CN113533585A - Method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust deposit by high-flux low-solvent - Google Patents
Method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust deposit by high-flux low-solvent Download PDFInfo
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Abstract
The invention provides a method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor deposited dust by using a high-flux low solvent, wherein the selection of an extraction solvent comprises the following steps: mixing a nonpolar solvent n-hexane and a polar solvent acetone according to a volume ratio of 3:1 to prepare a composite solvent for sample extraction; selection of extraction times: the same sample was extracted 2 times in succession. And then, by optimizing chromatographic conditions, the maximum spectrogram separation among the components is realized, and specific characteristic ions of each component are collected through the ion selection mode of the mass spectrum, so that the mutual interference is avoided, and the analysis sensitivity is improved. And finally, the internal standard substance is used to overcome the signal difference among multiple sample injections of the mass spectrum, and the stability and the accuracy of the result are ensured. The three components cooperate to realize accurate determination of a small amount of solvent on a small amount of sample. The invention reduces the sample size to 0.1g, and greatly improves the universality and feasibility of the method.
Description
Technical Field
The invention relates to the technical field of detection and analysis of polycyclic aromatic hydrocarbons and phthalic acid esters, in particular to a method for rapidly and simultaneously determining 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust by using a high-flux low solvent.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) refer to a large class of aromatic substances containing two or more benzene rings, and have carcinogenicity, mutagenicity, genetic toxicity, and the like, and cause damage to the respiratory system, circulatory system, nervous system, and the like of a human body. Phthalates (PAEs) are a generic term for esters of phthalic acid and comprise a large class of substances. Is generally used as a plasticizer for plastics and is widely used in toys, food packaging, medical materials, building materials, personal care products and the like. The substances belong to environmental hormones, and seriously threaten human health after entering organisms.
The human life spends 60-80% of the time in various indoor environments, the influence of indoor environmental pollution on human health is not negligible, Polycyclic Aromatic Hydrocarbons (PAHs) and Phthalic Acid Esters (PAEs) are important indoor semi-volatile organic matters, the Polycyclic Aromatic Hydrocarbons (PAHs) are mainly derived from indoor cooking, tobacco smoke and motor vehicle tail gas and fire coal in outdoor air, and the Phthalic Acid Esters (PAEs) are mainly derived from various indoor consumer products as plasticizers, such as personal care products, food packages, toys for children, building materials and the like. The two compounds are large in amount, high in toxicity and boiling point, most of the compounds exist in a particle state, are easy to aggregate with floating dust in air to form large particles, and are deposited in corners of living rooms in a dust fall mode for several years or even longer. Therefore, the indoor dust is an important distribution medium of the two pollutants and an important environment medium for human body exposure, and the concentration of the polycyclic aromatic hydrocarbon and the phthalic acid ester in the accumulated dust is used as a long-term indicator for indoor human body exposure, so that the long-term concentration level of the indoor environment and the human body exposure condition can be better reflected.
At present, the prior research in China detects polycyclic aromatic hydrocarbon and phthalic acid simultaneously and mostly focuses on soybean extract[1]Cosmetic composition[2]Water treatment process[3]Seawater, seawater[4]On one hand, compared with the early-stage research on a large amount of substances related to polycyclic aromatic hydrocarbons, phthalate serving as a new pollutant attracts people's attention in recent years, and a detection method thereof gradually matures, on the other hand, compared with three media, namely air, soil and water, indoor dust deposition is concerned for a later time, and no one considers the polycyclic aromatic hydrocarbons and the phthalate in the indoor dust deposition together.
At present, the pretreatment methods of the two substances in the deposited dust mainly comprise a Soxhlet extraction method, ultrasonic extraction and accelerated solvent extraction, and the detection method mainly comprises a high performance liquid chromatography and gas chromatography-mass spectrometry combined method. Because the two substances have different polarities, the pretreatment is complicated, and the extraction solvent is different. When in measurement, the corresponding parameter setting influences the detection sensitivity, and different substances are measured, and the parameter setting is different. Therefore, in the prior art documents for simultaneously detecting the two substances, the selection and the proportion of the solvent and the setting of the measurement parameters are all technical difficulties in the field.
The Soxhlet extraction method is a classical liquid-solid extraction method, has wide application range and complete extraction, but has long extraction period, usually requires more than ten hours, consumes dozens of milliliters of solvent, is not environment-friendly, has low efficiency and is not suitable for batch treatment. The accelerated solvent extraction method is a novel pretreatment method in recent years, has high extraction efficiency, but has expensive instruments and equipment and complicated operation, and is not beneficial to large-scale popularization. The ultrasonic method has simple equipment, strong operability and wide application, but the prior research mostly purifies the extract liquor by a silica gel column and then concentrates the extract liquor by a nitrogen blowing or rotary evaporator, and increases the operation steps. In the existing research, the required dust accumulation amount is large (1-5 g), enough sample amount is difficult to collect in some families, and detection cannot be carried out.
In the prior art, chinese patent application CN 103389348A discloses a method for detecting polycyclic aromatic hydrocarbons and phthalic acid esters in plant extracts, comprising the following steps: (1) pre-treating the plant extract; (2) and detecting polycyclic aromatic hydrocarbons and phthalic acid esters in the plant extract by adopting gas chromatography-tandem mass spectrometry. According to the technical scheme, the extracting solution for the pretreatment of the sample uses one of normal hexane, cyclohexane or normal hexane-acetone complex, but in the result, the recovery rate of the sample after the pretreatment of the cyclohexane or normal hexane-acetone complex extraction is mostly lower than 60% or 50%, and the minimum sample amount of the sample is 1 g.
In the prior art, the Liao glao 32704[5]The method comprises the steps of microwave extraction, anhydrous sodium sulfate dewatering, nitrogen blowing concentration, SPE purification and nitrogen blowing concentration, and is complex in operation process, on one hand, microwave heating extraction is used, loss of low-boiling-point components is easily caused, on the other hand, nitrogen blowing concentration is required twice in the process, time cost of pretreatment is increased, and excessive nitrogen blowing steps can cause loss of partial components. The detection device uses triple quadrupole tandem mass spectrometry, and the sensitivity is higher due to the single quadrupole. In the report, the sample amount is 15g, and the dust sample is difficult to collect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention establishes a simple, convenient, rapid and accurate determination method, only a small amount of samples are needed, the simple operation is carried out, 18 kinds of polycyclic aromatic hydrocarbons and 15 kinds of phthalic acid esters in the accumulated dust can be simultaneously determined by using a unipolar mass spectrum with lower price, namely a gas chromatography-mass spectrometry method, and the detection effect is better.
The invention adopts a liquid-liquid extraction method to directly extract 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust, the extract directly enters gas chromatography-mass spectrometry, an internal standard method is used for quantification, and a selective ion scanning mode is adopted to collect data so as to improve selectivity and sensitivity.
The invention provides an effective technical means for accurately developing pollution level investigation and long-term human body exposure evaluation of common persistent organic matters in indoor environment.
A method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust with high flux and low solvent is characterized by comprising the following steps:
1. collecting indoor dust sample
And (3) collecting the dust gently by using a clean brush in a place with more accumulated dust, carefully removing impurities such as hair, cotton wool, stone residue, paper sheets and the like, and sweeping the accumulated dust particles into a prepared tinfoil bag for sealing and storing.
2. Pre-treating the dust sample
The dust is mixed evenly, the mixture is sieved by a stainless steel screen with 80 meshes, and 0.1g of sample is weighed to be accurate to 0.0001 g. Adding 3ml of n-hexane-acetone composite solvent containing two internal standards, vortex for 1min, placing in ultrasonic wave, performing ice bath and ultrasonic treatment for 60min, immediately centrifuging at 4500rpm for 5min on a centrifuge, separating supernatant, adding 3ml of solvent, repeating the above operation, mixing the supernatants, and mixing for later use.
3. Preparation of detection instruments, materials and reagents
Detection instruments and materials include: gas chromatography/mass spectrometer; a chromatographic column; an ultrasonic cleaner; low-speed centrifuge
The reagent comprises: mixing 18 kinds of polycyclic aromatic hydrocarbons and 5 kinds of deuterated internal standard substances thereof, mixing 15 kinds of phthalate and 6 kinds of deuterated internal standard substances thereof, wherein the solvents are suitable for gas chromatography; the chromatogram is pure hexane and acetone.
4. Conditions of the apparatus employed
Chromatographic conditions are as follows: the carrier gas is helium gas 1.0 mL/min; a constant-current non-shunt sample inlet and no glass wool liner tube is filled; the sample injection volume is 1.0 μ l; the temperature of a sample inlet is 200 ℃; column box temperature programming: the initial temperature is 80 deg.C, and is maintained for 2min, 20 deg.C/min is increased to 160 deg.C, and is maintained for 1min, 10 deg.C/min is increased to 320 deg.C, and is maintained for 10 min.
Mass spectrum conditions: the interface temperature is 300 ℃; the temperature of the EI ion source is 240 ℃; the temperature of the four-level bar is 180 ℃; ionization voltage: 70 eV; delaying the solvent for 4 min; an acquisition mode SIM; the retention time and the quantity of ions of the polycyclic aromatic hydrocarbon and the phthalic acid ester are set according to the corresponding compounds.
5. Optimization of experimental conditions was carried out
Selection of extraction solvent: polycyclic aromatic hydrocarbon belongs to a low-polarity substance, phthalic acid ester belongs to a medium-polarity substance, and in order to give consideration to the extraction efficiency of two compounds, a nonpolar solvent n-hexane and a polar solvent acetone are mixed according to the volume ratio of 3:1 to prepare a composite solvent for sample extraction.
Selection of extraction times: the same sample was extracted 2 times in succession.
6. Determining conditions of sample inlet
Polycyclic aromatic hydrocarbons and phthalic acid esters are mostly high boiling point compounds, experiments show that the gasification efficiency of the high boiling point compounds is reduced and the chromatographic peak shape is poor due to the addition of glass wool into a sample inlet liner tube (figure 1), and in order to improve the detection sensitivity, the liner tube without the addition of the glass wool is adopted, and the sample introduction is not shunted, so that the lowest detection limit is obtained.
7. Determination of internal standards used
In the experiment, deuterons of the target substances are selected as internal standard substances of the internal standard substances and are grouped according to the peak-appearing time, and each group of analytes corresponds to one internal standard substance.
8. Sample detection and concentration calculation
And (3) detecting the supernatant to be detected obtained in the step 2 on a computer through the steps 3, 4, 5, 6 and 7, collecting data twice, respectively measuring the concentration of the polycyclic aromatic hydrocarbon and the phthalic acid ester in the extract liquor, and converting the concentration into the content in the dust per unit mass according to the weight of the dust.
9. Care should be taken to avoid the use of plastic articles or containers during sample collection and handling to eliminate interference with the phthalate.
And 4, setting the retention time and the quantitative ions of the polycyclic aromatic hydrocarbon and the phthalic acid ester according to the corresponding compounds, wherein the specific retention time and the quantitative ions are shown in the following two tables. Table 1 and table 2.
Table 118 PAHs retention times and quantitation of ions
TABLE 215 phthalate retention times and quantitation of ions
The step 5 further includes the following steps:
taking polycyclic aromatic hydrocarbon as an example, for the same sample, continuous extraction is carried out for 3 times, 3ml of solvent is added for each time, the content of polycyclic aromatic hydrocarbon in each extraction liquid is measured, and the concentration is compared with that in the first extraction, so that the extraction efficiency of the second time and the third time is obtained, and the results are shown in table 3. The second extraction liquid also contains polycyclic aromatic hydrocarbon with rather high concentration, which indicates that the first extraction is not complete enough, but the concentration of the analyte in the third extraction liquid is obviously reduced and is almost less than 3% of the concentration of the first extraction liquid, which indicates that the third extraction is not necessary, so the invention adopts a mode of twice equivalent extraction.
TABLE 3 extraction efficiency (%)
Compared with the prior art, the invention has the following advantages:
1. the method can simultaneously measure 30 common organic pollutants in the similar environments such as dust accumulation or floating dust by one-time pretreatment, fully improves the availability of samples, saves the analysis cost and enlarges the analysis range.
2. The amount of samples needed by analysis is small, only 100mg is needed for analysis, the sample collection difficulty is reduced, and the method is applicable to most indoor environments.
3. The manner of ultrasound extraction allows for simultaneous processing of large batches of samples, improving analysis throughput and efficiency.
4. Liquid-liquid extraction is carried out twice, and the extraction efficiency is higher than that of 1 time of extraction.
5. The extract is directly measured without concentration, so that the sample is protected from loss to the maximum extent, and the analysis efficiency is greatly improved.
6. The system of normal hexane and acetone is used, so that the weak polar substance and the neutral substance can be efficiently extracted at the same time, and higher extraction efficiency is obtained.
7. The single-stage mass spectrometry greatly reduces the operation cost and is beneficial to the popularization and the application of patents.
8. The non-shunting arrangement of the glass wool-free sample inlet can ensure the complete gasification of high-boiling-point components and ensure the sharp and symmetrical chromatographic peak shape.
9. The internal standard method can eliminate the errors caused by signal fluctuation and sample introduction of the instrument, and ensures the stability and high consistency of results.
10. The data acquisition by selecting the ion scanning mode effectively improves the detection sensitivity and reduces the detection limit of the method.
The innovation points of the invention are as follows: according to the chemical properties of polycyclic aromatic hydrocarbon and phthalic acid ester and the solubility of the polycyclic aromatic hydrocarbon and phthalic acid ester in different solvents, a composite solvent system which is formed by initially selecting nonpolar n-hexane and acetone with medium polarity according to the volume ratio of 3:1 is well compatible with polycyclic aromatic hydrocarbon and phthalic acid ester with different polarities, and the recovery rate is improved to more than 70%; the innovation point of the invention is that indoor dust accumulation is difficult to obtain in some areas, especially urban families, the sample volume is difficult to reach 1g, the inventor initially reduces the sample volume of the air dust accumulation to 0.1g, and the universality and feasibility of the method are greatly improved.
The innovation points of the invention are as follows: by optimizing chromatographic conditions, the maximum spectrogram separation among the components is realized, and specific characteristic ions of each component are collected through the ion selection mode of the mass spectrum, so that the mutual interference is avoided, and the analysis sensitivity is improved. And finally, the internal standard substance is used to overcome the signal difference among multiple sample injections of the mass spectrum, and the stability and the accuracy of the result are ensured. The three components cooperate to realize accurate determination of a small amount of solvent on a small amount of sample.
Drawings
FIG. 1 is a comparison of an inlet liner with and without glass wool;
FIG. 2 is a diagram of total ion flow of polycyclic aromatic hydrocarbons;
fig. 3, phthalate total ion flow diagram.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
first, instrument reagent description and experimental conditions
1. Instruments, reagents and materials
6890-5973N gas chromatography/Mass spectrometer (Agilent, USA); a chromatographic column: the stationary phase was a 5% phenylmethylpolysiloxane column (Agilent, USA); EDAA-2700T ultrasonic cleaner (ultrasonic instruments, Inc. of Kunshan); model BY-400C low speed centrifuge (beijing white ocean medical devices, ltd); the solvent is applicable to gas chromatography, and the solvent comprises 18 polycyclic aromatic hydrocarbon mixed labels and 5 deuterated internal standard substance mixed labels thereof (U.S. O2si company), 15 phthalate mixed labels and 6 deuterated internal standard substance mixed labels thereof (U.S. O2si company); the chromatogram is pure hexane, acetone (Merck, Germany).
2. Conditions of the apparatus
2.1 chromatographic conditions
The chromatographic column was HP-5MS (30 m.times.0.25 mm.times.0.25 μm); the carrier gas is helium gas 1.0 mL/min;
a constant-current non-shunt sample inlet and no glass wool liner tube is filled; the sample injection volume is 1.0 μ l; the temperature of a sample inlet is 200 ℃; column box temperature programming: the initial temperature is 80 deg.C, and is maintained for 2min, 20 deg.C/min is increased to 160 deg.C, and is maintained for 1min, 10 deg.C/min is increased to 320 deg.C, and is maintained for 10 min.
2.2 Mass Spectrometry conditions
The interface temperature is 300 ℃; the temperature of the EI ion source is 240 ℃; the temperature of the four-level bar is 180 ℃; ionization voltage: 70 eV; solvent delay 4. min; an acquisition mode SIM; the retention times and the quantitative ions of 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters are shown in tables 1 and 2 respectively
Table 118 PAHs retention times and quantitation of ions
TABLE 215 phthalate retention times and quantitation of ions
3 conditions of the experiment
3.1 selection of extraction solvent
Polycyclic aromatic hydrocarbon belongs to a low-polarity substance, phthalic acid ester belongs to a medium-polarity substance, and in order to give consideration to the extraction efficiency of two compounds, a non-polar solvent n-hexane and a polar solvent acetone are mixed according to the volume ratio of 3:1 to prepare a medium-polarity composite solvent for sample extraction.
3.2 selection of extraction times
Taking polycyclic aromatic hydrocarbon as an example, for the same sample, extracting for 3 times continuously, adding 3ml of solvent each time, measuring the content of polycyclic aromatic hydrocarbon in each extraction liquid, and comparing with the concentration in the first extraction to obtain the extraction efficiency of the second and third times, the results are shown in table 3:
TABLE 3 extraction efficiency (%)
As can be seen from the results, the second extract also contains a relatively high concentration of polycyclic aromatic hydrocarbons, indicating that the first extraction is not complete enough, but the concentration of the analyte in the third extract is significantly reduced and is almost less than 3% of the concentration of the first extract, indicating that the third extraction is not necessary, so the present invention adopts two equivalent extractions.
3.2 sample injection port conditions
Polycyclic aromatic hydrocarbons and phthalic acid esters are mostly high boiling point compounds, experiments show that the gasification efficiency of the high boiling point compounds is reduced and the chromatographic peak shape is poor due to the addition of glass wool into a sample inlet liner tube (figure 1), and in order to improve the detection sensitivity, the liner tube without the addition of the glass wool is adopted, and the sample introduction is not shunted, so that the lowest detection limit is obtained.
3.3 selection of Mass Spectrometry conditions
In order to improve the sensitivity and selectivity, mass spectrum parameters are set as selected ion scanning to collect data in the experiment, ions with the highest abundance are respectively selected as quantitative ions (table 1 and table 2) according to standard spectrograms of polycyclic aromatic hydrocarbon, phthalic acid ester and respective internal standard substances, and 2-3 ions with high identification degree are selected as auxiliary qualitative ions.
3.4 selection of internal standards
In order to eliminate instrument signal fluctuation and sampling errors during sampling, deuterated substances of target substances are selected as internal standard substances in experiments, the internal standard substances are grouped according to peak-out time, each group of analytes corresponds to one internal standard substance, and calibration curve drawing and sample determination are carried out by taking the quantitative ion abundance ratio of the analytes and the internal standard substances as a vertical coordinate. Fig. 2 and 3 are total ion flow diagrams of 18 polycyclic aromatic hydrocarbons and 15 phthalates, respectively.
Second, the operation steps
1. Preparation of Standard solutions and plotting of Standard curves
Because the concentrations of polycyclic aromatic hydrocarbons and phthalates in the samples were very different, standard series of different concentration levels were prepared according to tables 4 and 5, respectively:
TABLE 4 polycyclic aromatic hydrocarbons Standard series preparation (Total volume of solution 1.0mL)
TABLE 5 phthalate Standard series preparation (Total volume of solution 1.0mL)
And (3) taking 1 mu l of each concentration of the calibration series to enter a chromatogram, acquiring data according to the instrument conditions and the ion fragment parameters, carrying out parallel sample injection for 6 times for each concentration, drawing a standard curve by taking the component concentration as a horizontal coordinate and the mean value of the ratio of the component quantitative ions to the corresponding internal standard quantitative ions as a vertical coordinate, and calculating a regression equation.
2 sample Collection and Pre-treatment
And (3) collecting the dust gently by using a clean brush in a place with more accumulated dust, carefully removing impurities such as hair, cotton wool, stone residue, paper sheets and the like, and sweeping the accumulated dust particles into a prepared tinfoil bag for sealing and storing. The dust is mixed evenly, the mixture is sieved by a stainless steel screen with 80 meshes, and 0.1g of sample is weighed to be accurate to 0.0001 g. Adding 3ml of n-hexane-acetone composite solvent containing two types of internal standard substances, placing the mixture in ultrasonic waves for ice bath and ultrasonic treatment for 60min after vortex for 1min, immediately centrifuging the mixture on a centrifuge at 4500rpm for 5min, separating out supernatant, adding 3ml of solvent, repeating the operation, combining the supernatants, uniformly mixing, collecting data twice, respectively measuring the concentration of polycyclic aromatic hydrocarbon and phthalate in extract liquor, and converting the concentration into the content in unit mass of dust according to the weight of the dust.
Care should be taken to avoid the use of plastic articles or containers during sample collection and handling to eliminate interference with the phthalate.
Third, methodological characteristics of the invention
1. Linear Range and detection limits (polycyclic aromatic hydrocarbons for example)
The near blank solution was continuously measured 10 times or more, the average value and standard deviation of the response values were calculated, and the concentration corresponding to 3 times the standard deviation was set as the detection limit of the analyte. The detection limit and the quantitation limit of each analyte were obtained as shown in table 6, with the concentration corresponding to 10 times the standard deviation as the quantitation limit of the analyte, and the concentration range between the quantitation limit and the upper limit of the curve as the measurement range:
TABLE 6 detection Limit (LOD) and quantitation Limit (LOQ) of methods
2. Method precision and accuracy
The calibration solutions with the concentrations of the middle, the middle and the high in the calibration series are added into the quality control dust sample, the precision and the accuracy of each analyte are respectively measured, each concentration point is measured for 6 times, the relative standard deviation (RSD%) and the standard addition recovery mean value are calculated, and the precision and the accuracy range of the target object are shown in a table 7.
Precision and accuracy range of the method of table 7 (n ═ 6)
Example 2:
the inventor further reduces the sample amount to 0.05g, and the result shows that the detection rate of phthalate is not influenced, but the detection rate of polycyclic aromatic hydrocarbon is reduced, most components cannot be detected particularly in areas with light polycyclic aromatic hydrocarbon pollution, and in order to improve the detection rate, only the extract can be concentrated, but the operation not only increases the pretreatment step, but also increases the risk of component loss, so that the research finally determines that 0.1g is the minimum acceptable sample amount; the sensitivity of analysis can be obviously improved by increasing the sample size, but the use volume of the extracting solution is also increased, a plurality of times of organic solvent is required to be used for extraction in order to ensure the extraction efficiency, so that waste is caused, the environment-friendly principle is not easy to follow, and certain difficulty also exists in sample collection, so that the sample size is finally determined to be 0.1g in research, and the total sample needs to be fully screened and uniformly mixed to ensure the representativeness of the sample.
The invention can be used for measuring polycyclic aromatic hydrocarbon and phthalate in indoor dust, and can also be used for measuring polycyclic aromatic hydrocarbon and phthalate compounds in road dust and atmospheric floating dust, and can provide reference for measuring other semi-volatile organic compounds in the medium.
Reference to the literature
[1] High military rigidity, auspicious rainbow, He Qiang, et al gas chromatography-tandem mass spectrometry was used to determine 16 polycyclic aromatic hydrocarbons and 16 phthalates [ J ] in soybean extracts, analytical laboratory, 2013,32(005):65-70.
[2] Zhang Rui, Wang Chenxia, Li Xiong, etc. solid phase extraction-gas chromatography-mass spectrometry method simultaneously determines polycyclic aromatic hydrocarbon and phthalate ester substances [ J ] in cosmetics, daily chemical industry, 2018,48(006):356-362.
[3] Gaxu, guojinsong, buxiong, etc. conventional water treatment processes polycyclic aromatic hydrocarbons and phthalates are distributed in varying ways [ J ]. water supply and drainage, 2007,33(001):25-29.
[4] Liu jin Yu, Fourier, Jiangying, etc. solid phase extraction-gas chromatography mass spectrometry simultaneously determines polycyclic aromatic hydrocarbons and phthalic acid esters [ J ] in seawater, proceedings of Tianjin science and technology university, 2017(2).
[5] Liao, 32704m, Popule, Zhao Yunzhi, et al tandem quadrupole mass spectrometry (GC-QqQ-MS/MS) to determine phthalates and polycyclic aromatic hydrocarbons [ J ] in soil Chinese environmental monitoring, 2008,24(5):12-16.
Claims (5)
1. A method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust with high flux and low solvent is characterized by comprising the following steps:
1) collecting indoor dust samples;
2) preprocessing the dust sample;
3) preparation of detection instruments, materials and reagents;
4) the instrumentation conditions employed;
5) optimization of experimental conditions was performed
Selection of extraction solvent: mixing a nonpolar solvent n-hexane and a polar solvent acetone according to a volume ratio of 3:1 to prepare a composite solvent for sample extraction;
6) determining the conditions of the sample inlet;
7) determining the internal standard used;
8) sample detection and concentration calculation.
2. The method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust by using the high-flux low-solvent as claimed in claim 1, wherein the method comprises the following steps:
in step 4), chromatographic conditions: the carrier gas is helium gas 1.0 mL/min; a constant-current non-shunt sample inlet and no glass wool liner tube is filled; the sample injection volume is 1.0 μ l; the temperature of a sample inlet is 200 ℃; column box temperature programming: the initial temperature is 80 deg.C, and is maintained for 2min, 20 deg.C/min is increased to 160 deg.C, and is maintained for 1min, 10 deg.C/min is increased to 320 deg.C, and is maintained for 10 min.
3. The method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust by using the high-flux low-solvent as claimed in claim 2, wherein the method comprises the following steps:
in step 4), mass spectrum conditions: the interface temperature is 300 ℃; the temperature of the EI ion source is 240 ℃; the temperature of the four-level bar is 180 ℃; ionization voltage: 70 eV; delaying the solvent for 4 min; an acquisition mode SIM; the retention time and the quantity of ions of the polycyclic aromatic hydrocarbon and the phthalic acid ester are set according to the corresponding compounds.
4. The method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust by using the high-flux low-solvent as claimed in claim 1, wherein the method comprises the following steps:
in step 1) and step 2), plastic products or containers are avoided.
5. The method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust by using the high-flux low-solvent as claimed in claim 1, wherein the method comprises the following steps:
in step 5), selecting the extraction times: the same sample was extracted 2 times in succession.
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