CN113495108A - Method for simultaneously detecting 63 persistent organic pollutants in soil - Google Patents
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Abstract
The invention provides a method for simultaneously detecting 63 persistent organic pollutants in soil, which comprises the following steps: s1, preparing instruments, reagents and materials; s2, preparing 6 concentration series standard curves of 63 POPs; s3, processing a sample; and S4, measuring organic pollutants. The method solves the problems of high reagent dosage, long extraction time, relatively low ultrasonic extraction efficiency and poor stability of the traditional detection method such as Soxhlet extraction, has more batch processing advantages compared with accelerated solvent extraction, and has the advantages of high recovery rate, good reproducibility, low reagent consumption, rapidness, simplicity and convenience and capability of realizing batch processing of samples.
Description
Technical Field
The invention relates to the technical field of soil pollutant detection, in particular to a method for simultaneously detecting 63 persistent organic pollutants in soil.
Background
Polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), Polycyclic Aromatic Hydrocarbons (PAHs) and Phthalic Acid Esters (PAEs) are typical Persistent Organic Pollutants (POPs) and are widely present in the environment. POPs in soil can migrate and transform in the atmosphere, surface water and underground water in a volatilization, diffusion mode and other modes, and can finally enter a food chain through biological accumulation, thereby posing threats to the ecological environment and human health. Therefore, research on persistent organic pollutants in soil has been the focus of attention both at home and abroad.
The method for measuring POPs in soil mainly comprises the steps of extraction, concentration, purification, instrument measurement and the like, and has the advantages of long analysis period, large consumption of reagents and consumables and strong labor investment. Foreign detection methods for single organic pollutants are mature, and researchers tend to the synchronous analysis trend of multi-component compounds in recent years. The pollutants are compounds with weak polarity, have similar properties, have more common points in pretreatment and instrument analysis methods, and theoretically can realize simultaneous detection of multiple components. If the method can be simultaneously analyzed, the timeliness of the method is improved, and the monitoring cost can be reduced, but the high-throughput analysis method aiming at simultaneous pretreatment and instrumental determination of the four types of persistent organic pollutants in the soil is not few at present.
Most of the domestic existing standard analysis methods aim at the analysis of certain compounds, and the soil sample is generally required to be extracted within 7-10 days after being collected, so that the timeliness requirement is high. With the increasingly strict control of the country on the soil environment, the requirement on soil monitoring is increasing day by day, and for example, the development of a high-throughput analysis method for simultaneously measuring multi-component POPs in soil is of great significance in a multi-component organic analysis project for national soil investigation of a large number of samples.
From the Extraction point of view, due to the defects of large reagent dosage, long Extraction time, relatively low ultrasonic Extraction efficiency, poor stability and the like of the conventional Extraction mode such as soxhlet Extraction, researchers prefer rapid and efficient Extraction technologies such as Accelerated Solvent Extraction (ASE) and Microwave Assisted Extraction (MAE) to extract organic pollutants in soil. Compared with solvent extraction acceleration, the microwave-assisted extraction technology has the advantages of lower reagent consumption, less instrument pipelines, simple experimental operation, capability of simultaneously processing more than 40 samples, more batch processing advantage, novel green environment-friendly extraction technology and common use for extracting POPs (persistent organic solvents) in soil.
From the purification perspective, common purification methods for measuring organic pollutants include acid washing, composite silica gel chromatographic columns, gel permeation chromatography, solid phase extraction and the like, the acid washing or acidic silica gel purification effect is good, but organic chlorine pesticides, polycyclic aromatic hydrocarbons and phthalate compounds can be oxidized by concentrated sulfuric acid, the equipment investment of a gel permeation chromatograph is high, the number of instruments and pipelines is large, the interference of PAEs is easily introduced, and in order to realize a high-flux analysis method, a magnesium silicate small column with a broad spectrum is often selected for purification of an environmental matrix sample through solid phase extraction and purification.
Low-temperature partitioning (LTPE) is a purification technique that has been proven to be superior in recent years and is used to analyze organic contaminants in various matrices. The detection instrument comprises a High Performance Liquid Chromatography (HPLC), a gas chromatography (GC-ECD), a gas chromatography-mass spectrometer (GC-MS), a gas chromatography-tandem mass spectrometry (GC-MS/MS), a high resolution magnetic mass spectrometry (HRGC-HRMS) and the like. The GC-MS equipment is popularized, the probability of the occurrence of false positive samples is reduced by using a selective ion scanning mode for detection, the sensitivity and the selectivity are high, and the detection result is accurate and reliable.
A high-flux analysis method for simultaneously carrying out experimental treatment and instrument detection on 18 polychlorinated biphenyls, 23 organochlorine pesticides, 16 polycyclic aromatic hydrocarbons and 6 phthalic acid esters in soil by microwave-assisted extraction, low-temperature distribution purification, gas chromatography-mass spectrometry is established. Experiments show that the method has high recovery rate and good parallelism, can meet the detection and analysis requirements of the 63 POPs in the soil, has batch processing advantages when analyzing a large number of samples, and can greatly improve the working efficiency.
Disclosure of Invention
The technical problem solved by the invention is as follows: at present, POPs in soil are measured mainly by the steps of extraction, concentration, purification and instrument measurement, wherein the analysis period of the extraction and purification steps is long, the consumption of reagents and consumables is high, the labor investment is high, and the effects of high throughput and batch processing cannot be achieved.
The technical scheme of the invention is as follows:
a method for simultaneously detecting 63 persistent organic pollutants in soil, comprising the steps of:
s1, Instrument, reagent, and Material preparation
Wherein the material comprises: 16 kinds of polycyclic aromatic hydrocarbon mixed standard substances, 23 kinds of OCPs mixed standard substances, 18 kinds of PCBs mixed standard substances and 6 kinds of phthalate mixed standard substances, wherein the extraction internal standard substance is as follows: 5 deuterated polycyclic aromatic hydrocarbon mixed standard substances, 5 organic chlorine pesticides marked by 13C, 5 polychlorinated biphenyl marked by 13C, and an internal sample injection standard: d10-pyrene, 13C-p, p' -DDE, 13C-PCB 138;
s2, preparing 6 concentration series standard curves of 63 POPs
The concentration range of PCBs is 0.005, 0.01, 0.05, 0.1, 0.2, 0.5. mu.g/mL-1The concentrations of the extraction internal standard and the injection internal standard are both 0.1 mu g.mL-1The concentration range of OCPs is 0.02, 0.05, 0.1, 0.5, 1.0, 5.0. mu.g/mL-1The concentrations of the extraction internal standard and the injection internal standard are both 0.5 mu g.mL-1Concentrations of PAHs and PAEs are in the range of 0.1, 0.25, 0.5, 1.0, 5.0, 10.0 μ g/mL-1The concentrations of the extracted internal standard and the sample injection internal standard are both 1.0 ng.mL-1；
S3 sample treatment
Mixing and grinding fresh sample soil and a proper amount of anhydrous sodium sulfate, and adding n-hexane: after the acetone mixed reagent is extracted, placing the mixture into a low-temperature refrigerator for standing for 4 hours, and filtering the mixture to be detected;
s4, organic pollutant measurement
Organic contaminants were measured by gas chromatography-mass spectrometer.
Further, in step S1, the apparatus includes: the instrument comprises: two gas chromatography-mass spectrometer ally oneself with appearance, a microwave extraction appearance, a nitrogen blowing appearance, a low temperature refrigerator, the reagent includes: the low-temperature distribution technology is based on the principle of similarity and intermiscibility, under the low-temperature condition, the solubility of strong-polarity impurities or interfering matrixes in a weak-polarity organic solvent is rapidly reduced and analyzed out, or the purification purpose is achieved by means of the filtration of the microporous filter membrane, and the freezing time and the solubility of an extracting agent to the compounds are important factors influencing low-temperature distribution.
Further, in step S1, the material further includes: the soil contains 18 PCBs (polychlorinated biphenyls) certified standard substances, 23 OCPs certified standard substances, 16 PAHs (polycyclic aromatic hydrocarbons) certified standard substances and 6 PAEs certified standard substances, and is convenient for subsequent calculation of sample precision and accuracy.
Further, 5 deuterated polycyclic aromatic hydrocarbon mixed standards comprise: d8-naphthalene, D10-acenaphthene, D10-phenanthrene, D12-
D12-perylene, which facilitates the subsequent calculation of sample precision and accuracy.
Further, the 5 13C-labeled organochlorine pesticides include: 13C-alpha-hexachloro cyclohexane, 13C-gamma-chlordane, 13C-o, p ' -DDE, 13C-p, p ' -DDD, 13C-p, p ' -DDT, 5 kinds of 13C marked polychlorinated biphenyl comprise: the 13C-PCB28, the 13C-PCB52, the 13C-PCB 101, the 13C-PCB153 and the 13C-PCB180 are convenient for the subsequent calculation of the precision and the accuracy of the sample.
Preferably, step S3 specifically includes the following sub-steps:
s31, mixing and grinding 10.0g of soil of a fresh sample and a proper amount of anhydrous sodium sulfate uniformly, and filling the mixture into a teflon microwave tank;
s32, adding an isotope extraction internal standard, adding 30mL of n-hexane according to the volume ratio: extracting with acetone at a ratio of 1:1 at 115 deg.C for 15 min;
s33, performing rotary evaporation and concentration on the extracting solution, blowing to about 0.5mL by using n-hexane to transfer dissolved nitrogen, standing for 4h in a low-temperature refrigerator with the ambient temperature of-20 ℃, taking supernatant or filtering into a sample injection bottle by using a microporous filter membrane, adding a sample injection internal standard, and waiting for detection.
Preferably, in step S4, the organic contaminant is measured by a gas chromatograph-mass spectrometer, in the measurement process, the instrument conditions include gas chromatograph conditions and mass spectrometer conditions, and the gas chromatograph-mass spectrometer is configured with a Z-shaped channel at the rear end of the ion source, so that the interference of neutral impurities in the sample can be effectively removed, thereby reducing the matrix effect in the sample detection, which is expressed in that the noise reduction performance is superior, and the compound chromatographic peak can obtain a higher signal-to-noise ratio, so that the signal-to-noise ratios of the chromatographic peaks of samples with close matrix to each other have no obvious difference.
Preferably, the gas chromatographic conditions are: the chromatographic column is Rxi-XLB, the sample inlet temperature is 280 ℃, the carrier gas is helium with 99.999 percent purity, the flow rate of the column is 1.0mL/min, the sample injection amount is 1 mu L, the split-flow sample injection is not carried out, and the temperature rise program is as follows: after the temperature is kept at 70 ℃ for 2min, the temperature is raised to 140 ℃ at the speed of 25 ℃/min, then raised to 240 ℃ at the speed of 10 ℃/min, raised to 280 ℃ at the speed of 5 ℃/min and kept for 4min, and finally raised to 320 ℃ at the speed of 10 ℃/min and kept for 5 min.
Further preferably, the mass spectrometry conditions are: the ion source is an EI source, the electron energy is 70eV, the ion source temperature is 300 ℃, the transmission line temperature is 300 ℃, the ion source is one of the main components of the mass spectrometer, and the ion source is composed of an ionization chamber, an acceleration field of ion beams, a focusing lens and the like, and has the function of ionizing an analyte into molecular ions or fragment ions to realize a sample ionization area.
The invention has the beneficial effects that:
the method is rapid, simple and convenient, high in recovery rate and good in reproducibility, can meet the detection requirements of 63 POPs in soil, is simple to operate and has batch processing advantages compared with conventional pretreatment purification, and can greatly improve the working efficiency and save the monitoring cost when a large number of samples are analyzed.
Drawings
FIG. 1 is a graph of signal-to-noise ratio of target PCBs as a function of cryopreservation time;
FIG. 2 is a graph of signal-to-noise ratio of target PAEs as a function of cryopreservation time;
FIG. 3 is a graph of signal to noise ratio of OCPs as a function of cryopreservation time;
FIG. 4 is a graph of signal to noise ratio of target PAHs as a function of time at low temperature;
FIG. 5 is a schematic of the chromatographic peak signal-to-noise ratio for the non-decontamination experiment;
FIG. 6 is a graph of signal to noise ratio after cryogenic dispense purge;
FIG. 7 is a graph showing signal to noise ratio after solid phase extraction purification;
fig. 8 is a flow chart of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and "a plurality" typically includes at least two unless the context clearly indicates otherwise.
It should be understood that although the terms first, second, third, etc. may be used to describe … … in embodiments of the present invention, these … … should not be limited to these terms. These terms are used only to distinguish … …. For example, the first … … can also be referred to as the second … … and similarly the second … … can also be referred to as the first … … without departing from the scope of embodiments of the present invention.
Examples
As shown in fig. 8, a method for simultaneously detecting 63 persistent organic pollutants in soil comprises the following steps:
s1, Instrument, reagent, and Material preparation
Gas chromatography-mass spectrometer (Thermo, TSQ 8000EVO), gas chromatography-mass spectrometer (Waters, Micromass Quattro) microwave extractor (Milestone, ETHOS UP 44 site), rotary evaporator (BUCHI, V-100), nitrogen blower (EYELA, MG-2200), cryorefrigerator (sea, DW-40W 380).
N-hexane, dichloromethane, acetone (Honeywell, pesticide residue grade), magnesium silicate solid phase extraction column (CNW, 1g, glass material), microporous filter membrane (ampere spectrum, 0.22um), anhydrous sodium sulfate (guangzhou brand chemical reagent, analytical purification), and quartz sand (guangzhou brand chemical reagent, analytical purification).
16 kinds of polycyclic aromatic hydrocarbon mixed standard substances, 23 kinds of OCPs mixed standard substances, 18 kinds of PCBs mixed standard substances and 6 kinds of phthalate mixed standard substances are all purchased from Accustandard. Extracting an internal standard: 5 deuterated polycyclic aromatic hydrocarbon mixed standard products (including D8-naphthalene, D10-acenaphthene, D10-phenanthrene and D12-
D12-perylene), available from Accustandard; 5 kinds of 13C-labeled organochlorine pesticides (including 13C-alpha-hexachloro cyclohexane, 13C-gamma-chlordane, 13C-o, p ' -DDE, 13C-p, p ' -DDD, 13C-p, p ' -DDT) purchased from CIL; 5 kinds of 13C-labeled polychlorinated biphenyl (including 13C-PCB28, 13C-PCB52, 13C-PCB 101, 13C-PCB153,
13C-PCB180) purchased from CIL. Sample injection internal standard: d10-pyrene, available from Accustandard; 13C-p, p' -DDE and 13C-PCB138, available from CIL.
18 kinds of PCBs (Sigma-Aldrich, CRM962) in soil, 23 kinds of OCPs (ERA, 093) in soil, 16 kinds of PAHs (ERA, 722) in soil and 6 kinds of PAEs (RUM 001) in soil.
S2, preparing 6 concentration series standard curves of 63 POPs
The concentration range of PCBs is 0.005, 0.01, 0.05, 0.1, 0.2, 0.5. mu.g/mL-1，
Extraction ofThe concentrations of the internal standard and the sample injection internal standard are both 0.1 mug.mL-1The concentration range of OCPs is 0.02, 0.05, 0.1, 0.5, 1.0, 5.0. mu.g/mL-1The concentrations of the extraction internal standard and the injection internal standard are both 0.5 mu g.mL-1，
PAHs and PAEs concentration ranges of 0.1, 0.25, 0.5, 1.0, 5.0 and 10.0 mug/mL-1The concentrations of the extracted internal standard and the sample injection internal standard are both 1.0 ng.mL-1；
S3, sample processing, wherein the sample processing specifically comprises the following substeps:
s31, mixing and grinding 10.0g of soil of the fresh sample and a proper amount of anhydrous sodium sulfate, filling the mixture into a Teflon microwave tank,
s32, adding an isotope extraction internal standard, adding 30mL of n-hexane: acetone (1:1) mixed reagent, microwave extracting at 115 deg.C for 15min,
s33, performing rotary evaporation and concentration on the extracting solution, blowing the extracting solution to about 0.5mL by using n-hexane to transfer dissolved nitrogen, standing the extracting solution for 4 hours in a low-temperature refrigerator at the ambient temperature of 20 ℃ below zero, taking supernate or filtering the supernate into a sample injection bottle by using a microporous filter membrane, adding a sample injection internal standard, and waiting for detection;
s4, organic pollutant measurement
Measuring the organic pollutants by a gas chromatography-mass spectrometer, wherein in the measuring process, the gas chromatography conditions are as follows: the chromatographic column is Rxi-XLB, the sample inlet temperature is 280 ℃, the carrier gas is helium with 99.999 percent purity, the flow rate of the column is 1.0mL/min, the sample injection amount is 1 mu L, the split-flow sample injection is not carried out, and the temperature rise program is as follows: keeping the temperature at 70 ℃ for 2min, heating to 140 ℃ at the speed of 25 ℃/min, heating to 240 ℃ at the speed of 10 ℃/min, heating to 280 ℃ at the speed of 5 ℃/min, keeping for 4min, heating to 320 ℃ at the speed of 10 ℃/min, keeping for 5min, and carrying out mass spectrum analysis under the following conditions: the ion source is an EI source, the electron energy is 70eV, the ion source temperature is 300 ℃, the transmission line temperature is 300 ℃, an ion scanning mode is selected, and the quantification is performed by an isotope internal standard method. Table 1 shows the retention time, quantitative ion, qualitative ion and quantitative relationship of 18 PCBs, 23 OCPs, 16 PAHs and 6 PAEs with the internal standard.
Retention time, quantitation ion, auxiliary ion and quantitation internal standard for the compounds of table 1
Examples of the experiments
Verification experiment for optimal time of low-temperature distribution purification
The low-temperature distribution technology is based on the principle of similar and compatible solution, under the low-temperature condition, the solubility of strong-polarity impurities or interfering matrixes in a weak-polarity organic solvent is rapidly reduced and analyzed out, or the purification purpose is achieved by virtue of microporous membrane filtration, the freezing time and the solubility of an extracting agent to compounds are important factors influencing low-temperature distribution,
considering that the target objects PCBs, OCPs, PAHs and PAEs have low polarity, the experiment uses a proven reference substance as a sample, a solvent system for low-temperature distribution of extraction liquid selects normal hexane with low polarity commonly used for pretreatment of organic experiments as a reagent, time gradients of 0, 1, 2, 3, 4, 6, 8 and 16h are designed under the condition of-20 ℃, and the change of the signal-to-noise ratio of a compound chromatographic peak is measured in a full-scan mode.
The compound obtained by the determination of a gas chromatography-mass spectrometer (Thermo, TSQ 8000) has good response effect, and the signal-to-noise ratio of chromatographic peaks under different time conditions has no difference. The principle is as follows: the gas chromatography-mass spectrometer is provided with a Z-shaped channel at the rear end of an ion source, so that the interference of neutral impurities in a sample can be effectively removed, the matrix effect in the sample detection is reduced, the noise reduction performance is excellent, the chromatographic peak of a compound can obtain higher signal-to-noise ratio, and the signal-to-noise ratio of the chromatographic peak of the sample with the similar measured matrix has no obvious difference.
Therefore, the same condition detection was set with a gas chromatograph-mass spectrometer (Waters, Micromass Quattro) having a relatively weak noise reduction function.
The result shows that the sample content is lower, such as PCB126, PCB157, benzo [ a ] pyrene and the like, the signal-to-noise ratio is less than 20, and the reliability of comparison difference is low. Part of organochlorine pesticides such as endosulfan, aldrin, mirex and the like have very low response in the instrument, the signal-to-noise ratio is less than 10, and no statistical analysis is carried out.
FIG. 1 shows the variation of the signal-to-noise ratio of PCBs, the variation of the signal-to-noise ratio of PAEs, the variation of the signal-to-noise ratio of OCPs, the variation of OCPs, and the variation of PAHs. As can be seen from fig. 1 to 4, with the extension of the storage time, the signal-to-noise ratio of most of compound chromatographic peaks can be improved by 1.5 to 3 times in about 4 hours, and the signal-to-noise ratio is slightly fluctuated after 4 hours but has no significant difference, and it is presumed that the phase equilibrium is reached by low-temperature distribution after 4 hours, which is similar to the conclusion that the best extraction condition is obtained by a researcher s s.m. goulart (2010) keeping 3 hours at-20 ℃.
Therefore, it can be verified that the optimum condition for using the low-temperature distribution purification extract is to maintain for 4 hours at-20 ℃.
Method of Performance parameter measurement experiment
The content of PCBs is 1 mu g/kg-1The content of OCPs is 5 mug/kg-1The content of PAHs and PAEs is 10 mug/kg-1The quartz sand blank of (1) was subjected to 8 parallel analyses by adding a standard, and 2.998-fold standard deviation of the measurement results was calculated as a method detection limit, and 4-fold method detection limit was set as a measurement lower limit.
The soil matrix spiked samples at the two concentration levels were analyzed in parallel 6 times, respectively, and the precision and accuracy of the samples were calculated and the results are shown in table 2.
As shown in Table 2, when the sample volume was 10.0g and the final volume was 0.5 mL:
the detection limit of PCBs is 0.1-0.2 mug/kg-1The lower limit of the measurement is between 0.4 and 0.8 mu g/kg-1, and the content is 2.0 mu g/kg-1And 5.0. mu.g.kg-1The standard recovery range of the soil matrix is 96-113%, and the Relative Standard Deviation (RSD) is 0.9-4.1%.
The detection limit of OCPs by the method is 0.3-1.5 mu g/kg-1The lower limit of measurement is 1.2-6.0. mu.g/kg-1The content is 10.0 mu g/kg-1And 50.0. mu.g.kg-1The standard recovery range of the soil matrix is 80-119%, and the Relative Standard Deviation (RSD) is 0.5-7.9%.
The detection limit of PAHs is 0.4-1.9 mug/kg-1The lower limit of the measurement is 1.6 to 7.6. mu.g/kg-1The content is 20.0 mu g/kg-1And 200. mu.g.kg-1The standard recovery rate of the soil matrix is in a range of 76-111%, and the Relative Standard Deviation (RSD) is 0.4-3.8%.
The detection limit of PAEs is 1.0-2.2 mug.kg-1The lower limit of measurement is 4.0-8.8 mug/kg-1The content is 20.0 mu g/kg-1And 200. mu.g.kg-1The standard recovery rate of the soil matrix is 91-116%, and the Relative Standard Deviation (RSD) is 1.7-4.8%.
Method performance parameter determination table for 263 POPs
Actual soil sample analysis
The actual soil sample is analyzed for 3 times in parallel, and the recovery rate range of the isotope extraction internal standard is 79-119% according to the test result. No PCBs of 18 species were detected, most OCPs were not detected, only delta-hexachloro, p, p ' -DDE, p, p ' -DDD, p, p ' -DDT were detected,the concentration range is 0.5-14.5 mug/kg-1(RSD: 1.9% -7.0%), a detection rate of 100% of 16 PAHs, and a concentration range of 28.0 mug/kg-1-400μg·kg-1(RSD: 0.2% -11.1%), PAEs detection indexes are dibutyl phthalate, butyl benzyl phthalate and di (2-ethyl) hexyl phthalate, and the concentration range is 1.5-10.5 mu g/kg-1(RSD：0.7％-1.5％)。
The method is used for analyzing PCBs, OCPs, PAHs and PAEs standard substances in the soil (n is 3), as shown in Table 3, the measurement results of the PCBs, the OCPs and the PAHs are all in the compound quality control range, the PAEs standard substances in the soil only give extension uncertainty and do not give a qualified interval, as shown in Table 4, the recovery rate of the target substances is 56-89%, and the RSD is 0.1-3.2%.
TABLE 3 determination results of PCBs, OCPs and PAHs standard substances in soil
TABLE 4 determination of PAEs standard in soil
Comparison with related purification methods
The method comprises the following steps of selecting magnesium silicate small column solid phase extraction purification with high universality recommended by the existing environment-related standard and comparing with low-temperature distribution purification, concentrating extract liquor of soil proved reference substances to 0.5mL to be used as a non-purification reference sample, and selecting a commercialized glass magnesium silicate small column (1g) by using 9mL of n-hexane for a solid phase extraction purification test reference HJ 835: acetone (9:1) was eluted and concentrated to 0.5mL, and the low temperature partition purification assay was performed 3 replicates per treatment, according to the procedure described above.
The results of the assay show that as shown in table 5, the recovery of the compound is between 50% and 119%, and the recovery of the same compound is not significantly different in different treatment modes, showing the trend of no-purification control (54% to 119%) > low-temperature partition purification (50% to 114%) > magnesium silicate solid phase extraction purification (49% to 112%).
This shows that the experimental process is long, the operation is many, the sample will be lost to some extent, and the recovery rate will be reduced. The results of the three treatment methods are that PCBs, OCPs and PAHs are all in a qualified interval. The content of the proved reference substances of the PAEs is high, the relative concentration multiple of a synchronous experiment is large, the determination recovery rate of the compound is 56% -90%, but the qualified interval is not given by the standard substance, and the determination result is used as the reference. The relative standard deviation of the measured results shows that the RSD of the low-temperature distribution purification (0.1% -10.6%) is generally reduced and the height of the magnesium silicate solid phase extraction purification (0.23% -14.2%) is changed compared with that of the control non-purification (1.1% -13.0%). It is assumed that the RSD of the sample is better after the decontamination treatment because the background of the sample matrix is reduced after the decontamination, the sample repeatability is better, and the RSD is worse, probably because the experimental steps are prolonged and the compound parallelism is worse.
TABLE 5 recovery and relative standard deviation results for the three decontamination mode compounds
Analyzing the signal-to-noise ratio of the compound chromatographic peak, comparing the low-temperature distribution purification test with the solid-phase extraction purification test, wherein the response of individual compound instruments is lower, and the signal-to-noise ratio is not compared, fig. 5 is a schematic diagram of the signal-to-noise ratio of the partial chromatographic peak of the non-purification test, fig. 6 is a schematic diagram of the signal-to-noise ratio of the partial chromatographic peak of the low-temperature distribution purification, and fig. 7 is a schematic diagram of the signal-to-noise ratio of the partial chromatographic peak of the phase extraction purification.
As can be seen from FIGS. 5-7, the signal-to-noise ratio after the low-temperature distribution purification and the solid-phase extraction purification can be improved by about 1.5-3 times. Therefore, after the extraction liquid is distributed at low temperature, certain background interference can be reduced, the signal-to-noise ratio of a chromatographic peak is improved, and the purification effect is equivalent to that of magnesium silicate solid phase extraction. The method only needs to place the extraction concentrated solution in a low-temperature refrigerator, does not need manual operation in the purification process, reduces the investment of reagents and consumables, simplifies the experimental flow, and reduces the experimental secondary pollution of PAHs and PAEs in particular. In addition, compared with a non-purification test, the matrix background can be reduced after the sample is subjected to low-temperature distribution treatment, and the protection of a detection instrument is facilitated.
Conclusion
The method adopts microwave-assisted extraction-low-temperature distribution purification-GC/MS to establish a method for simultaneously analyzing 18 polychlorinated biphenyls, 23 organochlorine pesticides, 16 polycyclic aromatic hydrocarbons and 6 phthalic acid esters in soil, realizes the simultaneous extraction, purification and determination of the compounds in soil samples, meets the detection requirements of related environmental standard methods, improves the efficiency of analysis and test of mass samples, reduces the monitoring cost, and is an analytical method worth popularizing.
Claims (9)
1. A method for simultaneously detecting 63 persistent organic pollutants in soil is characterized by comprising the following steps:
s1, Instrument, reagent, and Material preparation
Wherein the material comprises: 16 kinds of polycyclic aromatic hydrocarbon mixed standard substances, 23 kinds of OCPs mixed standard substances, 18 kinds of PCBs mixed standard substances and 6 kinds of phthalate mixed standard substances, wherein the extraction internal standard substance is as follows: 5 deuterated polycyclic aromatic hydrocarbon mixed standard substances, 5 organic chlorine pesticides marked by 13C, 5 polychlorinated biphenyl marked by 13C, and an internal sample injection standard: d10-pyrene, 13C-p, p' -DDE, 13C-PCB 138;
s2, preparing 6 concentration series standard curves of 63 POPs
The concentration range of PCBs is 0.005, 0.01, 0.05, 0.1, 0.2, 0.5. mu.g/mL-1Concentration of extracted internal standard and injected internal standard0.1. mu.g/mL-1The concentration range of OCPs is 0.02, 0.05, 0.1, 0.5, 1.0, 5.0. mu.g/mL-1The concentrations of the extraction internal standard and the injection internal standard are both 0.5 mu g.mL-1Concentrations of PAHs and PAEs are in the range of 0.1, 0.25, 0.5, 1.0, 5.0, 10.0 μ g/mL-1The concentrations of the extracted internal standard and the sample injection internal standard are both 1.0 ng.mL-1；
S3 sample treatment
Mixing and grinding fresh sample soil and a proper amount of anhydrous sodium sulfate, and adding n-hexane: after the acetone mixed reagent is extracted, placing the mixture into a low-temperature refrigerator for standing for 4 hours, and filtering the mixture to be detected;
s4, organic pollutant measurement
Organic contaminants were measured by gas chromatography-mass spectrometer.
2. The method for simultaneously detecting 63 persistent organic pollutants in soil as claimed in claim 1, wherein in the step S1, the instrument comprises: two gas chromatography-mass spectrometer ally oneself with appearance, a microwave extraction appearance, a nitrogen blowing appearance, a low temperature refrigerator, the reagent includes: n-hexane, dichloromethane, acetone, magnesium silicate solid phase extraction column, microporous filter membrane, and quartz sand.
3. The method for simultaneously detecting 63 persistent organic pollutants in soil as claimed in claim 1, wherein in step S1, the material further comprises: the soil contains 18 PCBs (polychlorinated biphenyls) certified standard substances, 23 OCPs certified standard substances, 16 PAHs (polycyclic aromatic hydrocarbons) certified standard substances and 6 PAEs certified standard substances.
4. The method of claim 1, wherein the 5 deuterated polycyclic aromatic hydrocarbon mixed standards comprise: d8-naphthalene, D10-acenaphthene, D10-phenanthrene, D12-
D12-perylene.
5. The method of simultaneously detecting 63 persistent organic pollutants in soil as claimed in claim 1 wherein said 5 13C labeled organochlorine pesticides comprise: 13C-alpha-hexachloro cyclohexane, 13C-gamma-chlordane, 13C-o, p ' -DDE, 13C-p, p ' -DDD, 13C-p, p ' -DDT, 5 kinds of 13C marked polychlorinated biphenyl comprise: 13C-PCB28, 13C-PCB52, 13C-PCB 101, 13C-PCB153, 13C-PCB 180.
6. The method for simultaneously detecting 63 persistent organic pollutants in soil as claimed in claim 5, wherein the step S3 specifically comprises the following sub-steps:
s31, mixing and grinding 10.0g of soil of a fresh sample and a proper amount of anhydrous sodium sulfate uniformly, and filling the mixture into a teflon microwave tank;
s32, adding an isotope extraction internal standard, adding 30mL of n-hexane according to the volume ratio: extracting with acetone at a ratio of 1:1 at 115 deg.C for 15 min;
s33, performing rotary evaporation and concentration on the extracting solution, blowing to about 0.5mL by using n-hexane to transfer dissolved nitrogen, standing for 4h in a low-temperature refrigerator with the ambient temperature of-20 ℃, taking supernatant or filtering into a sample injection bottle by using a microporous filter membrane, adding a sample injection internal standard, and waiting for detection.
7. The method for simultaneously detecting 63 persistent organic pollutants in soil as claimed in claim 6, wherein in the step S4, the instrument conditions comprise gas chromatography conditions and mass spectrometry conditions during the measurement.
8. The method for simultaneously detecting 63 persistent organic pollutants in soil as claimed in claim 7, wherein the gas chromatographic conditions are as follows: the chromatographic column is Rxi-XLB, the sample inlet temperature is 280 ℃, the carrier gas is helium with 99.999 percent purity, the flow rate of the column is 1.0mL/min, the sample injection amount is 1 mu L, the split-flow sample injection is not carried out, and the temperature rise program is as follows: keeping the temperature at 70 ℃ for 2min, heating to 140 ℃ at the speed of 25 ℃/min, heating to 240 ℃ at the speed of 10 ℃/min, heating to 280 ℃ at the speed of 5 ℃/min, keeping for 4min, heating to 320 ℃ at the speed of 10 ℃/min, and keeping for 5 min.
9. The method for simultaneously detecting 63 persistent organic pollutants in soil as claimed in claim 8, wherein the mass spectrometry conditions are as follows: the ion source is an EI source, the electron energy is 70eV, the ion source temperature is 300 ℃, and the transmission line temperature is 300 ℃.
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