CN108008029A - The dispersive solid-phase extraction of Phthalates of Environment Hormone-gas chromatography-mass spectrum detection method in a kind of marine sediment - Google Patents
The dispersive solid-phase extraction of Phthalates of Environment Hormone-gas chromatography-mass spectrum detection method in a kind of marine sediment Download PDFInfo
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Abstract
The present invention relates to marine sediment pollution detection technical field, more particularly in a kind of marine sediment Phthalates of Environment Hormone dispersive solid-phase extraction gaschromatographic mass spectrometry detection method, comprise the following steps：(1) collection of sample；(2) sampling and ultrasonic extraction；(3) concentrate；(4) dispersive solid-phase extraction purifies；(5) constant volume is concentrated；(6) gaschromatographic mass spectrometry detector detects；(7) Specification Curve of Increasing；(8) determination of recovery rates.The present invention is easy to operate, and ultrasonic extraction is efficient, can be rapidly completed the pre-treatment of sample；First using Graphon as solid-phase adsorbent, dispersive solid-phase extraction is efficient, good purification；With higher sensitivity and the rate of recovery and reappearance, 16 kinds of phthalic acid ester detections are limited to 0.1~0.25 μ g/kg, the rate of recovery is 78~117%, and relative standard deviation (n=5) is 2.4~6.8%, can be applied to the Accurate Determining of phthalic acid ester content in marine sediment.
Description
Technical Field
The invention relates to the technical field of marine sediment pollution detection, in particular to a dispersed solid-phase extraction-gas chromatography-mass spectrometry detection method of phthalate ester environmental hormones in marine sediments.
Background
Phthalate, as an important environmental hormone, is widely distributed in various media such as atmosphere, water, soil, substrate sludge, food, animal and plant bodies, even human bodies and the like, has estrogen-like effect, interferes endocrine systems, and causes reproductive, development and behavior abnormalities, is mainly used as a plasticizer to be applied to food, textiles, toys for children and the like, and also can be used as a production raw material of chemical products such as pesticides, cosmetics, lubricants and the like, and is listed as a 'priority pollutant list' by a plurality of countries in the world. Although phthalate ester contamination has attracted global attention, it can persist because it is stable in nature in the environment. Marine sediments are important carriers, venues and accumulation areas for phthalate ester migration and transformation in the environment. Therefore, it is particularly important to analyze phthalates in marine sediments.
At present, soxhlet extraction, oscillation extraction, microwave-assisted extraction, quEChERS, accelerated solvent extraction, ultrasonic extraction, matrix solid-phase dispersion extraction and other extraction technologies are mainly adopted at home and abroad, one or two purification methods of chromatographic column purification, solid-phase extraction, concentrated sulfuric acid purification, dispersed solid-phase extraction, dispersed liquid-phase microextraction and the like are combined, and then the phthalate in sediment or soil samples is detected by adopting the technologies of gas chromatography, high performance liquid chromatography, gas chromatography-mass spectrometry, gas chromatography-tandem mass spectrometry and the like.
Phthalate is easy to hydrolyze under acidic or alkaline conditions, and chromatographic columns or solid phase extraction small columns are mainly selected for purification in literature reports. However, the chromatographic column or the solid phase extraction small column has good purification effect, but the operation is complex, the processes of extraction column activation, sample loading, leaching, elution and the like need to be carried out, the time consumption is long, and the method is not suitable for batch sample treatment. In addition, concentrated sulfuric acid purification, dispersive solid-phase extraction, and dispersive liquid-phase microextraction have also been reported in a small number. But the concentrated sulfuric acid purification method has low recovery rate, and the dispersion liquid-liquid microextraction is mainly suitable for simple liquid matrix samples, needs to be processed and converted into liquid matrix for complex solid matrix, and is easy to generate matrix effect. Zhang Yu and the like adopt microwave-assisted extraction, C18 adsorbent dispersed solid phase extraction and purification, and gas chromatography-mass spectrometry to determine phthalic acid ester in soil, the pretreatment of the method needs to add Flori silica into a soil sample, the matrix effect is obvious, the adsorbent is only dispersed in an acetone solution, and further research finds that C18 in acetone has strong adsorbability on dimethyl phthalate and diethyl phthalate, and cannot meet the requirements of analysis and detection. The phthalate esters have various types and large property difference, a proper dispersed solid phase adsorbent is searched, matrix effect is not brought, and meanwhile, a proper dispersing agent is selected to ensure the recovery rate of all phthalate esters to be analyzed, so that the method breaks through the key bottleneck of the existing method.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a dispersed solid-phase extraction-gas chromatography-mass spectrometry detection method of phthalate ester environmental hormones in marine sediments so as to realize the rapid and accurate determination of the phthalate ester content in the marine sediments.
In order to achieve the purpose, the invention adopts the following technical scheme:
a dispersed solid phase extraction-gas chromatography-mass spectrometry detection method of phthalate ester environmental hormones in marine sediments comprises the following steps:
(1) Collecting and preparing samples: placing a marine sediment sample to be detected in a freeze dryer for drying for 12-24 h, taking out the marine sediment sample, sieving the marine sediment sample with a stainless steel sieve of 80-100 meshes to obtain a sample to be detected, and placing the sample to be detected in the dryer; the marine sediment sample to be detected can be packaged by clean aluminum foil and sealed in a polyethylene bag for transportation;
(2) Sampling and ultrasonic extraction: weighing 2g of the sample to be detected, placing the sample into a glass centrifuge tube, adding 10-20 mL of normal hexane/ethyl acetate extractant with the volume ratio of 1; when the background of a sulfur-containing compound in a sample interferes, adding 1-3 g of copper powder for ultrasonic desulfurization, centrifuging at a high speed of 3000-6000 r/m for 3-5 min, taking supernatant to obtain n-hexane/ethyl acetate extracting solution, and allowing the n-hexane/ethyl acetate extracting solution to pass through an anhydrous sodium sulfate column; then adding 10-20 mL of normal hexane/dichloromethane extracting agent with the volume ratio of 1; mixing the n-hexane/ethyl acetate extracting solution and the n-hexane/dichloromethane extracting solution to obtain a mixed extracting solution;
when the extraction mode is selected, the traditional extraction methods such as oscillation extraction and Soxhlet extraction have long treatment period and large solvent consumption. The instrument and technology costs of microwave-assisted extraction, accelerated solvent extraction and the like are relatively high. QuEChERS proposed by Weilietron and the like extracts phthalic acid ester in soil, and only salt solutions such as magnesium sulfate, sodium chloride and the like are added into a soil matrix, so that the extraction efficiency is poor, and the impurity removal effect is poor. The matrix solid phase dispersion extracted by the method of Hao et al extracts phthalic acid ester in soil, and the dispersion liquid phase micro-extraction is combined after extraction, so that the operation is complex. The ultrasonic extraction method can effectively extract organic matters with stable structures from solid samples, has the advantages of high efficiency, low instrument price, simple operation and the like, and has not been reported at present. Therefore, the ultrasonic extraction method is selected for extracting the phthalate of the marine sediments.
(3) Concentration: evaporating the mixed extracting solution obtained in the step (2) to dryness by using a rotary evaporator under the conditions that the vacuum degree of a water pump is 0.08-0.09 Mpa, the water bath temperature is 35-40 ℃, and the rotating speed is 50-100 rpm, and adding 2mL of n-hexane for dissolving to obtain n-hexane dissolved solution;
(4) Dispersed solid phase extraction and purification: putting 100-200 mg of graphitized carbon black into a test tube, adding the n-hexane solution obtained in the step (3), carrying out vortex 30-60s, carrying out high-speed centrifugation at 3000-6000 r/m for 1-3 min, and taking supernatant a; adding 2mL of acetone into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant b; adding 2mL of dichloromethane into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant c; adding 2mL of methanol into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant fluid d; mixing the supernatants a, b, c and d to obtain mixed supernatant;
phthalate is easy to hydrolyze under acidic or alkaline conditions, and a chromatography column or a solid-phase extraction column is mainly selected for purification in literature reports when a purification mode is selected. However, the chromatographic column or the solid-phase extraction column has a good purification effect, but the operation is complex, the processes of extraction column activation, sample loading, leaching, elution and the like are required, the time consumption is long, and the method is not suitable for batch sample treatment. In addition, concentrated sulfuric acid purification, dispersive solid-phase extraction, and dispersive liquid-phase microextraction have also been reported in a small number. But the concentrated sulfuric acid purification method has low recovery rate, and the dispersion liquid-liquid microextraction is mainly suitable for simple liquid matrix samples, needs to be processed and converted into liquid matrix for complex solid matrix, and is easy to generate matrix effect. Zhang Yu and the like adopt microwave-assisted extraction, C18 adsorbent dispersed solid phase extraction purification and gas chromatography mass spectrometry to determine phthalic acid ester in soil, the pretreatment of the method needs to add Florisil into a soil sample, the matrix effect is obvious, the adsorbent is only dispersed in an acetone solution, and further research finds that the C18 in the acetone has strong adsorbability on dimethyl phthalate and diethyl phthalate and cannot meet the analysis and detection requirements. The phthalate esters are various in variety and have large property difference, a proper dispersed solid phase adsorbent is searched, matrix effect is not brought, and meanwhile, a proper dispersing agent is selected to ensure the recovery rate of all phthalate esters to be analyzed, so that the method is a key bottleneck for breaking through the existing method. The invention respectively inspects the impurity removal effect of adsorbents such as 200mg of N-propyl ethylenediamine, C18, graphitized carbon black, silica gel, florisil and the like, and the result shows that the purification effect of each adsorbent on the color of the dispersion liquid is that the graphitized carbon black, florisil, silica gel, N-propyl ethylenediamine and C18 are sequentially, the graphitized carbon black is used as the adsorbent, and the color of the dispersion liquid is colorless and transparent. All compounds were recovered at a relatively high recovery (78.5-115%) using graphitized carbon black. And finally, selecting graphitized carbon black as an adsorbent by comprehensively considering the color, impurity removal effect and recovery rate of the extracting solution.
According to the selected graphitized carbon black, the influence of 50mg, 100mg, 150mg, 200mg and 250mg of graphitized carbon black on the purification effect and the recovery rate is compared, and the result shows that the color of the extracting solution gradually becomes transparent along with the increase of the dosage of the adsorbent, but the recovery rates of dimethoxyethyl phthalate, diethoxyethyl phthalate, dibutoxyethyl phthalate, di-n-octyl phthalate and diphenyl phthalate gradually decrease, and the recovery rates of other components do not obviously change, so that 100-200 mg of graphitized carbon black is selected as the adsorbent in comprehensive consideration.
In the literature, only 1 dispersant is used when dispersed solid phase extraction is used for purifying phthalate in soil or biological samples. For example, C18 is dispersed in acetone and N-propylethylenediamine is dispersed in isopropanol. The invention discovers that the difference of the properties of different phthalic acid esters is large, and no matter which adsorbent is adopted, the good recovery rate of all phthalic acid ester compounds can not be realized by only using one dispersant. According to the selected 200mg graphitized carbon black, 2mL of normal hexane, acetone, methanol, isopropanol, ethyl acetate, acetonitrile and dichloromethane are respectively used as dispersing agents, and the adsorption effect of the graphitized carbon black on phthalate in different dispersing agents is studied. The result shows that the normal hexane is used, the absorption of most phthalic acid esters is not obvious, and the strong absorption recovery rate of the n-hexane is 32-62% only for dimethoxy ethyl phthalate, dibutoxy ethyl phthalate and diphenyl phthalate; with acetone, diphenyl phthalate adsorbs weakly; with dichloromethane, there was essentially no adsorption of diethoxyethyl phthalate; methanol is used, and the adsorption of dimethoxy ethyl phthalate, butyl benzyl phthalate, dibutoxyethyl phthalate and di-n-octyl phthalate is weaker than that of dimethoxy ethyl phthalate, butyl benzyl phthalate, dibutoxyethyl phthalate and di-n-octyl phthalate; and isopropanol, ethyl acetate and acetonitrile are adopted, so that most phthalic acid esters are adsorbed to different degrees, possibly because the distribution coefficients of different phthalic acid esters between different dispersants and graphitized carbon black are different. In order to achieve a high recovery rate for each analyte, 2mL of n-hexane, 2mL of acetone, 2mL of dichloromethane, and 2mL of methanol were used as dispersants.
(5) Concentrating and fixing volume: blowing nitrogen to evaporate the mixed supernatant obtained in the step (4) to dryness at the water bath temperature of 40-50 ℃, dissolving the mixed supernatant by using normal hexane, and fixing the volume to 1mL to obtain an upper machine solution;
(6) Detecting by a gas chromatography-mass spectrometer: a sample injection needle extracts the solution on the machine, and detection is carried out according to the set gas chromatography-mass spectrometry conditions;
(7) Drawing a standard curve: qualitative by selecting an ion monitoring mode and quantitative by an external standard method;
(8) And (3) recovery rate determination: operating the collected actual samples according to the requirements of the steps (1) to (6), comparing the actual samples with the standard curve obtained in the step (7), and finally obtaining the content of the 16 phthalic acid esters in the actual samples through conversion;
respectively carrying out five times of parallel operations on the standard adding samples with different standard adding concentrations according to the requirements of the steps (2) to (6), comparing the standard adding samples with the standard curve obtained in the step (7), and finally obtaining the measured concentrations of the 16 phthalic acid esters in the standard adding samples through conversion; the recovery was calculated according to the following formula:
in the formula: r-recovery,%;
C s -the measured concentration of 16 phthalates in the spiked sample,. Mu.g/kg;
C 0 -concentration of 16 phthalate esters in the actual sample,. Mu.g/kg;
c is the theoretical standard adding concentration of 16 phthalic acid esters in the standard adding sample, mu g/kg;
and (3) adding the phthalate into the actual sample pretreated in the step (1) to obtain a standard sample.
The method adopts ultrasonic extraction, dispersive solid-phase extraction purification and gas chromatography-mass spectrometry to measure the phthalic acid ester in the marine sediment, has simple operation, can quickly finish the pretreatment of samples, wherein graphitized carbon black is used as a solid-phase adsorbent for the first time and needs to be respectively dispersed in normal hexane, dichloromethane, acetone and methanol, the whole dispersive solid-phase extraction purification process only needs 5-15 min, all samples are colorless and transparent in the machine solution after dispersive solid-phase extraction purification, the result is accurate, the detection limit of 16 phthalic acid esters is 0.1-0.25 mug/kg, the recovery rate is 78-117%, the relative standard deviation (n = 5) is 2.4-6.8%, and the method has higher sensitivity, satisfactory recovery rate and repeatability and can be used for measuring the content of the phthalic acid ester in the marine sediment.
Preferably, in the step (8), the 16 kinds of phthalic acid esters are dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di-4-methyl-2-pentyl phthalate, dimethoxyethyl phthalate, di-n-pentyl phthalate, diethoxyethyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl phthalate, dibutoxyethyl phthalate, dicyclohexyl phthalate, di-n-octyl phthalate, diphenyl phthalate and dinonyl phthalate.
Preferably, in the step (6),
the chromatographic conditions detected by the gas chromatography-mass spectrometry detector are as follows: the temperature of a sample inlet is 260 ℃; the carrier gas is high-purity helium with the volume content of 99.999 percent, and the flow rate is 1mL/min; the sample injection volume is 1 mu L; the sample injection mode is non-shunt sample injection, and purging is carried out at 15mL/min after 0.75 min; the transmission line temperature is 260 ℃; the temperature program of the gas chromatographic column is as follows: the initial temperature is 100 ℃, and the temperature is increased to 290 ℃ at the speed of 10 ℃/min; keeping for 5.0min, and keeping the total operation time for 24min;
the mass spectrum conditions are as follows: an Electron Impact (EI) ion source with the temperature of 230 ℃ and the ionization energy of 70eV; delaying the solvent for 3min; the temperature of the four-level bar is 150 ℃, the scanning range is 50-450 amu, and the futon NIST is searched; selected ions for monitoring, qualitative and quantitative ions are shown in table 1:
TABLE 1 retention time, quantitative ion, qualitative ion of 16 phthalates of the invention
The gas chromatographic column adopts an HP-35MS capillary gas chromatographic column with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m, and the stationary phase is a mixed solution of diphenyl and dimethyl polysiloxane, wherein the mass fraction of the diphenyl is 35%, the mass fraction of the dimethyl polysiloxane is 65%, and the effective separation of 16 phthalic acid esters can be realized.
Preferably, in step (2), the copper powder is treated with dilute hydrochloric acid to remove the surface oxide film before use, then washed with distilled water to remove a small amount of acid attached to the surface, finally washed with acetone and blown dry under a high-purity nitrogen flow with the volume content of 99.999% to prevent the copper powder from being oxidized again.
Preferably, in the step (7), when the ion monitoring mode is selected for qualitative determination, the standard solution is operated according to the requirements of the step (6) to obtain a total ion flow chromatogram of the standard solution, qualitative ion and quantitative ion comparison is carried out on the total ion flow chromatogram of a single analyte, and meanwhile, the types of 16 phthalic acid esters are determined by combining retention time; the qualitative ions, the quantitative ions and the retention time of the 16 phthalic acid esters are used as the basis for identifying the chromatographic peaks of the 16 phthalic acid esters in the quantification by an external standard method; in the standard solution, the solute is phthalic acid ester, the solvent is n-hexane, and the concentration is 100 mu g/L;
when the external standard method is used for quantification, standard curve series solutions with different standard concentrations are used for establishing a standard curve according to the corresponding relation between the concentrations of the added phthalic acid ester and the integrated peak areas of corresponding quantitative ions; in the standard curve series solution, the solute is phthalic acid ester, the solvent is normal hexane, and the concentration ranges are 1-1000 mu g/L.
Therefore, the invention has the following beneficial effects:
(1) The operation is simple, the ultrasonic extraction efficiency is high, and the pretreatment of a sample can be quickly completed;
(2) Graphitized carbon black is used as a solid phase adsorbent for the first time, and the solid phase adsorbent is dispersed in a plurality of dispersing agents, so that the dispersed solid phase extraction efficiency is high, and the purification effect is good;
(3) The method has high sensitivity, recovery rate and reproducibility, the detection limit of 16 phthalic acid esters is 0.1-0.25 mu g/kg, the recovery rate is 78-117%, and the relative standard deviation (n = 5) is 2.4-6.8%, and the method can be applied to accurate determination of the content of the phthalic acid esters in marine sediments.
Drawings
FIG. 1 is a total ion flow chromatogram of a 16 phthalate standard solution (100. Mu.g/L).
FIG. 2 is a graph comparing the effect of different extractants on phthalate esters.
FIG. 3 is a graph comparing the effect of different adsorbents on phthalate purification.
FIG. 4 is a total ion flow chromatogram for different solid phase adsorbent purifications.
Fig. 5 is a graph showing the effect of graphitized carbon black on phthalate adsorption in different dispersants.
FIG. 6 is a total ion current chromatogram of the sediment sample (A) collected in the Arthropoda-Chilo area and the sediment sample (B) collected in the Arthropoda-Chilo area of Canada in example 3.
In the figure, dimethyl phthalate 1, diethyl phthalate 2, diisobutyl phthalate 3, dibutyl phthalate 4, di-4-methyl-2-pentyl phthalate 5, dimethoxyethyl phthalate 6, di-n-pentyl phthalate 7, diethoxyethyl phthalate 8, dihexyl phthalate 9, butylbenzyl phthalate 10, di-2-ethylhexyl phthalate 11, dibutoxyethyl phthalate 12, dicyclohexyl phthalate 13, di-n-octyl phthalate 14, diphenyl phthalate 15, dinonyl phthalate 16.
Detailed Description
The technical solution of the present invention is further specifically described below by specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
The following examples used a 7890B/5977A gas chromatograph mass spectrometer, manufactured by Agilent technologies, inc., USA.
Example 1
Determination of 16 polyphthalates in sediment samples collected at nail sampling sites in Ningbo Hangzhou Bay (northern Lenza, zhehai area coastal):
(1) Collecting and preparing samples: marine sediment samples collected at sampling points of Ningbo Hangzhou Bay (coastal areas of northern area and Zhenhai area) A are packaged by clean aluminum foil and sealed in polyethylene bags, then transported back to a laboratory by a portable refrigerating box, dried in a freeze dryer for 24 hours, taken out and screened by a 100-mesh stainless steel sieve to obtain a sample to be detected, and the sample to be detected is placed in a dryer;
(2) Sampling and ultrasonic extraction: weighing 2g of sediment samples collected from sampling points of Ningbo Hangzhou bay (northern area coastline and Zhenhai area coastline) A processed in the step (1), placing the sediment samples into a glass centrifuge tube, adding 15mL of n-hexane/ethyl acetate extractant with the volume ratio of 1, performing vortex for 2min, and performing ultrasonic extraction at 35 ℃ for 15min at 300W power; when the background of a sulfur-containing compound in a sample interferes, adding 2g of copper powder for ultrasonic desulfurization, centrifuging at a high speed of 3000r/m for 3min, taking supernatant to obtain n-hexane/ethyl acetate extracting solution, and enabling the n-hexane/ethyl acetate extracting solution to pass through an anhydrous sodium sulfate column; adding 15mL of a normal hexane/dichloromethane extracting agent with the volume ratio of 1 to the sample, and repeating the process to obtain a normal hexane/dichloromethane extracting solution; mixing the n-hexane/ethyl acetate extracting solution and the n-hexane/dichloromethane extracting solution to obtain a mixed extracting solution;
before the copper powder is used, dilute hydrochloric acid is used for treating the copper powder to remove an oxide film on the surface of the copper powder, then distilled water is used for washing the copper powder to remove a small amount of acid attached to the surface of the copper powder, and finally acetone is used for washing the copper powder and drying the copper powder under the flow of high-purity nitrogen with the volume content of 99.999 percent.
The invention selects dichloromethane and normal hexane: dichloromethane (1, v/v), n-hexane: ethyl acetate (1, v/v), n-hexane: dichloromethane/n-hexane: ethyl acetate (1, v/v) is used as an extractant, and an ultrasonic extraction effect comparison experiment is carried out, and fig. 2 is a comparison graph of extraction effects of different extractants on phthalic acid ester, and results show that when dichloromethane is used for repeated extraction for 2 times, the extraction efficiency of dimethyl phthalate, dimethoxyethyl phthalate and diethoxyethyl phthalate is relatively low (64-68%); using n-hexane: dichloromethane (1, v/v), dimethyl phthalate has low extraction efficiency, and dimethoxy ethyl phthalate, diethoxy ethyl phthalate and dibutoxy ethyl phthalate have relatively high extraction efficiency (92-114%); using n-hexane: ethyl acetate (1, v/v), dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, dicyclohexyl phthalate and di-n-octyl phthalate, and the extraction efficiency is relatively high (89-118%); using n-hexane: dichloromethane/n-hexane: ethyl acetate (1, v/v), the recovery rate of 16 phthalates ranged from 86 to 115%, and the overall recovery rate was the highest, so n-hexane was used in the present invention in order: dichloromethane (1, v/v), n-hexane: ethyl acetate (1, v/v) was extracted twice by sonication.
(3) Concentration: evaporating the mixed extracting solution obtained in the step (2) to dryness by using a rotary evaporator under the conditions that the vacuum degree of a water pump is 0.085Mpa, the water bath temperature is 38 ℃ and the rotating speed is 80rpm, and adding 2mL of n-hexane for dissolving to obtain n-hexane dissolved solution;
(4) Dispersed solid phase extraction and purification: transferring the n-hexane dissolved solution obtained in the step (3) into a test tube filled with 150mg of graphitized carbon black, performing vortex 45s and 4500r/m high-speed centrifugation for 2min, and taking supernatant a; adding 2mL of acetone into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant b (acetone solution); adding 2mL of dichloromethane into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant c (dichloromethane dissolved solution); adding 2mL of methanol into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant d (methanol solution); taking out the supernatants a, b, c and d in a test tube each time, and combining the supernatants a, b, c and d to obtain mixed supernatants;
the impurity removal effect of different adsorbents is shown in fig. 3 and 4, and by using N-propyl ethylenediamine, the recovery rates of dimethyl phthalate, diphenyl phthalate and dinonyl phthalate are low; the recovery rate of C18 dimethyl phthalate, dimethoxyethyl phthalate, diethoxyethyl phthalate and dibutoxyethyl phthalate is low, and impurity interference is generated near the di-n-pentyl phthalate; the recovery rate of dinonyl phthalate is lower by using silica gel; the recovery rates of dimethoxy ethyl phthalate and diethoxy ethyl phthalate are lower by using Florisil; with graphitized carbon black, all compounds are recovered at a relatively high recovery rate (78.5-115%). And finally, selecting graphitized carbon black as an adsorbent by comprehensively considering the color, impurity removal effect and recovery rate of the extracting solution.
Fig. 5 is a graph showing the effect of graphitized carbon black on phthalate adsorption in different dispersants. As shown in FIG. 5, the absorption of most phthalic acid esters is not obvious by using n-hexane, and the strong absorption recovery rate of only dimethoxyethyl phthalate, dibutoxyethyl phthalate and diphenyl phthalate is 32-62%; with acetone, diphenyl phthalate adsorbs weakly; with dichloromethane, there was essentially no adsorption of diethoxyethyl phthalate; methanol is used, and the adsorption of dimethoxy ethyl phthalate, butyl benzyl phthalate, dibutoxy ethyl phthalate and di-n-octyl phthalate is weaker than that of dimethoxy ethyl phthalate, butyl benzyl phthalate, dibutoxy ethyl phthalate and di-n-octyl phthalate; and isopropanol, ethyl acetate and acetonitrile are adopted to adsorb most phthalic acid esters to different degrees, which is probably because the distribution coefficients of different phthalic acid esters between different dispersants and graphitized carbon black are different. In order to achieve a high recovery rate for each analyte, 2mL of n-hexane, 2mL of acetone, 2mL of dichloromethane, and 2mL of methanol were used as dispersants.
(5) Concentrating and fixing volume: blowing nitrogen to evaporate the mixed supernatant obtained in the step (4) to dryness at the water bath temperature of 45 ℃, dissolving the mixed supernatant by using normal hexane, and fixing the volume to 1mL to obtain a machine feeding solution;
(6) Detecting by a gas chromatography-mass spectrometer: a sample injection needle extracts the solution on the machine, and detection is carried out according to the set gas chromatography-mass spectrometry conditions;
the chromatographic conditions detected by the gas chromatography-mass spectrometry detector are as follows: the temperature of a sample inlet is 260 ℃; the carrier gas is high-purity helium with the volume content of 99.999 percent, and the flow rate is 1mL/min; the sample injection volume is 1 mu L; the sample injection mode is non-shunt sample injection, and purging is carried out at 15mL/min after 0.75 min; the transmission line temperature is 260 ℃; the temperature rising procedure of the gas chromatographic column is as follows: the initial temperature is 100 ℃, and the temperature is increased to 290 ℃ at the speed of 10 ℃/min; keeping for 5.0min, and keeping the total operation time for 24min;
the mass spectrum conditions are as follows: an Electron Impact (EI) ion source with the temperature of 230 ℃ and the ionization energy of 70eV; delaying the solvent for 3min; the temperature of the quadrupole is 150 ℃, the scanning range is 50-450 amu, and the futon NIST is searched; selected ion monitoring, qualitative and quantitative ions are shown in table 1:
TABLE 1 Retention time, quantitative ion, qualitative ion of 16 phthalates of the invention
The gas chromatographic column adopts an HP-35MS capillary gas chromatographic column with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m, and the stationary phase is a mixed solution of diphenyl and dimethyl polysiloxane, wherein the mass fraction of the diphenyl is 35%, the mass fraction of the dimethyl polysiloxane is 65%, and the effective separation of 16 phthalic acid esters can be realized.
(7) Drawing a standard curve: qualitative by selecting an ion monitoring mode and quantitative by an external standard method;
when qualitative determination is carried out in a selective ion monitoring mode, 100 mu L of mixed standard use solution of phthalic acid esters of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di-4-methyl-2-pentyl phthalate, dimethoxyethyl phthalate, di-n-pentyl phthalate, diethoxyethyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl phthalate, dibutoxyethyl phthalate, dicyclohexyl phthalate, di-n-octyl phthalate, diphenyl phthalate and dinonyl phthalate is taken, and normal hexane is used for fixing the volume to 1mL to obtain a standard solution with the concentration of 100 mu g/L; operating the standard solution according to the requirements of the step (6) to obtain a total ion flow chromatogram of the standard solution, comparing the total ion flow chromatogram with the qualitative ions and the quantitative ions of the total ion flow chromatogram of a single analyte, and determining the types of the 16 phthalic acid esters by combining retention time; the qualitative ions, quantitative ions and retention time of the 16 phthalate esters are used as the basis for identifying the chromatographic peaks of the 16 phthalate esters in the quantification by an external standard method. FIG. 1 is a total ion current chromatogram of a standard solution.
When the external standard method is used for quantification, 10 and 50 mu L of phthalate standard solution with the concentration of 100 mu g/L and 50, 250, 500 and 1000 mu L of phthalate mixed standard using solution with the concentration of 1000 mu g/L are respectively taken, and normal hexane is used for metering the volume to 1mL to obtain a standard curve series solution with the six times of standard addition concentration ranges of 1-1000 mu g/L; and establishing standard curves for six standard curve series solutions with different standard concentrations according to the corresponding relation between the concentrations of the added phthalic acid ester and the integrated peak areas of corresponding quantitative ions.
Table 2 shows the linear regression equation, linear range, correlation coefficient and detection limit of the method of the invention. As can be seen from Table 2, each phthalate has a good linear relationship in the corresponding linear range, and the requirements of the analysis method are met.
TABLE 2 Linear regression equation, linear Range, correlation coefficient and detection limits for the method of the invention
Wherein, a: y and x represent the integrated peak area of the corresponding quantitative ion of the analyte and the theoretical concentration of the analyte in 1mL of n-hexane respectively; b: the linear range represents the concentration of the analyte in the standard curve series of solutions;
(8) And (3) recovery rate determination: collecting sediment samples collected at sampling points of Ningbo Hangzhou Bay (northern area coastal areas and Zhenhai area coastal areas), operating according to the requirements of the steps (1) to (6), comparing with the standard curve obtained in the step (7), and finally obtaining the content of 16 phthalic acid esters in the actual sample through conversion;
using the actual samples, after processing according to the requirements of the step (1), taking 2g of processed sediment samples collected from sampling points of Ningbo Hangzhou Bay (northern area coastal area and Zhehai area coastal area) A, adding 100 mu L of 100 mu g/L phthalate standard solution and 100 and 500 mu L of 1000 mu g/L phthalate mixed standard use solution respectively to prepare low (5 mu g/kg), medium (50 mu g/kg) and high (250 mu g/kg) sediment additive standard samples collected from sampling points of Ningbo Hangzhou Bay (northern area coastal area and Zhehai area coastal area) A with three additive concentration levels, performing five parallel operations according to the requirements of the steps (2) to (6), and performing five parallel operations with the sediment additive standard samples collected from the sampling points of Ningbo Hangzhou Bay (northern area coastal area and Zhehai area coastal area) A respectively
Comparing the standard curves obtained in the step (7), and finally obtaining the measured concentrations of the 16 phthalic acid esters in the standard sample through conversion; the recovery was calculated according to the following formula:
in the formula: r-recovery,%;
C s -the measured concentration of 16 phthalates in the spiked sample,. Mu.g/kg;
C 0 -the concentration of 16 phthalates in the actual sample,. Mu.g/kg;
c is the theoretical standard adding concentration of 16 phthalic acid esters in the standard adding sample, mu g/kg;
TABLE 3 spiking recovery test results for different spiking concentration levels in sediment samples collected at Ningbo Hangzhou Bay (northern run, zhenhai zone, coastal) A sampling points
According to detection, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and di-2-ethylhexyl phthalate in sediment samples collected at the sampling points of the methyl in Ningbo Hangzhou bay (the coastal areas of the northern area and the coastal areas of the Zhehai area) are detected, the content of the dimethyl phthalate, the diethyl phthalate, the diisobutyl phthalate, the dibutyl phthalate and the di-2-ethylhexyl phthalate are high, and the results of the standard adding recovery experiments of different standard adding concentration levels in the sediment samples collected at the sampling points of the methyl in Ningbo Hangzhou bay (the coastal areas of the northern area and the coastal areas of the Zhehai area) are shown in a table 3.
As can be seen from table 3, the recovery rate of the sediment sample collected from the sampling point of jia-minngbo gulf (northern area coastal, zhehai area coastal) is 83 to 115%, the relative standard deviation (n = 5) is 2.7 to 6.7%, and the requirements of the analysis method on the recovery rate and the reproducibility are met.
Example 2
Determination of 16 polyphthalates in sediment samples collected from b sampling points in the ningbo hangzhou bay (northern ran, zhehai zone, coastal):
(1) Collecting and preparing samples: collecting sediment samples at a sampling point B in Ningbo Hangzhou bay (northern area coastline and Zhenhai area coastline), packaging the sediment samples with clean aluminum foil, sealing the sediment samples in a polyethylene bag, transporting the sediment samples back to a laboratory by using a portable refrigerating box, drying the samples in a freeze dryer for 12 hours, taking out the samples, sieving the samples with a 80-mesh stainless steel sieve, and placing the samples in a dryer to be tested; (2) sampling and ultrasonic extraction: weighing 2g of sediment samples collected from sampling points of Ningbo Hangzhou bay (northern area coastline and Zhenhai area coastline) B processed in the step (1), placing the sediment samples into a glass centrifuge tube, adding 10mL of n-hexane/ethyl acetate extractant with the volume ratio of 1, performing vortex for 1min, and performing ultrasonic extraction at 30 ℃ for 10min at 400W power; when the background of a sulfur-containing compound in a sample interferes, adding 1g of copper powder for ultrasonic desulfurization, carrying out high-speed centrifugation at 6000r/m for 3min, taking supernatant to obtain n-hexane/ethyl acetate extracting solution, and enabling the n-hexane/ethyl acetate extracting solution to pass through an anhydrous sodium sulfate column; then adding 10mL of normal hexane/dichloromethane extracting agent with the volume ratio of 1; mixing the n-hexane/ethyl acetate extracting solution and the n-hexane/dichloromethane extracting solution to obtain a mixed extracting solution; (3) concentrating: evaporating the mixed extracting solution obtained in the step (2) to dryness by using a rotary evaporator under the conditions that the vacuum degree of a water pump is 0.08Mpa, the water bath temperature is 35 ℃, and the rotating speed is 50rpm, and adding 2mL of n-hexane for dissolving to obtain n-hexane dissolved solution;
(4) Dispersed solid phase extraction and purification: transferring the n-hexane dissolved solution obtained in the step (3) into a test tube filled with 100mg of graphitized carbon black, performing vortex 30s and 3000r/m high-speed centrifugation for 3min, and taking supernatant a; adding 2mL of acetone into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant b (acetone solution); adding 2mL of dichloromethane into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant c (dichloromethane dissolved solution); adding 2mL of methanol into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant d (methanol solution); taking out the supernatants a, b, c and d in a test tube each time, and combining the supernatants a, b, c and d to obtain mixed supernatants;
(5) Concentrating and fixing volume: blowing nitrogen to evaporate the mixed supernatant obtained in the step (4) to dryness at the water bath temperature of 40 ℃, dissolving the mixed supernatant by using normal hexane, and fixing the volume to 1mL to obtain a machine solution;
(6) Detecting by a gas chromatography-mass spectrometer: the test conditions were exactly the same as those of example 1;
(7) Drawing a standard curve: the test conditions were exactly the same as those of example 1;
(8) And (3) determining the recovery rate: exactly the same test conditions as in example 1.
Through detection, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and di-2-ethylhexyl phthalate in sediment samples collected at B sampling points of Ningbo Hangzhou Bay (northern area coastal areas and Zhenhai area coastal areas) are detected, the contents of the dimethyl phthalate, the diethyl phthalate, the diisobutyl phthalate, the dibutyl phthalate and the di-2-ethylhexyl phthalate are respectively 5.15 mu g/kg, 5.18 mu g/kg, 16.1 mu g/kg, 20.7 mu g/kg and 91.4 mu g/kg, other phthalate is not detected, the recovery rate of the sediment samples collected at B sampling points of Gangbo Hangzhou Bay (northern area coastal areas and Zhenhai area coastal areas) is 81-112%, and the relative standard deviation (n = 5) is 2.6-6.2%, so that the requirements of an analysis method on the recovery rate and the reproducibility are met.
Example 3
Determination of 16 polyphthalates in sediment samples collected in the arctic sea area of navigata:
(1) Collecting and preparing samples: packing sediment samples collected in the Shandong Chihai area by using clean aluminum foil and sealing the sediment samples in a polyethylene bag, then transporting the sediment samples back to a laboratory by using a portable refrigerator, drying the samples in a freeze dryer for 18 hours, taking out the samples, sieving the samples by using a 90-mesh stainless steel sieve, and placing the samples in a dryer to be tested;
(2) Sampling and ultrasonic extraction: weighing 2g of sediment sample collected in the polar sea area of Zhoushantong processed in the step (1), placing the sediment sample in a glass centrifuge tube, adding 20mL of n-hexane/ethyl acetate extracting agent with the volume ratio of 1; when the background of a sulfur-containing compound in a sample interferes, adding 3g of copper powder for ultrasonic desulfurization, centrifuging at a high speed of 4000r/m for 4min, taking supernate to obtain n-hexane/ethyl acetate extracting solution, and enabling the n-hexane/ethyl acetate extracting solution to pass through an anhydrous sodium sulfate column; adding 20mL of a normal hexane/dichloromethane extracting agent with the volume ratio of 1 to the sample, and repeating the process to obtain a normal hexane/dichloromethane extracting solution; mixing the n-hexane/ethyl acetate extracting solution and the n-hexane/dichloromethane extracting solution to obtain a mixed extracting solution;
(3) Concentration: evaporating the mixed extracting solution obtained in the step (2) to dryness by using a rotary evaporator under the conditions that the vacuum degree of a water pump is 0.09Mpa, the water bath temperature is 40 ℃, and the rotating speed is 100rpm, and adding 2mL of n-hexane for dissolving to obtain n-hexane dissolved solution;
(4) Dispersed solid phase extraction and purification: putting 200mg of graphitized carbon black into a test tube, adding the n-hexane solution obtained in the step (3), performing vortex 60s and 6000r/m high-speed centrifugation for 3min, and taking supernatant a; adding 2mL of acetone into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant liquid b; adding 2mL of dichloromethane into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant c; adding 2mL of methanol into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant fluid d; mixing the supernatants a, b, c and d to obtain mixed supernatant;
(5) Concentrating and fixing volume: blowing nitrogen to evaporate the mixed supernatant obtained in the step (4) to dryness at the water bath temperature of 50 ℃, dissolving the mixed supernatant by using n-hexane, and fixing the volume to 1mL to be used as a machine solution;
(6) Detecting by a gas chromatography-mass spectrometer: the test conditions were exactly the same as those of example 1;
(7) Drawing a standard curve: the test conditions were exactly the same as those of example 1;
(8) And (3) recovery rate determination: the test conditions were exactly the same as those of example 1;
according to detection, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and di-2-ethylhexyl phthalate in sediment samples collected in the Dongdi sea area of the Zhoushan are detected, the content of the dimethyl phthalate, the diethyl phthalate, the diisobutyl phthalate, the dibutyl phthalate and the di-2-ethylhexyl phthalate are higher, and the experimental results of the standard addition recovery of different standard addition concentration levels in the sediment samples collected in the Dongdi sea area of the Zhoushan are shown in Table 4. The total ion chromatogram of the sediment samples collected from the Shandong Jihai area and the sediment samples collected from the Jiabiao Shandong Jihai area are shown in FIG. 6.
TABLE 4 results of spiking recovery experiments for different spiking concentration levels in sediment samples collected from Dongli sea area of Zhoushan
As can be seen from Table 4, the recovery rate of the sediment sample collected in the Shandong polar sea area of Canadian boat was 78-117%, and the relative standard deviation (n = 5) was 2.4-6.8%, which satisfied the requirements of the analytical method on the recovery rate and reproducibility.
The method is simple to operate, high in ultrasonic extraction efficiency and capable of quickly finishing the pretreatment of the sample; graphitized carbon black is used as a solid phase adsorbent for the first time, and the solid phase adsorbent is dispersed in a plurality of dispersing agents, so that the dispersed solid phase extraction efficiency is high, and the purification effect is good; the method has high sensitivity, recovery rate and reproducibility, the detection limit of 16 phthalic acid esters is 0.1-0.25 mu g/kg, the recovery rate is 78-117%, and the relative standard deviation (n = 5) is 2.4-6.8%, and the method can be applied to accurate determination of the content of the phthalic acid esters in marine sediments.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (5)
1. A dispersed solid phase extraction-gas chromatography-mass spectrometry detection method of phthalate ester environmental hormones in marine sediments is characterized by comprising the following steps:
(1) Collecting and preparing samples: placing a marine sediment sample to be detected in a freeze dryer for drying for 12-24 h, taking out the marine sediment sample, sieving the marine sediment sample with a stainless steel sieve of 80-100 meshes to obtain a sample to be detected, and placing the sample to be detected in the dryer;
(2) Sampling and ultrasonic extraction: weighing 2g of the sample to be detected, placing the sample into a glass centrifuge tube, adding 10-20 mL of n-hexane/ethyl acetate extractant with the volume ratio of 1; when the background of a sulfur-containing compound in a sample interferes, adding 1-3 g of copper powder for ultrasonic desulfurization, centrifuging at a high speed of 3000-6000 r/m for 3-5 min, taking supernatant to obtain n-hexane/ethyl acetate extracting solution, and allowing the n-hexane/ethyl acetate extracting solution to pass through an anhydrous sodium sulfate column; then adding 10-20 mL of normal hexane/dichloromethane extracting agent with the volume ratio of 1; mixing the n-hexane/ethyl acetate extracting solution and the n-hexane/dichloromethane extracting solution to obtain a mixed extracting solution;
(3) Concentration: evaporating the mixed extracting solution obtained in the step (2) to dryness by using a rotary evaporator under the conditions that the vacuum degree of a water pump is 0.08-0.09 Mpa, the water bath temperature is 35-40 ℃, and the rotating speed is 50-100 rpm, and adding 2mL of n-hexane for dissolving to obtain n-hexane dissolving solution;
(4) Dispersed solid phase extraction and purification: putting 100-200 mg of graphitized carbon black into a test tube, adding the n-hexane solution obtained in the step (3), carrying out vortex 30-60s, carrying out high-speed centrifugation at 3000-6000 r/m for 1-3 min, and taking supernatant a; adding 2mL of acetone into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant liquid b; adding 2mL of dichloromethane into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant c; adding 2mL of methanol into the graphitized carbon black, repeating the vortex centrifugation process, and taking supernatant fluid d; mixing the supernatants a, b, c and d to obtain mixed supernatant;
(5) Concentrating and fixing volume: blowing nitrogen to evaporate to dryness at the temperature of 40-50 ℃ in water bath, dissolving by using n-hexane, and fixing the volume to 1mL to obtain upper machine solution;
(6) Detecting by a gas chromatography-mass spectrometer: a sample injection needle extracts the solution on the machine, and detection is carried out according to the set gas chromatography-mass spectrometry conditions;
(7) Drawing a standard curve: qualitative by selecting an ion monitoring mode and quantitative by an external standard method;
(8) And (3) determining the recovery rate: operating the collected actual samples according to the requirements of the steps (1) to (6), comparing the actual samples with the standard curve obtained in the step (7), and finally obtaining the content of the 16 phthalic acid esters in the actual samples through conversion;
respectively carrying out five times of parallel operations on the standard adding samples with different standard adding concentrations according to the requirements of the steps (2) to (6), comparing the standard adding samples with the standard curve obtained in the step (7), and finally obtaining the measured concentrations of the 16 phthalic acid esters in the standard adding samples through conversion; the recovery was calculated according to the following formula:
in the formula: r-recovery,%;
C s -the measured concentration of 16 phthalates in the spiked sample,. Mu.g/kg;
C 0 -concentration of 16 phthalate esters in the actual sample,. Mu.g/kg;
c is the theoretical standard adding concentration of 16 phthalic acid esters in the standard adding sample, mu g/kg;
the standard adding sample is a sample after phthalate is added into the actual sample pretreated in the step (1).
2. The method according to claim 1, wherein in step (8), the 16 phthalates are dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di-4-methyl-2-pentyl phthalate, dimethoxyethyl phthalate, di-n-pentyl phthalate, diethoxyethyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl phthalate, dibutoxyethyl phthalate, dicyclohexyl phthalate, di-n-octyl phthalate, diphenyl phthalate and dinonyl phthalate.
3. The method for detecting the phthalate ester environmental hormone in the marine sediments as claimed in claim 1 or 2, wherein in the step (6),
the chromatographic conditions detected by the gas chromatography-mass spectrometry detector are as follows: the temperature of a sample inlet is 260 ℃; the carrier gas is high-purity helium with the volume content of 99.999 percent, and the flow rate is 1mL/min; the sample injection volume is 1 mu L; the sample injection mode is non-shunt sample injection, and purging is carried out at 15mL/min after 0.75 min; the transmission line temperature is 260 ℃; the temperature rising procedure of the gas chromatographic column is as follows: the initial temperature is 100 ℃, and the temperature is increased to 290 ℃ at the speed of 10 ℃/min; keeping for 5.0min, and keeping the total operation time for 24min;
the mass spectrum conditions are as follows: an Electron Impact (EI) ion source with the temperature of 230 ℃ and the ionization energy of 70eV; delaying the solvent for 3min; the temperature of the four-level bar is 150 ℃, the scanning range is 50-450 amu, and the futon NIST is searched; selected ion monitoring, qualitative and quantitative ions are shown in table 1:
TABLE 1 Retention time, quantitative ion, qualitative ion of 16 phthalates of the invention
The gas chromatographic column is an HP-35MS capillary gas chromatographic column with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m, and the stationary phase is a mixed solution of diphenyl and dimethyl polysiloxane, wherein the mass fraction of the diphenyl is 35%, and the mass fraction of the dimethyl polysiloxane is 65%.
4. The method for detecting the phthalic acid ester environmental hormone in the marine sediment according to claim 1, which is characterized in that in the step (2), the copper powder is treated with dilute hydrochloric acid to remove an oxide film on the surface before use, then washed with distilled water to remove a small amount of acid attached to the surface, finally washed with acetone and dried under a high-purity nitrogen flow with the volume content of 99.999%.
5. The method for detecting the phthalate ester environmental hormone in the marine sediments by the dispersive solid-phase extraction-gas chromatography-mass spectrometry as claimed in claim 1, wherein in the step (7),
when an ion monitoring mode is selected for qualitative determination, operating the standard solution according to the requirements of the step (6) to obtain a total ion flow chromatogram of the standard solution, comparing qualitative ions and quantitative ions with the total ion flow chromatogram of a single analyte, and determining the types of 16 phthalic acid esters by combining retention time; the qualitative ions, the quantitative ions and the retention time of the 16 phthalic acid esters are used as the basis for identifying the chromatographic peaks of the 16 phthalic acid esters in the quantification by an external standard method; in the standard solution, the solute is phthalic acid ester, the solvent is n-hexane, and the concentration is 100 mu g/L;
when the external standard method is used for quantification, standard curve series solutions with different standard concentrations are used for establishing a standard curve according to the corresponding relation between the concentrations of the added phthalic acid ester and the integrated peak areas of corresponding quantitative ions; the solute in the standard curve series solution is phthalic acid ester, the solvent is normal hexane, and the concentration ranges are 1-1000 mug/L.
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