CN111892737B - Method for detecting polycyclic aromatic hydrocarbons in sea area sediments - Google Patents
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- G01N30/02—Column chromatography
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- G01N30/02—Column chromatography
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- G01N30/12—Preparation by evaporation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
- C08J2201/0542—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
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- G01N30/08—Preparation using an enricher
- G01N2030/085—Preparation using an enricher using absorbing precolumn
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
- G01N2030/126—Preparation by evaporation evaporating sample
Abstract
The invention discloses a method for detecting polycyclic aromatic hydrocarbons in sea area sediments, which reduces the extraction condition of polycyclic aromatic hydrocarbons in sediments by adding a hypercrosslinked microporous polymer into the sediments in the pretreatment, and improves the detection rate and precision of polycyclic aromatic hydrocarbons in sea area sediments by adding fulvic acid and sinapine in the purification. The hypercrosslinked microporous polymer is prepared from benzoic acid, alpha-terpineol and a crosslinking agent methylal, wherein benzoic acid ester is obtained by the benzoic acid and the alpha-terpineol in a solvent o-xylene under the action of a catalyst stannous oxide, and the hypercrosslinked microporous polymer is obtained by the benzoic acid and the crosslinking agent methylal in a solvent 1, 2-dichloroethane under the action of a catalyst ferric chloride.
Description
Technical Field
The invention belongs to the technical field of environmental monitoring, and particularly relates to a method for detecting polycyclic aromatic hydrocarbons in sea area sediments.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) are a class of important persistent organic pollutants with significant ecological and health risks, widely exist in various environmental media, and mainly originate from incomplete combustion or high-temperature pyrolysis of organic substances. Most PAHs have strong toxicity (carcinogenicity, teratogenicity and mutagenicity), 70-90% of cancer lesions of human and animals are caused by chemical substances in the environment, and the PAHs are the largest class of carcinogenic chemical substances in the environment. In the beginning of the 80 s of the 20 th century, 16 PAHs were selected by the environmental protection agency and listed in the priority pollutant control list. PAHs have low solubility and hydrophobicity and thus are easily combined with suspended matter to settle on the water bottom, so that the sediment is one of the main environmental sinks of PAHs. Meanwhile, PAHs can be released into the environment again through the resuspension effect, thereby causing secondary pollution.
The sediment sample can be lost in the long-distance transportation and long-time storage process, the accuracy of the experiment is influenced, the pretreatment process of the solvent extraction method is accelerated to be longer, and the extraction conditions and equipment requirements are high. The components in the sediment extracting solution are complex, and the accuracy and precision of detection are influenced.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a hypercrosslinked microporous polymer having a good polycyclic aromatic hydrocarbon adsorption capacity, which can extract polycyclic aromatic hydrocarbons in a deposit into a solvent, and improve an extraction process.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method of preparing a hypercrosslinked microporous polymer comprising: the super-crosslinked microporous polymer is prepared from benzoic acid, alpha-terpineol and a crosslinking agent. The specific preparation conditions are as follows: adding benzoic acid, terpineol, a catalyst stannous oxide and a solvent o-xylene into a three-mouth flask, heating and stirring, refluxing for 9-18h at the temperature of 150-; the addition amount of the benzoic acid is 20-40 wt% of the o-xylene, the addition amount of the terpineol is 20-45 wt% of the o-xylene, the addition amount of the catalyst is 0.01-1.25 wt% of the o-xylene, the concentration of the sodium hydroxide solution is 1-10 wt%, the addition amount of the tert-butanol is 40-80 wt% of the benzoic acid, and the addition amount of the tert-butanol is 150-300 wt% of the o-xylene. Under the protection of nitrogen, adding benzoate and a cross-linking agent methylal into a solvent 1, 2-dichloroethane, stirring for 10-30min, adding anhydrous ferric chloride, reacting at 30-50 ℃ for 6-12h, then heating to 60-90 ℃ for reaction for 12-24h, cooling to room temperature after the reaction is finished, washing with a mixed solution of methanol and diethyl ether, and vacuum drying to obtain a super-crosslinked microporous polymer; the addition amount of benzoate is 5-20 wt% of 1, 2-dichloroethane, the addition amount of cross-linking agent methylal is 3-15 wt% of 1, 2-dichloroethane, the addition amount of anhydrous ferric chloride is 0.5-8 wt% of 1, 2-dichloroethane, and the proportion of methanol and diethyl ether is 1: 0.3-3. After benzoic acid and alpha-terpineol generate benzoic ether, the super-crosslinked microporous polymer is obtained under the action of a cross-linking agent methylal, and the benzoic ether has stronger rigidity and high crosslinking degree under the super-branched crosslinking, so that molecular chains cannot be densely stacked, and holes formed by molecular chain segments cannot collapse in an extraction solvent, thereby forming a large number of hole structures. The skeleton of the hypercrosslinked microporous polymer is composed of benzoate molecules which are connected with each other through covalent bonds, and the hypercrosslinked microporous polymer has open pore channels and excellent pore properties, and compared with the fragile molecular network structure formed by non-covalent bond connection, the polymer is connected through covalent bonds, and the molecular network structure is more stable while the microporous properties of the material are maintained. The obtained super-crosslinked microporous polymer can be used for adsorbing polycyclic aromatic hydrocarbon in sediment.
Preferably, benzoic acid is added in an amount of 25-35 wt%, e.g., 26, 28, 30, 31, 33 wt%.
Preferably, the amount of alpha-terpineol added is 25-40 wt%, e.g. 26, 28, 30, 33, 34, 36, 38 wt%.
Preferably, methylal is added in an amount of 5-12 wt%, e.g., 6, 8, 9, 10, 11 wt%.
The invention also aims to provide a method for detecting polycyclic aromatic hydrocarbons in sea area sediments, which reduces the extraction conditions by adding the hypercrosslinked microporous polymer for co-extraction and improves the detection rate and precision of polycyclic aromatic hydrocarbons by adding fulvic acid and sinapine.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method for detecting polycyclic aromatic hydrocarbons in sea area sediment, comprising: the pre-treatment is added with a super-crosslinked microporous polymer. Grinding and sieving a sediment sample, diatomite, activated copper powder and a super-crosslinked microporous polymer by a ball mill to obtain sediment powder, wherein the addition amount of the diatomite is 1-10 wt% of the sediment, the addition amount of the activated copper powder is 1-10 wt% of the sediment, and the addition amount of the super-crosslinked microporous polymer is 5-20 wt% of the sediment. Transferring the sediment powder into an extraction tank, filling gaps in the extraction tank with quartz sand, wherein an extraction solvent is n-hexane: acetone (volume ratio 1: 0.2-5). The accelerated solvent extraction conditions were: the system pressure is 1000-1200psi, the temperature is 40-60 ℃, the heating is carried out for 3-10min, the static extraction is carried out for 3-10min, 50-70 percent of the volume of the extractor is washed, and the circulation is carried out for 2-3 times. After extraction, the solvent is transferred to a conical flask for purification. The method comprises the steps of grinding a super-crosslinked microporous polymer and a sediment together, enabling the super-crosslinked microporous polymer to be fully and uniformly mixed and fully contacted with a sediment sample, enabling the super-crosslinked microporous polymer to have a large number of ester bonds, unsaturated bonds and holes when an extraction solvent is added for extraction, enabling polycyclic aromatic hydrocarbons to generate weak interaction among atoms on the surface of the super-crosslinked microporous polymer to form a molecular layer near the surface through dispersion force, dipole interaction force, electrostatic attraction or hydrogen bonds to form adsorption force, and extracting the polycyclic aromatic hydrocarbons into a solution. The conditions for accelerating the solvent extraction process can be reduced by the special properties of the hypercrosslinked microporous polymer, thereby reducing the cost and the requirements for technical equipment.
Preferably, the amount of hypercrosslinked microporous polymer added is 5 to 15 wt%, for example, 6, 7, 9, 10, 12, 14, 14.5 wt%.
Purifying and detecting: and (3) filling the n-hexane into the column by a wet method, adding 10cm of n-hexane into the column, adding a little absorbent cotton if no barrier exists at the bottom of the column, wherein the anhydrous sodium sulfate is 1-2cm below the column, the florisil is 4-6cm in the middle, and the anhydrous sodium sulfate is 1-2cm above the column. Adding 5-10ml n-hexane to pre-wash the chromatographic column, discarding, and keeping the top end of the chromatographic column packing in a slightly moist state. The concentrated solution to be purified is transferred to a chromatographic column and purified by chromatography on a column packed with 50-100ml of a column containing n-hexane: the acetone (volume ratio 1: 0.1-1) eluent is eluted in three times, the flow rate is about 60-90 drops per minute, and the eluent is collected in a conical flask until about 150-300 mL. Fulvic acid and sinapine can also be added into the eluent, the addition amount of fulvic acid is 0.05-1 wt%, and the addition amount of sinapine is 0.05-1 wt%. In the polycyclic aromatic hydrocarbon extracting solution, adsorption balance exists between the super-crosslinked microporous polymer and the polycyclic aromatic hydrocarbon, when the free polycyclic aromatic hydrocarbon extracting solution flows through a column containing Florisil, the free polycyclic aromatic hydrocarbon is adsorbed on the Florisil to form distribution balance, and then the free polycyclic aromatic hydrocarbon is gradually eluted through eluent and detected; and polycyclic aromatic hydrocarbon in a composite state with the super-crosslinked microporous polymer can not be freely adsorbed on Florisil, so that the detection precision is reduced and the detection rate is low. The fulvic acid and sinapine contain groups such as benzene ring, hydroxyl, carboxyl, unsaturated bond, benzene ring, ether bond and the like, and compete adsorption with polycyclic aromatic hydrocarbon on the hypercrosslinked microporous polymer is formed, so that the polycyclic aromatic hydrocarbon is desorbed, and under the action of the polygroups, the complex matrix in the extracting solution is adsorbed in the compound formed by the hypercrosslinked microporous polymer, the fulvic acid and the sinapine, so that the polycyclic aromatic hydrocarbon extracting solution is purified, the detection rate of the polycyclic aromatic hydrocarbon is improved, and the RSD of detection is reduced.
Preferably, the fulvic acid is added in an amount of 0.1 to 1 wt%, for example 0.3, 0.5, 0.75, 0.8, 0.9 wt%.
Preferably sinapine is added in an amount of 0.1-1 wt%, e.g., 0.2, 0.25, 0.3, 0.5, 0.7, 0.9, 0.95 wt%.
Concentrating and fixing volume: concentrating the solution purified by a Florisil column method on a nitrogen blowing instrument, carrying out solvent replacement for many times, finally fixing the volume to 0.5-3ml by using n-hexane, and detecting by a GC-MS machine.
The invention adopts the hypercrosslinked microporous polymer in the pretreatment and adopts fulvic acid and sinapine in the purification, thereby having the following beneficial effects: the super-crosslinked microporous polymer forms adsorption acting force through dispersion force, dipole interaction force, electrostatic attraction or hydrogen bonds, so that polycyclic aromatic hydrocarbon generates weak interaction between atoms on the surface of the super-crosslinked microporous polymer to form a molecular layer near the surface, the detection rate of polycyclic aromatic hydrocarbon in sediments is improved, and the polycyclic aromatic hydrocarbon is better preserved under long-time placement; the fulvic acid and sinapine form competitive adsorption with polycyclic aromatic hydrocarbon on the hypercrosslinked micropore polymer under the phase action of functional groups, so that more polycyclic aromatic hydrocarbon is dissociated into the solution, the detection rate and the precision are improved, and the fulvic acid, sinapine and hypercrosslinked micropore polymer can also purify complex matrixes in sediment polycyclic aromatic hydrocarbon extracting solution and improve the precision of polycyclic aromatic hydrocarbon detection. Therefore, the method for detecting the polycyclic aromatic hydrocarbon in the sea area sediments reduces the extraction conditions, improves the detection rate and the precision of the polycyclic aromatic hydrocarbon.
Drawings
FIG. 1 is an infrared contrast diagram of benzoic acid, benzoate esters, hypercrosslinked microporous polymers;
FIG. 2 is a graph showing the adsorption amount of the hypercrosslinked microporous polymer to the polycyclic aromatic hydrocarbon.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
naphthalene, phenanthrene and pyrene have the property of polycyclic aromatic hydrocarbon, and naphthalene, phenanthrene and pyrene are used as representative substances of polycyclic aromatic hydrocarbon for detection.
The sediment sample is prepared by adding naphthalene, phenanthrene and pyrene standard substances into pure sea sediment respectively to obtain a concentration of 30 mg/kg.
Example 1:
a process for the preparation of a hypercrosslinked microporous polymer,
adding benzoic acid, terpineol, a catalyst stannous oxide and a solvent o-xylene into a three-neck flask, heating and stirring, refluxing for 12 hours at the temperature of 180 ℃, cooling to room temperature, adding a sodium hydroxide solution, reacting for 30 minutes at the temperature of 70 ℃, washing with hot water at 45 ℃ to be neutral, transferring an oil phase into the three-neck flask, heating to 160 ℃ to remove water and o-xylene, adding tert-butyl alcohol into a reaction solution, refluxing and recrystallizing at the temperature of 85 ℃, naturally cooling, filtering and drying to obtain benzoate; the addition amount of benzoic acid is 30 wt% of ortho-xylene, the addition amount of terpineol is 30 wt% of ortho-xylene, the addition amount of catalyst stannous oxide is 0.3 wt% of ortho-xylene, the concentration of sodium hydroxide solution is 10 wt%, the addition amount is 40-80 wt% of benzoic acid, and the addition amount of tertiary butanol is 200 wt% of ortho-xylene.
Under the protection of nitrogen, adding benzoate and a cross-linking agent methylal into a solvent 1, 2-dichloroethane, stirring for 15min, adding anhydrous ferric chloride, reacting at 40 ℃ for 8h, then heating to 70 ℃ for reacting for 16h, cooling to room temperature after the reaction is finished, washing with a mixed solution of methanol and diethyl ether, and drying in vacuum to obtain a super-crosslinked microporous polymer; the addition amount of benzoate is 10 wt% of 1, 2-dichloroethane, the addition amount of cross-linking agent methylal is 10 wt% of 1, 2-dichloroethane, the addition amount of anhydrous ferric chloride is 2 wt% of 1, 2-dichloroethane, and the proportion of methanol and diethyl ether is 1: 1.
example 2:
a method for detecting polycyclic aromatic hydrocarbon in sea area sediments,
pretreatment: and grinding and sieving a sediment sample, diatomite, activated copper powder and the super-crosslinked microporous polymer obtained in the example 1 by using a ball mill to obtain sediment powder, wherein the adding amount of the diatomite is 5 wt% of the sediment, the adding amount of the activated copper powder is 5 wt% of the sediment, and the adding amount of the super-crosslinked microporous polymer is 5 wt% of the sediment.
Enrichment and extraction: transferring the sediment powder into an extraction tank, filling gaps in the extraction tank with quartz sand, wherein an extraction solvent is n-hexane: acetone (volume ratio 1: 1). The accelerated solvent extraction conditions were: heating at 50 deg.C under 1000psi for 5min, static extracting for 5min, flushing with 60% of extractor volume, and circulating for 2 times. After extraction, the solvent is transferred to a conical flask for purification.
Purifying and detecting: and (3) filling the n-hexane into the column by a wet method, adding 10cm of n-hexane into the column, adding a little absorbent cotton if no barrier exists at the bottom of the column, wherein the anhydrous sodium sulfate is 2cm below the column, the florisil silica is 6cm in the middle of the column, and the anhydrous sodium sulfate is 1cm above the column. Adding 10ml of n-hexane to pre-wash the chromatographic column, discarding, and keeping the top end of the chromatographic column packing in a slightly moist state. The concentrated solution to be purified is transferred to a chromatography column, purified with 50ml of n-hexane: eluting with acetone (volume ratio of 1:1) at a flow rate of about 60-90 drops per minute three times, and collecting the eluate in a conical flask until the volume is about 150 mL.
Concentrating and fixing volume: concentrating the solution purified by a Florisil column method on a nitrogen blowing instrument, carrying out solvent replacement for many times, finally fixing the volume to 1ml by using n-hexane, and detecting on a GC-MS machine.
Example 3:
a method for detecting polycyclic aromatic hydrocarbon in sea area sediments,
pretreatment: and grinding and sieving a sediment sample, diatomite, activated copper powder and the super-crosslinked microporous polymer obtained in example 1 by using a ball mill to obtain sediment powder, wherein the adding amount of the diatomite is 5 wt% of the sediment, the adding amount of the activated copper powder is 5 wt% of the sediment, and the adding amount of the super-crosslinked microporous polymer is 12 wt% of the sediment.
Enrichment and extraction: transferring the sediment powder into an extraction tank, filling gaps in the extraction tank with quartz sand, wherein an extraction solvent is n-hexane: acetone (volume ratio 1: 1). The accelerated solvent extraction conditions were: heating at 50 deg.C under 1000psi for 5min, static extracting for 5min, flushing with 60% of extractor volume, and circulating for 2 times. After extraction, the solvent is transferred to a conical flask for purification.
Purifying and detecting: and (3) filling the n-hexane into the column by a wet method, adding 10cm of n-hexane into the column, adding a little absorbent cotton if no barrier exists at the bottom of the column, wherein the anhydrous sodium sulfate is 2cm below the column, the florisil silica is 6cm in the middle of the column, and the anhydrous sodium sulfate is 1cm above the column. Adding 10ml of n-hexane to pre-wash the chromatographic column, discarding, and keeping the top end of the chromatographic column packing in a slightly moist state. The concentrated solution to be purified is transferred to a chromatography column, purified with 50ml of n-hexane: eluting with acetone (volume ratio of 1:1) at a flow rate of about 60-90 drops per minute three times, and collecting the eluate in a conical flask until the volume is about 150 mL.
Concentrating and fixing volume: concentrating the solution purified by a Florisil column method on a nitrogen blowing instrument, carrying out solvent replacement for many times, finally fixing the volume to 1ml by using n-hexane, and detecting on a GC-MS machine.
Example 4:
a method for detecting polycyclic aromatic hydrocarbon in sea area sediments,
pretreatment: and grinding and sieving a sediment sample, diatomite, activated copper powder and the super-crosslinked microporous polymer obtained in example 1 by using a ball mill to obtain sediment powder, wherein the adding amount of the diatomite is 5 wt% of the sediment, the adding amount of the activated copper powder is 5 wt% of the sediment, and the adding amount of the super-crosslinked microporous polymer is 12 wt% of the sediment.
Enrichment and extraction: transferring the sediment powder into an extraction tank, filling gaps in the extraction tank with quartz sand, wherein an extraction solvent is n-hexane: acetone (volume ratio 1: 1). The accelerated solvent extraction conditions were: heating at 50 deg.C under 1000psi for 5min, static extracting for 5min, flushing with 60% of extractor volume, and circulating for 2 times. After extraction, the solvent is transferred to a conical flask for purification.
Purifying and detecting: and (3) filling the n-hexane into the column by a wet method, adding 10cm of n-hexane into the column, adding a little absorbent cotton if no barrier exists at the bottom of the column, wherein the anhydrous sodium sulfate is 2cm below the column, the florisil silica is 6cm in the middle of the column, and the anhydrous sodium sulfate is 1cm above the column. Adding 10ml of n-hexane to pre-wash the chromatographic column, discarding, and keeping the top end of the chromatographic column packing in a slightly moist state. The concentrated solution to be purified is transferred to a chromatography column, purified with 50ml of a solution containing n-hexane: eluting with acetone (volume ratio of 1:1) for three times, wherein the eluate also contains fulvic acid and sinapine, the addition amount of fulvic acid is 0.1 wt%, the addition amount of sinapine is 0.1 wt%, the flow rate is about 60-90 drops per minute, and collecting eluate in a conical flask until the volume is about 150 mL.
Concentrating and fixing volume: concentrating the solution purified by a Florisil column method on a nitrogen blowing instrument, carrying out solvent replacement for many times, finally fixing the volume to 1ml by using n-hexane, and detecting on a GC-MS machine.
Example 5:
a method for detecting polycyclic aromatic hydrocarbon in sea area sediments,
pretreatment: and grinding and sieving a sediment sample, diatomite, activated copper powder and the super-crosslinked microporous polymer obtained in example 1 by using a ball mill to obtain sediment powder, wherein the adding amount of the diatomite is 5 wt% of the sediment, the adding amount of the activated copper powder is 5 wt% of the sediment, and the adding amount of the super-crosslinked microporous polymer is 12 wt% of the sediment.
Enrichment and extraction: transferring the sediment powder into an extraction tank, filling gaps in the extraction tank with quartz sand, wherein an extraction solvent is n-hexane: acetone (volume ratio 1: 1). The accelerated solvent extraction conditions were: heating at 50 deg.C under 1000psi for 5min, static extracting for 5min, flushing with 60% of extractor volume, and circulating for 2 times. After extraction, the solvent is transferred to a conical flask for purification.
Purifying and detecting: and (3) filling the n-hexane into the column by a wet method, adding 10cm of n-hexane into the column, adding a little absorbent cotton if no barrier exists at the bottom of the column, wherein the anhydrous sodium sulfate is 2cm below the column, the florisil silica is 6cm in the middle of the column, and the anhydrous sodium sulfate is 1cm above the column. Adding 10ml of n-hexane to pre-wash the chromatographic column, discarding, and keeping the top end of the chromatographic column packing in a slightly moist state. The concentrated solution to be purified is transferred to a chromatography column, purified with 50ml of a solution containing n-hexane: eluting with acetone (volume ratio of 1:1) for three times, wherein the eluate also contains fulvic acid and sinapine, the addition amount of fulvic acid is 0.6 wt%, the addition amount of sinapine is 0.6 wt%, the flow rate is about 60-90 drops per minute, and collecting eluate in a conical flask until the volume is about 150 mL.
Concentrating and fixing volume: concentrating the solution purified by a Florisil column method on a nitrogen blowing instrument, carrying out solvent replacement for many times, finally fixing the volume to 1ml by using n-hexane, and detecting on a GC-MS machine.
Example 6:
a method for detecting polycyclic aromatic hydrocarbon in sea area sediments,
pretreatment: and grinding and sieving the sediment sample, diatomite and activated copper powder by using a ball mill to obtain sediment powder, wherein the addition amount of the diatomite is 5 wt% of the sediment, and the addition amount of the activated copper powder is 5 wt% of the sediment.
Enrichment and extraction: transferring the sediment powder into an extraction tank, filling gaps in the extraction tank with quartz sand, wherein an extraction solvent is n-hexane: acetone (volume ratio 1: 1). The accelerated solvent extraction conditions were: heating at 90 deg.C under 1600psi for 5min, static extracting for 5min, flushing with 60% of extractor volume, and circulating for 2 times. After extraction, the solvent is transferred to a conical flask for purification.
Purifying and detecting: and (3) filling the n-hexane into the column by a wet method, adding 10cm of n-hexane into the column, adding a little absorbent cotton if no barrier exists at the bottom of the column, wherein the anhydrous sodium sulfate is 2cm below the column, the florisil silica is 6cm in the middle of the column, and the anhydrous sodium sulfate is 1cm above the column. Adding 10ml of n-hexane to pre-wash the chromatographic column, discarding, and keeping the top end of the chromatographic column packing in a slightly moist state. The concentrated solution to be purified is transferred to a chromatography column, purified with 50ml of n-hexane: eluting with acetone (volume ratio of 1:1) at a flow rate of about 60-90 drops per minute three times, and collecting the eluate in a conical flask until the volume is about 150 mL.
Concentrating and fixing volume: concentrating the solution purified by a Florisil column method on a nitrogen blowing instrument, carrying out solvent replacement for many times, finally fixing the volume to 1ml by using n-hexane, and detecting on a GC-MS machine.
Comparative example 1:
this comparative example is compared to example 3, except that no hypercrosslinked microporous polymer was added.
Comparative example 2:
this comparative example is compared to example 3, except that no hypercrosslinked microporous polymer was added; fulvic acid and sinapine are added in the purification detection.
Comparative example 3:
this comparative example is compared to example 5, except that fulvic acid was added alone.
Comparative example 4:
this comparative example differs from example 5 only in that sinapine was added.
Comparative example 5:
this comparative example is compared to example 6, except that fulvic acid was added alone.
Comparative example 6:
this comparative example differs from example 6 only in that sinapine was added.
Comparative example 7:
this comparative example is compared to example 6, except that fulvic acid and sinapine were added.
Comparative example 8:
compared with example 5, the sediment of the near mouth of Yangtze river is selected for detection in the comparative example.
Comparative example 9:
compared with example 6, the sediment of the near mouth of Yangtze river is selected for detection in the comparative example.
Test example 1:
1. infrared characterization
Adopts KBr tablet pressing method for the benzoic acid, the benzoate and the super-crosslinked microporous polymer, and the scanning range is 500-4000cm-1Wherein the scanning times are 32, and the resolution is 4cm-1。
The detection result is shown in FIG. 1, wherein a is benzoic acid, b is benzoate, c is a super-crosslinked microporous polymer, and the infrared spectrum of the benzoate is 2500--1The peak of the carboxyl hydroxyl group of the benzoic acid disappears, which indicates that the benzoate is generated; the infrared patterns of benzoate and hypercrosslinked microporous polymers are compared, and the hypercrosslinked microporous polymers are connected by methyl at 2900-3000cm-1The alkyl hydrogen of (a) is different from the benzoate, which indicates that the synthesis obtains the super-crosslinked microporous polymer.
2. Adsorption Properties of Polymer
Washing 45mg of the hypercrosslinked microporous polymer with ultrapure water for 3min, transferring the hypercrosslinked microporous polymer into a beaker, adding 20mL of 2mmol/L naphthalene solution, stirring immediately at room temperature, sucking 2mL of pollutant solution at intervals of 30s, 1min, 2min, 3min, 4min, 5min, 6min, 7min and 8min by an injector, and filtering immediately. The naphthalene content of the filtrate was determined by GC-MS. And (3) sequentially replacing the pollutants with 2mmol/L phenanthrene, pyrene and PAHs (naphthalene: phenanthrene: pyrene ═ 1: 1:1) solution, and repeating the operation.
The result of the detection of the adsorption performance of the polymer on polycyclic aromatic hydrocarbons is shown in fig. 2, the super-crosslinked microporous polymer has the lowest adsorption amount on naphthalene and the highest adsorption amount on phenanthrene, and the adsorption effect in PAHs (naphthalene: phenanthrene: pyrene: 1:1) mixed solution is better.
Test example 2:
1. detection rate and relative standard deviation for detecting naphthalene, phenanthrene and pyrene
Precision: and (4) carrying out parallel determination on the naphthalene, phenanthrene and pyrene standard solutions for 5 times, and calculating the relative standard deviation.
And (3) the sample standard addition detection rate: naphthalene, phenanthrene and pyrene standard solutions were added to the sediment samples of the examples and comparative examples, and analysis was performed according to established experimental conditions to determine the rate of detection of the added standard of the samples.
The results of the detection of the normalized detectable rate of the sample are shown in table 1, the detectable rate of naphthalene in comparative example 1 is the lowest and is only 58.24%, and the detectable rate of naphthalene in example 5 is the highest and reaches 102.37%, which indicates that the naphthalene in example 5 has the best detection result. The following results were also obtained:
compared with example 3, the addition amount of the hypercrosslinked microporous polymer in example 3 is more than that in comparative example 2, which results in a decrease in the detection rate of naphthalene in example 3, indicating that the hypercrosslinked microporous polymer reduces the elution amount of naphthalene in the purification process while adsorbing naphthalene; compared with the comparative example 1, the detection rate of the embodiment 3 is superior to that of the comparative example 1 because the hypercrosslinked microporous polymer is added in the embodiment 3 for extracting the naphthalene, which shows that the hypercrosslinked microporous polymer has an adsorption effect on the naphthalene, although the elution amount is reduced in the purification process, the total concentration of the naphthalene in the solution is increased, and after the distribution balance is reached in the elution process, the effective concentration of the naphthalene in the solution is increased, and the detection rate of the naphthalene is increased; compared with the comparative example 2, the comparative example 2 has the advantages that after the fulvic acid and the sinapine are added, the detection rate of naphthalene is improved, and the fulvic acid and the sinapine improve the naphthalene content in the purification process, so that a better result is obtained; example 5 compared to example 3, the addition of fulvic acid and sinapine in example 5 resulted in the optimum naphthalene detection rate, and the resulting hypercrosslinked microporous polymer was able to adsorb naphthalene from the sediment into solution, but did not completely dissociate in the eluent during the purification process to give detectable naphthalene, which was desorbed from the hypercrosslinked microporous polymer by the fulvic acid and sinapine, thus increasing the detection rate.
Example 5 compared with comparative example 3 and comparative example 4, the elution with the fulvic acid and sinapine added in the purification process in example 5 gave better detection rate, while the detection rate with the fulvic acid added in comparative example 3 and sinapine added in comparative example 4 gave worse results than in example 5, and the difference from the results of example 3 without fulvic acid and sinapine was not obvious, which shows that the naphthalene detection rate could be improved only under the combined action of fulvic acid and sinapine.
Example 6 the detection rate of comparative example 7 was the best as compared to comparative examples 5, 6 and 7, indicating that the addition of fulvic acid and sinapine during the purification process had the effect of increasing the naphthalene detection rate.
The detection rate change of phenanthrene and pyrene is basically consistent with that of naphthalene.
The results of relative standard deviation measurements are shown in table 1, and in example 3, compared with comparative example 2, the relative standard deviation obtained by adding fulvic acid and sinapine in comparative example 2 is better than that of example 3, which shows that the addition of fulvic acid and sinapine can improve the precision of naphthalene detection and reduce the relative standard deviation of the detection results. Example 5 compared with comparative example 3 and comparative example 4, the relative deviation obtained by adding fulvic acid only in comparative example 3 and the relative standard deviation obtained by adding sinapine only in comparative example 4 are still large, which indicates that fulvic acid or sinapine can not improve detection precision, and the presence of only two substances plays a role in improving detection precision.
The precision changes of phenanthrene and pyrene are basically consistent with those of naphthalene.
TABLE 1 detection Rate and Relative Standard Deviation (RSD) of polycyclic aromatic hydrocarbons
2. Effect of the storage time
Taking an actual sediment sample containing 30mg/kg of each of naphthalene, phenanthrene and pyrene as an example, 5% of super-crosslinked microporous polymer is added, and the content of naphthalene, phenanthrene and pyrene in the sediment is detected after the sediment is respectively stored for 7 days, 14 days, 30 days and 60 days at 4 ℃ by taking the non-super-crosslinked microporous polymer as a control.
The detection results are shown in table 2, and with the extension of the standing time, after 5% of the hypercrosslinked microporous polymer is added into the sediment, the loss amount of naphthalene, phenanthrene and pyrene is less than that of the sample without the hypercrosslinked microporous polymer, which indicates that the hypercrosslinked microporous polymer and the sediment containing polycyclic aromatic hydrocarbon are mixed together and have the effect of preserving the polycyclic aromatic hydrocarbon in the sediment.
TABLE 2 polycyclic aromatic hydrocarbons measured after different storage times
3. Detection result of polycyclic aromatic hydrocarbon in sediments near Yangtze river offshore mouth
The results of polycyclic aromatic hydrocarbons detection of sediments in the offshore mouths of Yangtze river are shown in Table 3, and sixteen kinds of polycyclic aromatic hydrocarbons are detected, namely Naphthalene (NAP), Acenaphthylene (ACY), Acenaphthylene (ACT), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT), Fluoranthene (FLA), Pyrene (PYR), benzo [ a ], and]anthracene (BaA),
(CHR), benzo [ b ]]Fluoranthene (BbF), benzo [ k ]]Fluoranthene (BkF), benzo [ a ]]Pyrene (BaP), indeno [1, 2, 3-cd]Pyrene (IND), dibenzo [ a, h ]]Anthracene (DBA), benzo [ g, h, i]Perylene (BGP), the twelve of which have the lowest safety values, are shown in table 3, and comparative example 8, which is superior to comparative example 9, illustrates the superiority of the present method over the prior art.
TABLE 3 detection results of polycyclic aromatic hydrocarbons in sediments near Yangtze river offshore mouth
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (6)
1. A method for detecting polycyclic aromatic hydrocarbons in sea area sediment, comprising:
the pretreatment is an extraction step of polycyclic aromatic hydrocarbon in the sediment, and a hypercrosslinked microporous polymer is added in the pretreatment;
purifying the polycyclic aromatic hydrocarbon extract;
concentrating the purified polycyclic aromatic hydrocarbon to constant volume and then detecting by GC-MS;
the preparation method of the hypercrosslinked microporous polymer comprises the following steps: dissolving benzoic acid and alpha-terpineol in o-xylene to prepare benzoic ether; the super-crosslinked microporous polymer is prepared from the benzoate and a crosslinking agent in 1, 2-dichloroethane, wherein the crosslinking agent is methylal.
2. The method for detecting polycyclic aromatic hydrocarbons in sea sediment according to claim 1, wherein the method comprises the following steps: the addition amount of the super-crosslinked microporous polymer is 5-20 wt% of the sediment.
3. The method for detecting polycyclic aromatic hydrocarbons in sea sediment according to claim 1, wherein the method comprises the following steps: diatomite and activated copper powder are also added in the pretreatment.
4. The method for detecting polycyclic aromatic hydrocarbons in sea sediment according to claim 1, wherein the method comprises the following steps: the addition amount of the benzoic acid is 20-40 wt% of the o-xylene.
5. The method for detecting polycyclic aromatic hydrocarbons in sea sediment according to claim 1, wherein the method comprises the following steps: the addition amount of the alpha-terpineol is 20-45 wt% of the o-xylene.
6. The method for detecting polycyclic aromatic hydrocarbons in sea sediment according to claim 1, wherein the method comprises the following steps: the addition amount of the methylal is 3-15 wt% of 1, 2-dichloroethane.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059095A (en) * | 2010-12-09 | 2011-05-18 | 江南大学 | Method for preparing graphene composite material adsorbing polycyclic aromatic hydrocarbon pollutants |
| WO2013034581A1 (en) * | 2011-09-09 | 2013-03-14 | Unilever N.V. | Antimicrobial composition comprising thymol and a terpinyl derivative |
| CN107708652A (en) * | 2015-06-12 | 2018-02-16 | 宝洁公司 | Perfume composition and application thereof |
| CN108912312A (en) * | 2018-07-11 | 2018-11-30 | 吴慈 | A kind of preparation and its application of hydrophobic porous organic polymer material |
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| CN108503829B (en) * | 2018-03-28 | 2021-03-05 | 东华大学 | Modification method and application of high-nitrogen-content microporous polymer |
| CN110204775B (en) * | 2019-05-13 | 2021-07-20 | 湖北大学 | Super-crosslinked microporous polymer nano particle and preparation method and application thereof |
| CN110437489A (en) * | 2019-08-30 | 2019-11-12 | 济南大学 | A kind of method that waste and old expanded polystyrene (EPS) recycling prepares super cross-linked porous material |
| CN111040226A (en) * | 2019-12-02 | 2020-04-21 | 中南大学 | Preparation method of hypercrosslinked polymer rich in hydrogen bond acceptor oxygen atoms and application of hypercrosslinked polymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059095A (en) * | 2010-12-09 | 2011-05-18 | 江南大学 | Method for preparing graphene composite material adsorbing polycyclic aromatic hydrocarbon pollutants |
| WO2013034581A1 (en) * | 2011-09-09 | 2013-03-14 | Unilever N.V. | Antimicrobial composition comprising thymol and a terpinyl derivative |
| CN107708652A (en) * | 2015-06-12 | 2018-02-16 | 宝洁公司 | Perfume composition and application thereof |
| CN108912312A (en) * | 2018-07-11 | 2018-11-30 | 吴慈 | A kind of preparation and its application of hydrophobic porous organic polymer material |
Non-Patent Citations (2)
| Title |
|---|
| 催化合成乙酸松油酯研究进展;戚春杰;《精细石油化工进展》;20111031;第12卷(第10期);全文 * |
| 泛杭州湾海域沉积物中多环芳烃分布及源解析;胡小萌等;《海洋环境科学》;20170228;第36卷(第1期);全文 * |
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