realize quantitative measurement, show that this method can realize effective enrichment to the palycyclic aromatic in the environmental water sample palycyclic aromatic in the tap water.
With respect to magnesium oxide and commercial Sep-Pak C18; Realizing under the identical condition of enrichment factor; The magnesium oxide microsphere that this invention is modified with octadecyl is as solid phase extraction adsorbents; Set up a kind of enrichment method, and obtained higher extraction efficiency palycyclic aromatic in the environmental water sample.
Claims (5)
1. the enrichment method of palycyclic aromatic in the environmental water sample is characterized in that:
The magnesium oxide microsphere that utilizes the octadecyl modification is used for the palycyclic aromatic of enrichment environment water sample as solid phase extraction adsorbents, and its operation steps is following:
A) octadecyl is modified the preparation of magnesium oxide microsphere;
B) magnesium oxide microsphere of modifying with octadecyl is that filler prepares solid-phase extraction column;
C) use methylene chloride, organic modifier and the organic modifier WS that solid-phase extraction column is carried out activation successively; The water sample that will contain organic modifier is then gone up appearance;
D) use acetonitrile solution that solid-phase extraction column is carried out drip washing, and then solid-phase extraction column is carried out wash-out, get eluent with organic solvent;
E) promptly obtain palycyclic aromatic after the enrichment behind the eluent solvent flashing, use the acetonitrile solution constant volume then, and carry out efficient liquid phase chromatographic analysis.
2. according to the described enrichment method of claim 1, it is characterized in that: the quality of octadecyl modification magnesium oxide microsphere and the volume ratio of solid phase extraction tube are 200mg:6mL among the step b.
3. according to the described enrichment method of claim 1; It is characterized in that: when among the step c solid-phase extraction column being carried out activation; The organic modifier kind should be identical with the organic modifier kind of adding in the water sample, is in methyl alcohol, acetone or the isopropyl alcohol one or more; The volumetric concentration of the organic modifier WS should be identical with the concentration of organic modifier in the water sample; In the time of last kind, contain the organic modifier that volume ratio is 0%-20% in the water sample, purpose is to increase the solubleness of palycyclic aromatic in the WS, reduces the loss of palycyclic aromatic on tube wall in the SPE process; And when the column jecket volume of solid-phase extraction column was 6mL, last appearance flow speed control was at 1-5 mL/min, and the sample solution volume is controlled between the 20-250 mL.
4. according to the described enrichment method of claim 1; It is characterized in that: in the steps d; In the drip washing stage, when the column jecket volume of solid-phase extraction column is 6mL, use 1-4 mL volume ratio as the acetonitrile of 0%-20% (comprise and use water as eluent) or methanol in water as eluent; Enrichment that not only can the jamming target analyte, and can remove the segment polarity compound; The wash-out stage can adopt the organic solvent of polar intensity≤methylene chloride polar intensity or its mixed solution that solid-phase extraction column is carried out wash-out.
5. according to the described enrichment method of claim 1, it is characterized in that: the eluent evaporating solvent is to 50-100 mL among the step e, and purpose is to reduce the loss of the less palycyclic aromatic of molecular weight as far as possible.
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| CN106814156A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method of utilization matrix solid phase dispersion extractive analysis PAHs in soil |
| CN109154585A (en) * | 2016-02-03 | 2019-01-04 | 科思德株式会社 | For extracting the element of organic component |
| CN106282903B (en) * | 2016-09-12 | 2018-11-30 | 西北师范大学 | The technique that flame method prepares lumpy nanometer iron oxide coatings |
| CN106282903A (en) * | 2016-09-12 | 2017-01-04 | 西北师范大学 | The technique that flame method prepares lumpy nanometer iron oxide coatings |
| CN106932516A (en) * | 2017-04-18 | 2017-07-07 | 蔡明红 | Original position ultrasound washing device and ultrasonic elution process based on SPE sampling column |
| CN108645834B (en) * | 2018-04-18 | 2020-04-03 | 厦门大学 | Method for detecting polycyclic aromatic hydrocarbon in environmental water body |
| CN108645834A (en) * | 2018-04-18 | 2018-10-12 | 厦门大学 | The detection method of polycyclic aromatic hydrocarbon in a kind of environment water |
| CN109358149A (en) * | 2018-11-03 | 2019-02-19 | 浙江环境监测工程有限公司 | The fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water |
| CN110586053A (en) * | 2019-09-24 | 2019-12-20 | 山西医科大学 | Solid phase extraction polycyclic aromatic hydrocarbon adsorbent and preparation method thereof |
| CN110586053B (en) * | 2019-09-24 | 2022-06-03 | 山西医科大学 | Solid phase extraction polycyclic aromatic hydrocarbon adsorbent and preparation method thereof |
| CN114324670A (en) * | 2021-04-23 | 2022-04-12 | 新疆生产建设兵团第十三师红星医院 | Solid phase extraction column and application thereof |
| CN114324670B (en) * | 2021-04-23 | 2024-05-28 | 新疆生产建设兵团第十三师红星医院 | Solid phase extraction column and application thereof |
| CN113533593A (en) * | 2021-06-28 | 2021-10-22 | 济南大学 | Separation analysis method for complex oil-water emulsion system |
| CN115318814A (en) * | 2022-08-17 | 2022-11-11 | 北京化工大学 | Method for repairing polycyclic aromatic hydrocarbon polluted soil by organic solvent pretreatment in cooperation with ferric manganese ferrite activated persulfate |
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