CN112326841A - Detection and analysis method of halogenated carbazole in water body sediment - Google Patents
Detection and analysis method of halogenated carbazole in water body sediment Download PDFInfo
- Publication number
- CN112326841A CN112326841A CN202011354013.0A CN202011354013A CN112326841A CN 112326841 A CN112326841 A CN 112326841A CN 202011354013 A CN202011354013 A CN 202011354013A CN 112326841 A CN112326841 A CN 112326841A
- Authority
- CN
- China
- Prior art keywords
- sample
- temperature
- water body
- core sample
- concentrating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000001514 detection method Methods 0.000 title claims abstract description 15
- 239000013049 sediment Substances 0.000 title claims abstract description 15
- 238000004458 analytical method Methods 0.000 title claims abstract description 13
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title claims abstract description 9
- 239000000523 sample Substances 0.000 claims abstract description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000011084 recovery Methods 0.000 claims abstract description 21
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 9
- 230000008014 freezing Effects 0.000 claims abstract description 9
- 239000003480 eluent Substances 0.000 claims abstract description 8
- 238000005070 sampling Methods 0.000 claims abstract description 8
- 238000002137 ultrasound extraction Methods 0.000 claims abstract description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 7
- 238000004451 qualitative analysis Methods 0.000 claims abstract description 6
- 238000004445 quantitative analysis Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 239000012468 concentrated sample Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 229920000742 Cotton Polymers 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000000700 radioactive tracer Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 150000001716 carbazoles Chemical class 0.000 description 14
- 239000013076 target substance Substances 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9h-carbazole Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FNHISDQCWYSMTO-UHFFFAOYSA-N 1,3,6,8-tetrabromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC(Br)=C3NC2=C1Br FNHISDQCWYSMTO-UHFFFAOYSA-N 0.000 description 1
- XEUQVTHGXKXLBB-UHFFFAOYSA-N 1,3,6,8-tetrachloro-9h-carbazole Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC(Cl)=C3NC2=C1Cl XEUQVTHGXKXLBB-UHFFFAOYSA-N 0.000 description 1
- LMYCYTOEMHSFKR-UHFFFAOYSA-N 1,3,6-tribromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1Br LMYCYTOEMHSFKR-UHFFFAOYSA-N 0.000 description 1
- QIZKWIUIKHLXJQ-UHFFFAOYSA-N 1,8-dibromo-3,6-dichloro-9H-carbazole Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC(Br)=C3NC2=C1Br QIZKWIUIKHLXJQ-UHFFFAOYSA-N 0.000 description 1
- AAXKJEWUYLSARD-UHFFFAOYSA-N 1-bromo-3,6-dichloro-9H-carbazole Chemical compound BrC1=CC(=CC=2C3=CC(=CC=C3NC1=2)Cl)Cl AAXKJEWUYLSARD-UHFFFAOYSA-N 0.000 description 1
- BIMDTNQPZWJKPL-UHFFFAOYSA-N 3,6-dichloro-9h-carbazole Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC=C3NC2=C1 BIMDTNQPZWJKPL-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- CABSFELLEWZIAK-UHFFFAOYSA-N 3-chloro-9h-carbazole Chemical compound C1=CC=C2C3=CC(Cl)=CC=C3NC2=C1 CABSFELLEWZIAK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000185 dioxinlike effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a detection and analysis method of halogenated carbazole in water body sediments, which comprises the following steps of S1: freezing and storing the core sample, freezing and drying the sample before analysis, crushing the core sample, and sieving the crushed core sample by a 200-mesh sieve; s2: adding anhydrous sodium sulfate and copper powder into a sieved mud core sample, grinding, filtering, transferring to an extraction device, adding two tracing marks and 150mL of dichloromethane, performing ultrasonic extraction for 20-30 minutes, and performing Soxhlet extraction for 36-48 hours; s3: concentrating the extract, purifying with multi-chromatographic column, and eluting with mixed eluent of n-hexane and dichloromethane; s4: collecting eluate after passing through the column, concentrating the eluate to 1.5-2 mL under a vacuum condition, adding a normal hexane conversion solvent into the flask, and concentrating to 1.5-2 mL; s5: taking the concentrated sample in S4, and determining the recovery rate of the target object in a gas chromatography-mass spectrometer; s6: and (4) sampling the concentrated and volume-fixed sample in the S4 into a gas chromatography-mass spectrometry gas mass spectrometer for qualitative and quantitative analysis.
Description
Technical Field
The invention relates to the technical field of halogenated carbazole residue detection, in particular to a method for detecting and analyzing halogenated carbazole in water body sediments.
Background
Halogenated Carbazoles (PHCs) are a new class of halogenated organic pollutants with a similar structure to polychlorinated dibenzo-barking furans, first detected by Kuehl in Buffalo River deposits in the united states in the 80's of the 20 th century. PHCs have attracted attention in recent years due to their dioxin-like toxicity, persistence, bioaccumulation, and the like. At present, the research on the halogenated carbazole at home and abroad is still in a preliminary stage, relevant basic and background data are relatively lacking, and particularly, the problem of the source of the halogenated carbazole in the environment is not clear.
PHCs are novel pollutants which are concerned only in recent years, and no standard detection and analysis method in an environmental medium is established at home so far.
Few methods for detecting and analyzing PHCs have the defects of low target extraction rate, low sensitivity of detection limits of certain components, low extraction speed and the like.
Disclosure of Invention
The invention aims to provide a method for detecting and analyzing halogenated carbazole in water body sediments, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a detection and analysis method of halogenated carbazole in water body sediments comprises the following steps:
s1: freezing and storing the loam core sample at 0-minus 20 ℃, freezing and drying the sample at-20-minus 30 ℃ before analysis, removing impurities in the loam core sample after freezing and drying, crushing the loam core sample and sieving the loam core sample by a 200-mesh sieve;
s2: taking 10-15 g of sieved mud core sample, adding 1.5-2 g of anhydrous sodium sulfate and 1.5-2 g of copper powder, grinding, filtering, transferring to an extraction device, adding two carbon-containing isotope labeled organic substance tracer labels with similar polarity and 150mL of dichloromethane, performing ultrasonic extraction for 20-30 minutes, and performing Soxhlet extraction at 40-45 ℃ for 36-48 hours;
s3: concentrating the extract to 1.5-2.0 ml, purifying by using a multi-chromatography column with filler comprising absorbent cotton, anhydrous sodium sulfate, alumina, neutral silica gel and anhydrous sodium sulfate from bottom to top, and eluting the chromatography column by using an eluting agent mixed by normal hexane and dichloromethane;
s4: collecting eluate after passing through the column, concentrating the eluate to 1.5-2 mL under a vacuum condition, adding a normal hexane conversion solvent into the flask, and concentrating to 1.5-2 mL;
s5: adding an internal standard substance of the organic matters with similar polarities and marked by carbon isotopes into the concentrated sample obtained in the step S4, and determining the recovery rate of the target object by using a gas chromatography-mass spectrometer;
s6: and (4) sampling the concentrated and volume-fixed sample in the S4 into a gas chromatography-mass spectrometry gas mass spectrometer for qualitative and quantitative analysis.
As a further scheme of the invention: and in the step S1, vertically sampling and depositing a loam core sample through a 9-11cm polyethylene pipe, and after the loam core is lifted out of the water surface, ejecting the loam core upwards from the bottom by using a core ejector on site.
As a further scheme of the invention: in the step S2, the added tracer is marked as13C12-PCB141And13C12-PCB208。
as a further scheme of the invention: in the step S2, the temperature of Soxhlet extraction is controlled to be 40-45 ℃ by a water bath kettle.
As a further scheme of the invention: and the filling material of the multi-layer chromatographic column in the step S3 sequentially comprises absorbent cotton, 2g of anhydrous sodium sulfate, 8g of alumina, 4g of neutral silica gel and 2g of anhydrous sodium sulfate from bottom to top.
As a further scheme of the invention: the eluent in the step S3 is 100mL of a mixed solution of n-hexane and dichloromethane in a volume ratio of 4: 1.
As a further scheme of the invention: the eluent in the step S3 is 100mL of a mixed solution of n-hexane and dichloromethane in a volume ratio of 4: 1.
As a further scheme of the invention: and in the step S4, concentrating by using a rotary evaporator, keeping the rotating speed of the rotary evaporator at 30r/min when the n-hexane conversion solvent is not added for concentration, keeping the rotating speed unchanged after the n-hexane conversion solvent is added at the concentration water bath temperature of 45 ℃, heating the water bath to 50-55 ℃ for concentration, and adding 10mL of the n-hexane conversion solvent.
As a further scheme of the invention: in the step S5, a sample injection needle measures 100uL of the concentrated and constant volume sample in the step S4, and 5uL of internal standard substance is added, wherein the internal standard substance is13C12-PCB202。
As a further scheme of the invention: in the step S6, the sample injection amount is 2.0uL in the quantitative and qualitative analysis of the gas chromatography-mass spectrometry gas mass spectrometer; selecting an analysis method in an ion mode; adopting a non-shunting mode for sample injection; the chromatographic column used is DB-5 MS; the temperature-raising program is set as follows: maintaining the initial temperature of 70 deg.C for 2min, increasing the temperature to 120 deg.C at 10 deg.C/min, increasing the temperature to 200 deg.C at 5 deg.C/min, maintaining the temperature for 15min, and increasing the temperature to 280 deg.C at 5 deg.C/min; the ion source temperature is 250 ℃, and the injection port temperature is 280 ℃; the carrier gas was high purity helium with a flow rate of 1.0 mL/min.
Compared with the prior art, the invention has the beneficial effects that: by improving the extraction and concentration modes and the Soxhlet extraction temperature, compared with the detection method in the prior art, the method has the advantages that the target extraction rate is improved, the detection limit is lower, and the time is faster after the obtained target object is tested on a computer.
Drawings
FIG. 1 is a chromatogram of a target.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and 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.
Example 1
A detection and analysis method of halogenated carbazole in water body sediments comprises the following steps:
s1: using a 9-11cm polyethylene pipe to vertically sample and deposit a layer, and taking a top core on site after the mud core is lifted out of the water surfaceEjecting the sand core from the bottom upwards by the device, cutting the sand core by a cutter at intervals of 1.5cm, directly putting the well-cut sand core sample into a polyethylene sealed bag and numbering, freezing and storing at-20 ℃, freeze-drying the sand core sample at-30 ℃ until the water in the sand core sample is removed, removing impurities in the freeze-dried sand core sample, crushing and sieving by a 200-mesh sieve, weighing the sand core sample treated in the step four, transferring to a sealed centrifuge tube, sealing and standing for more than 3 weeks, and performing an on-machine test to test the sand core sample210Pb，40.2 5KeV；226Ra，300KeV；137Cs, 560Kev, completing the collection and pretreatment of samples, testing the age of the deposition column core of different cutting sections and providing conditions for analyzing the change characteristics of the halogenated carbazole in the deposition column core of different ages;
s2: accurately weighing 10g of sieved core sample into a mortar, adding 2g of anhydrous sodium sulfate and 2g of copper powder to remove residual moisture and sulfur respectively, fully grinding the mixture to be uniform, transferring the mixture to a glass fiber filter cylinder, transferring the glass fiber filter cylinder to an extraction tube, adding a tracer standard13C12-PCB141And13C12-PCB208the method comprises the following steps of firstly carrying out ultrasonic extraction for 30 minutes by using 150mL of dichloromethane as an extracting agent, and then carrying out Soxhlet extraction for 48 hours in a water bath kettle at the temperature of 40-45 ℃ to complete the extraction of a sample, wherein the ultrasonic extraction enables deposits to be uniformly mixed, so that a target object in the deposits can be more sufficiently separated out in the Soxhlet extraction stage, and the recovery rate of the target object is greatly increased by combining the ultrasonic extraction with the Soxhlet extraction;
s3: concentrating the extract by a rotary evaporator, purifying by adopting a multi-layer chromatographic column with filler comprising absorbent cotton, 2g of anhydrous sodium sulfate, 8g of alumina, 4g of neutral silica gel and 2g of anhydrous sodium sulfate from bottom to top in sequence, better preventing and treating the interference of other impurities by the absorbent cotton at the tail end of the column, adopting a Teflon plug for the multi-chromatographic column, and using 100mL of normal hexane: eluting the target substance by using the eluent with the dichloromethane ratio of 4:1 to complete the purification and purification of the sample;
s4: collecting eluate after passing through the column, putting the eluate in a flask, connecting the flask containing the extracting solution with a rotary evaporator, keeping the rotating speed at 30r/min under the condition of vacuumizing by connecting a circulating water vacuum pump, controlling the water bath temperature at 45 ℃, concentrating the extracting solution in the flat-bottomed flask to be less than 2ml, adding 10ml of n-hexane conversion solvent in the rotating process, keeping the rotating speed unchanged, heating the water bath to 50-55 ℃, concentrating the extracting solution in the flat-bottomed flask to about 2ml, and finishing the concentration of the extracting solution;
s5: the sample injection needle measures 100uL of sample after constant volume, and 5uL of sample is added13C12The recovery rate of the target object is measured by an internal standard substance of the PCB202 in a gas chromatography-mass spectrometer, and the recovery rate of the target object measured by the method is 96.23%;
s6: firstly, scanning single-standard products of carbazole and halogenated compounds thereof by using a gas chromatography-mass spectrometry gas chromatography, sampling a sample with a concentrated constant volume in S4 into the gas chromatography-mass spectrometry gas chromatography for qualitative and quantitative analysis, wherein a used chromatographic column is DB-5MS, the temperature rise program is that the initial temperature is 70 ℃ and is kept for 2min, 10 ℃/min is increased to 120 ℃, 5 ℃/min is increased to 200 ℃, the initial temperature is kept for 15min, 5 ℃/min is increased to 280 ℃, the ion source temperature is 250 ℃, the sampling port temperature is 280 ℃, the carrier gas is high-purity helium, the flow rate is 1.0mL/min, the sampling is carried out by adopting a non-shunt mode, the sampling amount is 2.0uL, an analysis method in an ion mode (SIM) is selected, and the retention time, the qualitative ions and the detection limit of a target compound are determined from a mass spectrogram (figure 1) of each substance detected by the instrument, see table 1.
TABLE 1
| Target object | Retention time | Quantitative and qualitative ion | Detection Limit (ng/g) |
| Carbazole | 17.75 | 139/167/166 | 0.061 |
| 3-chlorocarbazole | 22.35 | 166/201/203 | 0.112 |
| 3-bromocarbazole | 24.39 | 245/247/166 | 0.187 |
| 3, 6-dichlorocarbazole | 26.15 | 235/237/166 | 0.111 |
| 1,3,6, 8-tetrachlorocarbazole | 26.30 | 269/267/303/305 | 0.123 |
| 1-bromo-3, 6-dichlorocarbazole | 27.40 | 315/313/79/81 | 0.107 |
| 2, 7-dibromocarbazole | 28.91 | 325/323/247.2/245.2 | 0.321 |
| 3, 6-dibromocarbazole | 29.15 | 325/323/79/81 | 0.301 |
| 1, 8-dibromo-3, 6-dichlorocarbazole | 30.95 | 393/395/315/313 | 0.019 |
| 1,3, 6-tribromocarbazole | 32.98 | 404.9/402.9/325.1/323.1 | 0.131 |
| 1,3,6, 8-tetrabromocarbazole | 33.56 | 482.8/480.8/402.8/404.8 | 0.051 |
Referring to example 1 above, some important factors in the implementation were examined
Influence of the Soxhlet extraction temperature
In the study of the effect of the Soxhlet extraction temperature on the recovery rate, the other steps were the same as those in example 1, except that the Soxhlet extraction temperature was controlled differently in step S2, and the recovery rates of the target substances were examined when the Soxhlet extraction temperatures were respectively selected to 30 ℃, 35 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃ and 50 ℃, as shown in Table 2, and when the temperature was controlled to 40-45 ℃, the recovery efficiency of the extracted target substances was the highest, so 40-45 ℃ was selected as the Soxhlet extraction temperature.
TABLE 2
| Water bath temperature setting for Soxhlet extraction | Recovery rate of target |
| 30℃ | 43.1％ |
| 35℃ | 65.9％ |
| 40℃ | 89.9％ |
| 42℃ | 90.8％ |
| 45℃ | 90.3％ |
| 48℃ | 85.3％ |
| 50℃ | 82.8％ |
(II) influence of extraction means
In the study of the influence of the selection of the extraction means on the recovery rate, the other steps are the same as those in example 1, the difference is that the extraction selection means in the step S2 is different, and the recovery rates of the target substances in the case of soxhlet extraction only, ultrasonic extraction only and ultrasonic soxhlet combination extraction are examined, wherein the recovery rate of the target substance in the case of soxhlet extraction only reaches 89.11%, the recovery rate of the target substance in the case of ultrasonic extraction only reaches 85.23%, and the recovery rate of the target substance in the case of ultrasonic soxhlet combination extraction reaches 96.23%.
(III) Effect of concentration means of leacheate
In the study of the influence of the selection of the eluent concentration means on the recovery rate, the other steps were the same as those in example 1 except that the eluent concentration selection means in step S4 was different, and the recovery rates of the target substances were examined when the rotary evaporation concentration nitrogen blower and the rotary evaporation concentration apparatus under vacuum were used for the eluent after passing through the column, wherein the recovery rate of the target substance was 90.35% by the rotary evaporation concentration nitrogen blower and 97.12% by the rotary evaporation concentration apparatus under vacuum, and it was found that the recovery rate of the target substance was higher when the rotary evaporation concentration apparatus under vacuum was used, and therefore, the present invention was concentrated by rotary evaporation under vacuum.
The method for detecting and analyzing the halogenated carbazole in the water body sediment adopts a new extraction means in the field of detecting the halogenated carbazole, does not appear in the prior field of detecting the halogenated carbazole, greatly improves the recovery rate of the target object of the halogenated carbazole by improving the temperature of Soxhlet extraction and adopting rotary concentration under a vacuum condition, has the recovery rate of the target object of 96.23 percent, reduces the loss of the target object, has lower detection limit during subsequent on-machine test of concentrated solution, saves the operation time of the whole detection process, and lays a good foundation for establishing the standard of the method for detecting the halogenated carbazole in the sediment.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A detection and analysis method for halogenated carbazole in water body sediments is characterized by comprising the following steps:
s1: freezing and storing the loam core sample at 0-minus 20 ℃, freezing and drying the sample at-20-minus 30 ℃ before analysis, removing impurities in the loam core sample after freezing and drying, crushing the loam core sample and sieving the loam core sample by a 200-mesh sieve;
s2: taking 10-15 g of sieved mud core sample, adding 1.5-2 g of anhydrous sodium sulfate and 1.5-2 g of copper powder, grinding, filtering, transferring to an extraction device, adding two carbon-containing isotope labeled organic substance tracer labels with similar polarity and 150mL of dichloromethane, performing ultrasonic extraction for 20-30 minutes, and performing Soxhlet extraction at 40-45 ℃ for 36-48 hours;
s3: concentrating the extract to 1.5-2.0 ml, purifying by using a multi-chromatography column with filler comprising absorbent cotton, anhydrous sodium sulfate, alumina, neutral silica gel and anhydrous sodium sulfate from bottom to top, and eluting the chromatography column by using an eluting agent mixed by normal hexane and dichloromethane;
s4: collecting eluate after passing through the column, concentrating the eluate to 1.5-2 mL under a vacuum condition, adding a normal hexane conversion solvent into the flask, and concentrating to 1.5-2 mL;
s5: adding an internal standard substance of the organic matters with similar polarities and marked by carbon isotopes into the concentrated sample obtained in the step S4, and determining the recovery rate of the target object by using a gas chromatography-mass spectrometer;
s6: and (4) sampling the concentrated and volume-fixed sample in the S4 into a gas chromatography-mass spectrometry gas mass spectrometer for qualitative and quantitative analysis.
2. The method for detecting and analyzing halogenated carbazole in water body sediments according to claim 1, wherein in the step S1, a loam core sample is vertically sampled and deposited through a polyethylene pipe with the length of 9-11cm, and after the loam core is lifted out of the water surface, a core lifter is used on site to lift the loam core from the bottom upwards.
3. The method according to claim 1, wherein the tracer added in step S2 is labeled as13C12-PCB141And13C12-PCB208。
4. the method for detecting and analyzing halogenated carbazole in water body sediments according to claim 1, wherein in the step S2, the temperature of Soxhlet extraction is controlled to be 40-45 ℃ through a water bath.
5. The method according to claim 1, wherein the filler of the multi-layer chromatography column in the step S3 comprises absorbent cotton, 2g of anhydrous sodium sulfate, 8g of alumina, 4g of neutral silica gel, and 2g of anhydrous sodium sulfate from bottom to top.
6. The method for detecting and analyzing halogenated carbazole in water body sediments according to claim 1, wherein the eluent in the step S3 is 100mL of a mixed solution of n-hexane and dichloromethane in a volume ratio of 4: 1.
7. The method according to claim 1, wherein in the step S4, a rotary evaporator is used for concentration, and when n-hexane conversion solvent is not added for concentration, the rotary evaporator maintains the rotation speed of 30r/min and the concentration water bath temperature is 45 ℃, after the n-hexane conversion solvent is added, the rotation speed is kept unchanged, the water bath is heated to 50-55 ℃ for concentration, and the amount of the added n-hexane conversion solvent is 10 mL.
8. The method for detecting and analyzing halogenated carbazole in water body sediment according to claim 1, wherein in the step S5, a sample injection needle measures 100uL of the concentrated volume-determined sample in S4, and 5uL of an internal standard substance is added, wherein the internal standard substance is13C12-PCB202。
9. The method for detecting and analyzing halogenated carbazole in water body sediments according to claim 1, wherein in the step S6, the sample injection amount is 2.0uL in quantitative and qualitative analysis by adopting a gas chromatography-mass spectrometry gas mass spectrometer; selecting an analysis method in an ion mode; adopting a non-shunting mode for sample injection; the chromatographic column used is DB-5 MS; the temperature-raising program is set as follows: maintaining the initial temperature of 70 deg.C for 2min, increasing the temperature to 120 deg.C at 10 deg.C/min, increasing the temperature to 200 deg.C at 5 deg.C/min, maintaining the temperature for 15min, and increasing the temperature to 280 deg.C at 5 deg.C/min; the ion source temperature is 250 ℃, and the injection port temperature is 280 ℃; the carrier gas was high purity helium with a flow rate of 1.0 mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011354013.0A CN112326841A (en) | 2020-11-26 | 2020-11-26 | Detection and analysis method of halogenated carbazole in water body sediment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011354013.0A CN112326841A (en) | 2020-11-26 | 2020-11-26 | Detection and analysis method of halogenated carbazole in water body sediment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112326841A true CN112326841A (en) | 2021-02-05 |
Family
ID=74308966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011354013.0A Pending CN112326841A (en) | 2020-11-26 | 2020-11-26 | Detection and analysis method of halogenated carbazole in water body sediment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112326841A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111534458A (en) * | 2020-04-13 | 2020-08-14 | 浙江工业大学 | Achromobacter TBC-1 and application thereof in degradation of 1,3,6,8-tetrabromocarbazole |
| CN113376305A (en) * | 2021-07-13 | 2021-09-10 | 浙江省海洋水产研究所 | Solid-phase membrane extraction gas chromatography-mass spectrometry detection method for carbazole and polyhalogen carbazole in water body |
| CN114354790A (en) * | 2021-12-28 | 2022-04-15 | 舟山市食品药品检验检测研究院 | Method for detecting 7 halogenated carbazole compounds in aquatic product |
| CN114814054A (en) * | 2022-04-14 | 2022-07-29 | 舟山市食品药品检验检测研究院 | Method for detecting 10 halogenated carbazole compounds in marine sediments |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003041519A1 (en) * | 2001-11-09 | 2003-05-22 | Vector Tobacco Inc. | Extraction method for polyaromatic hydrocarbon analysis |
| CN104237436A (en) * | 2014-09-03 | 2014-12-24 | 上海大学 | Qualitative screening method of semi-volatile halogenated organic pollutants in sediments |
| CN106124661A (en) * | 2016-07-11 | 2016-11-16 | 环境保护部华南环境科学研究所 | The monomer stabilization carbon isotope analysis method of PBDE in deposit |
| CN107607648A (en) * | 2017-09-14 | 2018-01-19 | 浙江省海洋水产研究所 | The solid phase extraction GC MS detection method of phthalate compound in a kind of deposit |
| CN107703245A (en) * | 2017-09-25 | 2018-02-16 | 广东产品质量监督检验研究院 | The detection method of biocide in textile |
| CN109164176A (en) * | 2018-07-09 | 2019-01-08 | 江苏理工学院 | A kind of method of n-alkane in detection Atmospheric particulates |
| CN109187837A (en) * | 2018-09-27 | 2019-01-11 | 合肥学院 | The detection method of organo-chlorine pesticide in a kind of sedimentary column core |
| CN110927296A (en) * | 2019-12-20 | 2020-03-27 | 广电计量检测(合肥)有限公司 | Pretreatment and quantitative analysis method for linear alkylbenzene in soil/sediment |
| US20200225131A1 (en) * | 2019-01-11 | 2020-07-16 | King Fahd University Of Petroleum And Minerals | Ultrasound-assisted solvent extraction of analytes from porous membrane packed solid samples |
| CN111812229A (en) * | 2020-06-19 | 2020-10-23 | 广电计量检测(合肥)有限公司 | Analysis method for measuring 2-methylbenzothiazole in soil/sediment through gas chromatography-mass spectrometry |
-
2020
- 2020-11-26 CN CN202011354013.0A patent/CN112326841A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003041519A1 (en) * | 2001-11-09 | 2003-05-22 | Vector Tobacco Inc. | Extraction method for polyaromatic hydrocarbon analysis |
| CN104237436A (en) * | 2014-09-03 | 2014-12-24 | 上海大学 | Qualitative screening method of semi-volatile halogenated organic pollutants in sediments |
| CN106124661A (en) * | 2016-07-11 | 2016-11-16 | 环境保护部华南环境科学研究所 | The monomer stabilization carbon isotope analysis method of PBDE in deposit |
| CN107607648A (en) * | 2017-09-14 | 2018-01-19 | 浙江省海洋水产研究所 | The solid phase extraction GC MS detection method of phthalate compound in a kind of deposit |
| CN107703245A (en) * | 2017-09-25 | 2018-02-16 | 广东产品质量监督检验研究院 | The detection method of biocide in textile |
| CN109164176A (en) * | 2018-07-09 | 2019-01-08 | 江苏理工学院 | A kind of method of n-alkane in detection Atmospheric particulates |
| CN109187837A (en) * | 2018-09-27 | 2019-01-11 | 合肥学院 | The detection method of organo-chlorine pesticide in a kind of sedimentary column core |
| US20200225131A1 (en) * | 2019-01-11 | 2020-07-16 | King Fahd University Of Petroleum And Minerals | Ultrasound-assisted solvent extraction of analytes from porous membrane packed solid samples |
| CN110927296A (en) * | 2019-12-20 | 2020-03-27 | 广电计量检测(合肥)有限公司 | Pretreatment and quantitative analysis method for linear alkylbenzene in soil/sediment |
| CN111812229A (en) * | 2020-06-19 | 2020-10-23 | 广电计量检测(合肥)有限公司 | Analysis method for measuring 2-methylbenzothiazole in soil/sediment through gas chromatography-mass spectrometry |
Non-Patent Citations (15)
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111534458A (en) * | 2020-04-13 | 2020-08-14 | 浙江工业大学 | Achromobacter TBC-1 and application thereof in degradation of 1,3,6,8-tetrabromocarbazole |
| CN111534458B (en) * | 2020-04-13 | 2022-01-14 | 浙江工业大学 | Achromobacter TBC-1 and application thereof in degradation of 1,3,6,8-tetrabromocarbazole |
| CN113376305A (en) * | 2021-07-13 | 2021-09-10 | 浙江省海洋水产研究所 | Solid-phase membrane extraction gas chromatography-mass spectrometry detection method for carbazole and polyhalogen carbazole in water body |
| CN114354790A (en) * | 2021-12-28 | 2022-04-15 | 舟山市食品药品检验检测研究院 | Method for detecting 7 halogenated carbazole compounds in aquatic product |
| CN114354790B (en) * | 2021-12-28 | 2024-05-10 | 舟山市食品药品检验检测研究院 | Method for detecting 7 halogenated carbazole compounds in aquatic product |
| CN114814054A (en) * | 2022-04-14 | 2022-07-29 | 舟山市食品药品检验检测研究院 | Method for detecting 10 halogenated carbazole compounds in marine sediments |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112326841A (en) | Detection and analysis method of halogenated carbazole in water body sediment | |
| CN112051347B (en) | GC-MS quantitative method capable of simultaneously and rapidly analyzing 41 persistent organic matters in soil | |
| CN107884493B (en) | Method for analyzing short-chain chlorinated paraffin in environmental sample by using full-two-dimensional gas chromatography-time-of-flight mass spectrometry | |
| CN104280485B (en) | A kind of simultaneous extraction, purify and detect the method for chloro polycyclic aromatic hydrocarbon in soil | |
| CN111812229B (en) | Analysis method for determining 2-methylbenzothiazole in soil/sediment by gas chromatography-mass spectrometry | |
| CN113391015A (en) | Method for detecting 14 phenolic compounds in soil | |
| CN110927296A (en) | Pretreatment and quantitative analysis method for linear alkylbenzene in soil/sediment | |
| CN112684042A (en) | Method for simultaneously purifying various semi-volatile organic pollutants in soil analysis process | |
| CN113773332A (en) | Method for extracting ellagic acid from blue brave by using ultrasonic-assisted deep eutectic solvent | |
| CN111272909A (en) | Method for detecting anthraquinone and anthrone substances in soil and sediment | |
| CN107102074A (en) | The GC MS analysis methods of polycyclic aromatic hydrocarbon in a kind of quantitative analysis aquatic products | |
| Faraji et al. | β-cyclodextrin-bonded silica particles as novel sorbent for stir bar sorptive extraction of phenolic compounds | |
| Redondo et al. | Determination of pesticides in soil samples by solid phase extraction disks | |
| CN106908539B (en) | Method for detecting 1-hydroxybenzotriazole in soil and plants | |
| CN111337610B (en) | Method for detecting trace estrogen, nonyl phenol and bisphenol A in complex environment matrix | |
| CN113219093A (en) | Method for detecting pyridaphenthion, pyridaben, cypermethrin and lambda-cyhalothrin in soil or sediment | |
| CN110441427B (en) | Method for detecting unmetabolized polycyclic aromatic hydrocarbons in urine based on low-temperature freezing extraction technology | |
| CN111272932A (en) | Separation and purification method of sixteen polycyclic aromatic hydrocarbons in soil and detection method of stable carbon isotopes of monomers | |
| CN111044647A (en) | Sample pretreatment and quantitative analysis method for detecting linear alkylbenzene in water body | |
| CN111085006A (en) | Process for extracting organic pollutants in environment | |
| CN114814054B (en) | Method for detecting 10 halogenated carbazole compounds in marine sediments | |
| CN110879165A (en) | Sample pretreatment method of organochlorine pesticide residue sample | |
| CN113244902A (en) | Application of natural high molecular material loofah sponge as solid phase extraction adsorbent | |
| CN111220722A (en) | Method for simultaneously determining 8 p-hydroxybenzoate compounds in soil | |
| CN114660190B (en) | Method for detecting herbicidal ether pesticide residues in soil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210205 |
|
| RJ01 | Rejection of invention patent application after publication |